CN104326455A - Production method for preparing monopotassium phosphate and by-product special fertilizer for Taxus chinensis - Google Patents
Production method for preparing monopotassium phosphate and by-product special fertilizer for Taxus chinensis Download PDFInfo
- Publication number
- CN104326455A CN104326455A CN201410478329.9A CN201410478329A CN104326455A CN 104326455 A CN104326455 A CN 104326455A CN 201410478329 A CN201410478329 A CN 201410478329A CN 104326455 A CN104326455 A CN 104326455A
- Authority
- CN
- China
- Prior art keywords
- solution
- potassium
- fertilizer
- ramulus
- special fertilizer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Fertilizers (AREA)
Abstract
The invention relates to the field of chemical technique, especially to a production method for preparing monopotassium phosphate and a by-product a special fertilizer for Taxus chinensis. By changing coefficients such as temperature and the like of wet-process phosphoric acid preparation of monopotassium phosphate, purity of the product monopotassium phosphate is raised, and a compound fertilizer containing N, P and K combined forms can simultaneously be produced. In addition, formaldehyde is added into a filtrate to prepare a controlled-release compound fertilizer. By the method, purity of monopotassium phosphate can be raised, and the produced special fertilizer for Taxus chinensis has good absorptivity. Meanwhile, the produced special fertilizer for Taxus chinensis can meet nutritional requirements of each period of growth cycle of Taxus chinensis. The special fertilizer 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 potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer.
Background technology
Potassium primary phosphate, be widely used in the crop of the almost all types such as all types of cash crop, grain, melon and fruit, vegetables, there is remarkable increasing both production and income, the amount of changing optimizes many excellent effects such as quality, resistant to lodging, disease and insect resistance, control early ageing, and have and overcome the aging receptivity of plant growth later stage root system and decline and the malnourished effect that causes, belonging to novel high density phosphorus potassium Was Used compound manure, is efficient phosphorus potassium complex fertilizer agriculturally.Current domestic a lot of fertilizer producer is all at production compound fertilizer of potassium dihydrogen phosphate, its production method mainly contains neutralisation, extraction process, ion exchange method, double decomposition, direct method, crystallization process and electrolytic process etc., wherein double decomposition comprises thermal phosphoric acid and phosphoric acid by wet process produces potassium primary phosphate, and thermal phosphoric acid cost is larger, unsuitable as extensively promoting, therefore, Wet-process Phosphoric Acid Production potassium dihydrogen phosphate product becomes main method, and the basic step of wet process phosphoric acid for preparing phosphoric acid 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+KOH＝KH
2PO
4+H
2O+CO(NH
2)
2
React at 40 ~ 80 DEG C in whole reaction, there is not any change after the completion of reaction in a large amount of carboxamides, 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, K in filtrate
+, 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, meanwhile, the purity of the dipotassium hydrogen phosphate crystal of precipitation is not high.
Ramulus et folium taxi cuspidatae, also known as Japanese yew, Chi Baisong.It is the rare plants for anticancer being on the brink of to become extinct of generally acknowledging in the world.One of lonely left ancient seeds of quaternary glacier.Nearly 2,500,000 years are grown on earth.About the strain of wild Ramulus et folium taxi cuspidatae 2,500 ten thousand is only deposited at present in the tool report whole world.The organic evolution of slow length and gene genetic impart the internal structure of this species uniqueness, taxol (TAXOL), taxol are exactly one of extract of this plant, in state-owned 4 kind of 1 mutation, namely Chinese Ramulus et folium taxi cuspidatae, taxus chinensis in northeast, taxusyunnanensis, southerm yew, Xizang Taxus chinensis etc., be distributed in northeast, south China and southwest.The areas such as Sichuan is mainly distributed in Mao County, Heisui River, Maerkang, Wenchuan, Luding, Kangding, Xichang, can manages, Miyi.The wild taxus resource overcut of China increases the weight of day by day, wild taxus resource has suffered serious destruction, so need a large amount of artificial cultures, in Ramulus et folium taxi cuspidatae fertilizer practice, often when planting, use common farm manure, and then add nitrogen, phosphorus, potash fertilizer every year, the growing way of its Ramulus et folium taxi cuspidatae is slow, and soil compaction is serious.
According to another report:
The plant absorption utilization ratio of carboxamide, carbon ammonium is: 20%-46%;
The plant absorption utilization ratio of phosphate fertilizer (two ammoniums, an ammonium, coarse whiting) is: 10%-25%;
The plant absorption utilization ratio of common potash fertilizer is: 45%-60%.
Unabsorbed mixing is fertile, easily causes soil compaction, mixing simultaneously fertile release and lose too fast, the later stage soaks or fertilizer decompose themselves because of rainwater, causes the nutrition in soil cannot supply the needs of Ramulus et folium taxi cuspidatae, causes the growing way of Ramulus et folium taxi cuspidatae slow down or rest.
For in Wet-process Phosphoric Acid Production potassium primary phosphate process, the purity of potassium primary phosphate is not high, also containing a large amount of undecomposed carboxamide, K in filtrate
+, 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 Ramulus et folium taxi cuspidatae special fertilizer and the absorbing state of Ramulus et folium taxi cuspidatae are studied, effectively inquire into out and produce Ramulus et folium taxi cuspidatae special fertilizer from the filtrate of Wet-process Phosphoric Acid Production potassium primary phosphate, the purity solving Wet-process Phosphoric Acid Production potassium primary phosphate is not high, in filtrate, effective constituent such as cannot to utilize at the problem, the effect of the good and realizing controlled-release of the specific absorption of this special fertilizer simultaneously, at home in fertiliser production, have no report.
Summary of the invention
For above technical problem, the invention provides a kind of production method preparing potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer, by the process production design of uniqueness, improve the purity of potassium primary phosphate, make full use of the effective constituent of phosphoric acid by wet process potassium dihydrogen phosphate making simultaneously, produce out the Ramulus et folium taxi cuspidatae special fertilizer of applicable growth of taxol.
The present invention is achieved by the following technical solutions:
A kind of production method preparing potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer provided by the invention, mainly comprises the following steps:
1) adopt phosphoric acid to mix with carboxamide, and be that 6 DEG C/min is warming up to 160 DEG C from 80 DEG C with heat-up rate, stirring reaction 4-5h, be separated and obtain intermediate; This intermediate is adopted to mix with alkaline potassium salt again, adjust ph is 8.5-9.0, after reaction terminates, obtain nitrogenous, phosphorus, potassium slip, and the slip of nitrogenous, phosphorus, potassium is placed in cooling crystallizer cools to 35 ~ 40 DEG C, carry out crystallization filtration treatment, make filtrate circulation crystallization process in cooling crystallizer, the filter cake obtained is potassium dihydrogen phosphate product, detects the component content in filtrate;
2) in filtrate, formaldehyde solution is added, with the content of the pH value of calcium hydroxide, potassium hydroxide and phosphoric acid solution regulator solution and nitrogen, phosphorus, potassium, calcium component, mixed solution is put into retort, pressure is increased to 8 ~ 10 normal atmosphere, be rapidly heated 85 DEG C time, with the ramp of 5 ~ 6 DEG C/min, when reaching 120 DEG C, keep 2 ~ 3h;
3) by step 2) solution that obtains is divided into two parts,
Get the solution fast cooling to 60 DEG C of a deal and leave standstill under being depressurized to normal pressure, called after solution A,
The solution getting a deal puts into a retort, increases pressure, and simultaneous temperature with the ramp of 1 ~ 2 DEG C/min, when temperature reaches 95 DEG C, keeps 0.5 ~ 1h, called after solution B from 85 DEG C;
4) by step 3) solution A that obtains, be cooled to 60 ~ 65 DEG C after B mixing, and add a certain amount of H
2sO
4solution, regulates pH to the scope of 7.0 ~ 7.4, adds the one at least in a small amount of zinc sulfate, copper sulfate, manganous sulfate, ammonium molybdate, ferrous sulfate, chelated iron, borax, leave standstill 0.5 ~ 1h, obtain solution C;
5) by step 4) in the solution C that obtains be cooled to 20 ~ 25 DEG C, carry out crystallization filtration treatment, obtain chemical combination state composite fertilizer just finished product, when the content of the nitrogen component in chemical combination state composite fertilizer just finished product be 16-19%, phosphorus composition content is 3-7%, potassium component content is 11-14% time, calcium component content be 10-15% time, stop crystallization;
6) granulation is dried, in this step, first by step 5) the chemical combination state composite fertilizer of separating out just finished product be made into the particle that diameter is 0.2 ~ 0.4cm, be then placed in the ammonia environment that temperature is 45 ~ 50 DEG C, flow velocity is 3 ~ 4m/s and dry, make Ramulus et folium taxi cuspidatae special fertilizer.
The mol ratio that described phosphoric acid mixes with carboxamide is (1.2-1.5): 1.
The mol ratio that described intermediate mixes with alkaline potassium is 1:(1.1-1.4).
The mol ratio of the carboxamide contained in described formaldehyde and solution is (0.8 ~ 0.9): 1.
Described step 2) calcium hydroxide concentration is 35 ~ 40%, the concentration of potassium hydroxide is 30 ~ 35%, and the concentration of phosphoric acid solution is 20 ~ 25%.
Described step 2) pH value of regulator solution and nitrogen, phosphorus, potassium, calcium component content be specially: pH value is 8.5 ~ 9.0, and when the content of nitrogen component is 18-25%, phosphorus composition content is 4-8%, potassium component content is 12-16%, calcium component content is 12 ~ 18%.
Described step 3) increase pressure be specially: when rising to 2 normal atmosphere fast, with the speed of 50 ~ 100Pa/min increase normal atmosphere, remain unchanged when reaching 3 normal atmosphere.
Described step 4) sulfuric acid concentration be 5 ~ 15%.
Described Ramulus et folium taxi cuspidatae special fertilizer is the Chemical Mixed Fertilizer of chemical combination state.
The Chemical Mixed Fertilizer of described chemical combination state contains
the potassiumphosphate composite fertilizer of root, and a small amount of
the chemical combination state composite fertilizer of urea aldehyde.
In the present invention, by carboxamide and phosphoric acid at 80 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
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, when adding potassium ion compound, dihydrogen phosphate and potassium ion react and generate potassium primary phosphate, and in succession reach capacity simultaneously; 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, when carrying out intensification and pressure treatment, 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, there is following characteristics in the present invention:
1. in the filtrate of conventional wet lay phosphoric acid potassium dihydrogen phosphate making, be rich in carbon amide solution, the solubleness at the same temperature of carboxamide is relatively large, and isolated carboxamide crystal is rich in KH
2pO
4in other crystal, entered in the filtrate after cooling precipitation carboxamide crystal also containing a large amount of carboxamide, K simultaneously
+, H
2pO
4 -, HPO
4 2-, PO
4 3-utilize Deng not operatively, the temperature of phosphoric acid by wet process potassium dihydrogen phosphate making is adjusted to 80 ~ 160 DEG C by the present invention, and react from the environment of 80 DEG C to 160 DEG C with the intensification of the speed of 5 DEG C/min, not only make the potassium dihydrogen phosphate product purity of precipitation reach more than 98%, 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 planting yew cost and improve Ramulus et folium taxi cuspidatae quality,
2. the carboxamide composition containing part in filtrate, adds formaldehyde solution, under alkaline condition and certain pressure intensity and temperature, generates
deng urea aldehyde series composite fertilizer, this Ramulus et folium taxi cuspidatae special fertilizer can be made to reach the effect of realizing controlled-release;
3., in granulating and drying process, the ammonia that flow velocity is certain is passed into, can absorbed nitrogen element further, can be absorbed by plants fast after fertilising, ensure that the supply of Ramulus et folium taxi cuspidatae nutrition in early stage further;
4. this Ramulus et folium taxi cuspidatae special fertilizer has the advantages that specific absorption is good, realizing controlled-release formula is good.
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)-and (CO
5pN
2h
8)
+ion, when adding excessive and appropriate potassium ion, dihydrogen phosphate and potassium ion form potassium dihydrogen 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.
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, when heating up and pressurize, following reaction can occur:
Reaction formula five
Reaction formula six
Generate
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.
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 potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer that the present embodiment provides, mainly comprises the following steps:
1) adopt phosphoric acid to be that 1.2:1 mixes with carboxamide according to mol ratio, and be that 6 DEG C/min is warming up to 160 DEG C from 80 DEG C with heat-up rate, stirring reaction 4-5h, separation obtains intermediate; This intermediate and alkaline potassium salt is adopted to be that 1:1.4 mixes according to mol ratio again, adjust ph is 8.5, after reaction terminates, obtain nitrogenous, phosphorus, potassium slip, and the slip of nitrogenous, phosphorus, potassium is placed in cooling crystallizer cools to 35 ~ 40 DEG C, carry out crystallization filtration treatment, make filtrate circulation crystallization process in cooling crystallizer, the filter cake obtained is potassium dihydrogen phosphate product, detects the component content in filtrate;
2) in filtrate, formaldehyde solution is added, according to being that 0.8:1 mixes with the mol ratio of the carboxamide contained in solution, with calcium hydroxide, the pH value of potassium hydroxide and phosphoric acid solution regulator solution, wherein calcium hydroxide concentration is 40%, the concentration of potassium hydroxide is 30%, the concentration of phosphoric acid solution is 20%, when detecting that the pH value of solution is 9.0, the content of nitrogen component is 18-25%, phosphorus composition content is 4-8%, when potassium component content is 12-16%, when calcium component content is 12 ~ 18%, mixed solution is put into retort, pressure is increased to 8 ~ 10 normal atmosphere, be rapidly heated 85 DEG C time, with the ramp of 5 ~ 6 DEG C/min, when reaching 120 DEG C, keep 2 ~ 3h,
3) by step 2) solution that obtains is divided into two parts,
Get the solution fast cooling to 60 DEG C of a deal and leave standstill under being depressurized to normal pressure, called after solution A,
The solution getting a deal puts into a retort, when normal atmosphere rises to 2 normal atmosphere fast, normal atmosphere is increased with the speed of 50 ~ 100Pa/min, simultaneous temperature from 85 DEG C with the ramp of 1 ~ 2 DEG C/min, when reaching 3 normal atmosphere, temperature is when reaching 95 DEG C, keep 0.5 ~ 1h, called after solution B;
4) by step 3) solution A that obtains, be cooled to 60 ~ 65 DEG C after B mixing, and add a certain amount of H
2sO
4solution, regulate the scope of pH to 7.0, described sulfuric acid concentration is 15%, then adds the one at least in a small amount of zinc sulfate, copper sulfate, manganous sulfate, ammonium molybdate, ferrous sulfate, chelated iron, borax, leaves standstill 0.5 ~ 1h, obtains solution C;
5) by step 4) in the solution C that obtains be cooled to 20 ~ 25 DEG C, carry out crystallization filtration treatment, obtain a large amount of
the potassium phosphate salt of root, and a small amount of
deng the chemical combination state composite fertilizer just finished product of urea aldehyde, when the content of the nitrogen component in chemical combination state composite fertilizer just finished product be 16%, phosphorus composition content is 7%, potassium component content is 11% time, calcium component content be 15% time, stop crystallization;
6) granulation is dried, in this step, first by step 5) the chemical combination state composite fertilizer of separating out just finished product be made into the particle that diameter is 0.2 ~ 0.4cm, then be placed in the ammonia environment that temperature is 45 ~ 50 DEG C, flow velocity is 3 ~ 4m/s to dry, make Ramulus et folium taxi cuspidatae special fertilizer, this special fertilizer is the Chemical Mixed Fertilizer of chemical combination state.
Embodiment two
A kind of production method preparing potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer that the present embodiment provides, mainly comprises the following steps:
1) adopt phosphoric acid to be that 1.5:1 mixes with carboxamide according to mol ratio, and be that 6 DEG C/min is warming up to 160 DEG C from 80 DEG C with heat-up rate, stirring reaction 4-5h, separation obtains intermediate; This intermediate and alkaline potassium salt is adopted to be that 1:1.1 mixes according to mol ratio again, adjust ph is 8.5, after reaction terminates, obtain nitrogenous, phosphorus, potassium slip, and the slip of nitrogenous, phosphorus, potassium is placed in cooling crystallizer cools to 35 ~ 40 DEG C, carry out crystallization filtration treatment, make filtrate circulation crystallization process in cooling crystallizer, the filter cake obtained is potassium dihydrogen phosphate product, detects the component content in filtrate;
2) in filtrate, formaldehyde solution is added, according to being that 0.9:1 mixes with the mol ratio of the carboxamide contained in solution, with calcium hydroxide, the pH value of potassium hydroxide and phosphoric acid solution regulator solution, wherein calcium hydroxide concentration is 35%, the concentration of potassium hydroxide is 35%, the concentration of phosphoric acid solution is 25%, when detecting that the pH value of solution is 9.0, the content of nitrogen component is 18-25%, phosphorus composition content is 4-8%, when potassium component content is 12-16%, when calcium component content is 12 ~ 18%, mixed solution is put into retort, pressure is increased to 8 ~ 10 normal atmosphere, be rapidly heated 85 DEG C time, with the ramp of 5 ~ 6 DEG C/min, when reaching 120 DEG C, keep 2 ~ 3h,
3) by step 2) solution that obtains is divided into two parts,
Get the solution fast cooling to 60 DEG C of a deal and leave standstill under being depressurized to normal pressure, called after solution A,
The solution getting a deal puts into a retort, when normal atmosphere rises to 2 normal atmosphere fast, normal atmosphere is increased with the speed of 50 ~ 100Pa/min, simultaneous temperature from 85 DEG C with the ramp of 1 ~ 2 DEG C/min, when reaching 3 normal atmosphere, temperature is when reaching 95 DEG C, keep 0.5 ~ 1h, called after solution B;
4) by step 3) solution A that obtains, be cooled to 60 ~ 65 DEG C after B mixing, and add a certain amount of H
2sO
4solution, regulate the scope of pH to 7.4, described sulfuric acid concentration is 5%, then adds the one at least in a small amount of zinc sulfate, copper sulfate, manganous sulfate, ammonium molybdate, ferrous sulfate, chelated iron, borax, leaves standstill 0.5 ~ 1h, obtains solution C;
5) by step 4) in the solution C that obtains be cooled to 20 ~ 25 DEG C, carry out crystallization filtration treatment, obtain a large amount of
the potassium phosphate salt of root, and a small amount of
deng the chemical combination state composite fertilizer just finished product of urea aldehyde, when the content of the nitrogen component in chemical combination state composite fertilizer just finished product be 19%, phosphorus composition content is 3%, potassium component content is 14% time, calcium component content be 10% time, stop crystallization;
6) granulation is dried, in this step, first by step 5) the chemical combination state composite fertilizer of separating out just finished product be made into the particle that diameter is 0.2 ~ 0.4cm, then be placed in the ammonia environment that temperature is 45 ~ 50 DEG C, flow velocity is 3 ~ 4m/s to dry, make Ramulus et folium taxi cuspidatae special fertilizer, this special fertilizer is the Chemical Mixed Fertilizer of chemical combination state.
Embodiment three
A kind of production method preparing potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer that the present embodiment provides, mainly comprises the following steps:
1) adopt phosphoric acid to be that 1.3:1 mixes with carboxamide according to mol ratio, and be that 6 DEG C/min is warming up to 160 DEG C from 80 DEG C with heat-up rate, stirring reaction 4-5h, separation obtains intermediate; This intermediate and alkaline potassium salt is adopted to be 1:1.3 according to mol ratio again, mixing, adjust ph is 8.7, after reaction terminates, obtain nitrogenous, phosphorus, potassium slip, and the slip of nitrogenous, phosphorus, potassium is placed in cooling crystallizer cools to 35 ~ 40 DEG C, carry out crystallization filtration treatment, make filtrate circulation crystallization process in cooling crystallizer, the filter cake of acquisition is potassium dihydrogen phosphate product, detects the component content in filtrate;
2) in filtrate, formaldehyde solution is added, according to being that 0.85:1 mixes with the mol ratio of the carboxamide contained in solution, with calcium hydroxide, the pH value of potassium hydroxide and phosphoric acid solution regulator solution, wherein calcium hydroxide concentration is 37%, concentration of potassium hydroxide is 33%, the concentration of phosphoric acid solution is 22%, when detecting that the pH value of solution is 8.8, the content of nitrogen component is 18-25%, phosphorus composition content is 4-8%, when potassium component content is 12-16%, when calcium component content is 12 ~ 18%, mixed solution is put into retort, pressure is increased to 8 ~ 10 normal atmosphere, be rapidly heated 85 DEG C time, with the ramp of 5 ~ 6 DEG C/min, when reaching 120 DEG C, keep 2 ~ 3h,
3) by step 2) solution that obtains is divided into two parts,
Get the solution fast cooling to 60 DEG C of a deal and leave standstill under being depressurized to normal pressure, called after solution A,
The solution getting a deal puts into a retort, when normal atmosphere rises to 2 normal atmosphere fast, normal atmosphere is increased with the speed of 50 ~ 100Pa/min, simultaneous temperature from 85 DEG C with the ramp of 1 ~ 2 DEG C/min, when reaching 3 normal atmosphere, temperature is when reaching 95 DEG C, keep 0.5 ~ 1h, called after solution B;
4) by step 3) solution A that obtains, be cooled to 60 ~ 65 DEG C after B mixing, and add a certain amount of H
2sO
4solution, regulate the scope of pH to 7.2, described sulfuric acid concentration is 10%, then adds the one at least in a small amount of zinc sulfate, copper sulfate, manganous sulfate, ammonium molybdate, ferrous sulfate, chelated iron, borax, leaves standstill 0.5 ~ 1h, obtains solution C;
5) by step 4) in the solution C that obtains be cooled to 20 ~ 25 DEG C, carry out crystallization filtration treatment, obtain a large amount of
the potassium phosphate salt of root, and a small amount of
deng the chemical combination state composite fertilizer just finished product of urea aldehyde, when the content of the nitrogen component in chemical combination state composite fertilizer just finished product be 18%, phosphorus composition content is 5%, potassium component content is 13% time, calcium component content be 13% time, stop crystallization;
6) granulation is dried, in this step, first by step 5) the chemical combination state composite fertilizer of separating out just finished product be made into the particle that diameter is 0.2 ~ 0.4cm, then be placed in the ammonia environment that temperature is 45 ~ 50 DEG C, flow velocity is 3 ~ 4m/s to dry, make Ramulus et folium taxi cuspidatae special fertilizer, this special fertilizer is the Chemical Mixed Fertilizer of chemical combination state.
In order to prove the beneficial effect that the present invention reaches better, the present embodiment also provides following experimental example, specific as follows:
Experimental example one
Fertile in fertilizer with common N, P, K, Ca mixing, when wherein the content of nitrogen component is 16%, phosphorus composition content is 7%, potassium component content is 11%, calcium component content is 15%, make nutrient solution, soilless culture is carried out to Ramulus et folium taxi cuspidatae, cultivate after 30 days, detect the content of N, P, K, Ca composition in nutrient solution, observe its growing way, called after A1 simultaneously.
Experimental example two is to test example four
The Ramulus et folium taxi cuspidatae special fertilizer be successful to embodiment tripartite method with embodiment one is as fertilizer, make nutrient solution, soilless culture is carried out to Ramulus et folium taxi cuspidatae, cultivate after 15 days, 30 days, 50 days, detect the content of N, P, K, Ca composition in nutrient solution respectively, observe its growing way, respectively called after A2, A3, A4 simultaneously.
The concentration of the nutrient solution in above experimental example is suitable for, and be prior art, this experimental example seldom elaborates, above experimental example with 20 strain Ramulus et folium taxi cuspidatae for detected result is as table 1, table 2 and table 3:
Table 1: the content cultivating N, P, K, Ca composition after 15 days
Table 2: the content cultivating N, P, K, Ca composition after 30 days
Table 3: the content cultivating N, P, K, Ca composition after 50 days
| Numbering | The content (%) of N | The content (%) of P | The content (%) of K | The content (%) of Ca |
[0110]
| Initially | After | Initially | After | Initially | After | Initially | After | |
| A1 | 16 | 10.2 | 7 | 4.2 | 11 | 6.5 | 15 | 10.0 |
| A2 | 16 | 5.3 | 7 | 2.5 | 11 | 3.2 | 15 | 7.3 |
| A3 | 19 | 6.0 | 3 | 0.6 | 14 | 3.8 | 10 | 5.3 |
| A4 | 18 | 5.9 | 5 | 1.7 | 13 | 3.8 | 13 | 5.2 |
As can be seen from table 1 ~ 3, compared with the Ramulus et folium taxi cuspidatae special fertilizer produced with common composite fertilizer and the present invention, when cultivating detection in the 15th day, its N, P, K, the absorbing state difference of Ca is little, but when detecting by the 30th day, N in the Ramulus et folium taxi cuspidatae special fertilizer solution that the present invention produces, P, K, the content of Ca is starkly lower than common special fertilizer, when detecting by the 50th day, N in common composite fertilizer's nutrient solution, P, K, Ca component residue has 60 ~ 80% not absorb, and the N in the nutrient solution of the Ramulus et folium taxi cuspidatae special fertilizer that the present invention produces, P, K, Ca composition only remains 30 ~ 40% and is not absorbed, illustrate that the Ramulus et folium taxi cuspidatae special fertilizer that the present invention produces has the good feature of specific absorption.
Meanwhile, this experimental example also observes Ramulus et folium taxi cuspidatae the growing way situation of the 15th day, the 30th day, the 50th day, is specially and uses above-mentioned experimental example to cultivate 50 strain Ramulus et folium taxi cuspidatae respectively, observe its growing way situation, as table 4:
Table 4: Ramulus et folium taxi cuspidatae was the growing way situation of the 15th day, the 30th day, the 50th day
As can be seen from Table 4, in a short time, the Ramulus et folium taxi cuspidatae special fertilizer that common mixing fertilizer and the present invention produce is without much differences, when cultivation 30 days, there is malnutritive, the yellow phenomenon of leaf in the Ramulus et folium taxi cuspidatae that common mixed fertilizer is supported without earth culture, and the Ramulus et folium taxi cuspidatae that the Ramulus et folium taxi cuspidatae special fertilizer that the present invention produces is cultivated grows fine, its sprouting growing way is very fast, without yellow leaf phenomenon, during by the 50th day, stopping growing appears in the Ramulus et folium taxi cuspidatae that common mixed fertilizer is supported without earth culture, and yellow leaf phenomenon is serious simultaneously, and the growth of taxol that the Ramulus et folium taxi cuspidatae special fertilizer that the present invention produces is cultivated is comparatively slow, but without yellow leaf phenomenon.Illustrate that Ramulus et folium taxi cuspidatae special fertilizer that the present invention produces has the effect of realizing controlled-release.
Claims (10)
1. prepare a production method for potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer, mainly comprise the following steps:
1) adopt phosphoric acid to mix with carboxamide, and be that 6 DEG C/min is warming up to 160 DEG C from 80 DEG C with heat-up rate, stirring reaction 4-5h, be separated and obtain intermediate; This intermediate is adopted to mix with alkaline potassium salt again, adjust ph is 8.5-9.0, after reaction terminates, obtain nitrogenous, phosphorus, potassium slip, and the slip of nitrogenous, phosphorus, potassium is placed in cooling crystallizer cools to 35 ~ 40 DEG C, carry out crystallization filtration treatment, make filtrate circulation crystallization process in cooling crystallizer, the filter cake obtained is potassium dihydrogen phosphate product, detects the component content in filtrate;
2) in filtrate, formaldehyde solution is added, with the content of the pH value of calcium hydroxide, potassium hydroxide and phosphoric acid solution regulator solution and nitrogen, phosphorus, potassium, calcium component, mixed solution is put into retort, pressure is increased to 8 ~ 10 normal atmosphere, be rapidly heated 85 DEG C time, with the ramp of 5 ~ 6 DEG C/min, when reaching 120 DEG C, keep 2 ~ 3h;
3) by step 2) solution that obtains is divided into two parts,
Get the solution fast cooling to 60 DEG C of a deal and leave standstill under being depressurized to normal pressure, called after solution A,
The solution getting a deal puts into a retort, increases pressure, and simultaneous temperature with the ramp of 1 ~ 2 DEG C/min, when temperature reaches 95 DEG C, keeps 0.5 ~ 1h, called after solution B from 85 DEG C;
4) by step 3) solution A that obtains, be cooled to 60 ~ 65 DEG C after B mixing, and add a certain amount of H2SO4 solution, regulate the scope of pH to 7.0 ~ 7.4, add the one at least in a small amount of zinc sulfate, copper sulfate, manganous sulfate, ammonium molybdate, ferrous sulfate, chelated iron, borax, leave standstill 0.5 ~ 1h, obtain solution C;
5) by step 4) in the solution C that obtains be cooled to 20 ~ 25 DEG C, carry out crystallization filtration treatment, obtain chemical combination state composite fertilizer just finished product, when the content of the nitrogen component in chemical combination state composite fertilizer just finished product be 16-19%, phosphorus composition content is 3-7%, potassium component content is 11-14% time, calcium component content be 10-15% time, stop crystallization;
6) granulation is dried, in this step, first by step 5) the chemical combination state composite fertilizer of separating out just finished product be made into the particle that diameter is 0.2 ~ 0.4cm, be then placed in the ammonia environment that temperature is 45 ~ 50 DEG C, flow velocity is 3 ~ 4m/s and dry, make Ramulus et folium taxi cuspidatae special fertilizer.
2. a kind of production method preparing potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer as claimed in claim 1, is characterized in that: the mol ratio that described phosphoric acid mixes with carboxamide is (1.2-1.5): 1.
3. a kind of production method preparing potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer as claimed in claim 1, is characterized in that: the mol ratio that described intermediate mixes with alkaline potassium is 1:(1.1-1.4).
4. a kind of production method preparing potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer as claimed in claim 1, is characterized in that: the mol ratio of the carboxamide contained in described formaldehyde and solution is (0.8 ~ 0.9): 1.
5. a kind of production method preparing potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer as claimed in claim 1, it is characterized in that: described step 2) calcium hydroxide concentration is 35 ~ 40%, the concentration of potassium hydroxide is 30 ~ 35%, and the concentration of phosphoric acid solution is 20 ~ 25%.
6. a kind of production method preparing potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer as claimed in claim 1, it is characterized in that: described step 2) pH value of regulator solution and nitrogen, phosphorus, potassium, calcium component content be specially: pH value is 8.5 ~ 9.0, and when the content of nitrogen component is 18-25%, phosphorus composition content is 4-8%, potassium component content is 12-16%, calcium component content is 12 ~ 18%.
7. a kind of production method preparing potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer as claimed in claim 1, it is characterized in that: described step 3) increase pressure be specially: when rising to 2 normal atmosphere fast, increasing normal atmosphere with the speed of 50 ~ 100Pa/min, remaining unchanged when reaching 3 normal atmosphere.
8. a kind of production method preparing potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer as claimed in claim 1, is characterized in that: described step 4) sulfuric acid concentration be 5 ~ 15%.
9. a kind of production method preparing potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer as claimed in claim 1, is characterized in that: described Ramulus et folium taxi cuspidatae special fertilizer is the Chemical Mixed Fertilizer of chemical combination state.
10., as right wants a kind of production method preparing potassium primary phosphate by-product Ramulus et folium taxi cuspidatae special fertilizer as described in 9, it is characterized in that: the Chemical Mixed Fertilizer of described chemical combination state contains
the potassiumphosphate composite fertilizer of root, and a small amount of
the chemical combination state composite fertilizer of urea aldehyde.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410478329.9A CN104326455B (en) | 2014-09-19 | 2014-09-19 | A kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410478329.9A CN104326455B (en) | 2014-09-19 | 2014-09-19 | A kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104326455A true CN104326455A (en) | 2015-02-04 |
| CN104326455B CN104326455B (en) | 2016-08-31 |
Family
ID=52401284
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410478329.9A Expired - Fee Related CN104326455B (en) | 2014-09-19 | 2014-09-19 | A kind of production method preparing potassium dihydrogen phosphate by-product Chinese yew special fertilizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104326455B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104555964A (en) * | 2015-02-06 | 2015-04-29 | 胡渝涛 | Production method of acid potassium phosphate |
| CN104973975A (en) * | 2015-07-08 | 2015-10-14 | 常州市诚天电子有限公司 | Water-retention slow-release fertilizer for taxus chinensis and preparation method thereof |
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 |
| WO2000055104A1 (en) * | 1999-03-18 | 2000-09-21 | Oms Investments, Inc. | 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 |
| CN103803518A (en) * | 2014-01-24 | 2014-05-21 | 贵阳中化开磷化肥有限公司 | Method for preparing monopotassium phosphate by using wet-process phosphoric acid |
-
2014
- 2014-09-19 CN CN201410478329.9A patent/CN104326455B/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 |
| WO2000055104A1 (en) * | 1999-03-18 | 2000-09-21 | Oms Investments, Inc. | 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 |
| CN103803518A (en) * | 2014-01-24 | 2014-05-21 | 贵阳中化开磷化肥有限公司 | Method for preparing monopotassium phosphate by using wet-process phosphoric acid |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104555964A (en) * | 2015-02-06 | 2015-04-29 | 胡渝涛 | Production method of acid potassium phosphate |
| CN104555964B (en) * | 2015-02-06 | 2016-05-04 | 胡渝涛 | A kind of production method of acid potassium phosphate |
| CN104973975A (en) * | 2015-07-08 | 2015-10-14 | 常州市诚天电子有限公司 | Water-retention slow-release fertilizer for taxus chinensis and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104326455B (en) | 2016-08-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104326455A (en) | Production method for preparing monopotassium phosphate and by-product special fertilizer for Taxus chinensis | |
| CN104310329B (en) | A kind of production method preparing ammonium dihydrogen phosphate by-product Fructus Kaki special fertilizer | |
| CN104310344B (en) | A kind of production method preparing potassium dihydrogen phosphate by-product Fructus Pruni salicinae special fertilizer | |
| CN104326457B (en) | A kind of production method preparing dikalium phosphate by-product clube tree special fertilizer | |
| CN104291287B (en) | A kind of production method preparing ammonium dihydrogen phosphate by-product wax gourd special fertilizer | |
| CN104445123B (en) | A kind of production method preparing potassium dihydrogen phosphate by-product Radix Ipomoeae special fertilizer | |
| CN104291301B (en) | A kind of production method preparing dikalium phosphate by-product osmanthus fragrans special fertilizer | |
| CN104291300A (en) | Production method for preparing potassium dihydrogen phosphate and by-producing special fertilizer for gingko seedlings | |
| CN104326448B (en) | A kind of production method preparing ammonium dihydrogen phosphate by-product sugarcane special-purpose fertilizer | |
| CN104310347B (en) | A kind of production method preparing potassium dihydrogen phosphate by-product chrysanthemum special fertilizer | |
| CN104310361A (en) | Method for preparing potassium dihydrogen phosphate and preparing special fertilizer for peony as byproduct | |
| CN104386660A (en) | Production method for special watermelon fertilizer as ammonium dihydrogen phosphate preparation byproduct | |
| CN104310343A (en) | Production method of ammonium dihydrogen phosphate with by-product cherry special fertilizer | |
| CN104310356B (en) | Production method of monopotassium phosphate with by-product welsh onion special fertilizer | |
| CN104310345B (en) | Method for preparing potassium dihydrogen phosphate and preparing special fertilizer for hawthorn fruits as byproduct | |
| CN104310336B (en) | A kind of production method for preparing ammonium dihydrogen phosphate by-product ginger special fertilizer | |
| CN104261378A (en) | Production method for preparing monopotassium phosphate and byproduct special fertilizer for medlar | |
| CN104310340B (en) | Method for preparing ammonium dihydrogen phosphate and preparing special fertilizer for beet as byproduct | |
| CN104326462A (en) | Production method for preparing monocalcium phosphate and by-product special fertilizer for red bean | |
| CN104276561A (en) | Production method for preparing calcium hydrophosphate with special Chinese prickly ash fertilizer as byproduct | |
| CN104291299A (en) | Method for preparing sodium dihydrogen phosphate and coproducing special compound fertilizer for cowpea | |
| CN104326447A (en) | Production method for preparing ammonium dihydrogen phosphate and by-product special fertilizer for cucumber | |
| CN104310333A (en) | Method for preparing ammonium dihydrogen phosphate and preparing special fertilizer for corn as byproduct | |
| CN104310357A (en) | Production method of monopotassium phosphate with by-product cinnamon special fertilizer | |
| CN104326458A (en) | Production method for preparing monopotassium phosphate and by-product special fertilizer for strawberry |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20160713 Address after: 550000 Huaxi District, Guizhou, Guiyang Applicant after: Guizhou University Applicant after: Phosphorylcholine group limited-liability company is opened in Guizhou Applicant after: Guizhou Ke Xinhua smelting company limited Address before: 550000 Huaxi District, Guizhou, Guiyang Applicant before: Guizhou University Applicant before: Zhonghuakai Phosphorous Chemical Fertilizer Co., Ltd., Guiyang Applicant before: Guizhou Ke Xinhua smelting company limited |
|
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160831 Termination date: 20200919 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |