CN107720715B - A method of battery ferric phosphate is prepared using phosphatization slag for raw material - Google Patents
A method of battery ferric phosphate is prepared using phosphatization slag for raw material Download PDFInfo
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- CN107720715B CN107720715B CN201710900825.2A CN201710900825A CN107720715B CN 107720715 B CN107720715 B CN 107720715B CN 201710900825 A CN201710900825 A CN 201710900825A CN 107720715 B CN107720715 B CN 107720715B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- 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
-
- 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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- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of methods for preparing battery ferric phosphate using phosphatization slag for raw material.The present invention first carries out pickling to phosphatization slag with dust technology, to remove partial impurities metal；It is leached again with strong base solution, makes most of Fe3+、Fe2+And Zn2+Form hydroxide precipitating removal；Acquired solution makes Zn with activated carbon adsorption, decoloration and solvent extraction2+、Mn2+、Ni2+And Cu2+Etc. foreign metal ions further remove, raffinate is with phosphorus acid for adjusting pH；Add ferric nitrate to carry out precipitation reaction into acquired solution again, after suspension reaches certain pH value, is filtered separation, solid is washed, dries to get the phosphoric acid iron product for meeting " battery ferric phosphate (HG/T 4701-2014) " standard requirements to quality.Present invention process is simple, equipment investment is few, product quality is high, production cost is low, reclamation of phosphorus resource is high-efficient in phosphatization slag, has good prospects for commercial application.
Description
Invention field
The present invention relates to one kind to prepare electricity by raw material of phosphatization slag solid waste caused by ferrous metal product process
The method of pond ferric phosphate belongs to solid waste resource recovery utilization technology.
Background technique
In ferrous metal article manufacturing process, the phosphorating treatment of steel surface can generate phosphatization slag solid waste.Phosphatization
In slag in addition to containing a certain amount of moisture, main component is ferric phosphate and trbasic zinc phosphate.Analysis shows each component in phosphatization slag
Mass content is about are as follows: moisture accounts for 15 ~ 20%, TFe (Fe3+And Fe2+) account for 15 ~ 25%, Zn2+Account for 2 ~ 5%, PO4 3-Account for 50 ~ 55%.In addition,
Also contain a small amount of Ca in phosphatization slag2+、Mg2+、Mn2+、Ni2+、Cu2+Equal impurity elements, gross mass content is about 0.5 ~ 2.0%.
Currently, the yield of China's phosphatization slag accounts for about the 0.5 ~ 1.0% of steel product phosphorating treatment amount, every year thus caused by phosphatization
Slag solid waste is up to 500,000 tons or more.In recent years, with the continuous expansion of Iron and Steel Enterprises in China Steel further processing ability, made of metal
Processing/handling problems of phosphatization slag caused by product process have seriously affected the matter of the normal production and phosphorization product of enterprise
Amount.Simultaneously as phosphatization slag solid waste has been put into " National Hazard waste register ", if untreated random discharge, also will cause
Problem of environmental pollution and the valuableization production resource for wasting recoverable.
Currently, the treatment and recycling method of phosphatization slag mainly has: turning using phosphatization slag reproduction phosphating solution or containing rust
Change liquid；Utilize the products such as phosphatization slag preparing phosphoric acid sodium, trbasic zinc phosphate and iron oxide；Utilize phosphatization slag preparing phosphoric acid pigment salt and hydroxyl
Ferric phosphate etc..But the above method exists, and high production cost, the added value of product of recycling is lower, recovery process is cumbersome, is also easy to produce
Secondary pollution problems.And phosphate radical is recycled from phosphatization slag, and produce anode material for lithium ion battery ferric phosphate using it,
It is the phosphatization slag resource utilization new way with good economic benefit with biggish recycling potentiality and advantage.
Chinese invention CN105810943A discloses a kind of method of LiFePO4 that zinc doping is prepared using phosphatization slag, should
Method removes the micro zinc impurity in phosphatization slag by using acid wash, so that the higher ferric phosphate of purity is made, then
Lithium source, carbon source are mixed with ferric phosphate again, through ball milling, dries and is roasted in protective atmosphere, zinc doping is finally made
LiFePO4, to realize the resource utilization of main component ferric phosphate in phosphatization slag.However, according to the literature, phosphorus
Fe in slugging3+、Zn2+It removes and PO4 3-It is respectively formed the FePO of slightly solubility4And Zn3(PO4) 2Outside solid, Fe therein2+It can also be with
Zn2+、PO4 3-Between form that bond valence structure is more stable, the stronger more metal phosphate complex Zn of acid resistance2Fe(PO4)2, lead
Cause the method during pickling impurity removal of phosphatization slag, the Zn in complex2+It is difficult to be completely dissolved and remove separation, so that
Zn in prepared LiFePO4 product2+Impurity content is still higher, and product is difficult to meet " battery ferric phosphate (HG/T 4701-
2014) " standard is to wherein Zn2+Quality requirement (the Zn of content2+≤ 50 ppm), and then influence product of the product as battery material
Matter and performance.
Chinese invention CN106315535A, which is disclosed, a kind of prepares battery material presoma using iron content, zinc phosphatization slag solid waste
The method of ferric phosphate.The method first uses phosphoric acid,diluted to the Zn in phosphatization slag2+Impurity carries out partial removal, and dilute hydrochloric acid is recycled to make phosphorus
Slugging dissolution then makes Zn by adding ammonium hydroxide in the solution2+Complexing recycles phosphoric acid ester or amine extractant to make in solution
Fe3+、Zn2+It is separated, after being adjusted the pH value of raffinate phase, obtains ferric phosphate of the zinc impurity content lower than 100ppm and produce
Product.But on the one hand the method needs to consume a large amount of hydrochloric acid, will cause the evil of production environment in the acid dissolution of phosphatization slag
The environmental issue changed and acid waste water is brought to handle；On the other hand, due to the Zn in phosphatization slag2+Impurity content is higher, in salt
Will form higher concentration after acid dissolution contains Zn2+Solution, so that subsequent Zn2+The dosage of extractant increases when extraction and separation
Greatly, or because extraction is not thorough make Zn in final products2+Impurity content is difficult to meet " battery ferric phosphate (HG/T 4701-
2014) " the requirement of standard.Meanwhile above-mentioned both sides factor can also be such that the production cost of phosphoric acid iron product dramatically increases.
Summary of the invention
The present invention utilizes FePO4、Zn3(PO4) 2And its more metal-phosphate complex Zn2Fe(PO4)2Insoluble in nitric acid
It can be dissolved in the characteristic of strong base solution system, pickling is first carried out to phosphatization slag using dust technology, makes Ca therein2+、Mg2+、Mn2+、
Ni2+And Cu2+It is removed Deng a small amount of impurity element in part, then it is leached using aqueous alkali, make Fe therein3+、Fe2+
And Zn2+Obtained filtrate after filtering, is carried out adsorption-edulcoration using active carbon and taken off by the hydroxide precipitating of formation slightly solubility
Color, then through further solvent extraction and separation, make the Zn in filtrate2+、Mn2+、Ni2+And Cu2+Equal impurity are removed in depth, most
Source of iron solution is added by a certain percentage in resulting scavenging solution afterwards, it is solid to obtain ferric phosphate using the precipitation reaction between them
Body, solids are washed, obtained by drying to the battery phosphoric acid iron product for meeting HG/T 4701-2014 standard requirements.
It is that raw material prepares battery phosphorus that the present invention provides a kind of using phosphatization slag caused by ferrous metal product process
The method of sour iron, including pickling, alkali leaching, decoloration, extraction, precipitation reaction, specifically comprise the following steps:
1. pickling: dilute HNO being added into phosphatization slag3, pickling is carried out under agitation, and then suspension was carried out
Filter, washing, collect filter residue；
2. alkali soaks: strong base solution is added into step 1. gained filter residue, carries out leaching reaction under agitation, then to outstanding
Supernatant liquid is filtered, and collects filtrate；
3. decoloration: active carbon is added into step 2. gained filtrate, is adsorbed under agitation, then to suspension
It is filtered, collects filtrate；
4. extraction: extractant and organic solvent is added into step 3. gained filtrate, is extracted under agitation,
Then separating and extracting liquid and raffinate, gained extract liquor resulting extractant after diluted acid is stripped are recycled and reused for extraction process, institute
It obtains and is used to prepare ferric phosphate after adjusting its pH value by dropwise addition phosphoric acid in raffinate；
5. precipitation reaction: under agitation, surfactant is added into step 4. gained raffinate, then drip to it
Add iron nitrate solution that precipitation reaction occurs to be filtered suspension when the pH value of suspension reaches 1.5 ~ 3.5, gained is solid
Body is washed, is dried to get phosphoric acid iron product is arrived.
Further, step 1. in, dilute HNO3Mass concentration be 0.5 ~ 5.0%, preferably 1.0 ~ 3.0%；Dilute HNO3Dosage
For 5 ~ 15 times of phosphatization slag amount, preferably 7 ~ 10 times.
Further, step 1. in, pickling temperature be 40 ~ 70 DEG C, preferably 55 ~ 65 DEG C；Pickling time is 15min or more,
It is preferred that 15 ~ 40min, more preferable 20 ~ 30min；Speed of agitator is 60 ~ 120rpm, preferably 60 ~ 100rpm.
Further, step 2. in, the strong base solution is NaOH solution or/and KOH solution, preferably NaOH solution；
The mass concentration of strong base solution is 10 ~ 30%, preferably 18 ~ 25%；The dosage of strong base solution meet alkali/iron molar ratio be (2.7 ~
4.5): 1.0, preferably (3.0 ~ 3.5): 1.0.
Further, step 2. in, leach reaction temperature be 40 ~ 70 DEG C, preferably 55 ~ 65 DEG C；Leach the time of reaction
For 60 ~ 180min, preferably 90 ~ 150min；Speed of agitator is 60 ~ 120rpm, preferably 60 ~ 100rpm.
Further, step 3. in, the dosage of active carbon is 0.5 ~ 5%, preferably the 1 ~ 3% of filtrate quality.
Further, step 3. in, adsorption time be 15 ~ 40min, preferably 20 ~ 30min；The preferred room temperature of adsorption temp；It stirs
Mixing revolving speed is 40 ~ 120rpm, preferably 60 ~ 90rpm.
Further, step 4. in, the extractant is one or more of P204, P507 or N235, excellent
Select N235；The organic solvent is one or more of benzene, toluene or kerosene, preferably kerosene.
Further, step 4. in, the dosage of extractant is 30 ~ 60%, preferably the 40 ~ 50% of filtrate volume；Organic solvent
Dosage be 2 ~ 5 times, preferably 3 ~ 4 times of extractant volume.
Further, step 4. in, be added dropwise phosphoric acid adjust suspension pH value range be 5.0 ~ 8.0, preferably 6.5 ~
7.0。
Further, step 4. in, extraction time be 20 ~ 60min, preferably 30 ~ 40min；Speed of agitator be 60 ~
150rpm, preferably 90 ~ 120rpm.
Further, step 5. in, the surfactant be hexadecyltrimethylammonium chloride or/and cetyl
Trimethylammonium bromide, preferably hexadecyltrimethylammonium chloride；The dosage of surfactant be raffinate quality 0.05 ~
0.2%, preferably 0.1 ~ 0.15%.
Further, step 5. in, the mass concentration of iron nitrate solution is 10-30%, preferably 15 ~ 25%；The use of ferric nitrate
Amount is PO in raffinate4 3-0.60 ~ 0.90 times of molal quantity, preferably 0.75 ~ 0.85 times.
Further, step 5. in, the pH value of suspension preferably 2.0 ~ 2.5.
Further, step 5. in, the temperature of precipitation reaction is 40 ~ 80 DEG C, preferably 50 ~ 65 DEG C；The time of precipitation reaction
For 60 ~ 180min, preferably 90 ~ 120min；Speed of agitator is 60 ~ 150rpm, preferably 90 ~ 120rpm.
Further, step 5. in, drying temperature be 80 ~ 130 DEG C, preferably 100 ~ 120 DEG C；Drying time be 120 ~
300min, preferably 180 ~ 240min.
Using phosphoric acid iron product obtained by the above method, quality can reach " battery ferric phosphate (HG/T 4701-
2014) " standard requirements.The overall recovery of phosphate radical can be up to 80% or more in phosphatization slag.
The beneficial effects of the present invention are:
The present invention using phosphatization slag solid waste caused by ferrous metal product process as raw material, using pickling, alkali leaching,
Decoloration, extraction, precipitation reaction and etc. the method for preparing battery material phosphoric acid iron product, have simple process, equipment investment it is few,
The advantages that product quality is high, production cost is low, reclamation of phosphorus resource is high-efficient in waste residue is a kind of with good prospects for commercial application
Phosphatization slag resource utilization new technology.
Specific embodiment
The present invention is described in detail by following embodiment.
Embodiment 1
Take 10.0 g containing PO4 3-It is placed in a beaker for 51.8% phosphatization slag, it is 2.0% that 100mL mass concentration is added thereto
Dilute HNO3Solution, heating stirring 40min at a temperature of 80rpm speed of agitator and 50 DEG C, suspension is through centrifugal filtration, in gained
The NaOH solution that 65 mL mass concentrations are 10%, heating stirring 2h at a temperature of 80rpm speed of agitator and 60 DEG C are added in filter residue
Afterwards, suspension is added 0.5g active carbon in gained filtrate and is cleaned and decolourized, prepare N235 volume fraction through centrifugal filtration
Organic liquor 240mL is mixed for 20% N235- kerosene, takes the 80mL mixing organic liquor to be added to through active carbon and cleans and decoloration, mistake
It filters in obtained clear filtrate, 25min is stirred under 120rpm revolving speed, settle and separate obtains extract liquor and raffinate, repeats
The extraction process is twice.Finally the dilute sulfuric acid that resulting extract liquor mass concentration is 15% is stripped, the extractant of recycling repeats
For extraction process.The phosphoric acid solution that mass concentration is 15% is added dropwise in raffinate, adjusts the pH to 6.5 of solution.It weighs
1631) and the Fe(NO3)39H2O of 9.5g [Fe (NO hexadecyltrimethylammonium chloride (the i.e. CTAC, or of 0.10g3) 3·
9H2O] it is configured to the mixed solution of 200 mL, which is added drop-wise to above-mentioned raffinate at 90rpm speed of agitator and 60 DEG C
In liquid, until the pH of suspension system stops being added dropwise when reaching 2.0, continues to stir 120min, suspension be filtered, filter residue is through water
It washes, dry 4h at 120 DEG C to get phosphate dihydrate iron product is arrived.It through analysis measurement and calculates, product quality reaches " battery phosphorus
Sour iron (HG/T 4701-2014) " standard requirements, the overall recovery of phosphate radical is 77.3% in phosphatization slag.
Embodiment 2
Take 20.0 g containing PO4 3-It is placed in a beaker for 51.8% phosphatization slag, it is 2.0% that 150mL mass concentration is added thereto
Dilute HNO3Solution, heating stirring 30min at a temperature of 80rpm speed of agitator and 60 DEG C, suspension is through centrifugal filtration, in gained
The NaOH solution that 65 mL mass concentrations are 20%, heating stirring 2h at a temperature of 90rpm speed of agitator and 60 DEG C are added in filter residue
Afterwards, suspension is added 1.5g active carbon in gained filtrate and is cleaned and decolourized, prepare P204 volume fraction through centrifugal filtration
For 20% P204- toluene mix organic liquor 300mL, take the 150mL mixing organic liquor be added to through active carbon clean with decolourize,
It filters in obtained clear filtrate, 30min is stirred under 120rpm revolving speed, settle and separate obtains extract liquor and raffinate, weight
The multiple extraction process is primary.Finally the dilute sulfuric acid that resulting extract liquor mass concentration is 15% is stripped, the extractant weight of recycling
It is multiplexed in extraction process.The phosphoric acid solution that mass concentration is 15% is added dropwise in raffinate, adjusts the pH to 6.0 of solution.It weighs
1631) and the Fe(NO3)39H2O of 18.0g [Fe (NO hexadecyltrimethylammonium chloride (the i.e. CTAC, or of 0.25g3) 3·
9H2O] it is configured to the mixed solution of 250 mL, which is added drop-wise to above-mentioned raffinate at 90rpm speed of agitator and 60 DEG C
In liquid, until the pH of suspension system stops being added dropwise when reaching 2.5, continues to stir 120min, suspension be filtered, filter residue is through water
It washes, dry 3h at 120 DEG C to get phosphate dihydrate iron product is arrived.It through analysis measurement and calculates, product quality reaches " battery phosphorus
Sour iron (HG/T 4701-2014) " standard requirements, the overall recovery of phosphate radical is 76.4% in phosphatization slag.
Embodiment 3
Take 10.0 g containing PO4 3-It is placed in a beaker for 51.8% phosphatization slag, it is 1.0% that 100mL mass concentration is added thereto
Dilute HNO3Solution, heating stirring 20min at a temperature of 90rpm speed of agitator and 70 DEG C, suspension is through centrifugal filtration, in gained
The KOH solution that 60 mL mass concentrations are 15%, heating stirring 2h at a temperature of 120rpm speed of agitator and 60 DEG C are added in filter residue
Afterwards, suspension is added 0.5g active carbon in gained filtrate and is cleaned and decolourized, prepare N235 volume fraction through centrifugal filtration
For 15% N235- kerosene mix organic liquor 300mL, take the 100mL mixing organic liquor be added to through active carbon clean with decolourize,
It filters in obtained clear filtrate, 30min is stirred under 120rpm revolving speed, settle and separate obtains extract liquor and raffinate, weight
The multiple extraction process is twice.Finally the dilute sulfuric acid that resulting extract liquor mass concentration is 15% is stripped, the extractant weight of recycling
It is multiplexed in extraction process.The phosphoric acid solution that mass concentration is 15% is added dropwise in raffinate, adjusts the pH to 7.0 of solution.It weighs
The cetyl trimethylammonium bromide (i.e. CTAB) of 0.15g and the Fe(NO3)39H2O [Fe (NO of 10.0g3) 3·9H2O] it prepares
At the mixed solution of 200 mL, which is added drop-wise in above-mentioned raffinate at 90rpm speed of agitator and 60 DEG C, until outstanding
The pH of supernatant liquid system stops being added dropwise when reaching 2.3, continues to stir 120min, suspension is filtered, filter residue is through at washing, 120 DEG C
4h is dried to get phosphate dihydrate iron product is arrived.It through analysis measurement and calculates, product quality reaches " battery ferric phosphate (HG/T
4701-2014) " standard requirements, the overall recovery of phosphate radical is 81.4% in phosphatization slag.
Embodiment 4
Take 20.0 g containing PO4 3-It is placed in a beaker for 51.8% phosphatization slag, it is 1.5% that 200mL mass concentration is added thereto
Dilute HNO3Solution, heating stirring 45min at a temperature of 80rpm speed of agitator and 60 DEG C, suspension is through centrifugal filtration, in gained
The NaOH solution that 100 mL mass concentrations are 15%, heating stirring at a temperature of 80rpm speed of agitator and 60 DEG C are added in filter residue
After 2h, suspension is added 1.0g active carbon in gained filtrate and is cleaned and decolourized, prepare P507 volume point through centrifugal filtration
It counts and mixes organic liquor 300mL for 20% P507- toluene, take the 100mL mixing organic liquor to be added to through active carbon and clean and take off
In color, the obtained clear filtrate of filtering, 30min is stirred under 120rpm revolving speed, settle and separate obtains extract liquor and raffinate
Liquid repeats the extraction process twice.Finally the dilute sulfuric acid that resulting extract liquor mass concentration is 15% is stripped, the extraction of recycling
Agent is taken to be recycled and reused for extraction process.The phosphoric acid solution that mass concentration is 15% is added dropwise in raffinate, adjusts the pH to 6.5 of solution.
1631) and the Fe(NO3)39H2O [Fe of 18.0g hexadecyltrimethylammonium chloride (the i.e. CTAC, or of 0.25g is weighed
(NO3) 3·9H2O] it is configured to the mixed solution of 200 mL, which is added drop-wise at 90rpm speed of agitator and 60 DEG C
In above-mentioned raffinate, until the pH of suspension system stops being added dropwise when reaching 2.0, continues to stir 120min, suspension is filtered, filter
Slag arrives phosphate dihydrate iron product through 4h dry at washing, 120 DEG C.It through analysis measurement and calculates, product quality reaches " electricity
Pond is with ferric phosphate (HG/T 4701-2014) " standard requirements, the overall recovery of phosphate radical is 75.1% in phosphatization slag.
Embodiment 5
Take 10.0 g containing PO4 3-It is placed in a beaker for 51.8% phosphatization slag, it is 1.0% that 100mL mass concentration is added thereto
Dilute HNO3Solution, heating stirring 30min at a temperature of 80rpm speed of agitator and 70 DEG C, suspension is through centrifugal filtration, in gained
The NaOH solution that 65 mL mass concentrations are 10%, heating stirring 2h at a temperature of 80rpm speed of agitator and 70 DEG C are added in filter residue
Afterwards, suspension is added 0.5g active carbon in gained filtrate and is cleaned and decolourized, prepare P507 volume fraction through centrifugal filtration
Organic liquor 300mL is mixed for 15% P507- benzene, takes the 100mL mixing organic liquor to be added to through active carbon and cleans and decoloration, mistake
It filters in obtained clear filtrate, 30min is stirred under 120rpm revolving speed, settle and separate obtains extract liquor and raffinate, repeats
The extraction process is twice.Finally the dilute sulfuric acid that resulting extract liquor mass concentration is 15% is stripped, the extractant of recycling repeats
For extraction process.The phosphoric acid solution that mass concentration is 15% is added dropwise in raffinate, adjusts the pH to 7.0 of solution.It weighs
1631) and the Fe(NO3)39H2O of 10.0g [Fe (NO hexadecyltrimethylammonium chloride (the i.e. CTAC, or of 0.15g3) 3·
9H2O] it is configured to the mixed solution of 100 mL, which is added drop-wise to above-mentioned raffinate at 90rpm speed of agitator and 60 DEG C
In liquid, until the pH of suspension system stops being added dropwise when reaching 2.0, continues to stir 120min, suspension be filtered, filter residue is through water
It washes, dry 4h at 120 DEG C to get phosphate dihydrate iron product is arrived.It through analysis measurement and calculates, product quality reaches " battery phosphorus
Sour iron (HG/T 4701-2014) " standard requirements, the overall recovery of phosphate radical is 79.8% in phosphatization slag.
Embodiment 6
Take 10.0 g containing PO4 3-It is placed in a beaker for 51.8% phosphatization slag, it is 1.5% that 100mL mass concentration is added thereto
Dilute HNO3Solution, heating stirring 40min at a temperature of 80rpm speed of agitator and 50 DEG C, suspension is through centrifugal filtration, in gained
The KOH solution that 60 mL mass concentrations are 15%, heating stirring 2h at a temperature of 80rpm speed of agitator and 50 DEG C are added in filter residue
Afterwards, suspension is added 0.5g active carbon in gained filtrate and is cleaned and decolourized, prepare N235 volume fraction through centrifugal filtration
Organic liquor 240mL is mixed for 20% N235- kerosene, takes the 80mL mixing organic liquor to be added to through active carbon and cleans and decoloration, mistake
It filters in obtained clear filtrate, 30min is stirred under 120rpm revolving speed, settle and separate obtains extract liquor and raffinate, repeats
The extraction process is twice.Finally the dilute sulfuric acid that resulting extract liquor mass concentration is 15% is stripped, the extractant of recycling repeats
For extraction process.The phosphoric acid solution that mass concentration is 15% is added dropwise in raffinate, adjusts the pH to 6.5 of solution.It weighs
1631) and the Fe(NO3)39H2O of 10.0g [Fe (NO hexadecyltrimethylammonium chloride (the i.e. CTAC, or of 0.10g3) 3·
9H2O] it is configured to the mixed solution of 100 mL, which is added drop-wise to above-mentioned raffinate at 90rpm speed of agitator and 60 DEG C
In liquid, until the pH of suspension system stops being added dropwise when reaching 2.5, continues to stir 120min, suspension be filtered, filter residue is through water
It washes, dry 4h at 120 DEG C to get phosphate dihydrate iron product is arrived.It through analysis measurement and calculates, product quality reaches " battery phosphorus
Sour iron (HG/T 4701-2014) " standard requirements, the overall recovery of phosphate radical is 80.6% in phosphatization slag.
Claims (10)
1. a kind of method for preparing battery ferric phosphate using phosphatization slag for raw material, which is characterized in that including pickling, alkali leaching, take off
Color, extraction, precipitation reaction, specifically comprise the following steps:
1. pickling: dilute HNO being added into phosphatization slag3, pickling is carried out under agitation, then suspension is filtered, water
It washes, collects filter residue；
2. alkali soaks: strong base solution is added into step 1. gained filter residue, carries out leaching reaction under agitation, then to suspension
Liquid is filtered, and collects filtrate；
3. decoloration: to step 2. gained filtrate in active carbon is added, adsorbed under agitation, then to suspension into
Row filtering, collects filtrate；
4. extraction: extractant and organic solvent is added into step 3. gained filtrate, is extracted under agitation, then
Separating and extracting liquid and raffinate, gained extract liquor resulting extractant after diluted acid is stripped are recycled and reused for extraction process, gained extraction
Ferric phosphate is used to prepare after adjusting its pH value by dropwise addition phosphoric acid in extraction raffinate；
5. precipitation reaction: under agitation, surfactant is added into step 4. gained raffinate, then nitre is added dropwise to it
Sour ferrous solution occurs precipitation reaction and is filtered when the pH value of suspension reaches 1.5 ~ 3.5 to suspension, obtained solid warp
Washing is dried to get phosphoric acid iron product is arrived.
2. the method according to claim 1 for preparing battery ferric phosphate using phosphatization slag for raw material, which is characterized in that step
Suddenly 1. in, dilute HNO3Mass concentration be 0.5 ~ 5.0%；Dilute HNO3Dosage be 5 ~ 15 times of phosphatization slag amount；Pickling temperature is
40~70℃。
3. the method according to claim 1 for preparing battery ferric phosphate using phosphatization slag for raw material, which is characterized in that step
Suddenly 2. in, the strong base solution be NaOH solution or/and KOH solution；The mass concentration of strong base solution is 10 ~ 30%；Highly basic is molten
It is (2.7 ~ 4.5)/1.0 that the dosage of liquid, which meets alkali/iron molar ratio,；The temperature of leaching reaction is 40 ~ 70 DEG C；Leach the time of reaction
For 60 ~ 180min.
4. the method according to claim 1 for preparing battery ferric phosphate using phosphatization slag for raw material, which is characterized in that step
Suddenly 3. in, the dosage of active carbon is the 0.5 ~ 5% of filtrate quality；Adsorption time is 15 ~ 40min；Adsorption temp is room temperature.
5. the method according to claim 1 for preparing battery ferric phosphate using phosphatization slag for raw material, which is characterized in that step
Suddenly 4. in, the extractant is one or more of P204, P507 or N235；The organic solvent is benzene, first
One or more of benzene or kerosene.
6. the method according to claim 1 for preparing battery ferric phosphate using phosphatization slag for raw material, which is characterized in that step
Suddenly 4. in, the dosage of extractant is the 30 ~ 60% of filtrate volume；The dosage of organic solvent is 2 ~ 5 times of extractant volume.
7. the method according to claim 1 for preparing battery ferric phosphate using phosphatization slag for raw material, which is characterized in that step
Suddenly 4. in, be added dropwise phosphoric acid adjust suspension pH value range be 5.0 ~ 8.0.
8. the method according to claim 1 for preparing battery ferric phosphate using phosphatization slag for raw material, which is characterized in that step
Suddenly 5. in, the surfactant be hexadecyltrimethylammonium chloride or/and cetyl trimethylammonium bromide；Surface is living
Property agent dosage be raffinate quality 0.05 ~ 0.2%；The mass concentration of iron nitrate solution is 10-30%；The dosage of ferric nitrate is
PO in raffinate4 3-0.60 ~ 0.90 times of molal quantity.
9. the method according to claim 1 for preparing battery ferric phosphate using phosphatization slag for raw material, which is characterized in that step
Suddenly 5. in, the temperature of precipitation reaction is 40 ~ 80 DEG C；The time of precipitation reaction is 60 ~ 180min.
10. the method according to claim 1 for preparing battery ferric phosphate using phosphatization slag for raw material, which is characterized in that
Step 5. in, the pH value of suspension is 2.0 ~ 2.5.
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| CN109694049B (en) * | 2019-01-23 | 2021-10-29 | 瓮福（集团）有限责任公司 | Treatment method of phosphated slag containing zinc, calcium and iron |
| CN109626351B (en) * | 2019-01-31 | 2022-08-19 | 王东升 | Preparation method of carbon-doped lithium iron phosphate |
| CN109795997A (en) * | 2019-04-04 | 2019-05-24 | 湘潭大学 | A kind of improved method preparing high-purity phosphoric acid iron using the slag of phosphatization containing zinc |
| CN110422831A (en) * | 2019-08-02 | 2019-11-08 | 湖北昊瑞新能源有限公司 | A method of recycling ferric phosphate from ferric phosphate lithium cell |
| CN112678794A (en) * | 2021-01-29 | 2021-04-20 | 刘娱雪 | Method for preparing multi-element doped lithium iron phosphate from phosphorized slag |
| CN114249313A (en) * | 2021-12-14 | 2022-03-29 | 福州大学 | Method for recovering battery-grade iron phosphate from waste lithium iron phosphate powder |
| CN115744851A (en) * | 2022-10-19 | 2023-03-07 | 锂源(深圳)科学研究有限公司 | Method for recycling and preparing battery-grade iron phosphate |
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