CN107317029B - A kind of preparation method of ferric phosphate - Google Patents
A kind of preparation method of ferric phosphate Download PDFInfo
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- CN107317029B CN107317029B CN201710483503.2A CN201710483503A CN107317029B CN 107317029 B CN107317029 B CN 107317029B CN 201710483503 A CN201710483503 A CN 201710483503A CN 107317029 B CN107317029 B CN 107317029B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
The present invention provides a kind of preparation methods of ferric phosphate: filtering after source of iron is mixed with acid solution, pH value will be obtained adjusting after filtrate mixes with phosphoric acid to 0.5~1, pH value is adjusted after mixing again with inducer to 1.5~2.5, carry out precipitation reaction, obtain ferric phosphate, wherein, the ratio between amount of substance of iron ion and phosphoric acid is 1:1 in filtrate, and the phosphoric acid without excessive addition still ensures that obtaining for the ferric phosphate of better crystallinity degree.The present invention can not only realize the regulation to reaction environment through two step alkaline process, moreover it is possible to partial over-alkali be avoided to form iron hydroxide；Without excessive phosphate radical, the raising of Phosphorus From Wastewater content is avoided, cost is reduced.
Description
Technical field
The present invention relates to electrode material technical field more particularly to a kind of preparation methods of ferric phosphate.
Background technique
Relative to petroleum, for the non-renewable resources such as coal, lithium ion battery has sustainable charging and repeatedly makes
With the advantages of, and pollution will not be generated in use.Therefore as secondary clean energy lithium ion battery relative to
Consumptive petroleum Coal Energy Source product has obviously advantage.
LiFePO4 has excellent thermal stability；And without the heavy metal element being harmful to the human body, safety is good；In
Under the conditions of 100% deep discharge, superior cycle performance that can be charge and discharge 2000 times or more, and then iron lithium phosphate is considered as lithium
The ideal positive electrode of ion battery.
Ferric phosphate (FePO4) be a kind of rice white or pale powder, have skeleton structure and excellent catalysis characteristics, from
Sub- exchange capacity and chemical property are the good raw materials for preparing lithium ion battery anode material lithium iron phosphate.
The preparation process of ferric phosphate is varied at present, but is all mainly to be with soluble trivalent iron salt or divalent iron salt
Source of iron and phosphate prepares ferric phosphate as raw material, and not only to the strict demand that has of source of iron, and phosphate radical rubs in phosphate
Your number is more excessive by 30% or more than iron ion, improves preparation cost and waste water dephosphorization cost.Such as Chinese patent
CN201310571978.9 discloses a kind of preparation method of battery-grade iron phosphate, and the amount of the specific substance for limiting phosphate radical is up to
3~3.5 times of iron ion content.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of preparation method of ferric phosphate, preparation side provided by the invention
Method under the premise of realizing the regulation to the environment of reaction process, avoids partial over-alkali from forming iron hydroxide through two step alkaline process；
Without excessive phosphate radical, the raising of Phosphorus From Wastewater content is avoided, cost is reduced.
In order to achieve the above-mentioned object of the invention, the present invention the following technical schemes are provided:
The present invention provides a kind of preparation methods of ferric phosphate, comprising the following steps:
(1) it is filtered after mixing source of iron with acid solution, obtains filtrate；
(2) pH value is adjusted after mixing the filtrate that the step (1) obtains with phosphoric acid to 0.5~1, obtains mixed liquor；Institute
Stating the ratio between amount of substance of iron ion and phosphoric acid in filtrate is 1:1；
(3) pH value is adjusted after mixing the mixed liquor that the step (2) obtains with inducer to 1.5~2.5, is precipitated
Reaction, obtains ferric phosphate.
Preferably, the source of iron is the iron-containing waste that the content of iron is 63~70wt%.
Preferably, the iron-containing waste is the neodymium iron boron waste material for completing rare earth recovery, completes lithium LiFePO4 after the recovery
Waste material or corrosion iron-containing waste.
Preferably, the inducer is ferric phosphate seed crystal；The mass ratio of the inducer and phosphoric acid in the step (2) is
(0.5~2): (64~65).
Preferably, acid solution includes sulfuric acid and auxiliary acid in the step (1), and the auxiliary acid is hydrochloric acid, nitric acid and height
One of chloric acid is a variety of.
Preferably, pH value regulator is adjusted in the step (2) includes sodium hydroxide and/or potassium hydroxide.
Preferably, pH value regulator is adjusted in the step (3) includes one of sodium carbonate, sodium bicarbonate and ammonium hydroxide
Or it is a variety of.
Preferably, mixing, pH value are adjusted in mixed process, the adjustment process of pH value and step (3) in the step (2)
Process and the temperature of precipitation reaction independently are 80~95 DEG C.
Preferably, after the precipitation reaction further include post-processing to the precipitation reaction product, comprising: to the precipitating
The product of reaction is successively aged, is separated by solid-liquid separation, pickling and drying.
Preferably, the pickling is acid solution that phosphate concentration is 0.05~0.1mol/L with cleaning solution.
The present invention provides a kind of preparation methods of ferric phosphate: filtering after source of iron is mixed with acid solution, will obtain filtrate
PH value is adjusted after mixing with phosphoric acid to 0.5~1, then pH value is adjusted after mix with inducer to 1.5~2.5, progress precipitation reaction,
Obtain ferric phosphate, wherein the ratio between amount of substance of iron ion and phosphoric acid is 1:1 in filtrate, and the phosphoric acid without excessive addition remains to
Guarantee obtaining for the ferric phosphate of better crystallinity degree.The present invention can not only realize the regulation to reaction environment through two step alkaline process, also
It is avoided that partial over-alkali forms iron hydroxide；Without excessive phosphate radical, the raising of Phosphorus From Wastewater content is avoided, cost is reduced.
Detailed description of the invention
Fig. 1 is the XRD spectrum for the ferric phosphate that embodiment 1 and comparative example 1 are prepared and the comparative diagram with standard card；
Fig. 2 is that the XRD spectrum of ferric phosphate and the comparative diagram of standard card is prepared in Examples 1 to 3 and comparative example 2.
Specific embodiment
The present invention provides a kind of preparation methods of ferric phosphate, comprising the following steps:
(1) it is filtered after mixing source of iron with acid solution, obtains filtrate；
(2) pH value is adjusted after mixing the filtrate that the step (1) obtains with phosphoric acid to 0.5~1, obtains mixed liquor；Institute
Stating the ratio between amount of substance of iron ion and phosphoric acid in filtrate is 1:1；
(3) pH value is adjusted after mixing the mixed liquor that the step (2) obtains with inducer to 1.5~2.5, is precipitated
Reaction, obtains ferric phosphate.
The present invention is without excessive phosphoric acid,, can not only be real through two step alkaline process after source of iron is mixed with acid solution
Now to the regulation of reaction environment, moreover it is possible to avoid partial over-alkali from forming iron hydroxide, overcoming in the prior art must be using excessive
Phosphoric acid to avoid alkali formula hypophosphite monohydrate iron generation the problem of, and then improve the purity of ferric phosphate being prepared.
Preparing the presence of iron hydroxide and alkali formula hypophosphite monohydrate iron during ferric phosphate, to will lead to iron phosphorus ratio in product remote
Much larger than 1, the purity of ferric phosphate is influenced, and then influences the electric property that positive electrode is prepared, the phosphoric acid that the present invention obtains
The iron phosphorus ratio of iron is preferably 0.97~1.02.
The present invention filters after mixing source of iron with acid solution, obtains filtrate.In the present invention, the source of iron is preferably iron
Content is the iron-containing waste of 63~70wt%, further preferably 63.95~68.65wt%, more preferably 65~66wt%.In
In the present invention, it is useless that the iron-containing waste preferably completes the neodymium iron boron waste material of rare earth recovery, completion lithium LiFePO4 after the recovery
Material or corrosion iron-containing waste；The present invention is to the neodymium iron boron waste material for completing rare earth recovery, completion lithium LiFePO4 after the recovery
The specific source of waste material and corrosion iron-containing waste does not have particular/special requirement, using well-known to those skilled in the art.This hair
It is bright that ferric phosphate can be prepared according to technical solution provided by the invention using iron-containing waste as source of iron, preparation cost is reduced,
And realize making full use of for waste material.
In the present invention, the acid solution preferably includes sulfuric acid solution and auxiliary acid solution.In the present invention, the sulfuric acid is molten
The volume ratio of liquid and auxiliary acid solution is preferably (0.8~1): (0.8~1), further preferably (0.85~0.9): 1.At this
In invention, the mass concentration of the sulfuric acid solution is preferably 40~60%, and further preferably 50%；The auxiliary acid solution
Concentration is preferably 25~36%, and further preferably 30~35%.In the present invention, the auxiliary acid solution be preferably hydrochloric acid,
One of nitric acid and perchloric acid are a variety of.The present invention does not have special want to the source of the sulfuric acid, hydrochloric acid, nitric acid and perchloric acid
It asks, using commercial product well-known to those skilled in the art.In the present invention, can there is sulfate radical in the acid solution
Effect inhibits when precipitation reaction synthesis ferric phosphate due to alkali formula hypophosphite monohydrate iron and hydroxide caused by not using excess phosphoric acid
The formation of iron, it is ensured that obtain the higher ferric phosphate of purity.
In the present invention, the quality of the iron-containing waste and the volume ratio of acid solution are preferably 1g:4mL, avoid sour dosage
When few, the iron dissolution rate in waste material is not high, and caused source of iron cannot make full use of, the sour excessive later period tune pH value alkali charge of dosage
Greatly, caused cost increases.In the present invention, the mixing preferably carries out under agitation, and the rate of the stirring is preferred
For 200~500rpm, further preferably 220~480rpm, more preferably 300rpm；The time of the stirring is preferably 10~
30min, further preferably 15~20min.Mixed process of the present invention realizes dissolution of the acid solution to iron-containing waste.
In the present invention, the iron-containing waste preferably provides in a form of slurry；The slurry preferably passes through the iron content
Waste material is mixed to get with water, and the quality of the iron-containing waste and the volume ratio of water are preferably 1g:1mL, strict control iron-containing waste
Solid-to-liquid ratio during sizing mixing promotes iron-containing waste to mix with acid solution, further plays sulfuric acid in acid solution and is hydrated phosphorus to alkali formula
The inhibiting effect of sour iron and iron hydroxide, it is ensured that obtain the higher ferric phosphate of purity.In slurry preparation process of the present invention
Mixing preferably carry out under agitation, the revolving speed of the stirring is preferably 500~1000rpm, further preferably 550~
900rpm, more preferably 600rpm.
After the mixing for completing the iron-containing waste and acid solution, the present invention is filtered to obtain filtrate to the mixed liquor.
In the present invention, iron ion is preferably comprised in the obtained filtrate.The present invention does not have particular/special requirement to the mode of the filtering,
Using mixed liquor filter type well-known to those skilled in the art.
After obtaining filtrate, the present invention adjusts pH value to 0.5~1 after mixing the filtrate with phosphoric acid, obtains mixed liquor.In
In the present invention, the ratio between amount of substance of iron ion and phosphoric acid is 1:1 in the filtrate.The present invention does not have the source of the phosphoric acid
Particular/special requirement, using phosphoric acid well-known to those skilled in the art；In an embodiment of the present invention, the phosphoric acid is preferably
Pure phosphoric acid solution is analyzed, the mass concentration of the phosphoric acid solution is preferably 85%.
In the present invention, the mixed temperature of the filtrate and phosphoric acid is preferably 80~95 DEG C, further preferably 80.5
~94 DEG C, more preferably 82~90 DEG C, most preferably 85 DEG C.In the present invention, the mixing preferably carries out under agitation；
The rate of the stirring is preferably 50~200rpm, further preferably 70~150rpm, more preferably 100~120rpm；Institute
The time for stating stirring is preferably 20~60min, further preferably 30~40min, more preferably 35min.
After the completion of the mixing of filtrate and phosphoric acid, the present invention carries out the adjusting of pH value to the mixed solution being mixed to get,
Obtain mixed liquor.The present invention adjusts pH value to 0.5~1, further preferably 0.55~0.8, more preferably 0.6~0.75.In
In the present invention, the adjusting pH value is preferably sodium hydroxide and/or potassium hydroxide with regulator.In the present invention, the adjusting
Agent preferably provides as a solution, and the mass concentration for adjusting agent solution is preferably 20~40%, further preferably
30%.The present invention does not have particular/special requirement to the dosage of the regulator, can obtain the mixed liquor of target ph.
In the present invention, the adjusting of the pH value is preferably completed by the way that the regulator is added to the mixed liquor.In
In the present invention, the time of the addition is preferably 10min~20min；The present invention does not require the mode of the addition, uses
The mode well-known to those skilled in the art to add materials into solution.
After obtaining mixed liquor, the present invention adjusts pH value to 1.5~2.5 after mixing the mixed liquor with inducer, carries out
Precipitation reaction obtains ferric phosphate.In the present invention, the mass ratio of the inducer and phosphoric acid described in above-mentioned technical proposal is preferred
For (0.5~2): (64~65), further preferably (0.55~1.5): (64~65), more preferably (1.0~1.3): (64~
65).The quality of the i.e. described inducer is preferably the quality of ferric phosphate identical with the amount of phosphoric acid substance described in above-mentioned technical proposal
0.5~2%, further preferably 0.55~1.5%, more preferably 1.0~1.3%.
In the present invention, the inducer is preferably ferric phosphate seed crystal.In the present invention, the middle grain of the ferric phosphate seed crystal
Diameter is preferably 5~6 μm；The iron phosphorus of the ferric phosphate seed crystal is than preferably 0.97~1.02.In the present invention, the inducer energy
It enough induces ferric phosphate fast nucleation and effectively reduces the synthesis of alkali formula hypophosphite monohydrate iron.The present invention is to the ferric phosphate seed crystal
Source does not have particular/special requirement, is voluntarily prepared using commercial product well-known to those skilled in the art or preparation method.When
When voluntarily preparing, the ferric phosphate seed crystal preferably passes through phosphoric acid and iron chloride is prepared；The present invention is to the ferric phosphate seed crystal
Preparation method there is no particular/special requirement, using well-known to those skilled in the art.
In the present invention, the mixing temperature of the mixed liquor and inducer is preferably 80~95 DEG C, and further preferably 82
~93.5 DEG C, more preferably 85~90 DEG C, most preferably 88 DEG C.The present invention does not have the hybrid mode of the mixed liquor and inducer
There is particular/special requirement, using the hybrid mode of solution well-known to those skilled in the art.In the present invention, the mixing is excellent
Choosing carries out under agitation；The rate of the stirring is preferably 300~500rpm, further preferably 350~450rpm, more
Preferably 400~425rpm, most preferably 415rpm；The time of the stirring is preferably 10~60min, and further preferably 15
~50min, more preferably 30min.
After the mixing for completing the mixed liquor and inducer, after the present invention carries out the adjusting of pH value to obtained mixed solution
Precipitation reaction is carried out, ferric phosphate is obtained.Present invention adjusting pH value is more excellent to 1.5~2.5, further preferably 1.55~2.45
It is selected as 1.8~2.2, most preferably 2.0.In the present invention, the adjusting pH value preferably includes sodium carbonate, bicarbonate with regulator
One of sodium and ammonium hydroxide are a variety of.In the present invention, the regulator preferably provides as a solution, and the regulator is molten
The mass concentration of liquid is preferably 20~30%, and further preferably 22~28%, more preferably 25%.The present invention is to the adjusting
The dosage of agent does not have particular/special requirement, can obtain the mixed solution of target ph.In the present invention, the pH value was adjusted
The temperature of journey is preferably 80~95 DEG C, further preferably 81~90 DEG C, more preferably 85~86 DEG C.
Under the premise of the present invention realizes the regulation to the environment of reaction process using two step alkaline process, partial over-alkali shape is avoided
At iron hydroxide.In the present invention, the first step uses sodium hydroxide or potassium hydroxide alkali tune to can be reduced reaction in two step alkaline process
Time and reaction volume；Second step carries out alkali tune with the alkalescent substance of such as sodium carbonate, sodium bicarbonate or ammonium hydroxide, and reduction is being adjusted
Iron hydroxide is formed during alkali because of partial over-alkali, and pH accurately preferably can be transferred to target value.
In the present invention, the adjusting of the pH value is preferably completed by the way that the regulator is added to the mixed liquor.In
In the present invention, the time of the addition is preferably 60min~90min；The addition of the regulator preferably under agitation into
Row, convenient for the mixing of regulator and mixed liquor.In the present invention, the rate of the stirring is preferably 100~500rpm, further
Preferably 120~400rpm, more preferably 200~300rpm.The present invention does not require the mode of the addition, using ability
The mode to add materials known to field technique personnel into solution.
The present invention carries out precipitation reaction under the pH value condition.In the present invention, the temperature of the precipitation reaction is preferred
It is 80~95 DEG C, further preferably 80.5~94.5 DEG C, more preferably 83~91 DEG C, most preferably 90 DEG C.In the present invention,
The time of the precipitation reaction is preferably 1h~2h.In the present invention, the precipitation reaction preferably carries out under agitation；Institute
The revolving speed for stating stirring is preferably 50~300rpm, further preferably 100~220rpm, more preferably 120~150rpm.At this
In invention, the combination reaction of phosphate anion and iron ion is realized in the precipitation reaction, generates ferric phosphate.
In the present invention, it is also preferable to include the post-processings to the precipitation reaction product after the precipitation reaction, comprising: right
The product of the precipitation reaction is successively aged, is separated by solid-liquid separation, pickling, drying and high-temperature calcination.In the present invention, described old
The time of change is preferably 2h~4h；The temperature of the ageing is preferably 80~95 DEG C, and further preferably 85~90 DEG C, more preferably
It is 88 DEG C.The present invention does not have particular/special requirement to the specific embodiment of the ageing, and use is well-known to those skilled in the art
Aging.In the present invention, the ageing dissolves the little crystal grain formed in reaction process gradually, and big crystal grain is gradually grown
Greatly；With the dissolution of little crystal grain, it is adsorbed, occludes and contains the foreign ion inside precipitating and reenter solution, make phosphoric acid
The purity of iron is higher.
After the ageing, the ageing product is preferably separated by solid-liquid separation by the present invention.The present invention is to the separation of solid and liquid
Mode does not have particular/special requirement, using solid-liquid separation method well-known to those skilled in the art.
The present invention preferably carries out pickling to the obtained solid that is separated by solid-liquid separation.In the present invention, the pickling washing
Liquid is the acid solution that phosphate concentration is preferably 0.05~0.1mol/L.In the present invention, the acid solution preferably by
Substance including phosphate radical is mixed to get with the acidic materials for not including phosphate radical.In the present invention, described includes phosphate radical
Substance is preferably one of phosphoric acid, tertiary sodium phosphate, dibastic sodium phosphate and disodium hydrogen phosphate or a variety of；Described does not include phosphate radical
Acidic materials are preferably one of hydrochloric acid, sulfuric acid, nitric acid and perchloric acid or a variety of.In the present invention, the acid solution
PH value is preferably 1~3, and further preferably 1.5~2.5, more preferably 2.In the present invention, the acidity is contained with detergent
Phosphate radical guarantees that product will not be transformed into iron hydroxide because pH is increased in washing process.
In the present invention, the pickling is preferably adverse current pickling；The present invention is not special to the mode of the adverse current pickling
It is required that using adverse current pickling mode well-known to those skilled in the art.In the present invention, the number of the pickling is preferred
It is 3~5 times；The time of the pickling is preferably 10~60min, further preferably 40~50min, more preferably 45min.In
In the present invention, the countercurrent washing makes full use of phosphate radical, reduces the whole dosage of phosphate radical.
After completing the pickling, the present invention is preferably dried the acid-leached product.In the present invention, the drying
Temperature is preferably 80~100 DEG C, and further preferably 85~95 DEG C.The present invention does not have particular/special requirement to the time of the drying,
Using dry materials mode well-known to those skilled in the art.
After the drying, the present invention preferably carries out high-temperature calcination to the desciccate.In the present invention, the high temperature is forged
The temperature of burning is preferably 500~600 DEG C, and further preferably 550 DEG C；The time of the high-temperature calcination is preferably 30~60min,
Further preferably 50min.In the present invention, the high-temperature calcination can remove the crystallization water in desciccate.
It is described in detail below with reference to preparation method of the embodiment to ferric phosphate provided by the invention, but cannot be
They are interpreted as limiting the scope of the present invention.
Embodiment 1
The neodymium iron boron waste material 160g that the mass percentage for weighing iron is 65% is poured into 2L beaker, and 160mL water is added to stir
It sizes mixing, 640mL mixed acid solution is added, wherein nitration mixture is the sulfuric acid solution and 320mL mass concentration that 320mL mass concentration is 50%
The stirring of 20min is carried out with the stirring rate of 200rpm for 30% hydrochloric acid solution, filters, is filtered after solution clarification
Liquid.The analysis pure phosphoric acid that 82.5mL mass fraction is 85% is added into filtrate to stir, solution is heated to be 90 under stirring condition
DEG C and maintain temperature constant, the sodium hydroxide solution that concentration is 30wt%, which is added dropwise, makes solution ph be adjusted to 0.5, controls sodium hydroxide
The time for adding of solution is 10min.0.8g ferric phosphate seed crystal is then added, then the sodium carbonate liquor that concentration is 30wt% is added dropwise,
PH value of solution is set to be adjusted to 1.5, the time for adding for controlling sodium carbonate liquor is 1h, controls the constant continuation of reaction temperature still with 300rpm's
Revolving speed stirs 1h.After completing aforesaid operations, stop stirring heat preservation ageing 2h.Aged substance is separated by solid-liquid separation, solid pH value
For 1.5 and phosphate concentration is 0.1mol/L acid solution countercurrent washing 3 times.After the completion of washing, dried 1 hour at 100 DEG C
It is obtained up to the phosphate dihydrate iron product of 328.2g by the phosphate dihydrate iron being prepared in 500 DEG C of progress high-temperature calcination 60min
To 266.4g ferric phosphate, compared with the Theoretical Mass of product, yield 95%.
Embodiment 2
The neodymium iron boron waste material 160g that the mass percentage for weighing iron is 66% is poured into 2L beaker, and 160mL water is added to stir
It sizes mixing, 640mL mixed acid solution is added, wherein nitration mixture is the sulfuric acid solution and 320mL mass concentration that 320mL mass concentration is 50%
The stirring of 60min is carried out with the stirring rate of 50rpm for 30% hydrochloric acid solution, is filtered after solution clarification, obtains filtrate.
The analysis pure phosphoric acid that 83.8mL mass fraction is 85% is added into filtrate to stir, solution is heated to be 95 DEG C simultaneously under stirring condition
Maintain temperature constant, the sodium hydroxide solution that concentration is 30wt%, which is added dropwise, makes solution ph be adjusted to 1.0, controls sodium hydroxide solution
Time for adding be 10min.1.6g ferric phosphate seed crystal is then added, then the sodium carbonate liquor that concentration is 30wt% is added dropwise, makes molten
Liquid pH is adjusted to 2, and the time for adding for controlling sodium carbonate liquor is 1h, still controls the constant continuation of reaction temperature and is stirred with the revolving speed of 50rpm
Mix 1h.After completing aforesaid operations, stop stirring heat preservation ageing 2h.Aged substance is separated by solid-liquid separation, solid pH value is 2 and phosphorus
Acid group concentration is acid solution countercurrent washing 3 times of 0.05mol/L.After the completion of washing, 1 hour is dried at 100 DEG C to obtain the final product
The phosphate dihydrate iron product of 333.2g is obtained by the phosphate dihydrate iron being prepared in 600 DEG C of progress high-temperature calcination 50min
270.5g ferric phosphate is compared with the Theoretical Mass of product, yield 95%.
Embodiment 3
The neodymium iron boron waste material 160g that the mass percentage for weighing iron is 70% is poured into 2L beaker, and 160mL water is added to stir
It sizes mixing, 640mL mixed acid solution is added, wherein nitration mixture is the sulfuric acid solution and 320mL mass concentration that 320mL mass concentration is 50%
The stirring of 40min is carried out with the stirring rate of 150rpm for 30% perchloric acid solution, filters, is filtered after solution clarification
Liquid.The analysis pure phosphoric acid that 88.9mL mass fraction is 85% is added into filtrate to stir, solution is heated to be 85 under stirring condition
DEG C and maintain temperature constant, the sodium hydroxide solution that concentration is 30wt%, which is added dropwise, makes solution ph be adjusted to 1, and control sodium hydroxide is molten
The time for adding of liquid is 10min.1.6g ferric phosphate seed crystal is then added, then the sodium carbonate liquor that concentration is 30wt% is added dropwise, makes
PH value of solution is adjusted to 2.5, and the time for adding for controlling sodium carbonate liquor is 1h, still controls the constant continuation of reaction temperature and is turned with 150rpm
Speed stirring 1h.After completing aforesaid operations, stop stirring heat preservation ageing 2h.Aged substance is separated by solid-liquid separation, solid is with pH value
2.5 and phosphate concentration be acid solution countercurrent washing for 3 times of 0.05mol/L.After the completion of washing, 1 hour is dried at 100 DEG C i.e.
The phosphate dihydrate iron product for obtaining 346.0g is obtained by the phosphate dihydrate iron being prepared in 550 DEG C of progress high-temperature calcination 60min
280.86g ferric phosphate, compared with the Theoretical Mass of product, yield 93%.
Comparative example 1
Ferric phosphate is prepared according to the method for embodiment 1, and difference is, the sodium hydroxide solution that concentration is 30wt%, which is added dropwise, to be made
Solution ph is not necessarily to that ferric phosphate seed crystal is added after being adjusted to 0.5, and the sodium carbonate liquor that concentration is 30wt% is directly added dropwise again, makes solution
PH is adjusted to 1.5.
The ferric phosphate that embodiment 1 and comparative example 1 are prepared carries out XRD analysis, by obtained XRD spectrum and standard card
Piece is compareed, as a result as shown in Figure 1, adding seed crystal XRD in the XRD spectrum corresponding diagram 1 for the product that wherein embodiment 1 is prepared
Seed crystal XRD spectrum is not added in the XRD spectrum corresponding diagram 1 for the product that comparative example 1 is prepared in map.As shown in Figure 1, add seed crystal
Can form well-crystallized's preferable ferric phosphate corresponding with standard card peak position, be not added seed crystal formation only amorphous state alkali formula
Hypophosphite monohydrate iron.
Comparative example 2
Ferric phosphate is prepared according to the method for comparative example 1, difference is, the dosage for the phosphoric acid being added is phosphorus in comparative example 1
3 times of sour dosage.
The ferric phosphate that Examples 1 to 3 and comparative example 2 are prepared carries out XRD analysis, by obtained XRD spectrum with
Standard card is compareed, as a result as shown in Figure 2.As shown in Figure 2, method provided by the invention can be prepared well-crystallized with
Standard card peak position corresponds to preferable ferric phosphate；Seed crystal is not added using excessive phosphoric acid during prior art preparation, is crystallized
Preferable ferric phosphate well corresponding with standard card peak position.It is found that preparation method provided by the invention, which can overcome, does not use excess
Caused by phosphoric acid the drawbacks of the generation of alkali formula hypophosphite monohydrate iron, the ferric phosphate of purity is high can be obtained.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (7)
1. a kind of preparation method of ferric phosphate, comprising the following steps:
(1) it is filtered after mixing source of iron with acid solution, obtains filtrate；
(2) pH value is adjusted after mixing the filtrate that the step (1) obtains with phosphoric acid to 0.5~1, obtains mixed liquor；The filter
The ratio between amount of substance of iron ion and phosphoric acid is 1:1 in liquid；
(3) pH value is adjusted after mixing the mixed liquor that the step (2) obtains with inducer to 1.5~2.5, precipitate anti-
It answers, obtains ferric phosphate；
The source of iron is the iron-containing waste that the content of iron is 63~70wt%；
The iron-containing waste is the neodymium iron boron waste material for completing rare earth recovery, completes lithium LiFePO4 waste material after the recovery or corrode to contain
Iron waste material；
The acid solution includes sulfuric acid and auxiliary acid；
The quality of the inducer is the 0.55~1.5% of the quality of ferric phosphate identical with the amount of phosphoric acid substance in step (2)；
It further include the post-processing to the precipitation reaction product after the precipitation reaction, comprising: to the product of the precipitation reaction
It is successively aged, is separated by solid-liquid separation, pickling and drying.
2. preparation method according to claim 1, which is characterized in that the inducer is ferric phosphate seed crystal.
3. preparation method according to claim 1, which is characterized in that the auxiliary acid is in hydrochloric acid, nitric acid and perchloric acid
It is one or more.
4. preparation method according to claim 1, which is characterized in that adjust pH value regulator packet in the step (2)
Include sodium hydroxide and/or potassium hydroxide.
5. preparation method according to claim 1, which is characterized in that adjust pH value regulator packet in the step (3)
Include one of sodium carbonate, sodium bicarbonate and ammonium hydroxide or a variety of.
6. preparation method according to claim 1, which is characterized in that the adjusting of mixed process, pH value in the step (2)
The temperature of mixing, pH value adjustment process and precipitation reaction independently is 80~95 DEG C in process and step (3).
7. preparation method according to claim 1, which is characterized in that the pickling is that phosphate concentration is with cleaning solution
The acid solution of 0.05~0.1mol/L.
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| CN107978753B (en) * | 2017-11-30 | 2020-02-07 | 湘潭大学 | Ferric phosphate @ bowl-shaped hollow carbon sphere/graphene composite material and preparation method and application thereof |
| CN108706562A (en) * | 2018-08-14 | 2018-10-26 | 武汉轻工大学 | A method of preparing ferric phosphate using pyrite cinder |
| CN108913877A (en) * | 2018-08-17 | 2018-11-30 | 广东省稀有金属研究所 | A kind of method of iron vitriol slag Ore Leaching drop iron separating indium and zinc |
| CN111363923A (en) * | 2020-03-23 | 2020-07-03 | 蒋央芳 | Treatment method of waste rare earth permanent magnet material |
| CN111498823A (en) * | 2020-06-09 | 2020-08-07 | 艾姆新能源(江苏)有限公司 | Method for preparing battery-grade iron phosphate by using iron oxide |
| CN115806279A (en) * | 2021-09-15 | 2023-03-17 | 贵州川恒化工股份有限公司 | Method for preparing iron phosphate by using iron-containing waste material |
| CN114477118A (en) * | 2022-02-15 | 2022-05-13 | 合肥国轩循环科技有限公司 | Comprehensive treatment method for waste lithium iron phosphate battery positive electrode powder |
| CN115676790B (en) * | 2022-10-28 | 2024-04-02 | 贵州川恒化工股份有限公司 | Preparation method of high-tap-density spherical battery-grade ferric phosphate |
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Address after: 341000 No.62 Yingbin Avenue, Ganzhou economic and Technological Development Zone, Jiangxi Province Patentee after: Ganzhou Nonferrous Metallurgy Research Institute Co.,Ltd. Address before: 341000 No.62 Yingbin Avenue, Ganzhou economic and Technological Development Zone, Jiangxi Province Patentee before: GANZHOU NONFERROUS METALLURGICAL Research Institute |