CN108117055A - The preparation method and process units of a kind of battery-grade iron phosphate - Google Patents
The preparation method and process units of a kind of battery-grade iron phosphate Download PDFInfo
- Publication number
- CN108117055A CN108117055A CN201711493056.5A CN201711493056A CN108117055A CN 108117055 A CN108117055 A CN 108117055A CN 201711493056 A CN201711493056 A CN 201711493056A CN 108117055 A CN108117055 A CN 108117055A
- Authority
- CN
- China
- Prior art keywords
- phosphate
- iron
- battery
- reaction kettle
- reaction
- 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
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
- C01P2006/40—Electric properties
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
A kind of preparation method of battery-grade iron phosphate, includes the following steps, prepares iron salt solutions, prepares phosphorus source solution, oxidation precipitation reaction, and for the feed liquid after reaction through plate-frame filtering, filter cake is washed, sintering, finally obtains phosphoric acid iron product.Process units includes molysite storage tank, phosphate storage tank, reaction kettle, delay kettle and sheet frame, and molysite storage tank and phosphate storage tank are communicated to the top of reaction kettle by feeding pipe respectively, and the reaction kettle, delay kettle and sheet frame are sequentially connected.Above-mentioned preparation process makes state of the oxidation precipitation reaction in dynamic equilibrium, the reaction time is short, the ferric phosphate stable quality of production, size tunable, realizes the serialization industrial production of ferric phosphate using the process units of continuous feed, discharging.
Description
Technical field
The present invention relates to the technical field of ferric phosphate preparation process, particularly a kind of ferric phosphate for being suitable for manufacture battery
Production technology.
Background technology
Ferric phosphate (FePO4·nH2O, n=0-2) also known as ferric orthophosphate or high ferric phosphate, with the reduction of the crystallization water, face
Color gradually turns yellow, and anhydrous iron phosphate is yellow-white powder.It mainly for the manufacture of LiFePO4, in addition also act as catalyst and
Manufacture ceramics etc..The properties of product of ferric phosphate are most important for the LiFePO4 for preparing anode, main performance index
For phase analyzed laser-light scattering, iron phosphorus ratio, specific surface area, tap density etc..At present, the producer of battery-grade iron phosphate is produced both at home and abroad
Have very much, since the production technology and quality control standard of each producer are different, properties of product are also irregular.Chinese patent
CN101244813B describes the system of a kind of alkali formula ammonium ferric phosphate and preparation method, the preparation method of ferric phosphate and LiFePO 4
Preparation Method, ferrous sulfate is carried out part oxygen by it with hydrogen peroxide first using ferrous sulfate, hydrogen peroxide, phosphoric acid, ammonium hydroxide as raw material
Change, form the mixed liquor of ferric sulfate and ferrous sulfate, then phosphoric acid is added in into molysite mixture.Then with ammonium hydroxide tune pH value, make
It obtains alkali formula ferric phosphate to be precipitated out, precipitation needs to continue to keep the temperature 4-16h after being formed.Finally feed liquid is filtered, wash, is roasted
It burns, so as to obtain phosphoric acid iron product.Above-mentioned technique is there are shortcomings, and the reaction conversion ratio of ferric phosphate first is low, reaction time
It is long, be not suitable for large-scale industrial production；Using phosphoric acid, ammonium hydroxide as primary raw material, production cost is higher；What co-precipitation came out
Product is amorphous state, is susceptible to hardened after sintering, and the size distribution that ultimately results in ferric phosphate finished product is wide, specific surface area is small.
Patent CN104944400B describes the technique that Hydrolyze method prepares ferric phosphate, it is with ferrous sulfate, hydrogen peroxide, phosphoric acid
For raw material, six oxidized, hydrolysis, filtering, conversion, washing, drying steps finally obtain phosphoric acid iron product.Wherein hydrolysis
It is to be carried out in 90-95 DEG C of hot water, due to consuming a large amount of hot water, energy consumption is relatively high.This condition can cause water simultaneously
It solves insufficient, reduces yield, the phase analyzed laser-light scattering of product is uneven.
Chinese patent CN 106379877A disclose a kind of continuous preparation device of ferric phosphate, are fed by feed bin, screw rod
Device, continuous conduit reactor, water pump, liquid meter charge pump, horizontal centrifuge and pipeline are formed together.It is added by screw rod
Molysite, phosphate are separately added into continuous conduit reactor and are dissolved in water into solution by glassware, and two kinds of solution are in proportion into company
Continuous pipeline reactor 1 reacts, and pH is adjusted in continuous conduit reactor 2 as neutrality, by horizontal centrifuge, washes away foreign ion,
Obtain ferric phosphate solid.Since ferric sulfate is sl. sol. salt in water, and solution rate is slow, cannot be formed in a short time
Iron salt solutions can be only formed ferric sulfate suspension, and in addition ferric sulfate also has slowly hydrolysis, forms ferric hydroxide colloid.Institute
It is blocked be easy to causeing not molten solid in pipeline 1, causes charging unstable, local concentration is excessively high, can not obtain property stabilization
Product.
The content of the invention
The technical problems to be solved by the invention are to overcome the defect of prior art, provide a kind of system of battery-grade iron phosphate
Preparation Method and process units, it makes shape of the oxidation precipitation reaction in dynamic equilibrium using the process units of continuous feed, discharging
State, the reaction time is short, the ferric phosphate stable quality of production, size tunable, realizes the serialization industrial production of ferric phosphate.
Technical problem of the present invention is solved with following technical proposals：
A kind of preparation method of battery-grade iron phosphate, preparation carry out as follows：
A, iron salt solutions are prepared, source of iron is dissolved in pure water, iron salt solutions is made, the quality hundred of solution ferrous ions
It is 5%-8% to divide specific concentration, and the source of iron is one kind in ferrous sulfate, frerrous chloride or ferrous oxalate；
B, phosphorus source solution is prepared, phosphorus source is dissolved in pure water, oxidant and surfactant are added in after dissolving, stirring is equal
Even to be made phosphorus source solution, the mass percent concentration of phosphate radical is 14.5%-18.0% in solution, phosphorus source is sodium phosphate,
One kind in potassium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate or ammonium phosphate；
C, oxidation precipitation reacts, and iron salt solutions and phosphorus source solution is added continuously in reaction kettle respectively, continuously stirring makes
Feed liquid is uniformly mixed and fully reacts, and as liquid level rises in the addition reaction kettle of solution, stops and opens reaction after a certain period of time
The outlet valve in bottom portion, the feed liquid after reaction continuously slowly flow out；
D, the feed liquid released in step c enters plate-frame filtering, and filter cake is washed, sintering, finally obtains phosphoric acid iron product.
The preparation method of above-mentioned battery-grade iron phosphate, the surfactant include PEG-200, PEG-400, PEG-600,
One or more in PVP-K15, neopelex, cetyl trimethylammonium bromide or trihydroxy ethylamine oleate soap.
The preparation method of above-mentioned battery-grade iron phosphate, the oxidant are hydrogen peroxide；The surfactant is three ethyl alcohol
Amine oleate soap.
The preparation method of above-mentioned battery-grade iron phosphate, the mass percent of phosphate radical is dense in phosphorus source solution in the step b
It spends for 15.5%, the concentration of hydrogen peroxide is 2.5%, and the concentration of trihydroxy ethylamine oleate soap is 0.2%.
The preparation method of above-mentioned battery-grade iron phosphate, iron ion and phosphate anion raw materials components mole ratio are in the step c
0.95-1.10:1；Speed of agitator is 300-500rpm；Residence time of the feed liquid in reaction kettle is 40min-50min.
The preparation method of above-mentioned battery-grade iron phosphate, in the step c by adjust iron salt solutions and phosphorus source solution plus
Doses, the temperature for controlling feed liquid in reaction kettle are 50 DEG C -60 DEG C, pH value 3.0-4.0.
A kind of process units using battery-grade iron phosphate preparation method, including molysite storage tank, phosphate storage tank, reaction
Kettle is detained kettle and sheet frame, and the molysite storage tank and phosphate storage tank are communicated to the top of reaction kettle, institute by feeding pipe respectively
Reaction kettle, delay kettle and sheet frame is stated to be sequentially connected.
The above-mentioned process units for preparing battery-grade iron phosphate is respectively equipped with filter and metering pump on the feeding pipe.
The above-mentioned process units for preparing battery-grade iron phosphate, the end of the feeding pipe set distributor.
The continuous production processes that the present invention uses are that iron salt solutions and phosphorus source solution are continuously added into reaction kettle, is continuously gone out
The reaction process of material, reaction full process automatization control, eliminates the quality difference of batch production and artificial disturbing factor, production
Quality is stablized, and the lot stability of battery production is ensure that from source, so as to improve the security performance of lithium battery.Together
When, cost of labor is reduced, improves production efficiency, realizes the serialization industrial production of ferric phosphate.
The present invention effectively controls the particle size and grain of iron phosphate grains by adjusting the technological parameter that oxidation precipitation reacts
Footpath is distributed, and by adjusting the concentration and material of surfactant, the residence time controls the grain size of iron phosphate grains in a kettle
Size, by adjusting the distribution of iron ion and phosphate anion raw materials components mole ratio, speed of agitator and controlling reaction temperature grain size.
Small using the ferric phosphate crystallization primary particle size of above-mentioned continuous processing production, second particle disperses, even particle size, particle diameter distribution
Narrow, wherein D50 distributions are between 1-3 μm, and D90 is in the range of 3-10 μm；Avoid the ferric phosphate of conventional method preparation
The shortcomings of distribution of particles is uneven, and granule-morphology is random, and agglomeration is serious between particle.The promotion of material uniformity helps to improve
Compacted density, available for the battery for preparing high power capacity.Therefore, the ferric phosphate excellent product performance of production, chemical property is good, matter
Amount is stablized, and the LiFePO4 to prepare high-quality lays good basis.
Continuous production processes make oxidation precipitation reaction be in dynamic balance state, and the reaction time is short, it is only necessary to and 40-50 minutes,
Reduce the back-mixing of material, iron phosphate grains crystallization is uniform, and surface roughness is big, the moderate (10m of specific surface area2/ g), after being
Continuous filtering, the processing of sintering circuit provide advantage.Processing speed is accelerated in press filtration process, reduces the production of waste water
It is raw, energy consumption is reduced, meets the policy of national energy-saving emission reduction.In sintering circuit phosphoric acid iron product be not susceptible to reunite and it is hardened, easily
In broken classification, shorten processing time, reduce the time of material ingress of air, reduce the water content of material.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention；
Fig. 2 is scanning electron microscope (SEM) figure of 1 gained ferric phosphate of embodiment；
Fig. 3 is x-ray diffraction (XRD) figure of 1 gained ferric phosphate of embodiment.
Each list of reference numerals is in figure：1st, molysite storage tank, 2, phosphate storage tank, 3, filter, 4, metering pump, 5, reaction kettle,
6th, it is detained kettle, 7, sheet frame, 8, distributor, 9, conveying pipeline.
Specific embodiment
The present invention is described in further detail below in conjunction with the accompanying drawings.
The preparation method of ferric phosphate of the present invention, includes the following steps：
Step a, iron salt solutions are prepared：Source of iron is dissolved in 15 DEG C -40 DEG C of pure water, iron salt solutions are made, the solution Central Asia
The mass percent concentration of iron ion is 5%-8% (wt), and solution ph is 2.0-4.0 after dissolving.The source of iron is sub- for sulfuric acid
One kind in iron, frerrous chloride, ferrous nitrate or ferrous oxalate.
Iron powder can also be placed in reaction in sulfuric acid, hydrochloric acid, nitric acid or oxalic acid solution and obtain iron salt solutions.
Step b, phosphorus source solution is prepared：Phosphorus source is added in the pure water that temperature is 20 DEG C -35 DEG C, oxidant is added in after dissolving
And surfactant, it stirs evenly and phosphorus source solution is made.The pH value of solution is 7-8.5.
Phosphorus source is one kind in sodium phosphate, potassium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate or ammonium phosphate, and phosphorus source is molten
In liquid the mass percent concentration of phosphate radical be 14.5%-18.0%, preferably 15.5%.The oxidant includes hydrogen peroxide, oxygen
Gas or ozone, preferably hydrogen peroxide.The amount that hydrogen peroxide adds in is the content 2.0-3.0% (wt) of hydrogen peroxide in the solution, preferably
2.5%.Surfactant includes PEG-200, PEG-400, PEG-600, PVP-K15, neopelex, cetyl
One or more in trimethylammonium bromide or trihydroxy ethylamine oleate soap, preferably trihydroxy ethylamine oleate soap, surfactant add in
It measures as the 0.1-0.5% of phosphorus source solution, preferably 0.2%.Trihydroxy ethylamine oleate soap has excellent as nonionic surfactant
Lubricity and dispersiveness, oxidation precipitation reaction in play iris action, effectively prevent from reuniting between particle, make the phosphoric acid to be formed
Iron particle is uniform, and particle diameter distribution is narrow.Simultaneously because itself is organic compound, do not increase foreign ion in reaction system, it is right
Reaction influence is small, and the waste water of generation is disposable.
Step c, oxidation precipitation reacts：Iron salt solutions and phosphorus source solution are added continuously in reaction kettle respectively, iron ion
It is (0.90-1.10) with phosphate anion raw materials components mole ratio:1, preferred molar ratio 0.98:1.Continuously stirring makes material mixing equal
Even and fully react, speed of agitator 300-500rpm, preferably rotating speed are 400rpm.With liquid level in the addition reaction kettle of solution
Rise, reach the outlet valve of opening reactor bottom after certain residence time, the feed liquid after reaction continuously slowly flows out.Adjust into
Material and the speed of discharging, it is 40-50min to make the residence time of material in a kettle.
The charging rate of two kinds of solution is adjusted, the temperature range for controlling solution in reaction kettle is 50 DEG C -60 DEG C, preferable temperature
57℃.Since, due to hydrogen peroxide and ferrous generation oxidation reaction, heat release is violent, by adjusting material concentration, control in reaction process
System charging and the speed of discharging, make to reach thermal balance in reaction kettle, realize temperature-controllable.Iron salt solutions and phosphorus source solution ratio are true
Fixed, after reaction feed and discharging reach balance, material composition need not be added and adjust pH agent in stable state in kettle, reaction
The pH stable of system is in the range of 3.0-4.0, preferable ph 3.5.Due to realizing the temperature and pH value of reaction solution
Self-contr ol, successive reaction have the characteristics of stability is good, less energy consumption, and processing step is simple
Step d, the feed liquid released in step c enters plate-frame filtering, and filter cake is washed, sintering, finally obtains ferric phosphate production
Product.
As shown in Figure 1, the process units of the present invention includes molysite storage tank 1, phosphate storage tank 2, reaction kettle 5,6 and of delay kettle
Sheet frame 7, the molysite storage tank 1 and phosphate storage tank 2 are communicated to the top of reaction kettle 5, the reaction by feeding pipe 9 respectively
Kettle 5, delay kettle 6 and sheet frame 7 are sequentially connected.Reaction kettle and the tank body peripheral hardware insulating layer for being detained kettle.In molysite storage tank and phosphate
Storage tank, which is communicated on the feeding pipe of reaction kettle, is respectively equipped with filter 3 and metering pump 4, and the filter 3 is fine filter, with essence
Suspended matter and other impurity in filter filtering solution can guarantee that stable system runs and reduces impurity content in product；Meter
Amount pump is reciprocating type plunger metering pump, and the pressure that it is provided is big, it is ensured that the flow of charging is accurate and stablizes.
9 end of feeding pipe enters reaction kettle from the top of reaction kettle 5, the end set distributor 8 of feeding pipe,
Iron salt solutions and phosphorus source solution are equably sprayed onto in reaction kettle by distributor, can ensure to feed in a manner that sprinkling feeds
Uniformly, avoid local concentration excessively high.
The course of work of the present invention is described further below：
Source of iron solid is added in molysite storage tank 1, is dissolved in 15 DEG C -40 DEG C of pure water and is configured to iron salt solutions, it will
Phosphorus source solid is added in phosphate storage tank 2, after being dissolved in 20 DEG C -35 DEG C of pure water, is added in oxidant and surfactant, is stirred
It mixes and is uniformly configured to phosphorus source solution.Iron salt solutions and phosphorus source solution are delivered to filter 3 and metering pump 4 by conveying pipeline respectively,
Reaction kettle 5 is squeezed into after refined filtration and accurate metering.
Two kinds of spray solutions carry out oxidation precipitation reaction in reaction kettle in reaction kettle.By the way that inlet amount is controlled to make
The temperature stabilization of reaction system is at 50 DEG C -60 DEG C, and pH value is in the range of 3.0-4.0.When the material reaction residence time in kettle
In 40-50min, the outlet valve of reactor bottom is opened, material, which continuously outflows to enter, is detained kettle.By adjusting what is fed and discharge
Speed can control reaction process.Be detained kettle and be for by accumulation of material to a certain amount of, supply sheet frame progress press filtration.It is detained kettle
Feed liquid is through plate-frame filtering, and precipitation after filtering is washed, drying and sintering obtains ferric phosphate finished product.
Embodiment 1
In the phosphate storage tank of 1000L, 235.0kg disodium hydrogen phosphates solid and 700.0kg pure water are added in, is added after dissolving
Enter 70.8kg hydrogen peroxide (concentration of hydrogen peroxide be 30%) and 2.0kg trihydroxy ethylamine oleate soaps, stir evenly rear spare, phosphorus is made
Source solution, the concentration of phosphate anion is 15.60% in solution.In the molysite storage tank of another 2000L, it is dense to prepare 1200kg
It spends spare for 14.0% solution of ferrous chloride, is made iron salt solutions, the concentration 6.17% of iron ion in solution.
10kg pure water is previously added in the reaction kettle of a 100L, with two metering pumps simultaneously by the phosphorus source by filtering
Solution and iron salt solutions are added in reaction kettle, and the temperature of feed liquid is 57 DEG C in reaction kettle, and the addition of phosphorus source solution is
0.616kg/min, the addition of ferrous iron solution are 0.984kg/min, mixing speed 400rpm.Material stop 45min in kettle
Afterwards, start continuously to extract material out, be consistent discharging speed and charging rate.The reaction solution for collecting 1h carries out pressure filtering cleaning
It washs, phosphoric acid iron product is obtained after sintering.The ferric phosphate of preparation is analyzed, granularity data is：D10=0.415 μm, D50=
1.205 μm, D90=3.314 μm.Show that the grain size of product is small, particle diameter distribution is narrow according to granularity data.
SEM, XRD analysis are carried out to phosphoric acid iron product obtained, as shown in Figure 2,3.By electromicroscopic photograph as can be seen that obtaining
The ferric phosphate product particle size obtained is more uniform, and primary particle size scope has the structure of corynebacterium between 50-200nm.
Ferric phosphate XRD standard cards are compareed in XRD diffracting spectrums and confirm that products obtained therefrom is hexagonal structure.
Embodiment 2
In the phosphate storage tank for taking a 1000L, add in 256.0kg disodium hydrogen phosphates solids, 700.0kg pure water,
70.8kg hydrogen peroxide (concentration 30%) and 2.5kg PEG-400, stir evenly rear spare, are made phosphorus source solution, phosphorus in solution
The concentration of acid ion is 16.64%.In the molysite storage tank of another 2000L, the chlorine that 1200kg concentration is 14.0% is prepared
Change ferrous iron solution is iron salt solutions.
40kg pure water is previously added in the reaction kettle of a 250L, then with two metering pumps simultaneously by the phosphorus after filtering
Source, iron salt solutions are added in reaction kettle, and material in reactor temperature is 50 DEG C, sets phosphorus source metering pump as 0.616kg/min, Asia
Iron metering pump 0.923kg/min, mixing speed 300rpm.In kettle after material stop 40min, start continuously to extract material out,
It is consistent discharging speed and charging rate.The reaction solution for collecting 1h carries out pressure filtration washing, and phosphoric acid iron product is obtained after sintering.System
Standby ferric phosphate granularity data is：D10=0.512 μm, D50=3.328 μm, D90=12.129 μm.
Embodiment 3
In the phosphate storage tank for taking a 1000L, it is double to add in 324.0kg sodium phosphates solid, 700.0kg pure water, 88.0kg
Oxygen water and 3.0kg PEG-600, stir evenly rear spare for phosphorus source solution, and the concentration of phosphate anion is 16.8% in solution.
In the molysite storage tank of another 2000L, it is iron salt solutions to prepare the solution of ferrous chloride that 1200kg concentration is 14.0%.
10kg pure water is previously added in the reaction kettle of a 100L, then phosphorus source, molysite are molten simultaneously with two metering pumps
Liquid is added in reaction kettle, and material in reactor temperature is 58 DEG C, sets phosphorus source metering pump as 0.629kg/min, ferrous metering pump
0.984kg/min, mixing speed 350rpm.In kettle after material stop 48min, start continuously to extract material out, make discharging fast
Degree and charging rate are consistent.The reaction solution for collecting 1h carries out pressure filtration washing, and phosphoric acid iron product is obtained after sintering.The phosphoric acid of preparation
Abrasive grit degrees of data is：D10=0.671 μm, D50=2.015 μm, D90=4.694 μm.
Embodiment 4
In the phosphate storage tank for taking a 1000L, add in 230.0kg sodium dihydrogen phosphates solids, 700.0kg pure water,
80.8kg hydrogen peroxide and 2.0kg cetyl trimethylammonium bromides stir evenly rear spare for phosphorus source solution, phosphate radical in solution
The concentration of ion is 17.98%.In the molysite storage tank of another 2000L, it is sub- to prepare the sulfuric acid that 1200kg concentration is 14.0%
Ferrous solution is iron salt solutions, the concentration 5.16% of iron ion in solution.
10kg pure water is previously added in the reaction kettle of a 100L, then with two metering pumps simultaneously by phosphorus source solution and
Iron salt solutions are added in reaction kettle, and material in reactor temperature is 50 DEG C, sets phosphorus source metering pump as 0.616kg/min, ferrous iron
Metering pump 1.294kg/min, mixing speed 500rpm.In kettle after material stop 40min, start continuously to extract material out, make
Discharging speed and charging rate are consistent.The reaction solution for collecting 1h carries out pressure filtration washing, and phosphoric acid iron product is obtained after sintering.It prepares
Ferric phosphate granularity data be：D10=0.330 μm, D50=2.557 μm, D90=10.265 μm.
Embodiment 5
In the phosphate storage tank for taking a 1000L, it is double to add in 265.0kg potassium phosphates solid, 500.0kg pure water, 70.8kg
Oxygen water and 2.0kg triethanolamine oil soaps, stir evenly rear spare, are made phosphorus source solution, the concentration of phosphate anion is in solution
14.17%.In the molysite storage tank of another 2000L, the solution of ferrous chloride that preparation 1200kg concentration is 14.0% is spare, system
Into iron salt solutions.
10kg pure water is previously added in the reaction kettle of a 100L, so with two metering pumps simultaneously by phosphorus source solution and iron
Salting liquid is added in reaction kettle, and material in reactor temperature is 55 DEG C, sets phosphorus source metering pump as 0.629kg/min, ferrous meter
Amount pump 0.923kg/min, mixing speed 400rpm.In kettle after material stop 45min, start continuously to extract material out, use
Material speed and charging rate are consistent.The reaction solution for collecting 1h carries out pressure filtration washing, and phosphoric acid iron product is obtained after sintering.It prepares
Ferric phosphate granularity data is：D10=0.807 μm, D50=2.414 μm, D90=8.520 μm.
Electro-chemical test is done to the sample obtained by above-described embodiment, it is as a result as shown in table 1 below.
1 electrochemical test data of table
First effect is more than 97% in test result, and 0.2C is more than 157,1C and is more than 149,2C more than 140, made from explanation
The chemical property of ferric phosphate is good.
Claims (9)
1. a kind of preparation method of battery-grade iron phosphate, which is characterized in that preparation carries out as follows：
A, iron salt solutions are prepared, source of iron is dissolved in pure water, iron salt solutions is made, the mass percent of solution ferrous ions
Concentration is 5%-8%, and the source of iron is one kind in ferrous sulfate, frerrous chloride, ferrous nitrate or ferrous oxalate；
B, phosphorus source solution is prepared, phosphorus source is dissolved in pure water, oxidant and surfactant, the system of stirring evenly are added in after dissolving
Into phosphorus source solution, the mass percent concentration of phosphate radical is 14.5%-18.0% in solution, and phosphorus source is sodium phosphate, phosphoric acid
One kind in potassium, disodium hydrogen phosphate, sodium dihydrogen phosphate or ammonium phosphate；
C, oxidation precipitation reacts, and iron salt solutions and phosphorus source solution is added continuously in reaction kettle respectively, continuously stirring makes feed liquid
It is uniformly mixed and fully reacts, as liquid level rises in the addition reaction kettle of solution, stop and open reaction kettle bottom after a certain period of time
The outlet valve in portion, the feed liquid after reaction continuously slowly flow out；
D, the feed liquid released in step c enters plate-frame filtering, and filter cake is washed, sintering, finally obtains phosphoric acid iron product.
2. the preparation method of battery-grade iron phosphate according to claim 1, which is characterized in that the surfactant includes
PEG-200, PEG-400, PEG-600, PVP-K15, neopelex, cetyl trimethylammonium bromide or three ethyl alcohol
One or more in amine oleate soap.
3. the preparation method of battery-grade iron phosphate according to claim 2, which is characterized in that the oxidant is dioxygen
Water；The surfactant is trihydroxy ethylamine oleate soap.
4. the preparation method of battery-grade iron phosphate according to claim 3, which is characterized in that phosphorus source is molten in the step b
The mass percent concentration of phosphate radical is 15.5% in liquid, and the concentration of hydrogen peroxide is 2.5%, and the concentration of trihydroxy ethylamine oleate soap is
0.2%.
5. the preparation method of battery-grade iron phosphate according to claim 4, which is characterized in that iron ion in the step c
It is 0.95-1.10 with phosphate anion raw materials components mole ratio:1；Speed of agitator is 300-500rpm；Stop of the feed liquid in reaction kettle
Time is 40min-50min.
6. the preparation method of battery-grade iron phosphate according to claim 5, which is characterized in that pass through tune in the step c
The feeding quantity of iron salt solutions and phosphorus source solution is saved, the temperature for controlling feed liquid in reaction kettle is 50 DEG C -60 DEG C, pH value 3.0-4.0.
7. a kind of using the process units that battery-grade iron phosphate is prepared such as any one of claim 1-6 the method, feature exists
In including molysite storage tank (1), phosphate storage tank (2), reaction kettle (5), delay kettle (6) and sheet frame (7), the molysite storage tank (1)
It is communicated to the top of reaction kettle (5) by feeding pipe (9) respectively with phosphate storage tank (2), the reaction kettle is detained kettle and plate
Frame is sequentially connected.
8. the process units according to claim 7 for preparing battery-grade iron phosphate, which is characterized in that on the feeding pipe
It is respectively equipped with filter (3) and metering pump (4).
9. the process units according to claim 8 for preparing battery-grade iron phosphate, which is characterized in that the feeding pipe
End sets distributor (8).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711493056.5A CN108117055B (en) | 2017-12-30 | 2017-12-30 | Preparation method and production device of battery-grade iron phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711493056.5A CN108117055B (en) | 2017-12-30 | 2017-12-30 | Preparation method and production device of battery-grade iron phosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108117055A true CN108117055A (en) | 2018-06-05 |
| CN108117055B CN108117055B (en) | 2021-07-16 |
Family
ID=62233780
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711493056.5A Active CN108117055B (en) | 2017-12-30 | 2017-12-30 | Preparation method and production device of battery-grade iron phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108117055B (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761209A (en) * | 2019-03-06 | 2019-05-17 | 深圳海纳百川科技有限公司 | A kind of production technology and its production equipment of ferric phosphate |
| CN110204102A (en) * | 2019-07-10 | 2019-09-06 | 安徽瑞迪工程科技有限公司 | One kind resource recovering system of acid waste water containing ferrous ion and method |
| CN110902666A (en) * | 2019-12-26 | 2020-03-24 | 湖南雅城新材料有限公司 | Preparation method of flaky ferric phosphate dihydrate |
| CN112320780A (en) * | 2020-09-25 | 2021-02-05 | 湖北金泉新材料有限公司 | Method for recovering iron phosphate waste |
| CN112408352A (en) * | 2020-11-25 | 2021-02-26 | 衢州华友钴新材料有限公司 | Linkage production process of battery-grade iron phosphate and refined phosphoric acid |
| CN112499610A (en) * | 2020-12-09 | 2021-03-16 | 靖西湘潭电化新能源材料有限公司 | Preparation method of battery-grade iron phosphate material |
| CN113479861A (en) * | 2021-07-01 | 2021-10-08 | 广东邦普循环科技有限公司 | Preparation method of low-sulfur-content nano iron phosphate |
| CN114644325A (en) * | 2021-12-07 | 2022-06-21 | 上海安赐环保科技股份有限公司 | Device and method for preparing battery-grade iron phosphate by using by-product ferrous sulfate |
| WO2022127322A1 (en) * | 2020-12-15 | 2022-06-23 | 广东邦普循环科技有限公司 | Preparation method and application of iron phosphate |
| CN115285958A (en) * | 2022-01-24 | 2022-11-04 | 昆明理工大学 | Preparation method of battery-grade iron phosphate |
| CN115701828A (en) * | 2022-11-25 | 2023-02-14 | 宁波新福钛白粉有限公司 | Quasi-continuous method for preparing battery-grade anhydrous iron phosphate by using ferrous sulfate |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920948A (en) * | 2009-06-09 | 2010-12-22 | 中国电子科技集团公司第十八研究所 | Method for preparing granularity controllable ferric orthophosphate powder |
| CN102491302A (en) * | 2011-12-15 | 2012-06-13 | 湖北万润新能源科技发展有限公司 | Battery-grade anhydrous iron phosphate and preparation method thereof |
| CN103752222A (en) * | 2011-12-06 | 2014-04-30 | 魏宇 | Continuous metering charging system of reaction vessel |
| CN203781852U (en) * | 2014-03-17 | 2014-08-20 | 江苏华东锂电技术研究院有限公司 | Lithium iron phosphate continuous preparing device |
| CN105118995A (en) * | 2015-10-14 | 2015-12-02 | 湖南省正源储能材料与器件研究所 | Production method of battery-grade iron phosphate |
| CN105800578A (en) * | 2016-03-02 | 2016-07-27 | 杨第伦 | Method for producing ultra-micro and nano iron phosphate by virtue of gas bubble liquid membrane process |
| CN107285292A (en) * | 2017-08-01 | 2017-10-24 | 中盐安徽红四方新能源科技有限公司 | The method that reaction of high order prepares battery-grade iron phosphate |
| CN107337189A (en) * | 2017-08-23 | 2017-11-10 | 江西艾德纳米科技有限公司 | The method of ferric phosphate continuous production system and continuous production ferric phosphate |
| CN107473196A (en) * | 2017-09-30 | 2017-12-15 | 贵州微化科技有限公司 | A kind of method of continuous production LITHIUM BATTERY high compacted density nano ferric phosphate |
-
2017
- 2017-12-30 CN CN201711493056.5A patent/CN108117055B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101920948A (en) * | 2009-06-09 | 2010-12-22 | 中国电子科技集团公司第十八研究所 | Method for preparing granularity controllable ferric orthophosphate powder |
| CN103752222A (en) * | 2011-12-06 | 2014-04-30 | 魏宇 | Continuous metering charging system of reaction vessel |
| CN102491302A (en) * | 2011-12-15 | 2012-06-13 | 湖北万润新能源科技发展有限公司 | Battery-grade anhydrous iron phosphate and preparation method thereof |
| CN203781852U (en) * | 2014-03-17 | 2014-08-20 | 江苏华东锂电技术研究院有限公司 | Lithium iron phosphate continuous preparing device |
| CN105118995A (en) * | 2015-10-14 | 2015-12-02 | 湖南省正源储能材料与器件研究所 | Production method of battery-grade iron phosphate |
| CN105800578A (en) * | 2016-03-02 | 2016-07-27 | 杨第伦 | Method for producing ultra-micro and nano iron phosphate by virtue of gas bubble liquid membrane process |
| CN107285292A (en) * | 2017-08-01 | 2017-10-24 | 中盐安徽红四方新能源科技有限公司 | The method that reaction of high order prepares battery-grade iron phosphate |
| CN107337189A (en) * | 2017-08-23 | 2017-11-10 | 江西艾德纳米科技有限公司 | The method of ferric phosphate continuous production system and continuous production ferric phosphate |
| CN107473196A (en) * | 2017-09-30 | 2017-12-15 | 贵州微化科技有限公司 | A kind of method of continuous production LITHIUM BATTERY high compacted density nano ferric phosphate |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761209A (en) * | 2019-03-06 | 2019-05-17 | 深圳海纳百川科技有限公司 | A kind of production technology and its production equipment of ferric phosphate |
| CN110204102A (en) * | 2019-07-10 | 2019-09-06 | 安徽瑞迪工程科技有限公司 | One kind resource recovering system of acid waste water containing ferrous ion and method |
| CN110902666B (en) * | 2019-12-26 | 2021-12-31 | 湖南雅城新材料有限公司 | Preparation method of flaky ferric phosphate dihydrate |
| CN110902666A (en) * | 2019-12-26 | 2020-03-24 | 湖南雅城新材料有限公司 | Preparation method of flaky ferric phosphate dihydrate |
| CN112320780A (en) * | 2020-09-25 | 2021-02-05 | 湖北金泉新材料有限公司 | Method for recovering iron phosphate waste |
| CN112320780B (en) * | 2020-09-25 | 2023-08-29 | 湖北金泉新材料有限公司 | Method for recycling iron phosphate waste |
| CN112408352A (en) * | 2020-11-25 | 2021-02-26 | 衢州华友钴新材料有限公司 | Linkage production process of battery-grade iron phosphate and refined phosphoric acid |
| CN112499610B (en) * | 2020-12-09 | 2021-08-03 | 广西裕宁新能源材料有限公司 | Preparation method of battery-grade iron phosphate material |
| CN112499610A (en) * | 2020-12-09 | 2021-03-16 | 靖西湘潭电化新能源材料有限公司 | Preparation method of battery-grade iron phosphate material |
| WO2022127322A1 (en) * | 2020-12-15 | 2022-06-23 | 广东邦普循环科技有限公司 | Preparation method and application of iron phosphate |
| GB2617725A (en) * | 2020-12-15 | 2023-10-18 | Guangdong Brunp Recycling Technology Co Ltd | Preparation method and application of iron phosphate |
| CN113479861A (en) * | 2021-07-01 | 2021-10-08 | 广东邦普循环科技有限公司 | Preparation method of low-sulfur-content nano iron phosphate |
| WO2023273742A1 (en) * | 2021-07-01 | 2023-01-05 | 广东邦普循环科技有限公司 | Preparation method for nano ferric phosphate with low sulphur content |
| CN113479861B (en) * | 2021-07-01 | 2023-02-14 | 广东邦普循环科技有限公司 | Preparation method of low-sulfur-content nano iron phosphate |
| GB2616230A (en) * | 2021-07-01 | 2023-08-30 | Guangdong Brunp Recycling Technology Co Ltd | Preparation method for nano ferric phosphate with low sulphur content |
| CN114644325A (en) * | 2021-12-07 | 2022-06-21 | 上海安赐环保科技股份有限公司 | Device and method for preparing battery-grade iron phosphate by using by-product ferrous sulfate |
| CN115285958A (en) * | 2022-01-24 | 2022-11-04 | 昆明理工大学 | Preparation method of battery-grade iron phosphate |
| CN115701828A (en) * | 2022-11-25 | 2023-02-14 | 宁波新福钛白粉有限公司 | Quasi-continuous method for preparing battery-grade anhydrous iron phosphate by using ferrous sulfate |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108117055B (en) | 2021-07-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108117055A (en) | The preparation method and process units of a kind of battery-grade iron phosphate | |
| CN107720716A (en) | The technique for preparing battery-level lithium carbonate and ferric phosphate from crude product lithium phosphate recovery lithium phosphorus | |
| CN107640792A (en) | A kind of high compact small particle nickel cobalt manganese hydroxide and preparation method thereof | |
| CN103100722B (en) | Preparation method of high tap density monodisperse silver powder | |
| WO2022267420A1 (en) | Iron phosphate precursor, preparation method therefor and use thereof | |
| CN104418388B (en) | The technique of a kind of ultra-fine powder of cobalt carbonate of continuous production and device thereof | |
| CN101473467A (en) | Method and apparatus for continuously mixing battery pastes | |
| CN101837966B (en) | Method for preparing nanometer ferric phosphate | |
| CN101229928A (en) | Method for preparing spherical nickel-cobalt lithium manganate material | |
| WO2016197425A1 (en) | Device system and preparation process for preparing submicron material by continuous hydrothermal method | |
| CN104478699B (en) | Preparation method of high-purity superfine cobalt oxalate powder | |
| CN114132907A (en) | Method for recovering lithium from lithium precipitation mother liquor of high-purity lithium carbonate | |
| CN111115606A (en) | Preparation method for preparing superfine spherical iron phosphate by combining liquid-phase precipitation with spray drying | |
| CN115490273A (en) | Method for continuously preparing large-ratio table ternary precursor and precursor prepared by method | |
| CN101525752B (en) | Clean production method for high-purity cobaltosic oxide powder | |
| CN114516625A (en) | Iron phosphate and preparation method and application thereof | |
| CN114572957A (en) | Preparation method of sodium vanadium phosphate material | |
| US11701600B2 (en) | Method for crystallization of β-ammonium tetramolybdate | |
| CN110980679A (en) | Preparation method of spheroidal low-sulfur iron phosphate | |
| CN115701828A (en) | Quasi-continuous method for preparing battery-grade anhydrous iron phosphate by using ferrous sulfate | |
| CN113788501B (en) | Method for preparing cobalt oxyhydroxide | |
| CN111233036B (en) | Is composed of Sb 2 O 3 Direct preparation of Sb with aqueous hydrochloric acid 4 O 5 Cl 2 Method (2) | |
| CN102627264B (en) | Square monodisperse ferric phosphate and its preparation method | |
| CN104478700A (en) | Large-particle size cobalt oxalate and preparation method thereof | |
| CN115872457B (en) | Preparation method of cobalt carbonate and cobalt carbonate |
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 | ||
| CB02 | Change of applicant information |
Address after: 061600 east side of national highway 104, Dazhang village, Lianzhen Town, Dongguang County, Cangzhou City, Hebei Province Applicant after: HEBEI CAIKE CHEMICAL Co.,Ltd. Address before: 061600 east side of national highway 104, Dazhang village, Lianzhen Town, Dongguang County, Cangzhou City, Hebei Province Applicant before: TSAKER CHEMICAL (DONGGUANG) Co.,Ltd. |
|
| CB02 | Change of applicant information | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221212 Address after: 257000 Hekou Blue Economic Development Zone, Dongying City, Shandong Province (east of caoqiaogou and south of Mingyuan Road) Patentee after: Shandong caike New Material Co.,Ltd. Patentee after: Cangzhou Caike New Energy Co.,Ltd. Address before: 061600 east side of national highway 104, Dazhang village, Lianzhen Town, Dongguang County, Cangzhou City, Hebei Province Patentee before: HEBEI CAIKE CHEMICAL Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 257000 Hekou Blue Economic Development Zone, Dongying City, Shandong Province (east of caoqiaogou and south of Mingyuan Road) Patentee after: Shandong caike New Material Co.,Ltd. Patentee after: Cangzhou Caike Lithium Energy Co.,Ltd. Address before: 257000 Hekou Blue Economic Development Zone, Dongying City, Shandong Province (east of caoqiaogou and south of Mingyuan Road) Patentee before: Shandong caike New Material Co.,Ltd. Patentee before: Cangzhou Caike New Energy Co.,Ltd. |
|
| CP01 | Change in the name or title of a patent holder |