CN108751156A - A method of preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock - Google Patents
A method of preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock Download PDFInfo
- Publication number
- CN108751156A CN108751156A CN201810607741.4A CN201810607741A CN108751156A CN 108751156 A CN108751156 A CN 108751156A CN 201810607741 A CN201810607741 A CN 201810607741A CN 108751156 A CN108751156 A CN 108751156A
- Authority
- CN
- China
- Prior art keywords
- ammonium chloride
- double superhosphate
- purity
- phosphate rock
- preparing high
- 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
Classifications
-
- 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
- C01B25/321—Methods for converting an alkaline earth metal ortho-phosphate into another ortho-phosphate
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B1/00—Superphosphates, i.e. fertilisers produced by reacting rock or bone phosphates with sulfuric or phosphoric acid in such amounts and concentrations as to yield solid products directly
- C05B1/04—Double-superphosphate; Triple-superphosphate; Other fertilisers based essentially on monocalcium phosphate
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The present invention relates to industrial solid wastes to utilize technical field, specifically a kind of method for preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock.The present invention is in CaCl2Sub-molten salt system is using ammonium chloride as stealthy acid medium, using ground phosphate rock as raw material, it reacts with ammonium chloride in calcium chloride sub-molten salt system and generates coarse whiting product and release ammonia, no sulfuric acid consumption and ardealite discharge, and the lower double superhosphate of the purity containing sour insoluble impurities is dissolved in hydrochloric acid, it removes precipitation and takes filtrate, then by filtrate in CaCl2It under sub-molten salt system status, is reacted in 140 DEG C or more, the HCl that reaction is formed is made largely to volatilize, and so that this is swift in response and carried out to direction, to obtain the higher double superhosphate of a large amount of purity.The method of the present invention is a kind of no sulfuric acid consumption and ardealite discharge, and the higher method for preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock of gained double superhosphate purity.
Description
Technical field
It is specifically a kind of to prepare high-purity mistake again using ammonium chloride decomposing phosphate rock the present invention relates to phosphorus ore processing technology field
The method of calcium phosphate.
Background technology
Traditional coarse whiting uses " addition " production technology, often produces 1 ton of coarse whiting and at least needs to consume 0.46 ton of sulfuric acid, generates
0.93 ton of ardealite.
Ardealite is the industrial residue of generation during Wet-process Phosphoric Acid Production.1 ton of phosphoric acid is often produced (with P2O5Meter), generally
Generate 4-5 tons of ardealites.The main component of ardealite is calcium sulphate dihydrate or half-H 2 O calcium sulphate, and containing a small amount of quartz, not
Apatite, the water solubility P of decomposition2O5, insoluble P2O5, eutectic P2O5, fluoride and fluorine, aluminium, the phosphate of magnesium and sulfate etc..
Ardealite delays (tune) and coagulates agent, building gypsum plaster, Thistle board, fiber mainly for the production of building material, including cement at present
Plasterboard and pit filler and road foundation material etc..Due in ardealite titanium pigment, fluorine and other impurity to phosphorus stone
Cream building material performance has an adverse effect, such as the extension of gypsum setting time, hardenite strength reduction, crystal structure are loose,
And its water content is high, and thus causing ardealite to prepare, building material poor quality, added value are low, market transportation radius is short.This
Outside, the solubility product due to calcium sulfate and calcium carbonate in ammonium sulfate differs more than 3000 times, and calcium sulfate is easy to pass through carbonating
Reaction process is converted into solid product calcium carbonate and synchronous production ammonium sulfate liquor, and ammonium sulfate liquor can also be further inverted
Prepare the sulfenyls compound fertilizer product such as potassium sulfate and ammonium chloride potassium.However, on the one hand since the impurity almost all in ardealite enters
In solid product, thus lead to that gained calcium carbonate product particle is tiny, purity and whiteness are poor, added value is low, it is difficult to extensive sharp
With；On the other hand, the calcium sulfate in ardealite needs to consume a large amount of ammonia after being converted into calcium carbonate, and the ammonia consumed finally converts
For the low value-added product such as ammonium sulfate or ammonium chloride, overall technology economy difficulty is thus caused to reach a standard.
Based on this, for a large amount of ardealites of attached production and ardealite carbonic acid in existing traditional dihydrate wet phosphoric acid extraction process
Change conversion and prepare the bad outstanding problem of calcium carbonate Technical Economy, it is therefore desirable to find a kind of no ardealite generation phosphorite stope
Method.
Double superhosphate is colourless anorthic system crystallization or white crystalline powder.Relative density 2.22 (16 DEG C).Slightly
Hygroscopicity is soluble in hydrochloric acid, nitric acid, is slightly soluble in cold water, is practically insoluble in ethyl alcohol.At 30 DEG C, solvable di(2-ethylhexyl)phosphate in 100ml water
Hydrogen calcium 1.8g.The aobvious acidity of aqueous solution, heating aqueous solution are then hydrolyzed to Cafos.Lose the crystallization water at 109 DEG C, 203 DEG C
Shi Ze resolves into calcium metaphosphate.Double superhosphate (coarse whiting), ingredient Ca (H2PO4)2, it can be dissolved in water, fertilizer efficiency is (more general than calcium superphosphate
Calcium) it is high, it preferably mixes and applies with farm manure, but cannot be mixed with alkaline matter, it may occur that react H as follows2PO4(-)+2OH
(-)=2H2O+PO4(3-) generate slightly solubility calcium phosphate and reduce fertilizer efficiency.Double superhosphate is suitable for fertilizer, for various soil and
Crop can be used as base manure, top dressing and compound (mixed) fertile raw material.Be widely used in rice, wheat, corn, jowar, cotton, melon and fruit,
The various cereal crops such as vegetables and industrial crops.It is additionally operable to glass manufacture, plastics stability, livestock auxiliary fodder.
The production of calcium superphosphate at present mainly uses two kinds of techniques of diluted acid miberal powder method and concentrated acid pulp process.Double superhosphate is given birth to
The traditional handicraft of production is to use sulfuric acid decomposition phosphorus ore, by leaching and being obtained by filtration phosphoric acid,diluted, then concentrated rear this concentrated phosphoric acid
The higher secondary phosphorus ore of quality is decomposed, is made and contains higher P2O5Double superhosphate.The traditional processing technology, to being used to give birth to
The requirement for producing phosphorus ore, that is, secondary mine of double superhosphate is very high, but with the long-term exploitation and consumption of phosphate rock resource, high-grade phosphorus
Mine is fewer and fewer.In addition, the sulphur inadequate resource in China, mainly by production of sulfur from pyrite acid, thus sulfuric acid is in short supply.2008
Since year, international Sulfur price is constantly soaring, and domestic sulfuric acid price advantage is stimulated to raise up.And China's Mid-and low-grade phosphate rock resources compared with
It is more, there are many enterprise's by-product hydrochloric acids, hydrochloric acid is more than needed, cheap.Therefore, there are many enterprise sulfuric acid decomposition phosphorus is replaced with hydrochloric acid
Mine produces double superhosphate co-production calcium chloride, but the method can consume a large amount of hydrochloric acid and generate a large amount of calcium chloride, and has phosphorus
Sour association, since the economic benefit of calcium chloride is relatively low.
To sum up, searching is a kind of preparing double superhosphate by decomposing phosphate rock, and the method without ardealite generation is
The task of top priority.
Invention content
In order to solve the above technical problems existing in the prior art, the present invention provides
A method of high-purity double superhosphate being prepared using ammonium chloride decomposing phosphate rock, is included the following steps：
(1) it is mixed with ammonium chloride solution after smashing phosphorus ore, stirs slurrying；
(2) phosphorus ore slurry is added to CaCl2In sub-molten salt, reacted；
(3) fully add water to be diluted into reactant after reaction, discharge, filtering respectively obtains filtrate and filter cake；
(4) dechlorination is washed with water in filter cake, then filter cake is dried, obtain double superhosphate；
(5) obtained double superhosphate is added to the water, stirs slurrying, hydrochloric acid is added thereto, is reacted；
(6) it after it is fully reacted after slurries, is filtered, respectively obtains filtrate and filter cake,
(7) filtrate is heated to obtaining stable sub-molten salt system, is reacted in 140 DEG C or more；
(8) it waits for after reaction, collecting solid product to get high-purity double superhosphate.
Preferably, the phosphorus ore is smashed, and is that phosphorus ore is broken into powder.The phosphorus ore for breaking into powder is easier to ammonium chloride solution
Reaction, makes reaction faster be more easy to slurrying.
Preferably, the ammonium chloride solution is supersaturated ammonium chloride solution.It is further preferred that the supersaturation ammonium chloride
Solution is 60 DEG C of supersaturated solution.Supersaturated ammonium chloride solution contains more ammonium chloride, and will be molten being reacted with ore
It can be supplemented in time after ammonium chloride consumption in liquid, chloride leach degree is larger in the case of 60 DEG C, and supersaturated ammonium chloride is molten
Ammonium chloride contained in liquid is also more, and the increase of ammonium chloride amount of hydrolysis will not be caused to cause damages because temperature is excessively high.
Preferably, the CaCl of the step (2)2Sub-molten salt is by CaCl2It is stirred after being mixed with the water of its weight 50-150%
It mixes uniformly, is warming up to 170 DEG C -180 DEG C, keep stablizing to obtain the final product.CaCl at this time2Sub-molten salt system is relatively stable.
Preferably, the step (2), CaCl is added to by phosphorus ore slurry2It is during sub-molten salt, phosphorus ore slurry is slow
It is added.Cause quickly to generate a large amount of foams to avoid due to phosphorus ore slurry rapidly joins, causes to overflow, and influence reaction speed.
Preferably, the step (2), reaction time control in 2h or more.It is carried out with reacting fully.
Preferably, the step (3), adds water to be diluted, and is the water that reactant weight 15-40% is added.It dilutes at this time
Effect is preferable, and dosage is also relatively mild, will not be caused due to the more amount for causing double superhosphate to be dissolved in water of water is added and increases
Double superhosphate loses.
Preferably, the step (7), is reacted at 160 DEG C.When being reacted at 160 DEG C reaction speed compared with
Soon, and phosphoric acid will not be caused to change and lead to loss of material.
Preferably, the gas released is carried out absorption processing in reaction process by the step (7) using alkaline solution.
The gas released in reaction process is mainly HCl gases, cannot be discharged directly into air.
Preferably, the step (7) carries out condensing reflux in reaction process.Condensing reflux can reduce the damage of water and phosphoric acid
It loses, reaction consumption is made to reduce.
Preferably, the step (7) is collected the gas released in reaction process.It is released in reaction process
Gas is mainly HCl gases, is utilized after can collecting.
The method of the present invention is in CaCl2Sub-molten salt system is used as stealthy acid medium using ammonium chloride, using ground phosphate rock as raw material,
It reacts with ammonium chloride in calcium chloride sub-molten salt system and generates coarse whiting product and release ammonia, no sulfuric acid consumption and phosphorus stone
Cream discharges.
The key reaction equation of the present invention is as follows：
When phosphorus ore ammonium chloride decomposes：
2Ca5(PO4)3F+12NH4Cl=3Ca (H2PO4)2+CaF2+12NH3↑+6CaCl2
(reaction condition：160-180 DEG C, CaCl2Sub-molten salt system)
CaCO3+CaSiO3+2NH4Cl=2NH3↑+H2O+CaCl2+CO2↑+SiO2·2H2O
(reaction condition：160-180 DEG C, CaCl2Sub-molten salt system)
Ca (the H of generation are reacted at this time2PO4)2For microsolubility substance, SiO2·2H2O is insoluble substance, and step (3) obtains
Filter cake mainly by the two at being grouped as, cause the purity of double superhosphate not high, thus using free hydrochloric acid by filter cake into
Row separation, then in CaCl2Back reaction is carried out under sub-molten salt system status, to obtain the higher double superhosphate of purity.
When double superhosphate purifies：
3Ca(H2PO4)2Sour insoluble slag+2HCl=2H3PO4+CaCl2+ acid insoluble slag ↓
(reaction condition：100 DEG C of <)
2H3PO4+CaCl2=Ca (H2PO4)2+2HCl
(reaction condition：140 DEG C of >, CaCl2Sub-molten salt system)
In the solution, the acidity of HCl is better than H3PO4, therefore H3PO4With CaCl2It can not react, and Ca (H2PO4)2
It can react instead with HCl, generate H3PO4With CaCl2, it is, therefore, usually considered that CaCl2With H3PO4Directly prepare weight peroxophosphoric acid
Calcium is unworkable, Ca (H in the solution2PO4)2It reacts with HCl, generates H3PO4With CaCl2Specific reaction equation such as
Under：
Ca(H2PO4)2+ 2HCl=2H3PO4+CaCl2
(strong acid occurs in the solution and sets weak acid reaction)
And in CaCl2Under sub-molten salt system status, above-mentioned reaction can inversely occur, and specific reaction equation is as follows：
2H3PO4+CaCl2=Ca (H2PO4)2+2HCl
(reaction condition：140 DEG C of >, CaCl2Sub-molten salt system)
At this point, above-mentioned reaction reversible process each other, can pass through CaCl2With H3PO4It reacts to obtain Ca (H2PO4)2With
HCl, but the colleague that above-mentioned reaction at this time occurs in forward direction is also inversely occurring, and can obtain double superhosphate, but cross phosphorus again
Still contain more CaCl in sour calcium2, cause the purity of double superhosphate relatively low.
At this point, by that in 140 DEG C of >, the HCl that reaction is formed can be made largely to volatilize, and 160 reaction temperature control
Reaction speed is very fast when being reacted at DEG C, and phosphoric acid will not be caused to change and lead to loss of material, and makes the reaction
It is carried out to direction rapidly, obtains a large amount of double superhosphate, gained double superhosphate purity is higher.
Compared with prior art, the technique effect of the invention is embodied in：
The present invention is in CaCl2Sub-molten salt system is used as stealthy acid medium using ammonium chloride, using ground phosphate rock as raw material, in chlorination
It reacts with ammonium chloride in calcium sub-molten salt system and generates coarse whiting product and release ammonia, no sulfuric acid consumption and ardealite row
It puts, and the lower double superhosphate of the purity containing sour insoluble impurities is dissolved in hydrochloric acid, remove precipitation and take filtrate, then
By filtrate in CaCl2It under sub-molten salt system status, is reacted in 140 DEG C or more, the HCl that reaction is formed is made largely to volatilize, and
Make this be swift in response to carry out to direction, to obtain the higher double superhosphate of a large amount of purity.The method of the present invention is without sulphur
Acid consumption and ardealite discharge, and gained double superhosphate purity is higher, and it is a large amount of to eliminate traditional GCC production process consumption
Sulfuric acid and the problem of bring a large amount of ardealites to discharge, be a kind of no sulfuric acid consumption and ardealite discharge, and gained weight peroxophosphoric acid
The higher method for preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock of calcium purity.
Specific implementation mode
It is limited with reference to specific embodiment technical scheme of the present invention is further, but claimed
Range describes made by being not only limited to.
Embodiment 1
(1) 200g phosphorus ores are broken into after powder and are mixed with ammonium chloride solution, stir slurrying, the ammonium chloride solution is
230g ammonium chlorides are dissolved in the ammonium chloride saturated solution that 280ml water obtains at 60 DEG C；
(2) phosphorus ore slurry is added to CaCl2In sub-molten salt, 2h, the CaCl are reacted2Sub-molten salt is by 800gCaCl2
It is stirred evenly after being mixed with the water of its weight 100%, is warming up to 175 DEG C, keep stably obtaining；
(3) water that reactant weight 25% is added fully after reaction into reactant is diluted, and is discharged, is filtered, respectively
Obtain filtrate and filter cake；
(4) dechlorination is washed with water in filter cake, then filter cake is dried, obtain double superhosphate；
(5) obtained double superhosphate is added to the water, stirs slurrying, hydrochloric acid is added thereto, is reacted；
(6) it after it is fully reacted after slurries, is filtered, respectively obtains filtrate and filter cake,
(7) filtrate is heated to obtaining stable sub-molten salt system, is reacted in 160 DEG C, the gas that reaction is released
Body carries out absorption processing using alkaline solution；
(8) it waits for after reaction, collecting solid product to get high-purity double superhosphate.
P in phosphorus ore used2O5Content is 35.62%, CaO content 50.84%.
Embodiment 2
(1) 200g phosphorus ores are broken into after powder and are mixed with ammonium chloride solution, stir slurrying, the ammonium chloride solution is
230g ammonium chlorides are dissolved in the ammonium chloride supersaturated solution that 400ml water obtains at 40 DEG C；
(2) phosphorus ore slurry is added to CaCl2In sub-molten salt, 1h, the CaCl are reacted2Sub-molten salt is by 800gCaCl2
It is stirred evenly after being mixed with the water of its weight 50%, is warming up to 180 DEG C, keep stably obtaining；
(3) water that reactant weight 15% is added fully after reaction into reactant is diluted, and is discharged, is filtered, respectively
Obtain filtrate and filter cake；
(4) dechlorination is washed with water in filter cake, then filter cake is dried, obtain double superhosphate；
(5) obtained double superhosphate is added to the water, stirs slurrying, hydrochloric acid is added thereto, is reacted；
(6) it after it is fully reacted after slurries, is filtered, respectively obtains filtrate and filter cake,
(7) filtrate is heated to obtaining stable sub-molten salt system, is reacted in 140 DEG C, the gas that reaction is released
Body carries out absorption processing using alkaline solution；
(8) it waits for after reaction, collecting solid product to get high-purity double superhosphate.
P in phosphorus ore used2O5Content is 35.62%, CaO content 50.84%.
Embodiment 3
(1) 200g phosphorus ores are broken into after powder and are mixed with ammonium chloride solution, stir slurrying, the ammonium chloride solution is
230g ammonium chlorides are dissolved in the ammonium chloride supersaturated solution that 230ml water obtains at 80 DEG C；
(2) phosphorus ore slurry is added to CaCl2In sub-molten salt, 3h, the CaCl are reacted2Sub-molten salt is by 800gCaCl2
It is stirred evenly after being mixed with the water of its weight 150%, is warming up to 170 DEG C, keep stably obtaining；
(3) water that reactant weight 40% is added fully after reaction into reactant is diluted, and is discharged, is filtered, respectively
Obtain filtrate and filter cake；
(4) dechlorination is washed with water in filter cake, then filter cake is dried, obtain double superhosphate；
(5) obtained double superhosphate is added to the water, stirs slurrying, hydrochloric acid is added thereto, is reacted；
(6) it after it is fully reacted after slurries, is filtered, respectively obtains filtrate and filter cake,
(7) filtrate is heated to obtaining stable sub-molten salt system, is reacted in 180 DEG C, the gas that reaction is released
Body carries out absorption processing using alkaline solution；
(8) it waits for after reaction, collecting solid product to get high-purity double superhosphate.
P in phosphorus ore used2O5Content is 35.62%, CaO content 50.84%.
Embodiment 4
(1) 200g phosphorus ores are broken into after powder and are mixed with ammonium chloride solution, stir slurrying, the ammonium chloride solution is
230g ammonium chlorides are dissolved in the ammonium chloride saturated solution that 280ml water obtains at 60 DEG C；
(2) phosphorus ore slurry is slowly added into CaCl2In sub-molten salt, 2h, the CaCl are reacted2Sub-molten salt, be by
800gCaCl2It is stirred evenly after being mixed with the water of its weight 100%, is warming up to 175 DEG C, keep stably obtaining；
(3) water that reactant weight 25% is added fully after reaction into reactant is diluted, and is discharged, is filtered, respectively
Obtain filtrate and filter cake；
(4) dechlorination is washed with water in filter cake, then filter cake is dried, obtain double superhosphate；
(5) obtained double superhosphate is added to the water, stirs slurrying, hydrochloric acid is added thereto, is reacted；
(6) it after it is fully reacted after slurries, is filtered, respectively obtains filtrate and filter cake,
(7) filtrate is heated to obtaining stable sub-molten salt system, is reacted in 160 DEG C, the gas that reaction is released
Body carries out absorption processing using alkaline solution；
(8) it waits for after reaction, collecting solid product to get high-purity double superhosphate.
P in phosphorus ore used2O5Content is 35.62%, CaO content 50.84%.
Embodiment 5
(1) 200g phosphorus ores are broken into after powder and are mixed with ammonium chloride solution, stir slurrying, the ammonium chloride solution is
230g ammonium chlorides are dissolved in the ammonium chloride saturated solution that 280ml water obtains at 60 DEG C；
(2) phosphorus ore slurry is added to CaCl2In sub-molten salt, 2h, the CaCl are reacted2Sub-molten salt is by 800gCaCl2
It is stirred evenly after being mixed with the water of its weight 100%, is warming up to 175 DEG C, keep stably obtaining；
(3) water that reactant weight 25% is added fully after reaction into reactant is diluted, and is discharged, is filtered, respectively
Obtain filtrate and filter cake；
(4) dechlorination is washed with water in filter cake, then filter cake is dried, obtain double superhosphate；
(5) obtained double superhosphate is added to the water, stirs slurrying, hydrochloric acid is added thereto, is reacted；
(6) it after it is fully reacted after slurries, is filtered, respectively obtains filtrate and filter cake,
(7) filtrate is heated to obtaining stable sub-molten salt system, is reacted, is carried out in reaction process cold in 160 DEG C
The gas that reaction releases is carried out absorption processing by solidifying reflux using alkaline solution；
(8) it waits for after reaction, collecting solid product to get high-purity double superhosphate.
P in phosphorus ore used2O5Content is 35.62%, CaO content 50.84%.
Embodiment 6
(1) 200g phosphorus ores are broken into after powder and are mixed with ammonium chloride solution, stir slurrying, the ammonium chloride solution is
230g ammonium chlorides are dissolved in the ammonium chloride saturated solution that 280ml water obtains at 60 DEG C；
(2) phosphorus ore slurry is added to CaCl2In sub-molten salt, 2h, the CaCl are reacted2Sub-molten salt is by 800gCaCl2
It is stirred evenly after being mixed with the water of its weight 100%, is warming up to 175 DEG C, keep stably obtaining；
(3) water that reactant weight 25% is added fully after reaction into reactant is diluted, and is discharged, is filtered, respectively
Obtain filtrate and filter cake；
(4) dechlorination is washed with water in filter cake, then filter cake is dried, obtain double superhosphate；
(5) obtained double superhosphate is added to the water, stirs slurrying, hydrochloric acid is added thereto, is reacted；
(6) it after it is fully reacted after slurries, is filtered, respectively obtains filtrate and filter cake,
(7) filtrate is heated to obtaining stable sub-molten salt system, is reacted in 160 DEG C, is received in reaction process
Collect the gas released；
(8) it waits for after reaction, collecting solid product to get high-purity double superhosphate.
P in phosphorus ore used2O5Content is 35.62%, CaO content 50.84%.
Each embodiment is compared, acquired results are as follows：
From the foregoing, it will be observed that the method for the present invention can effectively purify double superhosphate, it is insoluble miscellaneous to remove acid therein
Matter obtains the higher double superhosphate of purity.
Finally it is pointed out that above example is only the more representational example of the present invention.Obviously, technology of the invention
Scheme is not limited to above-described embodiment, and acceptable there are many deformations.Those skilled in the art can be from disclosed by the invention
All deformations that content is directly exported or associated, are considered as protection scope of the present invention.
Claims (10)
1. a kind of method preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock, which is characterized in that including walking as follows
Suddenly：
(1) it is mixed with ammonium chloride solution after smashing phosphorus ore, stirs slurrying；
(2) phosphorus ore slurry is added to CaCl2In sub-molten salt, reacted；
(3) fully add water to be diluted into reactant after reaction, discharge, filtering respectively obtains filtrate and filter cake；
(4) dechlorination is washed with water in filter cake, then filter cake is dried, obtain double superhosphate；
(5) obtained double superhosphate is added to the water, stirs slurrying, hydrochloric acid is added thereto, is reacted；
(6) it after it is fully reacted after slurries, is filtered, respectively obtains filtrate and filter cake,
(7) filtrate is heated to obtaining stable sub-molten salt system, is reacted in 140 DEG C or more；
(8) it waits for after reaction, collecting solid product to get high-purity double superhosphate.
2. the method according to claim 1 for preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock, feature
It is, the phosphorus ore is smashed, and is that phosphorus ore is broken into powder.
3. the method according to claim 1 for preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock, feature
It is, the ammonium chloride solution is supersaturated ammonium chloride solution.
4. the method according to claim 3 for preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock, feature
It is, the supersaturation ammonium chloride solution, is 60 DEG C of supersaturated solution.
5. the method according to claim 1 for preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock, feature
It is, the CaCl of the step (2)2Sub-molten salt is by CaCl2It stirs evenly, heats up after being mixed with the water of its weight 50-150%
To 170 DEG C -180 DEG C, keep stablizing to obtain the final product.
6. the method according to claim 1 for preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock, feature
It is, phosphorus ore slurry is added to CaCl by the step (2)2During sub-molten salt, phosphorus ore slurry is slowly added to.
7. the method according to claim 1 for preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock, feature
It is, the step (3) adds water to be diluted, and is the water that reactant weight 15-40% is added.
8. the method according to claim 1 for preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock, feature
It is, the step (7), the gas released is subjected to absorption processing using alkaline solution in reaction process.
9. the method according to claim 1 for preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock, feature
It is, the step (7), condensing reflux is carried out in reaction process.
10. the method for preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock according to claim 1 or 9,
It is characterized in that, the step (7), the gas released is collected in reaction process.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810607741.4A CN108751156B (en) | 2018-06-13 | 2018-06-13 | Method for preparing high-purity triple superphosphate by decomposing phosphorite with ammonium chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810607741.4A CN108751156B (en) | 2018-06-13 | 2018-06-13 | Method for preparing high-purity triple superphosphate by decomposing phosphorite with ammonium chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108751156A true CN108751156A (en) | 2018-11-06 |
| CN108751156B CN108751156B (en) | 2020-11-20 |
Family
ID=64022656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810607741.4A Expired - Fee Related CN108751156B (en) | 2018-06-13 | 2018-06-13 | Method for preparing high-purity triple superphosphate by decomposing phosphorite with ammonium chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108751156B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85107209A (en) * | 1985-09-24 | 1986-05-10 | 陕西省化学肥料工业公司 | The low grade calcareous phosphorous ore fractionation |
| CN1285312A (en) * | 1999-08-22 | 2001-02-28 | 李怀然 | novel process for preparing fodder grade calcium hydrophosphate and by-product calcium carbonate and ammonium chloride by hydrochloric acid method |
| CN1962421A (en) * | 2006-11-19 | 2007-05-16 | 武善东 | Phosphorite acidolysis method |
| WO2010043262A1 (en) * | 2008-10-16 | 2010-04-22 | Ecophos Sa | Process for the production of high purity phosphoric acid |
| CN102659089A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院过程工程研究所 | Producing method of calcium hydrogen phosphate |
-
2018
- 2018-06-13 CN CN201810607741.4A patent/CN108751156B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85107209A (en) * | 1985-09-24 | 1986-05-10 | 陕西省化学肥料工业公司 | The low grade calcareous phosphorous ore fractionation |
| CN1285312A (en) * | 1999-08-22 | 2001-02-28 | 李怀然 | novel process for preparing fodder grade calcium hydrophosphate and by-product calcium carbonate and ammonium chloride by hydrochloric acid method |
| CN1962421A (en) * | 2006-11-19 | 2007-05-16 | 武善东 | Phosphorite acidolysis method |
| WO2010043262A1 (en) * | 2008-10-16 | 2010-04-22 | Ecophos Sa | Process for the production of high purity phosphoric acid |
| CN102659089A (en) * | 2012-04-25 | 2012-09-12 | 中国科学院过程工程研究所 | Producing method of calcium hydrogen phosphate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108751156B (en) | 2020-11-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107720716B (en) | The technique for preparing battery-level lithium carbonate and ferric phosphate from crude product lithium phosphate recycling lithium phosphorus | |
| CN101337657A (en) | Process for disassembling phosphate ore by mixed acid and coproducing potassium dihydrogen phosphate, hydrogen phosphate and combined fertilizer | |
| CN103539165B (en) | Method for producing potassium sulfate by utilizing insoluble rocks containing potassium | |
| CN104744175A (en) | Method for producing nitrogen-phosphorus-potassium mixed fertilizer by utilizing phosphorus-potassium associated ore | |
| CN109250736A (en) | The method for preparing activated magnesia using reverse flotation phosphorus tailing | |
| CN107473775B (en) | Method for recovering phosphorus and fluorine in phosphoric acid concentrated slag acid and co-producing low-fluorine water-soluble fertilizer | |
| US2683075A (en) | Digestion of phosphate rock | |
| US4217333A (en) | Process for the production of potassium magnesium phosphate | |
| CN106744764B (en) | A method of producing potassium dihydrogen phosphate | |
| US4088738A (en) | Process for producing phosphoric acid using mixed acid feed and a dicalcium phosphate intermediate | |
| CN103663499A (en) | Method for preparing potassium fluoride and coproducing ultrafine white carbon black from ammonium fluorosilicate byproduct in phosphate fertilizer production | |
| CN105776221A (en) | Method for recycling fluorine resources in phosphate fertilizer production | |
| US5035872A (en) | Method of preparing potassium magnesium phosphate | |
| CN110217769B (en) | Method for producing calcium ammonium nitrate byproduct feed-grade DCP | |
| CN108751156A (en) | A method of preparing high-purity double superhosphate using ammonium chloride decomposing phosphate rock | |
| CN108821299B (en) | Method for preparing calcium silicate by decomposing phosphate ore by using ammonium chloride | |
| CN112758937B (en) | Method for preparing potassium fluosilicate and NPK compound fertilizer from associated phosphate-potassium ore | |
| US3785797A (en) | Production of nitrophosphate fertilizer | |
| US3684435A (en) | Method of preparing calcium fluoride and soluble phosphate from fluorine containing phosphate rock | |
| CN108726552B (en) | Method for circularly preparing light calcium carbonate by decomposing phosphate ore by using ammonium chloride | |
| CN103803517B (en) | The method of the low silicon ardealite of high silicon Phosphate Rock acid by-product | |
| CN108793115B (en) | Method for decomposing phosphorite by using ammonium chloride and preparing fiber cement board by using impurities | |
| US2750270A (en) | Production of soluble phosphates | |
| US2985527A (en) | Nitric acid process for the production of soluble phosphates | |
| WO2019082207A1 (en) | Energy efficient synthesis of sulphate of potash using ammonia as a catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201120 Termination date: 20210613 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |