CN106744768A - A kind of light phosphoric acid prepares feed-level calcium biphosphate method - Google Patents
A kind of light phosphoric acid prepares feed-level calcium biphosphate method Download PDFInfo
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- CN106744768A CN106744768A CN201611207257.XA CN201611207257A CN106744768A CN 106744768 A CN106744768 A CN 106744768A CN 201611207257 A CN201611207257 A CN 201611207257A CN 106744768 A CN106744768 A CN 106744768A
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- phosphoric acid
- feed
- light
- level calcium
- calcium biphosphate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
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Abstract
Feed-level calcium biphosphate method is prepared the invention discloses a kind of light phosphoric acid, methods described utilizes phosphoric acid by wet process to be reacted with Paris white after one section concentrates, vaporizing extract process defluorination process to concentration is 40~45wt% in the light phosphoric acid that ageing trench bottom after filtering sedimentation is returned, and feed-level calcium biphosphate is obtained after standing filtering.The present invention increases substantially phosphoric acid extraction concentration；Direct concentration prepares feed-level calcium biphosphate, realizes light phosphate resourcesization increment and utilizes, and production cost is greatly lowered, and significantly improves economic benefit.
Description
Technical field
Feed grade di(2-ethylhexyl)phosphate is prepared the invention belongs to feed-level calcium biphosphate technical field, more particularly to a kind of light phosphoric acid
Hydrogen calcium method.
Background technology
Calcium hydrophosphate fodder is a kind of rich in phosphorus, calcium two kinds of poultry of nutrient, domestic animal feed additives, due to it
In phosphorus calcium ratio (1：1.29) with animal skeleton in phosphorus calcium than closest, and can all be dissolved in animal hydrochloric acid in gastric juice, very
It is easily accessible in animal body and participates in its metabolism, the important life such as hormone, enzyme and vitamin required for composition animal body
Material, caused by keeping the phosphorus calcium in skeleton than that can promote to be prevented while animal body fast-growth animal because lacking phosphorus calcium
Various diseases, calcium hydrophosphate fodder is currently one of best feed mineral additive generally acknowledged both at home and abroad.Typically in animal
The 1~3% of feed total amount is added in feed, then poultry, the meat of domestic animal, egg, milk averagely increase production 15%~20%, its economic benefit
It is very notable.
Current feed-level calcium biphosphate mainly has three productions method：A kind of method is to be diluted with water to thermal phosphoric acid
P2O5Content 54wt%, with content calcium compound (calcium carbonate, calcium oxide, calcium hydroxide, defluorinated tricalcium phosphate) dry powder or liquid phase
Neutralization reaction, generates monobasic calcium phosphate slurry, then slurry is spray-dried or air-flow expansion drying generation semi-finished product, half into
Product curing rotary kiln drying, obtains finished product.
Second method is that Some Enterprises take wet method thickening-purification technology phosphoric acid, adds the thermal phosphoric acid of 50wt%, is configured to
The P of low impurity content2O5The phosphoric acid of content 54wt%, then with content calcium compound (calcium oxide, calcium hydroxide, phosphoric acid defluorination three
Calcium) dry powder or liquid phase neutralization reaction, monobasic calcium phosphate slurry is generated, then slurry is spray-dried or expansion drying generation
Semi-finished product, semi-finished product curing revolution or flash evaporation drying, obtain finished product.
The third method is to be carried out in two steps production, the first step, and phosphorus ore extracts light phosphorus using inorganic acid (sulfuric acid, hydrochloric acid)
Acid, light phosphoric acid adds calcium containing compound (calcium oxide, calcium hydroxide) liquid phase neutralization reaction defluorinate, and defluorinate wintercherry takes mechanical filter point
From fluorochemical (CaF2、CaSiF6) while generating Ca (H2PO4)2·H2O、Fe3(PO4)2、AlPO4Deng filtering acid sludge production
Fertile calcium hydrophosphate is used, and obtains phosphoric acid defluorination, the light phosphoric acid of defluorinate and liquid phase calcium containing compound (calcium carbonate, calcium oxide, hydroxide
Calcium, defluorinated tricalcium phosphate) generation calcium monohydrogen phosphate CaHPO4·2H2O contains wet semi-finished product, and drying obtains calcium monohydrogen phosphate finished product.Second
Step, in calcium monohydrogen phosphate CaHPO4·2H2O adds P in containing wet semifinished or finished goods2O5Content 54wt% thermal phosphoric acids 30wt% and
, there is liquid-solid reaction in 20wt% wet method defluorinate concentrated phosphoric acids, generation calcium dihydrogen phosphate slurry or calcium dihydrogen phosphate contain wet semi-finished product,
Spray-dried or expansion drying, obtains finished product respectively.
Above-mentioned existing manufacturing technique method has the following disadvantages：
First and second kind of technique productions method shortcoming be thermal phosphoric acid production process in energy consumption it is too high, be directed at hot method phosphorus
Sour production cost is high, and uncooked feed level calcium biphosphate is uneconomical, while product crystallizes tiny, poor fluidity, easily caking.
The third technique productions method the method, is also to raise the production method that calcium production is commonly used at present.Production process
The low value-added fertilizer calcium hydrophosphate amount of middle generation accounts for the 30wt% of calcium dihydrogen phosphate finished product total amount, and phosphrus reagent is low, product knot
Brilliant tiny, poor fluidity, easily caking.In order to ensure ratio of the water-soluble phosphorus in total phosphorus more than 90wt%, and the hot method added
Phosphoric acid accounts for more than the 30wt% of total phosphoric acid amount, and heat hair phosphoric acid high cost directly increases calcium dihydrogen phosphate production cost.
The Chinese patent application of Application No. CN01107387.X discloses one kind low concentration phosphoric acid by wet process directly and phosphorus
The method that sour hydrogen calcium produces feed-level calcium biphosphate.It is produced by low concentration phosphoric acid by wet process, is produced with the acid and calcium monohydrogen phosphate
Calcium dihydrogen phosphate slurry and granulation drying process composition, slubbing technique extract raw phosphoric acid operation, add carbon by with phosphate ore pulp, sulfuric acid
Sour calcium powder, calcium oxide powder and precipitating reagent make raw phosphoric acid removing impurities purify the operation composition for producing low concentration phosphoric acid by wet process.The patent is deposited
Need to be dried in reaction slurry, energy consumption is larger, and fluorine is not removed in phosphoric acid, causes feeding calcium to be difficult to up to standard.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of light phosphoric acid and prepares feed-level calcium biphosphate method, this hair
, by directly preparing feed-level calcium biphosphate after concentration defluorinating, one side is significantly for light phosphoric acid in bright utilization Wet-process Phosphoric Acid Production
Degree improves phosphoric acid by wet process concentration, on the other hand realizes light phosphate resourcesization increment and utilizes.The feed grade phosphoric acid of the method production
Calcium dihydrogen has reached GB/T22548-2008 requirements.
Technical scheme is as follows：A kind of light phosphoric acid prepares feed-level calcium biphosphate method, and methods described is utilized
The light phosphoric acid that phosphoric acid by wet process is aged trench bottom return after sedimentation is filtered is 40 through one section of concentration, vaporizing extract process defluorination process to concentration
Reacted with Paris white after~45wt%, feed-level calcium biphosphate is obtained after standing filtering.
Further, phosphorus fluorine ratio is more than 250 after the light Phosphoric Acid Concentration.
Further, the Paris white purity is more than 99.9wt%.
Further, the light phosphoric acid is controlled 4.9~6.8 with Paris white slurry pH value, and reaction temperature is 70~90
℃。
The mass fraction of light phosphoric acid major impurity of the present invention is Fe2O3≤ 1%, Al2O3≤ 0.8%, MgO≤
1.3%, F≤0.5%.
The mechanism that the present invention can prepare feed-level calcium biphosphate using low concentration phosphoric acid is as follows：Using wet production phosphorus
Being aged trench bottom after sedimentation is filtered when sour can produce substantial amounts of light phosphoric acid, those skilled in the art in production SPA technique
In order to avoid phosphoric acid is wasted, therefore the light phosphoric acid for reclaiming is back to extraction tank and is used as acid reflux, will not used elsewhere, seen
Fig. 1, and reclaim light phosphoric acid and be recovered to extraction tank technique and be on the one hand greatly lowered phosphoric acid extraction concentration, increase concentration load；Separately
One side acid reflux increases the load of extraction tank, makes the reduction of phosphoric acid extraction efficiency, but can only also reclaim in order to avoid phosphoric acid is wasted.
It is comparatively laborious additionally, due to the process for detecting light phosphate composition, and those skilled in the art only focus on the recovery of light phosphoric acid, i.e.,
Detection is also only detected the content of phosphoric acid in light phosphoric acid, be not concerned with impurity content, those skilled in the art do not carry out impurity substantially
Content detection is tested.Impurity content is far below phosphoric acid extraction during the present invention accidentally detects the light phosphoric acid in the part, in phosphoric acid extraction
Fe2O3>=1.5%, Al2O3>=1.5%, MgO >=2.0%, F >=1.0%, and the mass fraction of light phosphoric acid major impurity is Fe2O3
≤ 1%, Al2O3≤ 0.8%, MgO≤1.3%, F≤0.5%, present invention proposes by the light phosphoric acid in the part be used for produce phosphorus
The technical scheme of acid dihydride calcium, the program is not allowed to be readily conceivable that, and has reached beneficial technique effect.
The present invention is using the phosphoric acid by wet process light phosphoric acid that ageing trench bottom is reclaimed after sedimentation is filtered through one section of concentration, vaporizing extract process
Defluorination process, to be reacted with Paris white after 40~45wt%, feed-level calcium biphosphate is obtained after standing filtering to concentration, is seen
Fig. 2, produces calcium dihydrogen phosphate (phosphoric acid needs to concentrate twice, and impurity content is high) and compares with prior art, and power consumption is few, high efficiency,
Low cost, wherein, one section of concentration and air- extraction defluorinate belong to existing conventional techniques, simple to operate.
Compared with prior art, the invention has the advantages that：It is dense that the present invention increases substantially extraction phosphoric acid by wet process
Degree；Light phosphate resourcesization increment is realized to utilize；Oil repellent in light phosphoric acid is very low, and the air lift defluorinate time is short, is greatly lowered
Production cost, significantly improves economic benefit.
Brief description of the drawings
Fig. 1 is the production technology simple process figure of phosphoric acid；
Fig. 2 is production technology simple process figure of the invention.
Specific embodiment
Technical scheme is described in further details with reference to specific embodiment.
The mass fraction of phosphoric acid and major impurity is in light phosphoric acid in following examples：Fe2O3It is 0.87%, Al2O3For
0.63%, MgO are that 1.18%, F is 0.43%, P2O5It is 21.56%.
Embodiment 1
Light phosphatase 11 000g is taken in rotary evaporator, through sedimentation after concentration, supernatant strips defluorinate, SPA phosphorus fluorine ratio
It is 287, P2O5Mass concentration is 42.56%, and the calcium carbonate hybrid reaction temperature for adding stoichiometric proportion is 72 DEG C, reaction time
79min, slurry pH are controlled 5.3.Drying-granulating after slurry reaction, the feed-level calcium biphosphate of production has reached GB/
T22548-2008 requirements.
Embodiment 2
Light phosphatase 11 000g is taken in rotary evaporator, through sedimentation after concentration, supernatant strips defluorinate, SPA phosphorus fluorine ratio
It is 274, P2O5Mass concentration is 42.23%, and the calcium carbonate hybrid reaction temperature for adding stoichiometric proportion is 76 DEG C, reaction time
241min, slurry pH are controlled 5.9.Drying-granulating after slurry reaction, the feed-level calcium biphosphate of production has reached GB/
T22548-2008 requirements.
Embodiment 3
Light phosphatase 11 000g is taken in rotary evaporator, through sedimentation after concentration, supernatant strips defluorinate, SPA phosphorus fluorine ratio
It is 289, P2O5Mass concentration is 42.17%, and the calcium carbonate hybrid reaction temperature for adding stoichiometric proportion is 78 DEG C, reaction time
404min, slurry pH are controlled 6.7.Drying-granulating after slurry reaction, the feed-level calcium biphosphate of production has reached GB/
T22548-2008 requirements.
Claims (5)
1. a kind of light phosphoric acid prepares feed-level calcium biphosphate method, it is characterised in that methods described is using phosphoric acid by wet process in mistake
Filter sedimentation after be aged trench bottom return light phosphoric acid through one section concentration, vaporizing extract process defluorination process to concentration be 40~45wt% after with
Paris white is reacted, and feed-level calcium biphosphate is obtained after standing filtering.
2. feed-level calcium biphosphate method is prepared after the concentrated defluorinate of light phosphoric acid according to claim 1, its feature exists
In phosphorus fluorine ratio is more than 250 after the Phosphoric Acid Concentration.
3. feed-level calcium biphosphate method is prepared after the concentrated defluorinate of light phosphoric acid according to claim 1, its feature exists
In the Paris white purity is more than 99.9wt%.
4. feed-level calcium biphosphate method is prepared after the concentrated defluorinate of light phosphoric acid according to claim 1, its feature exists
In the phosphoric acid is controlled 4.9~6.8 with Paris white slurry pH value, and reaction temperature is 70~90 DEG C.
5. according to preparing feed-level calcium biphosphate method after any described concentrated defluorinate of light phosphoric acid of Claims 1 to 4, its
It is characterised by, the mass fraction of the light phosphoric acid major impurity is Fe2O3≤ 1%, Al2O3≤ 0.8%, MgO≤1.3%, F≤
0.5%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108910853A (en) * | 2018-09-11 | 2018-11-30 | 云南磷化集团有限公司 | The method for producing granular calcium dihydrogen phosphate using granulating of concentrated phosphoric acid |
| CN113955731A (en) * | 2021-12-08 | 2022-01-21 | 昆明云盘山农牧科技有限公司 | Preparation method of granular feed-grade monocalcium phosphate |
| CN114956024A (en) * | 2021-12-31 | 2022-08-30 | 贵州长泰源纳米钙业科技有限公司 | Process for producing feed-grade monocalcium phosphate |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101264873A (en) * | 2008-04-11 | 2008-09-17 | 李进 | Method for producing feed-grade calcium phosphate |
| CN101288440A (en) * | 2008-04-21 | 2008-10-22 | 李进 | Production method of feed grade calcium phosphate acidity agent |
| CN105217592A (en) * | 2015-09-17 | 2016-01-06 | 中化云龙有限公司 | The production method of the granular monocalcium phosphate of feed grade |
-
2016
- 2016-12-23 CN CN201611207257.XA patent/CN106744768B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101264873A (en) * | 2008-04-11 | 2008-09-17 | 李进 | Method for producing feed-grade calcium phosphate |
| CN101288440A (en) * | 2008-04-21 | 2008-10-22 | 李进 | Production method of feed grade calcium phosphate acidity agent |
| CN105217592A (en) * | 2015-09-17 | 2016-01-06 | 中化云龙有限公司 | The production method of the granular monocalcium phosphate of feed grade |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108910853A (en) * | 2018-09-11 | 2018-11-30 | 云南磷化集团有限公司 | The method for producing granular calcium dihydrogen phosphate using granulating of concentrated phosphoric acid |
| CN113955731A (en) * | 2021-12-08 | 2022-01-21 | 昆明云盘山农牧科技有限公司 | Preparation method of granular feed-grade monocalcium phosphate |
| CN113955731B (en) * | 2021-12-08 | 2024-03-01 | 昆明云盘山农牧科技有限公司 | Preparation method of granular feed-grade monocalcium phosphate |
| CN114956024A (en) * | 2021-12-31 | 2022-08-30 | 贵州长泰源纳米钙业科技有限公司 | Process for producing feed-grade monocalcium phosphate |
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