CN104276560B - A kind of production method preparing tricalcium phosphate by-product Flos Carthami special fertilizer - Google Patents
A kind of production method preparing tricalcium phosphate by-product Flos Carthami special fertilizer Download PDFInfo
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Abstract
The present invention relates to chemical technology field, especially a kind of production method preparing tricalcium phosphate by-product Flos Carthami special fertilizer, by in production process, the mol ratio of raw material, in crystallisation step, the accurate analysis of filtrate and detection, the quality making the safflower compounded fertilizer produced is guaranteed, and with adjusting the mode of filtrate component content, using the raw material as composite heat transfer of the waste liquid in chemical products production process, avoid the discharge of waste liquid, reduce composite heat transfer cost, there is the significant value of environmental protection and economic benefit.
Description
Technical field
The present invention relates to chemical technology field, especially a kind of production method preparing tricalcium phosphate by-product Flos Carthami special fertilizer.
Background technology
Flos Carthami, (Classification system: CarthamustinctoriusL.), another name: red blue flower, thorn Flos Carthami, Compositae, Flos Carthami platymiscium, dry tubular flower, orange red, floral tube is narrow carefully, tip 5 splits, sliver is narrow linear, flower pesticide yellow, is unified into pipe, exceeding outside sliver, its central authorities have stigma to expose. Have special fragrance, mildly bitter flavor. To spend, length of a film, color be scarlet, the soft person of matter is preferred. Have. Promoting blood circulation to restore menstrual flow, eliminating stasis to stop pain, contribute to controlling amenorrhea, dysmenorrhea, lochia, obstruction of qi in the chest and cardialgia, the stagnant stomachache of the stasis of blood, breast side of body twinge, traumatic injury, skin infection swell and ache curative effect. Blood circulation promoting and blood stasis dispelling, wet dissipation is had to go the effect swollen. In existing Flos Carthami planting technology, the method to Flos Carthami fertilising is to adopt mu to execute 1～1.5 ton of farm manure, 8～10 carbamide, 8～10 phosphate fertilizer, 1 zinc fertilizer, available potassium lower than 350/following plot mu executes 35 potash fertilizer. Before ploughing, all make base manure uniformly spread fertilizer over the fields ground, then plough deeply and bury, and then npk nutrient and other nutrients are provided for Flos Carthami, for Flos Carthami normal growth; But, it is reported, crop is relatively low to the absorbance of n-p-k element, the absorbance of nitrogen is generally not above 25%, to the absorbance of phosphate fertilizer substantially about 40%, and for the absorbance also super only 60% of potash fertilizer, therefore it is appreciated that, after during azophoska is manured into soil, substantial amounts of n-p-k element can be remained among soil, and then make n-p-k element resource be caused substantial amounts of waste, also result in soil simultaneously and eat thinner and thinner, cause that soil nutrient structure sheaf changes, and then affect the regeneration of soil, there is serious ecology influence.
In preparation technology simultaneously for tricalcium phosphate product, it is common that the mode through crystallization produces, this technique generally requires and tricalcium phosphate is carried out degree of depth crystallization, and then the waste of the element resources such as nitrogen phosphorus calcium is reduced with this, improve the yield of tricalcium phosphate, reduce production cost; But this degree of depth crystallization brings impact will to the purity of tricalcium phosphate product, and then affects the quality of tricalcium phosphate product; And the waste liquid amount after crystallization treatment is relatively big, will also result in the pollution of environment.
For this, this research worker through efforts of many years with exploration, Flos Carthami special fertilizer production technology is combined with tricalcium phosphate product processes, using the waste liquid that produces in tricalcium phosphate production technology as the raw material in Flos Carthami special fertilizer production technology, and it is added to potassium element and other trace element, and by obtaining Flos Carthami special fertilizer after concentrate drying, the production producing Flos Carthami special fertilizer for tricalcium phosphate product provides a kind of new approaches.
Summary of the invention
In order to solve the above-mentioned technical problem existed in prior art, the present invention provides a kind of and can the production technology of the production technology of tricalcium phosphate product with Flos Carthami special fertilizer be combined, and then reduce the discharging of waste liquid amount in tricalcium phosphate product processes, reduce the loss of nitrogen P elements, improve the yield of addition product, improve the purity of tricalcium phosphate, reduce the production method preparing tricalcium phosphate by-product Flos Carthami special fertilizer of production cost.
It is achieved particular by techniques below scheme:
A kind of production method preparing tricalcium phosphate by-product Flos Carthami special fertilizer, phosphoric acid is adopted to react with phosphoamide, generate urea phosphate, and adjust temperature at 130-140 DEG C, the structural formula generation ionizing making urea phosphate separates, forming dihydrogen phosphate ions and phosphoamide cation, then adopt phosphoamide cation and phosphoric acid close, forming structural formula isIntermediate-ion body, it is added thereto to calcium ion again, calcium ion is reacted with dihydrogen phosphate, generate tricalcium phosphate product slip, and tricalcium phosphate product slip is carried out crystallisation by cooling and centrifugal filtration process, when crystallization treatment, detect nitrogen phosphorus calcium content therein for (4-6): (4-6): time (0.5-0.7), for crystallization terminal, it is thus achieved that tricalcium phosphate filter cake and filtrate, tricalcium phosphate product is placed in the drying baker that temperature is 80-90 DEG C, be dried to moisture be 1-4% time, the tricalcium phosphate product that purity is 96-98.5% can be obtained, and using filtrate as raw material, after being added to potassium composition, make the content of N P and K composition therein than being (4-5): (4-5): time (1-2), obtain Flos Carthami special fertilizer slip, and be placed under the environment that temperature is 100-120 DEG C to be concentrated into moisture by Flos Carthami special fertilizer slip be 11-17%, Flos Carthami special fertilizer slip after being concentrated again is sent in comminutor and is carried out pelletize process, after treating that pelletize completes, it is placed in dehydrator, adopt 90 DEG C temperature dry to moisture be 2-3% time, sterilization packaging, Flos Carthami special fertilizer can be obtained.
Mol ratio when described phosphoric acid reacts with phosphoamide is (2.1-2.7): 1.
Temperature when described phosphoric acid reacts with phosphoamide is 80 DEG C, and adopt mixing speed be 60-70r/min be stirred process 30-50min.
The source of described calcium ion is by a kind of offer in calcium chloride, calcium sulfide, calcium bicarbonate, calcium oxalate.
Described calcium ion, its addition is 2-3 times of phosphoamide gross weight, and its concentration is 37%.
Described crystallisation by cooling is to temperature≤40 DEG C by tricalcium phosphate slip cooling down, and standing processes 2-3h.
Its source of described potassium composition is by any one offer in Potassium monosulfide., potassium bicarbonate, potassium chloride, potassium sulfate, potassium nitrate.
Described its concentration of potassium composition is 25-40%.
Described interpolation potassium composition, needs the mixing speed adopting mixing speed to be 30-45r/min to carry out at the uniform velocity stir process when adding.
Described Flos Carthami special fertilizer is chemical combination state N P and K double salt compound fertilizer, its effective ingredient is In one or more mixture.
While adding potassium composition, farm manure can also be adopted to be added after pulverizing, and the trace-element fertilizer such as zinc fertilizer, boron fertilizer can also be added, and when adding, still to be stirred reaction 2-3h, meet the trace-element fertilizer added and carry out sufficient combination reaction with the effective ingredient in double salt fertilizer so that Flos Carthami special fertilizer forms the double salt structure fertilizer of a kind of chemical combination state.
By phosphoric acid and urea reaction, and it is controlled by temperature, mol ratio and other technological parameters so that complicated polyreaction occurs the structural formula of urea phosphate so that it is formedIntermediate-ion, this intermediate-ion has stronger stability, and between carbon oxygen atom, there is also coordinate bond, containing substantial amounts of dihydrogen phosphate simultaneously in the solution that this ion exists, therefore, when adding calcium ion in the solution exist this intermediate-ion, calcium ion reacts with the dihydrogen phosphate in solution gradually, form dalcium biphosphate, the amount added along with potassium ion is gradually increased, and regulated value pH value, and dalcium biphosphate progressively changes into dicalcium phosphate, and suitable excessive calcium ion, until form tricalcium phosphate; Then intermediate-ion and calcium ion react, and replace out part ammonium radical ion so that intermediate-ion chelating becomesIntermediate-ion, and with positive charge, and then when solution participates in other electronegative ions or compound, it will form compound salt with this ion, the further nutritional labeling in abundant product.
As added potassium sulfate in solution, adjust the Determination of Potassium in solution, then can generate sulfenyl double salt chemical combination state compound fertilizer.
As added potassium nitrate in solution, adjust the Determination of Potassium in solution and nitrogen element content, then can generate nitrate compound salt compound fertilizer.
Compared with prior art, the technique effect of technical scheme is embodied in:
1. by needing fertilizer according to Flos Carthami, effective absorbtivity of n-p-k element is analyzed, and the constituent content in production process is adjusted and collocation, the compound fertilizer making the chemical combination state prepared can meet the demand of Flos Carthami to greatest extent, and reduce in composite heat transfer because of element mismatch, the high cost caused, further avoids too much element to put among soil, causes the solidification of compound fertilizer and contaminated environment.
2. cross the process conditions to producing to be controlled, make in Flos Carthami special fertilizer preparation process, highly purified tricalcium phosphate product can be produced, compensate for remove impurity cost when traditional wet phosphoric acid prepares tricalcium phosphate product, the purity making the tricalcium phosphate product prepared reaches more than 94%, reduce production cost, there is significant economic benefit.
3. by production process, the mol ratio of raw material, in crystallisation step, the accurate analysis of filtrate and detection so that the quality of the safflower compounded fertilizer produced is guaranteed, and with adjusting the mode of filtrate component content, using the raw material as composite heat transfer of the waste liquid in chemical products production process, avoid the discharge of waste liquid, reduce composite heat transfer cost, there is the significant value of environmental protection and economic benefit.
4. by technical parameter in chemical combination state compound fertilizer production technology, namely it is exactly temperature, the control of material concentration and proportioning, after making phosphoric acid and urea reaction, generate urea phosphate product, urea phosphate product itself has stronger acidity, and be the chemical combination state double salt that is combined together to form of the mode by coordinate bond between phosphoric acid and carbamide, also it is fertile as crop in conventional art, and the absorbance comparison carbamide that crop is to this chemical combination state double salt, ammonium carbonate, the unitary such as ammonium nitrate, binary fertilizer absorbance is one chemical combination state compound fertilizer all preferably, but, this chemical combination state double salt is under the environment that phosphoric acid exists, at the temperature of 80-250 DEG C, the decomposition polyreaction of complexity can be there is, urea phosphate is made to form (H2PO4)-(H2NCONH3)+Two ions, (H2NCONH3)+Ion is close with phosphoric acid, and under the environment that temperature is 80-160 DEG C, is formedIntermediate-ion and dihydrogen phosphate, and between C and O, form coordinate bond, this intermediate-ion can form multielement intermediate-ion with centering element compound chelating, and then can continue to the compound electronegative with other or ion formation chelate, improve constituent content in double salt, and then the nutrient content in the double salt that this ion exists can be adjusted, simultaneously, this chelate can be hydrolyzed again and absorbed by crops, and then effectively long-term can provide fertilizer efficiency for crop, simultaneously, in conjunction with the mensuration of constituent content in the solution that this ion is existed, and then adjust each constituent content when double salt is formed, dry and obtain the compound fertilizer containing chemical combination state double salt structure, improve the quality of Flos Carthami special fertilizer.
Detailed description of the invention
Below in conjunction with specific embodiment technical scheme done further restriction, but the scope claimed is not only limited to the description made.
Principle illustrates:
The present invention carries out research and discussion by the mechanism that phosphoric acid and phosphoamide are reacted, and recognizes in conjunction with prior art literature, and phosphoric acid and phosphoamide react generation urea phosphate, and its molecular formula is: CO (NH2)2.H3PO4Under the environment of higher temperature, the chemical bond meeting dialysis between H and O in phosphoric acid, hydrion is combined with carbamide and forms the ionic state containing positive charge, urea phosphate is made to form 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 under the environment that phosphoric acid exists, (H therein2NCONH3)+Cation is close with phosphoric acid, forms the intermediate-ion of C → O coordinate bond, is (CO5PN2H8)+, and then make in urea phosphate intermediate containing substantial amounts of (H2PO4)-and (CO5PN2H8)+Ion, when adding excessive and appropriate calcium ion, dihydrogen phosphate and calcium ion form tricalcium phosphate crystal and are precipitated, and by detecting the content of the nitrogen phosphorus calcium element analyzed in filtrate, and add potassium element, magnesium elements, ferrum element and other medium trace element according to the demand of Fructus Piperis, adjust the trophic structure in filtrate so that trophic structure layer meets the demand of Fructus Piperis, then dry the Fructus Piperis special chemical combination state compound fertilizer that can be prepared by containing N, P, K and other elements.
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 there is coordinate bond between C atom and O atom.
Tricalcium phosphate product to be crystallized out after, then in filtrate, add potassium element and other elements, then can with the dihydrogen phosphate remained in filtrate, hydrogen phosphate and
Intermediate-ion react, generate Multiple salts forms chemical combination state Flos Carthami composite fertilizer special.
Noun illustrates:
Urea phosphate (Ureaphosphate, UP), No. CAS is 4861-19-2, and molecular formula is CH7N2O5P, is represented by CO (NH2)2·H3PO4:
It it is a kind of fine chemical product being widely used in the fields such as animal husbandry, industry, agricultural, its solid is white crystals or crystalline powder, soluble in water and alcohol, insoluble in ethers, toluene and carbon tetrachloride, aqueous solution, in acidity, starts time melted to decompose to give off carbon dioxide and ammonia.
Embodiment: with concrete operation embodiment, the present invention is further elaborated below.
Embodiment 1
A kind of production method preparing tricalcium phosphate by-product Flos Carthami special fertilizer, phosphoric acid is adopted to react with phosphoamide, generate urea phosphate, and adjust temperature at 130 DEG C, the structural formula generation ionizing making urea phosphate separates, forming dihydrogen phosphate ions and phosphoamide cation, then adopt phosphoamide cation and phosphoric acid close, forming structural formula isIntermediate-ion body, it is added thereto to calcium ion again, calcium ion is reacted with dihydrogen phosphate, generate tricalcium phosphate product slip, and tricalcium phosphate product slip is carried out crystallisation by cooling and centrifugal filtration process, when crystallization treatment, detect nitrogen phosphorus calcium content therein when being 4:6:0.7, for crystallization terminal, it is thus achieved that tricalcium phosphate filter cake and filtrate; Tricalcium phosphate product is placed in the drying baker that temperature is 80 DEG C, be dried to moisture be 3% time, the tricalcium phosphate product that purity is 96% can be obtained; And using filtrate as raw material; after being added to potassium composition; make the content ratio of N P and K composition therein during for 5:4:1; obtain Flos Carthami special fertilizer slip; and be placed under the environment that temperature is 100 DEG C to be concentrated into moisture by Flos Carthami special fertilizer slip be 11%; Flos Carthami special fertilizer slip after being concentrated again is sent in comminutor and is carried out pelletize process; after treating that pelletize completes; it is placed in dehydrator; adopt 90 DEG C temperature dry to moisture be 2% time; sterilization packaging, can obtain Flos Carthami special fertilizer.
Mol ratio when phosphoric acid reacts with phosphoamide is 2.1:1.
Temperature when phosphoric acid reacts with phosphoamide is 80 DEG C, and adopt mixing speed be 60r/min be stirred process 30min.
The source of calcium ion is provided by calcium chloride.
Calcium ion, its addition is 2 times of phosphoamide gross weight, and its concentration is 37%.
Crystallisation by cooling is that standing processes 2h by tricalcium phosphate slip cooling down to temperature 40 DEG C.
Its source of potassium composition is provided by Potassium monosulfide..
Its concentration of potassium composition is 25%.
Add potassium composition, need when adding the mixing speed adopting mixing speed to be 30r/min to carry out at the uniform velocity stir process 1h.
Embodiment 2
A kind of production method preparing tricalcium phosphate by-product Flos Carthami special fertilizer, phosphoric acid is adopted to react with phosphoamide, generate urea phosphate, and adjust temperature at 140 DEG C, the structural formula generation ionizing making urea phosphate separates, forming dihydrogen phosphate ions and phosphoamide cation, then adopt phosphoamide cation and phosphoric acid close, forming structural formula isIntermediate-ion body, it is added thereto to calcium ion again, calcium ion is reacted with dihydrogen phosphate, generate tricalcium phosphate product slip, and tricalcium phosphate product slip is carried out crystallisation by cooling and centrifugal filtration process, when crystallization treatment, detect nitrogen phosphorus calcium content therein when being 6:4:0.5, for crystallization terminal, it is thus achieved that tricalcium phosphate filter cake and filtrate; Tricalcium phosphate product is placed in the drying baker that temperature is 90 DEG C, be dried to moisture be 1% time, the tricalcium phosphate product that purity is 98.5% can be obtained; And using filtrate as raw material; after being added to potassium composition; make the content ratio of N P and K composition therein during for 5:5:2; obtain Flos Carthami special fertilizer slip; and be placed under the environment that temperature is 120 DEG C to be concentrated into moisture by Flos Carthami special fertilizer slip be 17%; Flos Carthami special fertilizer slip after being concentrated again is sent in comminutor and is carried out pelletize process; after treating that pelletize completes; it is placed in dehydrator; adopt 90 DEG C temperature dry to moisture be 3% time; sterilization packaging, can obtain Flos Carthami special fertilizer.
Mol ratio when phosphoric acid reacts with phosphoamide is 2.7:1.
Temperature when phosphoric acid reacts with phosphoamide is 80 DEG C, and adopt mixing speed be 70r/min be stirred process 50min.
The source of calcium ion is provided by calcium bicarbonate, and its addition is 3 times of phosphoamide gross weight, and its concentration is 37%.
Crystallisation by cooling is that standing processes 3h by tricalcium phosphate slip cooling down to temperature 35 DEG C.
Its source of potassium composition is provided by potassium chloride, and its concentration of potassium composition is 40%.
Add potassium composition, need when adding the mixing speed adopting mixing speed to be 45r/min to carry out at the uniform velocity stir process 3h.
Embodiment 3
A kind of production method preparing tricalcium phosphate by-product Flos Carthami special fertilizer, phosphoric acid is adopted to react with phosphoamide, generate urea phosphate, and adjust temperature at 135 DEG C, the structural formula generation ionizing making urea phosphate separates, forming dihydrogen phosphate ions and phosphoamide cation, then adopt phosphoamide cation and phosphoric acid close, forming structural formula isIntermediate-ion body, it is added thereto to calcium ion again, calcium ion is reacted with dihydrogen phosphate, generate tricalcium phosphate product slip, and tricalcium phosphate product slip is carried out crystallisation by cooling and centrifugal filtration process, when crystallization treatment, detect nitrogen phosphorus calcium content therein when being 5:5:0.6, for crystallization terminal, it is thus achieved that tricalcium phosphate filter cake and filtrate; Tricalcium phosphate product is placed in the drying baker that temperature is 85 DEG C, be dried to moisture be 2% time, the tricalcium phosphate product that purity is 97.1% can be obtained; And using filtrate as raw material; after being added to potassium composition; make the content ratio of N P and K composition therein during for 4:4:1; obtain Flos Carthami special fertilizer slip; and be placed under the environment that temperature is 110 DEG C to be concentrated into moisture by Flos Carthami special fertilizer slip be 14%; Flos Carthami special fertilizer slip after being concentrated again is sent in comminutor and is carried out pelletize process; after treating that pelletize completes; it is placed in dehydrator; adopt 90 DEG C temperature dry to moisture be 3% time; sterilization packaging, can obtain Flos Carthami special fertilizer.
Mol ratio when phosphoric acid reacts with phosphoamide is 2.3:1, and temperature when phosphoric acid reacts with phosphoamide is 80 DEG C, and adopt mixing speed be 65r/min be stirred process 40min.
The source of calcium ion is provided by calcium oxalate, and its addition is 3 times of phosphoamide gross weight, and its concentration is 37%.
Crystallisation by cooling is that standing processes 3h by tricalcium phosphate slip cooling down to temperature 38 DEG C.
Its source of potassium composition is provided by potassium nitrate, and its concentration of potassium composition is 40%.
Add potassium composition, need when adding the mixing speed adopting mixing speed to be 38r/min to carry out at the uniform velocity stir process 2h.
It is important to point out at this; above example is only limitted to technical scheme is further elaborated and understands; it it is not the further restriction to technical scheme; and above example does not have the embodiment of fully exhaustive technical scheme; also simply according to how technical scheme further is operated doing simple introduction; therefore; the innovation and creation of the non-significant progress that those skilled in the art make on this basis, still fall within the protection category of the present invention.
Claims (10)
1. the production method preparing tricalcium phosphate by-product Flos Carthami special fertilizer, it is characterized in that, phosphoric acid is adopted to react with phosphoamide, generate urea phosphate, and adjusting temperature at 130-140 DEG C so that the structural formula generation ionizing of urea phosphate separates, and forms dihydrogen phosphate ions and phosphoamide cation, adopting phosphoamide cation and phosphoric acid close again, forming structural formula isIntermediate-ion body, it is added thereto to calcium ion again, calcium ion is reacted with dihydrogen phosphate, generate tricalcium phosphate product slip, and tricalcium phosphate product slip is carried out crystallisation by cooling and centrifugal filtration process, when crystallization treatment, detect nitrogen phosphorus calcium content therein for (4-6): (4-6): time (0.5-0.7), for crystallization terminal, it is thus achieved that tricalcium phosphate filter cake and filtrate, tricalcium phosphate product is placed in the drying baker that temperature is 80-90 DEG C, be dried to moisture be 1-4% time, the tricalcium phosphate product that purity is 96-98.5% can be obtained, and using filtrate as raw material, after being added to potassium composition, make the content of N P and K composition therein than being (4-5): (4-5): time (1-2), obtain Flos Carthami special fertilizer slip, and be placed under the environment that temperature is 100-120 DEG C to be concentrated into moisture by Flos Carthami special fertilizer slip be 11-17%, Flos Carthami special fertilizer slip after being concentrated again is sent in comminutor and is carried out pelletize process, after treating that pelletize completes, it is placed in dehydrator, adopt 90 DEG C temperature dry to moisture be 2-3% time, sterilization packaging, Flos Carthami special fertilizer can be obtained.
2. prepare the production method of tricalcium phosphate by-product Flos Carthami special fertilizer as claimed in claim 1, it is characterised in that mol ratio when described phosphoric acid reacts with phosphoamide is (2.1-2.7): 1.
3. prepare the production method of tricalcium phosphate by-product Flos Carthami special fertilizer as claimed in claim 1, it is characterised in that temperature when described phosphoric acid reacts with phosphoamide is 80 DEG C, and adopt mixing speed be 60-70r/min be stirred process 30-50min.
4. prepare the production method of tricalcium phosphate by-product Flos Carthami special fertilizer as claimed in claim 1, it is characterised in that the source of described calcium ion is by a kind of offer in calcium chloride, calcium sulfide, calcium bicarbonate, calcium oxalate.
5. preparing the production method of tricalcium phosphate by-product Flos Carthami special fertilizer as claimed in claim 1, it is characterised in that described calcium ion, its addition is 2-3 times of phosphoamide gross weight, and its concentration is 37%.
6. preparing the production method of tricalcium phosphate by-product Flos Carthami special fertilizer as claimed in claim 1, it is characterised in that described crystallisation by cooling is to temperature≤40 DEG C by tricalcium phosphate product slip cooling down, standing processes 2-3h.
7. prepare the production method of tricalcium phosphate by-product Flos Carthami special fertilizer as claimed in claim 1, it is characterised in that its source of described potassium composition is by any one offer in Potassium monosulfide., potassium bicarbonate, potassium chloride, potassium sulfate, potassium nitrate.
8. prepare the production method of tricalcium phosphate by-product Flos Carthami special fertilizer as claimed in claim 1, it is characterised in that described its concentration of potassium composition is 25-40%.
9. prepare the production method of tricalcium phosphate by-product Flos Carthami special fertilizer as claimed in claim 1, it is characterised in that described interpolation potassium composition, need when adding the mixing speed adopting mixing speed to be 30-45r/min to carry out at the uniform velocity stir process.
10. prepare the production method of tricalcium phosphate by-product Flos Carthami special fertilizer as claimed in claim 1, it is characterised in that described Flos Carthami special fertilizer is chemical combination state N P and K double salt compound fertilizer, its effective ingredient is
In one or more mixture.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004076348A1 (en) * | 2003-02-27 | 2004-09-10 | Visweswara Rao Abburi | A process for the manufacture of feed grade dicalcium phosphate |
| EP2075231A1 (en) * | 2007-12-28 | 2009-07-01 | Universidad de Vigo | Biphasic calcium phosphate and method for obtaining same from fish bones |
| 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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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004076348A1 (en) * | 2003-02-27 | 2004-09-10 | Visweswara Rao Abburi | A process for the manufacture of feed grade dicalcium phosphate |
| EP2075231A1 (en) * | 2007-12-28 | 2009-07-01 | Universidad de Vigo | Biphasic calcium phosphate and method for obtaining same from fish bones |
| 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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