CN1051527C - Combined depositting defluorinating method for fodder grade calcium hydrophosphate by wet process from phosphate - Google Patents
Combined depositting defluorinating method for fodder grade calcium hydrophosphate by wet process from phosphate Download PDFInfo
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- CN1051527C CN1051527C CN97112458A CN97112458A CN1051527C CN 1051527 C CN1051527 C CN 1051527C CN 97112458 A CN97112458 A CN 97112458A CN 97112458 A CN97112458 A CN 97112458A CN 1051527 C CN1051527 C CN 1051527C
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- defluorinate
- defluorination
- calcium hydrophosphate
- phosphoric acid
- grade calcium
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Abstract
The present invention relates to a composite precipitation defluorination method for preparing feed grade calcium hydrophosphate by using a wet-process phosphoric acid. The present invention is characterized in that step-by-step defluorination is carried out by using a chemical precipitation method. First, a phosphoric acid is prepared by extraction through the reaction between phosphate rock powder and an acid, and simultaneously, defluorination is carried out to the phosphate rock powder and the acid by using silicon dioxide and sodium chloride (potassium chloride); after solid-liquid separation is carried out, filter cakes are returned to an extraction crystallization tank. Through the step-by-step defluorination, feed grade calcium hydrophosphate is produced by using a wet-process phosphoric acid, the recovery rate of P2O5 can reach 80% to 96%, the defluorination is relatively thorough and the manufacture cost is low.
Description
The present invention is the composite precipitation defluorination method that a kind of phosphoric acid by wet process is made calcium hydrophosphate fodder.
Make the defluorination method of calcium hydrophosphate fodder by phosphoric acid by wet process, in the prior art, generally influence the effect of defluorinate, make the defluorinate instability, do not reach the HG2636-94 standard-required because of the variation that is subjected to temperature and ground phosphate rock quality with defluorination by chemical precipitation.And adopt in one section and the method for defluorinate, though can reach standard-required, this method weak point is the P in the phosphoric acid
2O
5Only having an appointment 60% can form calcium hydrophosphate fodder, has 40% to form the fertilizer grade secondary calcium phosphate approximately.For improving the ratio of calcium hydrophosphate fodder, can reach the requirement of defluorinate simultaneously again, the Chinese invention patent application discloses application number 94113063.0 " method of calcium hydrophosphate fodder is produced in the circulation defluorinate ", has made P in the calcium hydrophosphate fodder
2O
5Proportion is brought up to 70-95%, this characteristic feature of an invention is: will go up precipitation that the neutralization of one section of a round-robin forms some or all be dissolved in phosphoric acid by wet process after add defluorinating agent and take off fluorine one time with chemical precipitation method, filtering then makes solid-liquid separation, its filtrate carry out one section defluorinate again that neutralizes.Filtrate after the secondary defluorinate, two sections neutralizations generate calcium hydrophosphate fodder again.But the weak point of this method is that the independent defluorinate of secondary has increased operation sequence, comparatively bothers, though make P in the calcium hydrophosphate fodder
2O
5Shared ratio is brought up to 70-95%, but still can form small part fertilizer grade secondary calcium phosphate.
The defluorination method that the purpose of this invention is to provide a kind of efficient high yield.This method can make P in the calcium hydrophosphate fodder
2O
5(or P) proportion is brought up to 80-96%, and does not produce the fertilizer grade secondary calcium phosphate, and fluorine content can reach the HG2636-94 standard-required in the product, and simultaneously, this method is not subjected to the influence of envrionment temperature and ground phosphate rock quality change, and the defluorinate stable performance is simple to operate.
Defluorination method of the present invention is achieved like this: the applied chemistry precipitator method are divided two step defluorinates.The first step is to put in extraction tank in ground phosphate rock and the acid, adds defluorinating agent such as silicon-dioxide or water glass, adds soluble sodium salt or sylvite in crystallization reaction tank, makes a part of fluorochemical generate SiF through reaction
4Gas evolution, a part generates the Sodium Silicofluoride (potassium) of indissoluble, removes by filter with phosphogypsum.Then, in certain density extraction liquid, after adjusting acidity, add CaCO
3Or Ca (OH)
2Or the two composition.Under the condition of 2.6-3.0, add the defluorinate auxiliary agent at pH value, make the CaF of remaining most fluorine generation indissolubles in the phosphoric acid extraction liquid
2, remove after filtration.Filtrate P
2O
5: F 〉=260: 1 makes calcium hydrophosphate fodder through neutralization, and a small amount of filter cake that forms can directly return the dissolved defluorinate again of extractive crystallization groove.Carry out cyclical operation according to this.
Defluorination method of the present invention compared with prior art has following advantage:
(1) is filtered because extraction process adds the defluorinating agent defluorinate, and with phosphogypsum and removes, reduced independent defluorinate and filtering operation sequence;
(2) since in PH＞2.6 o'clock through for the second time in one section and defluorinate, formed throw out is less, can directly return the dissolved defluorinate again of extractive crystallization groove, therefore, can add defluorinating agent again with the phosphoric acid dissolving separately and carry out the defluorinate operation;
(3) since the present invention under the condition of PH 〉=2.6-3.0, the throw out that defluorinate produced is less, so output is higher, and above-mentioned patent adopt one section in and the throw out that produced of defluorinate more, even phosphoric acid liquid that can not the amount of being added into all dissolves, and form part fertilizer grade secondary calcium phosphate, so output is lower;
(4) because used defluorinating agent is generally salt and lime, so cost is low, therefore, produce calcium hydrophosphate fodder with present method defluorinate, not only make P in the phosphoric acid liquid
2O
5Loss reduces, and simple to operate, and cost is low.
Present method is applicable to that also the defluorinate of general calcium leaching liquid prepares calcium hydrophosphate fodder.
Embodiment 1:
(1) extraction and defluorinate: in extraction tank, add in ground phosphate rock and the acid, add 2% SiO
2And 4%NaCl.Stirring reaction finishes after-filtration, and filter cake discards, and filtrate is sent the defluorinate operation.
(2) defluorinate: the phosphorolytic cleavage liquid 3M that in the defluorinate groove, adds extraction
3(phosphorus content 24.04g/L) adjusts acidity, under agitation slowly adds CaCO then
3(concentration is 10%-15%) is neutralized to PH=2.8.Continue to stir again and filtered in 40 minutes, filter cake returns extraction tank.The average 4.2M of filtrate
3(phosphorus content is 16.73g/L, and F is 0.06g/L, P
2O
5: F=275: 1), through Ca (OH)
2Calcium hydrophosphate fodder product, average out to 414.6Kg are made in neutralization.Product is through chemically examining: P=16.74%, F=0.16%.In the product P content be in the phosphoric acid P content 96.23%.
Embodiment 2
(1) leaching and defluorinate: one ton of general calcium and 4%NaCl are put into the leaching groove, add suitable quantity of water, agitation and filtration, filter cake can be made fertilizer usefulness, and filtrate is sent the defluorinate operation.
(2) defluorinate: leaching liquid is put into the defluorinate groove, adjust acidity, under agitation slowly add Ca (OH)
2Breast stirs filtration in 30 minutes to PH=3.0, and filter cake returns the leaching groove, and the calcium hydrophosphate fodder product is made in the filtrate neutralization.
For the general calcium of slaking more than 2.5 months, leaching liquid directly can be neutralized into product.
Claims (2)
1. make the composite precipitation defluorination method of calcium hydrophosphate fodder with phosphoric acid by wet process for one kind, it is characterized in that:
(1) when ground phosphate rock is with acid extraction system phosphoric acid, add defluorinating agent and carry out defluorinate, its defluorinating agent is active SIO
2And NaCL, consumption is respectively 2% and 4% of ground phosphate rock weight,
(2) extraction liquid is carried out the secondary defluorinate, its defluorinating agent is CaCO
3, concentration is 10-15%, add-on be when making the pH value of solution reach 2.6-3.0 till,
(3) the defluorinate slag of defluorinate for the second time returns the extractive crystallization groove again, carries out cyclical operation.
2. method according to claim 1 is characterized in that, after the defluorinate second time, and the P in the defluorinate liquid
2O
5/ F (quality) 〉=260.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97112458A CN1051527C (en) | 1997-06-10 | 1997-06-10 | Combined depositting defluorinating method for fodder grade calcium hydrophosphate by wet process from phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97112458A CN1051527C (en) | 1997-06-10 | 1997-06-10 | Combined depositting defluorinating method for fodder grade calcium hydrophosphate by wet process from phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1201755A CN1201755A (en) | 1998-12-16 |
| CN1051527C true CN1051527C (en) | 2000-04-19 |
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ID=5172274
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97112458A Expired - Fee Related CN1051527C (en) | 1997-06-10 | 1997-06-10 | Combined depositting defluorinating method for fodder grade calcium hydrophosphate by wet process from phosphate |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962421B (en) * | 2006-11-19 | 2010-04-14 | 武善东 | Phosphorite acidolysis method |
| CN105819452B (en) * | 2016-04-01 | 2018-01-30 | 龚家竹 | A kind of method that fluorine resource is reclaimed in the defluorination residues from feed phosphate |
| CN106698379A (en) * | 2017-01-20 | 2017-05-24 | 昆明川金诺化工股份有限公司 | Method for improving defluorination yield by two-stage white fertilizer re-dissolution |
| CN110467167B (en) * | 2019-09-27 | 2021-05-28 | 云南磷化集团有限公司 | Wet phosphoric acid defluorination method with coupling of precipitation predefluorination and stripping defluorination |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043481A (en) * | 1989-08-31 | 1990-07-04 | 路文兴 | Technology for calcium bydrogen phosphate forage |
| CN1146427A (en) * | 1996-08-23 | 1997-04-02 | 四川绵竹龙蟒矿物质饲料集团有限公司 | Method for producing feed-grade calcium hydrophosphate |
-
1997
- 1997-06-10 CN CN97112458A patent/CN1051527C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1043481A (en) * | 1989-08-31 | 1990-07-04 | 路文兴 | Technology for calcium bydrogen phosphate forage |
| CN1146427A (en) * | 1996-08-23 | 1997-04-02 | 四川绵竹龙蟒矿物质饲料集团有限公司 | Method for producing feed-grade calcium hydrophosphate |
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| Publication number | Publication date |
|---|---|
| CN1201755A (en) | 1998-12-16 |
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