CN107317029A - A kind of preparation method of ferric phosphate - Google Patents
A kind of preparation method of ferric phosphate Download PDFInfo
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- CN107317029A CN107317029A CN201710483503.2A CN201710483503A CN107317029A CN 107317029 A CN107317029 A CN 107317029A CN 201710483503 A CN201710483503 A CN 201710483503A CN 107317029 A CN107317029 A CN 107317029A
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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
- H01—ELECTRIC ELEMENTS
- 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
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2006/80—Compositional purity
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Abstract
The invention provides a kind of preparation method of ferric phosphate：Filtered after source of iron is mixed with acid solution, regulation pH value will be obtained after filtrate mix with phosphoric acid to 0.5~1, then adjust pH value to 1.5~2.5 after being mixed with derivant, carry out precipitation reaction, ferric phosphate is obtained, wherein, the ratio between amount of material of iron ion and phosphoric acid is 1 in filtrate:1, 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 and control to reaction environment through two step alkaline process, moreover it is possible to avoid partial over-alkali formation iron hydroxide；Without excessive phosphate radical, it is to avoid the raising of Phosphorus From Wastewater content, cost is reduced.
Description
Technical field
The present invention relates to electrode material technical field, more particularly to a kind of preparation method of ferric phosphate.
Background technology
Relative to oil, for the non-renewable resources such as coal, lithium ion battery, which has, sustainable to charge and repeatedly makes
Advantage, and pollution will not be produced in use.Therefore as secondary clean energy lithium ion battery relative to
Consumptive oil Coal Energy Source product has obviously advantage.
LiFePO4 has excellent heat endurance；And without harmful heavy metal element, security is good；
Under the conditions of 100% deep discharge, can discharge and recharge more than 2000 times superior cycle performance, 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, with 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 technology of current ferric phosphate is varied, but it is main be all using soluble trivalent iron salt or divalent iron salt as
Source of iron and phosphate prepare ferric phosphate as raw material, not only have rubbing for phosphate radical in strict demand, and phosphate to source of iron
Your number is more excessive by more than 30% 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 material for limiting phosphate radical is up to
3~3.5 times of iron ion content.
The content of the invention
In view of this, it is an object of the invention to provide a kind of preparation method of ferric phosphate, the preparation side that the present invention is provided
Method, through two step alkaline process, on the premise of realizing the regulation and control to the environment of course of reaction, it is to avoid partial over-alkali formation iron hydroxide；
Without excessive phosphate radical, it is to avoid the raising of Phosphorus From Wastewater content, cost is reduced.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of preparation method of ferric phosphate, comprise the following steps：
(1) filtered after source of iron is mixed with acid solution, obtain filtrate；
(2) pH value is adjusted after the filtrate for obtaining the step (1) mixes with phosphoric acid to 0.5~1, mixed liquor is obtained；Institute
It is 1 to state the ratio between amount of material of iron ion and phosphoric acid in filtrate:1；
(3) pH value is adjusted after the mixed liquor for obtaining the step (2) is mixed with derivant to 1.5~2.5, is precipitated
Reaction, obtains ferric phosphate.
It is preferred that, the source of iron be iron content be 63~70wt% iron-containing waste.
It is preferred that, the iron-containing waste is to complete the neodymium iron boron waste material of rare earth recovery, complete the LiFePO4 after lithium is reclaimed
Waste material or corrosion iron-containing waste.
It is preferred that, the derivant is ferric phosphate seed crystal；The mass ratio of the derivant and phosphoric acid in the step (2) is
(0.5~2)：(64~65).
It is preferred that, acid solution includes sulfuric acid and auxiliary acid in the step (1), and the auxiliary acid is hydrochloric acid, nitric acid and height
One or more in chloric acid.
It is preferred that, regulation pH value includes sodium hydroxide and/or potassium hydroxide with conditioning agent in the step (2).
It is preferred that, regulation pH value includes one kind in sodium carbonate, sodium acid carbonate and ammoniacal liquor with conditioning agent in the step (3)
Or it is a variety of.
It is preferred that, mixing, pH value regulation in mixed process, the regulation process of pH value and step (3) in the step (2)
Process and the temperature of precipitation reaction independently are 80~95 DEG C.
It is preferred that, the post processing to the precipitation reaction product is also included after the precipitation reaction, including：To the precipitation
The product of reaction is aged successively, separation of solid and liquid, pickling and drying.
It is preferred that, the pickling is with the acid solution that cleaning solution is that phosphate concentration is 0.05~0.1mol/L.
The invention provides a kind of preparation method of ferric phosphate：Filtered after source of iron is mixed with acid solution, filtrate will be obtained
PH value is adjusted after being mixed with phosphoric acid to 0.5~1, then regulation pH value is to 1.5~2.5 after mix with derivant, progress precipitation reaction,
Ferric phosphate is obtained, wherein, the ratio between amount of material of iron ion and phosphoric acid is 1 in filtrate:1, the phosphoric acid without excessive addition is remained to
Ensure that the ferric phosphate of better crystallinity degree is obtained.The present invention can not only realize the regulation and control to reaction environment through two step alkaline process, also
It is avoided that partial over-alkali formation iron hydroxide；Without excessive phosphate radical, it is to avoid the raising of Phosphorus From Wastewater content, cost is reduced.
Brief description of the drawings
Fig. 1 is the XRD spectrum for the ferric phosphate that embodiment 1 and comparative example 1 are prepared and the compares figure with standard card；
Fig. 2 is that embodiment 1~3 and comparative example 2 prepare the XRD spectrum of ferric phosphate and the compares figure of standard card.
Embodiment
The invention provides a kind of preparation method of ferric phosphate, comprise the following steps：
(1) filtered after source of iron is mixed with acid solution, obtain filtrate；
(2) pH value is adjusted after the filtrate for obtaining the step (1) mixes with phosphoric acid to 0.5~1, mixed liquor is obtained；Institute
It is 1 to state the ratio between amount of material of iron ion and phosphoric acid in filtrate:1；
(3) pH value is adjusted after the mixed liquor for obtaining the step (2) is mixed with derivant to 1.5~2.5, is precipitated
Reaction, obtains ferric phosphate.
The present invention need not be using 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 and control of reaction environment, moreover it is possible to avoid partial over-alkali formation iron hydroxide, overcoming in the prior art must be using excessive
The problem of generation of the phosphoric acid to avoid alkali formula hypophosphite monohydrate iron, and then improve the purity of the ferric phosphate prepared.
Preparing the presence of iron hydroxide and alkali formula hypophosphite monohydrate iron during ferric phosphate can cause iron phosphorus ratio in product remote
Much larger than 1, the purity of ferric phosphate is influenceed, and then influences to prepare the electric property of positive electrode, the phosphoric acid that the present invention is obtained
The iron phosphorus ratio of iron is preferably 0.97~1.02.
The present invention is filtered after source of iron is mixed with acid solution, obtains filtrate.In the present invention, the source of iron is preferably iron
Content is 63~70wt% iron-containing waste, more preferably more preferably 63.95~68.65wt%, 65~66wt%.
In the present invention, the LiFePO4 after the iron-containing waste is preferably the neodymium iron boron waste material of completion rare earth recovery, completion lithium is reclaimed gives up
Material or corrosion iron-containing waste；The present invention is to the LiFePO4 after the neodymium iron boron waste material for completing rare earth recovery, completion lithium recovery
The no particular/special requirement in the specifically source of waste material and corrosion iron-containing waste, using well-known to those skilled in the art.This hair
The bright technical scheme provided using iron-containing waste as source of iron according to the present invention can prepare ferric phosphate, and reduction prepares cost,
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), more preferably (0.85~0.9):1.At this
In invention, the mass concentration of the sulfuric acid solution is preferably 40~60%, and more preferably 50%；The auxiliary acid solution
Concentration is preferably 25~36%, and more preferably 30~35%.In the present invention, it is described auxiliary acid solution be preferably hydrochloric acid,
One or more in nitric acid and perchloric acid.The present invention does not have special want to the source of the sulfuric acid, hydrochloric acid, nitric acid and perchloric acid
Ask, using commercially available prod well-known to those skilled in the art.In the present invention, in the acid solution can there be sulfate radical
Due to not using alkali formula hypophosphite monohydrate iron and hydroxide caused by excess phosphoric acid during effect suppression precipitation reaction synthesis ferric phosphate
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, it is to avoid sour consumption
When few, the iron dissolution rate in waste material is not high, and caused source of iron can not make full use of, and the sour consumption excessive later stage adjusts pH value alkali charge
Greatly, caused cost increases.In the present invention, the mixing is preferably carried out under agitation, and the speed of the stirring is preferred
For 200~500rpm, more preferably more preferably 220~480rpm, 300rpm；The time of the stirring is preferably 10~
30min, more preferably 15~20min.Mixed process of the present invention realizes dissolving of the acid solution to iron-containing waste.
In the present invention, the iron-containing waste is preferably provided 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, strictly controls iron-containing waste
Solid-to-liquid ratio during sizing mixing, promotes iron-containing waste to be mixed with acid solution, further plays sulfuric acid in acid solution and is hydrated phosphorus to alkali formula
The inhibitory action 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 rotating speed of the stirring is preferably 500~1000rpm, more preferably 550~
900rpm, more preferably 600rpm.
After the mixing for completing the iron-containing waste and acid solution, the present invention carries out being filtrated to get 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.
Obtain after filtrate, regulation pH value obtains mixed liquor to 0.5~1 after the present invention mixes the filtrate with phosphoric acid.
In the present invention, the ratio between amount of material of iron ion and phosphoric acid is 1 in the filtrate:1.The present invention does not have to 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 temperature of the mixing of the filtrate and phosphoric acid is preferably 80~95 DEG C, more preferably 80.5
~94 DEG C, most preferably more preferably 82~90 DEG C, 85 DEG C.In the present invention, the mixing is preferably carried out under agitation；
The speed of the stirring is preferably 50~200rpm, more preferably 70~150rpm, more preferably 100~120rpm；Institute
The time for stating stirring is preferably 20~60min, more preferably 30~40min, more preferably 35min.
After the completion of the mixing of filtrate and phosphoric acid, the present invention carries out the regulation of pH value to the mixed solution being mixed to get,
Obtain mixed liquor.The present invention adjusts pH value to 0.5~1, more preferably 0.55~0.8, more preferably 0.6~0.75.
In the present invention, the regulation pH value is preferably sodium hydroxide and/or potassium hydroxide with conditioning agent.In the present invention, the regulation
Agent is preferably provided as a solution, and the mass concentration of the regulation agent solution is preferably 20~40%, more preferably
30%.The present invention does not have particular/special requirement to the consumption of the conditioning agent, can obtain the mixed liquor of target ph.
In the present invention, the regulation of the pH value is preferably by the way that the conditioning agent is completed added to the mixed liquor.
In the present invention, the time of the addition is preferably 10min~20min；The present invention is not required the mode of the addition, is used
The mode well-known to those skilled in the art added materials into solution.
Obtain after mixed liquor, regulation pH value is carried out to 1.5~2.5 after the present invention mixes the mixed liquor with derivant
Precipitation reaction, obtains ferric phosphate.In the present invention, the mass ratio of the derivant and the phosphoric acid described in above-mentioned technical proposal is preferred
For (0.5~2)：(64~65), more preferably (0.55~1.5)：(64~65), more preferably (1.0~1.3)：(64~
65).The quality of i.e. described derivant is preferably the quality with the amount identical ferric phosphate of phosphoric acid substance described in above-mentioned technical proposal
0.5~2%, more preferably 0.55~1.5%, more preferably 1.0~1.3%.
In the present invention, the derivant is preferably ferric phosphate seed crystal.In the present invention, the middle grain of the ferric phosphate seed crystal
Footpath is preferably 5~6 μm；The iron phosphorus ratio preferably 0.97~1.02 of the ferric phosphate seed crystal.In the present invention, the derivant energy
Enough induction ferric phosphate fast nucleation and the effectively synthesis of reduction alkali formula hypophosphite monohydrate iron.The present invention is to the ferric phosphate seed crystal
Originate no particular/special requirement, voluntarily prepared using commercially available prod well-known to those skilled in the art or preparation method.When
When voluntarily preparing, the ferric phosphate seed crystal is preferably prepared by phosphoric acid and iron chloride；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 derivant is preferably 80~95 DEG C, more preferably 82
~93.5 DEG C, most preferably more preferably 85~90 DEG C, 88 DEG C.The present invention does not have to the hybrid mode of the mixed liquor and derivant
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 is carried out under agitation；The speed of the stirring is preferably 300~500rpm, more preferably 350~450rpm, more
Preferably 400~425rpm, most preferably 415rpm；The time of the stirring is preferably 10~60min, and more preferably 15
~50min, more preferably 30min.
After the mixing for completing the mixed liquor and derivant, the present invention is carried out after the regulation of pH value to obtained mixed solution
Precipitation reaction is carried out, ferric phosphate is obtained.Present invention regulation pH value is more excellent to 1.5~2.5, more preferably 1.55~2.45
Elect 1.8~2.2, most preferably 2.0 as.In the present invention, the regulation pH value preferably includes sodium carbonate, bicarbonate with conditioning agent
One or more in sodium and ammoniacal liquor.In the present invention, the conditioning agent is preferably provided as a solution, and the conditioning agent is molten
The mass concentration of liquid is preferably 20~30%, more preferably 22~28%, more preferably 25%.The present invention is to the regulation
The consumption 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, more preferably 81~90 DEG C, more preferably 85~86 DEG C.
On the premise of the present invention realizes the regulation and control to the environment of course of reaction using two step alkaline process, it is to avoid partial over-alkali shape
Into iron hydroxide.In the present invention, the first step can reduce reaction using sodium hydroxide or potassium hydroxide alkali tune in two step alkaline process
Time and reaction volume；Second step carries out alkali tune with the alkalescent material of such as sodium carbonate, sodium acid carbonate or ammoniacal liquor, reduces and is adjusting
Iron hydroxide is formed during alkali because of partial over-alkali, and pH can be accurately preferably transferred to desired value.
In the present invention, the regulation of the pH value is preferably by the way that the conditioning agent is completed added to the mixed liquor.
In the present invention, the time of the addition is preferably 60min~90min；The addition of the conditioning agent is preferably entered under agitation
OK, it is easy to the mixing of conditioning agent and mixed liquor.In the present invention, the speed of the stirring is preferably 100~500rpm, further
Preferably 120~400rpm, more preferably 200~300rpm.The present invention is not required the mode of the addition, using ability
The mode added materials into solution known to field technique personnel.
The present invention carries out precipitation reaction under the pH value condition.In the present invention, the temperature of the precipitation reaction is preferred
For 80~95 DEG C, more preferably 80.5~94.5 DEG C, most preferably more preferably 83~91 DEG C, 90 DEG C.In the present invention,
The time of the precipitation reaction is preferably 1h~2h.In the present invention, the precipitation reaction is preferably carried out under agitation；Institute
The rotating speed for stating stirring is preferably 50~300rpm, more 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, the post processing to the precipitation reaction product is preferably also included after the precipitation reaction, including：It is right
The product of the precipitation reaction is aged successively, separation of solid and liquid, pickling, drying and high-temperature calcination.In the present invention, it is described old
The time of change is preferably 2h~4h；The temperature of the ageing is preferably 80~95 DEG C, more preferably 85~90 DEG C, more preferably
For 88 DEG C.The present invention does not have particular/special requirement to the embodiment of the ageing, using well-known to those skilled in the art
Aging.In the present invention, the ageing makes the little crystal grain formed in course of reaction gradually dissolve, and big crystal grain is gradually long
Greatly；With the dissolving of little crystal grain, adsorbed, occlusion and the foreign ion contained inside precipitation reenter solution, make phosphoric acid
The purity of iron is higher.
After the ageing, the ageing product is preferably carried out separation of solid and liquid 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 solid that separation of solid and liquid described in preferred pair of the present invention is obtained carries out pickling.In the present invention, the pickling washing
Liquid be phosphate concentration be preferably 0.05~0.1mol/L acid solution.In the present invention, the acid solution be preferably by
Material including phosphate radical is mixed to get with the acidic materials not comprising phosphate radical.In the present invention, it is described including phosphate radical
Material is preferably the one or more in phosphoric acid, tertiary sodium phosphate, dibastic sodium phosphate and disodium hydrogen phosphate；It is described not include phosphate radical
Acidic materials are preferably the one or more in hydrochloric acid, sulfuric acid, nitric acid and perchloric acid.In the present invention, the acid solution
PH value is preferably 1~3, more preferably 1.5~2.5, more preferably 2.In the present invention, the acidity is contained with detergent
Phosphate radical ensures that product will not be transformed into iron hydroxide because pH is raised 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 times of the pickling is preferred
For 3~5 times；The time of the pickling is preferably 10~60min, more preferably 40~50min, more preferably 45min.
In the present invention, the countercurrent washing makes full use of phosphate radical, reduces the overall consumption of phosphate radical.
Complete after the pickling, acid-leached product described in preferred pair of the present invention is dried.In the present invention, the drying
Temperature is preferably 80~100 DEG C, more 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, desciccate described in preferred pair of the present invention carries out high-temperature calcination.In the present invention, the high temperature is forged
The temperature of burning is preferably 500~600 DEG C, more preferably 550 DEG C；The time of the high-temperature calcination is preferably 30~60min,
More preferably 50min.In the present invention, the high-temperature calcination can remove the crystallization water in desciccate.
The preparation method of ferric phosphate provided with reference to embodiment the present invention is described in detail, but can not be
They are interpreted as limiting the scope of the present invention.
Embodiment 1
The weight/mass percentage composition of iron is weighed to pour into 2L beakers for 65% neodymium iron boron waste material 160g, plus the stirring of 160mL water
Size mixing, add 640mL mixed acid solutions, wherein nitration mixture is the sulfuric acid solution and 320mL mass concentrations that 320mL mass concentrations are 50%
For 30% hydrochloric acid solution, with 200rpm stir speed (S.S.), 20min stirring is carried out, filters, is filtered after after solution clarification
Liquid.82.5mL mass fractions are added into filtrate to stir for 85% analysis pure phosphoric acid, and solution is heated to be 90 under stirring condition
DEG C and maintain temperature constant, concentration is added dropwise makes solution ph be adjusted to 0.5 for 30wt% sodium hydroxide solution, controls sodium hydroxide
The time for adding of solution is 10min.It is subsequently added 0.8g ferric phosphate seed crystals, then is added dropwise the sodium carbonate liquor that concentration is 30wt%,
PH value of solution is set to be adjusted to 1.5, the time for adding for controlling sodium carbonate liquor is 1h, the still constant continuation of controlling reaction temperature is with 300rpm's
Rotating speed stirs 1h.Complete after aforesaid operations, stop stirring insulation ageing 2h.Aged substance is subjected to separation of solid and liquid, solid pH value
For 1.5 and phosphate concentration be 0.1mol/L acid solution countercurrent washing 3 times.After the completion of washing, dried 1 hour at 100 DEG C
328.2g phosphate dihydrate iron product is produced, the phosphate dihydrate iron prepared is subjected to high-temperature calcination 60min at 500 DEG C, obtained
To 266.4g ferric phosphates, compared with the Theoretical Mass of product, yield is 95%.
Embodiment 2
The weight/mass percentage composition of iron is weighed to pour into 2L beakers for 66% neodymium iron boron waste material 160g, plus the stirring of 160mL water
Size mixing, add 640mL mixed acid solutions, wherein nitration mixture is the sulfuric acid solution and 320mL mass concentrations that 320mL mass concentrations are 50%
For 30% hydrochloric acid solution, with 50rpm stir speed (S.S.), 60min stirring is carried out, is filtered after after solution clarification, obtains filtrate.
83.8mL mass fractions are added into filtrate to stir for 85% analysis pure phosphoric acid, and solution is heated to be 95 DEG C simultaneously under stirring condition
Maintain temperature constant, concentration is added dropwise makes solution ph be adjusted to 1.0 for 30wt% sodium hydroxide solution, controls sodium hydroxide solution
Time for adding be 10min.1.6g ferric phosphate seed crystals are subsequently added, then the sodium carbonate liquor that concentration is 30wt% is added dropwise, are made molten
Liquid pH is adjusted to 2, and the time for adding for controlling sodium carbonate liquor is 1h, and the still constant continuation of controlling reaction temperature is stirred with 50rpm rotating speed
Mix 1h.Complete after aforesaid operations, stop stirring insulation ageing 2h.Aged substance is subjected to separation of solid and liquid, solid pH value is 2 and phosphorus
The acid solution countercurrent washing that acid group concentration is 0.05mol/L 3 times.After the completion of washing, produced within 1 hour in 100 DEG C of drying
333.2g phosphate dihydrate iron product, carries out high-temperature calcination 50min at 600 DEG C by the phosphate dihydrate iron prepared, obtains
270.5g ferric phosphates are compared with the Theoretical Mass of product, and yield is 95%.
Embodiment 3
The weight/mass percentage composition of iron is weighed to pour into 2L beakers for 70% neodymium iron boron waste material 160g, plus the stirring of 160mL water
Size mixing, add 640mL mixed acid solutions, wherein nitration mixture is the sulfuric acid solution and 320mL mass concentrations that 320mL mass concentrations are 50%
For 30% perchloric acid solution, with 150rpm stir speed (S.S.), 40min stirring is carried out, filters, is filtered after after solution clarification
Liquid.88.9mL mass fractions are added into filtrate to stir for 85% analysis pure phosphoric acid, and solution is heated to be 85 under stirring condition
DEG C and maintain temperature constant, concentration is added dropwise makes solution ph be adjusted to 1 for 30wt% sodium hydroxide solution, and control sodium hydroxide is molten
The time for adding of liquid is 10min.1.6g ferric phosphate seed crystals are subsequently added, then the sodium carbonate liquor that concentration is 30wt% is added dropwise, are made
PH value of solution is adjusted to 2.5, and the time for adding for controlling sodium carbonate liquor is 1h, still the constant continuation of controlling reaction temperature turning with 150rpm
Speed stirring 1h.Complete after aforesaid operations, stop stirring insulation ageing 2h.Aged substance is subjected to separation of solid and liquid, solid is with pH value
2.5 and phosphate concentration for 0.05mol/L acid solution countercurrent washing 3 times.After the completion of washing, it is within 1 hour in 100 DEG C of drying
346.0g phosphate dihydrate iron product is obtained, the phosphate dihydrate iron prepared is subjected to high-temperature calcination 60min at 550 DEG C, obtained
280.86g ferric phosphates, compared with the Theoretical Mass of product, yield is 93%.
Comparative example 1
Method according to embodiment 1 prepares ferric phosphate, and difference is, concentration is added dropwise to be made for 30wt% sodium hydroxide solution
Solution ph need not add ferric phosphate seed crystal after being adjusted to 0.5, 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 with collection of illustrative plates, the XRD spectrum corresponding diagram 1 for the product that comparative example 1 is prepared.As shown in Figure 1, plus seed crystal
Can form well-crystallized's preferable ferric phosphate corresponding with standard card peak position, be not added with seed crystal formation simply amorphous state alkali formula
Hypophosphite monohydrate iron.
Comparative example 2
Method according to comparative example 1 prepares ferric phosphate, and difference is, the consumption of the phosphoric acid added is phosphorus in comparative example 1
3 times of sour consumption.
The ferric phosphate that embodiment 1~3 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, the method that provides of the present invention can prepare well-crystallized with
The preferable ferric phosphate of standard card peak position correspondence；Seed crystal is not added with using excessive phosphoric acid in prior art preparation process, crystallized
Preferable ferric phosphate well corresponding with standard card peak position.Understand, the preparation method that the present invention is provided, which can overcome, does not use excess
The drawbacks of generation of alkali formula hypophosphite monohydrate iron caused by phosphoric acid, the high ferric phosphate of purity can be obtained.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of ferric phosphate, comprises the following steps：
(1) filtered after source of iron is mixed with acid solution, obtain filtrate；
(2) pH value is adjusted after the filtrate for obtaining the step (1) mixes with phosphoric acid to 0.5~1, mixed liquor is obtained；The filter
The ratio between amount of material of iron ion and phosphoric acid is 1 in liquid:1；
(3) pH value is adjusted after the mixed liquor for obtaining the step (2) is mixed with derivant to 1.5~2.5, progress precipitates anti-
Should, obtain ferric phosphate.
2. preparation method according to claim 1, it is characterised in that the source of iron is that the content of iron is 63~70wt%'s
Iron-containing waste.
3. preparation method according to claim 2, it is characterised in that the iron-containing waste is the neodymium iron for completing rare earth recovery
LiFePO4 waste material or corrosion iron-containing waste after boron waste material, completion lithium recovery.
4. preparation method according to claim 1, it is characterised in that the derivant is ferric phosphate seed crystal；The induction
The mass ratio of agent and phosphoric acid in the step (2) is (0.5~2)：(64~65).
5. preparation method according to claim 1, it is characterised in that acid solution includes sulfuric acid and auxiliary in the step (1)
Acid is helped, the auxiliary acid is the one or more in hydrochloric acid, nitric acid and perchloric acid.
6. preparation method according to claim 1, it is characterised in that regulation pH value conditioning agent bag in the step (2)
Include sodium hydroxide and/or potassium hydroxide.
7. preparation method according to claim 1, it is characterised in that regulation pH value conditioning agent bag in the step (3)
Include the one or more in sodium carbonate, sodium acid carbonate and ammoniacal liquor.
8. preparation method according to claim 1, it is characterised in that mixed process, the regulation of pH value in the step (2)
The temperature of mixing, pH value regulation process and precipitation reaction independently is 80~95 DEG C in process and step (3).
9. preparation method according to claim 1, it is characterised in that also include after the precipitation reaction anti-to the precipitation
The post processing of product is answered, including：The product of the precipitation reaction is aged successively, separation of solid and liquid, pickling and drying.
10. preparation method according to claim 9, it is characterised in that the pickling is that phosphate concentration is with cleaning solution
0.05~0.1mol/L acid solution.
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| CN107978753A (en) * | 2017-11-30 | 2018-05-01 | 湘潭大学 | A kind of bowl-shape hollow carbon sphere/graphene composite materials of ferric phosphate@and its preparation method and application |
| 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 |
| 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 |
| CN115676790A (en) * | 2022-10-28 | 2023-02-03 | 贵州川恒化工股份有限公司 | Preparation method of high-tap spherical battery-grade iron phosphate |
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| CN107978753A (en) * | 2017-11-30 | 2018-05-01 | 湘潭大学 | A kind of bowl-shape hollow carbon sphere/graphene composite materials of ferric phosphate@and its preparation method and application |
| 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 |
| CN115676790A (en) * | 2022-10-28 | 2023-02-03 | 贵州川恒化工股份有限公司 | Preparation method of high-tap spherical battery-grade iron phosphate |
| 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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