CN107720715A - A kind of method for preparing battery ferric phosphate using phosphatization slag for raw material - Google Patents
A kind of method for preparing battery ferric phosphate using phosphatization slag for raw material Download PDFInfo
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- CN107720715A CN107720715A CN201710900825.2A CN201710900825A CN107720715A CN 107720715 A CN107720715 A CN 107720715A CN 201710900825 A CN201710900825 A CN 201710900825A CN 107720715 A CN107720715 A CN 107720715A
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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
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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
- C01B25/37—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- 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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Abstract
The present invention relates to a kind of method for preparing battery ferric phosphate using phosphatization slag for raw material.It is of the invention that pickling is first carried out to phosphatization slag with dust technology, to remove partial impurities metal；Leached again with strong base solution, make most of Fe3+、Fe2+And Zn2+Hydroxide precipitation is formed to remove；Resulting solution makes Zn with charcoal absorption, decolouring and solvent extraction2+、Mn2+、Ni2+And Cu2+Further removed etc. foreign metal ion, raffinate is with phosphorus acid for adjusting pH；Add ferric nitrate to carry out precipitation reaction into resulting solution again, after suspension reaches certain pH value, be separated by filtration, solid is scrubbed, drying, that is, obtains quality and meet《Battery ferric phosphate（HG/T 4701‑2014）》The phosphoric acid iron product of standard requirement.Present invention process is simple, equipment investment is few, product quality is high, production cost is low, reclamation of phosphorus resource efficiency high in phosphatization slag, has good prospects for commercial application.
Description
Invention field
The present invention relates to one kind electricity is prepared by raw material of phosphatization slag solid waste caused by ferrous metal product process
The method of pond ferric phosphate, belong to solid waste resource recovery utilization technology.
Background technology
In ferrous metal article manufacturing process, the phosphorating treatment of steel surface can produce phosphatization slag solid waste.Phosphatization
In slag in addition to containing a certain amount of moisture, its main component is ferric phosphate and trbasic zinc phosphate.Analysis shows, each component in phosphatization slag
Mass content is about：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+Deng impurity element, its gross mass content is about 0.5 ~ 2.0%.
At present, the yield of China's phosphatization slag accounts for the 0.5 ~ 1.0% of steel product phosphorating treatment amount, every year thus caused phosphatization
Slag solid waste is up to more than 500,000 tons.In recent years, with the continuous expansion of Iron and Steel Enterprises in China Steel further processing ability, its metal system
Processing/handling problems of phosphatization slag caused by product process have had a strong impact on normal production and the matter of phosphorization product of enterprise
Amount.Simultaneously as phosphatization slag solid waste has been put into " National Hazard waste register ", if untreated arbitrarily discharge, can also be caused
Problem of environmental pollution and the valuableization production resource for wasting recoverable.
At present, the processing of phosphatization slag and recoverying and utilizing method mainly have：Turn 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 there is production cost height in the above method, the added value of product of recovery is relatively low, recovery process is cumbersome, is also easy to produce
Secondary pollution problems.And phosphate radical is reclaimed from phosphatization slag, and anode material for lithium ion battery ferric phosphate is produced using it,
It is a phosphatization slag recycling new way with good economic benefit with larger recycling potentiality and advantage.
Chinese invention CN105810943A discloses a kind of method for the LiFePO4 that zinc doping is prepared using phosphatization slag, should
Method removes by using acid wash to the micro zinc impurity in phosphatization slag, so as to which the higher ferric phosphate of purity be made, then
Lithium source, carbon source are mixed with ferric phosphate again, is calcined through ball milling, drying and in protective atmosphere, zinc doping is finally made
LiFePO4, it is achieved thereby that in phosphatization slag main component ferric phosphate recycling.However, according to the literature, phosphorus
Fe in slugging3+、Zn2+Remove and PO4 3-The FePO of slightly solubility is formed respectively4And Zn3(PO4) 2Outside solid, Fe therein2+Can also be with
Zn2+、PO4 3-Between form more metal phosphate complex Zn that bond valence structure is more stable, acid resistance is stronger2Fe(PO4)2, lead
The method is caused during the pickling impurity removal of phosphatization slag, the Zn in complex2+It is difficult to be completely dissolved and removes 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 discloses one kind and prepares battery material presoma using iron content, zinc phosphatization slag solid waste
The method of ferric phosphate.The method is first using phosphoric acid,diluted to the Zn in phosphatization slag2+Impurity carries out partial removal, recycles watery hydrochloric acid to make phosphorus
Slugging is dissolved, and then makes Zn by adding ammoniacal liquor in the solution2+Complexing, phosphoric acid ester or amine extractant is recycled to make in solution
Fe3+、Zn2+Separated, after the pH value of adjusted raffinate phase, obtain ferric phosphate of the zinc impurity content less than 100ppm and produce
Product.But on the one hand the method needs to consume substantial amounts of hydrochloric acid, can cause the evil of production environment in the acid dissolution of phosphatization slag
The environmental issue for changing and bringing acid waste water to handle；On the other hand, due to the Zn in phosphatization slag2+Impurity content is higher, and it is in salt
Higher concentration can be formed after acid dissolving contains Zn2+Solution, so that follow-up Zn2+The dosage of extractant increases during extract and separate
Greatly, or because extract it 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 dramatically increase the production cost of phosphoric acid iron product.
The content of the invention
The present invention utilizes FePO4、Zn3(PO4) 2And its more metal-phosphate complex Zn2Fe(PO4)2Insoluble in nitric acid
The characteristic of strong base solution system can be dissolved in, pickling is first carried out to phosphatization slag using dust technology, makes Ca therein2+、Mg2+、Mn2+、
Ni2+And Cu2+Removed Deng a small amount of impurity element in part, then it is leached using aqueous alkali, make Fe therein3+、Fe2+
And Zn2+The hydroxide precipitation of formation slightly solubility, after filtering, resulting filtrate is subjected to adsorption-edulcoration using activated carbon and taken off
Color, then through further solvent extraction and separation, make the Zn in filtrate2+、Mn2+、Ni2+And Cu2+Deep removal is obtained Deng impurity, most
After adding source of iron solution in the scavenging solution of gained by a certain percentage, obtain ferric phosphate using the precipitation reaction between them and consolidate
Body, solids is scrubbed, drying to the battery phosphoric acid iron product for meeting the requirement of HG/T 4701-2014 standards.
The invention provides one kind battery phosphorus is prepared using phosphatization slag caused by ferrous metal product process for raw material
The method of sour iron, including the step such as pickling, alkali leaching, decolouring, extraction, precipitation reaction, specifically comprise the following steps：
1. pickling：Dilute HNO is added into phosphatization slag3, pickling is carried out under agitation, then suspension is filtered, water
Wash, 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 suspension
Filtered, collect filtrate；
3. decolourize：Activated carbon is added into step 2. gained filtrate, is adsorbed, suspension is carried out under agitation then
Filtering, collect filtrate；
4. extract：Extractant and organic solvent are added into step 3. gained filtrate, is extracted under agitation, then
Separating and extracting liquid and raffinate, gained extract extractant of gained after diluted acid is stripped are recycled and reused for extraction process, gained extraction
It is used to after its pH value prepare ferric phosphate by the way that phosphoric acid is added dropwise and adjusts in extraction raffinate；
5. precipitation reaction：Under agitation, surfactant is added into step 4. gained raffinate, then nitre is added dropwise to it
Precipitation reaction occurs for sour ferrous solution, and when the pH value of suspension reaches 1.5 ~ 3.5, suspension is filtered, gained solid warp
Washing, dry, that is, obtain ferric phosphate product.
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 more than 15min,
It is preferred that 15 ~ 40min, more preferably 20 ~ 30min；Speed of agitator is 60 ~ 120rpm, preferably 60 ~ 100rpm.
Further, step 2. in, described 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 mol ratio for (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 activated carbon is 0.5 ~ 5%, preferably the 1 ~ 3% of filtrate quality.
Further, step 3. in, adsorption time is 15 ~ 40min, preferably 20 ~ 30min；The preferred normal temperature of adsorption temp；Stir
Mix rotating speed is 40 ~ 120rpm, preferably 60 ~ 90rpm.
Further, step 4. in, described extractant is more than one or both of P204, P507 or N235, excellent
Select N235；Described organic solvent is more than one or both 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 regulation suspension pH value scope for 5.0 ~ 8.0, preferably 6.5 ~
7.0。
Further, step 4. in, extraction time is 20 ~ 60min, preferably 30 ~ 40min；Speed of agitator be 60 ~
150rpm, preferably 90 ~ 120rpm.
Further, step 5. in, described surfactant is hexadecyltrimethylammonium chloride or/and cetyl
Trimethylammonium bromide, preferably hexadecyltrimethylammonium chloride；The dosage of surfactant for 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
Measure as 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 preferably 2.0 ~ 2.5 of suspension.
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 the phosphoric acid iron product obtained by the above method, its quality can reach《Battery ferric phosphate（HG/T 4701-
2014）》Standard requirement.The overall recovery of phosphate radical can be up to more than 80% in phosphatization slag.
The beneficial effects of the present invention are：
The present invention using pickling, alkali leaching, takes off using phosphatization slag solid waste caused by ferrous metal product process as raw material
The method that the steps such as color, extraction, precipitation reaction prepare battery material phosphoric acid iron product, with technique is simple, equipment investment is few, production
Quality is high, production cost is low, in waste residue the advantages that reclamation of phosphorus resource efficiency high, is a kind of to have good prospects for commercial application
Phosphatization slag recycling new technology.
Embodiment
The present invention is described in detail by following examples.
Embodiment 1
10.0 g are taken to contain PO4 3-Be placed in for 51.8% phosphatization slag in beaker, add thereto 100mL mass concentrations be 2.0% it is dilute
HNO3Solution, the heating stirring 40min at a temperature of 80rpm speeds of agitator and 50 DEG C, suspension is through centrifugal filtration, in gained filter residue
It is middle to add the NaOH solution that 65 mL mass concentrations are 10%, after heating stirring 2h at a temperature of 80rpm speeds of agitator and 60 DEG C,
Through centrifugal filtration, addition 0.5g activated carbons are cleaned and decolourized suspension in gained filtrate, are prepared N235 volume fractions and are
20% N235- kerosene mixing organic liquor 240mL, takes the 80mL mixing organic liquors to add to through activated carbon and cleans with decolourizing, filtering
In resulting clear filtrate, 25min is stirred under 120rpm rotating speeds, standing separation, obtains extract and raffinate, repeating should
Extraction process is twice.Finally the dilute sulfuric acid that the extract mass concentration of gained is 15% is stripped, the extractant of recovery repeats to use
In extraction process.The phosphoric acid solution that mass concentration is 15% is added dropwise in raffinate, adjusts the pH to 6.5 of solution.Weigh 0.10g
Hexadecyltrimethylammonium chloride（That is CTAC, or 1631）With 9.5g Fe(NO3)39H2O【Fe(NO3) 3·9H2O】Match somebody with somebody
200 mL mixed solution is made, the mixed solution is added drop-wise in above-mentioned raffinate at 90rpm speeds of agitator and 60 DEG C, extremely
The pH of suspension system stops being added dropwise when reaching 2.0, continues to stir 120min, suspension is filtered, and filter residue is through washing, 120 DEG C
Lower dry 4h, that is, obtain phosphate dihydrate iron product.Through analysis measure and calculate, product quality reaches《Battery ferric phosphate（HG/T
4701-2014）》Standard requires that the overall recovery of phosphate radical is 77.3% in phosphatization slag.
Embodiment 2
20.0 g are taken to contain PO4 3-Be placed in for 51.8% phosphatization slag in beaker, add thereto 150mL mass concentrations be 2.0% it is dilute
HNO3Solution, the heating stirring 30min at a temperature of 80rpm speeds of agitator and 60 DEG C, suspension is through centrifugal filtration, in gained filter residue
It is middle to add the NaOH solution that 65 mL mass concentrations are 20%, after heating stirring 2h at a temperature of 90rpm speeds of agitator and 60 DEG C,
Through centrifugal filtration, addition 1.5g activated carbons are cleaned and decolourized suspension in gained filtrate, are prepared P204 volume fractions and are
20% P204- toluene mixing organic liquor 300mL, takes the 150mL mixing organic liquors to add to through activated carbon and cleans and decolouring, mistake
In clear filtrate obtained by filter, 30min is stirred under 120rpm rotating speeds, standing separation, obtains extract and raffinate, repeated
The extraction process is once.Finally the dilute sulfuric acid that the extract mass concentration of gained is 15% is stripped, the extractant of recovery repeats
For extraction process.The phosphoric acid solution that mass concentration is 15% is added dropwise in raffinate, adjusts the pH to 6.0 of solution.Weigh
0.25g hexadecyltrimethylammonium chloride（That is CTAC, or 1631）With 18.0g Fe(NO3)39H2O【Fe(NO3) 3·
9H2O】250 mL mixed solution is configured to, the mixed solution is added drop-wise to above-mentioned raffinate at 90rpm speeds of agitator and 60 DEG C
In liquid, stop being added dropwise when reaching 2.5 to the pH of suspension system, continue to stir 120min, suspension is filtered, filter residue is through water
Wash, 3h is dried at 120 DEG C, that is, obtain phosphate dihydrate iron product.Through analysis measure and calculate, product quality reaches《Battery phosphorus
Sour iron（HG/T 4701-2014）》Standard requires that the overall recovery of phosphate radical is 76.4% in phosphatization slag.
Embodiment 3
10.0 g are taken to contain PO4 3-Be placed in for 51.8% phosphatization slag in beaker, add thereto 100mL mass concentrations be 1.0% it is dilute
HNO3Solution, the heating stirring 20min at a temperature of 90rpm speeds of agitator and 70 DEG C, suspension is through centrifugal filtration, in gained filter residue
It is middle to add the KOH solution that 60 mL mass concentrations are 15%, after heating stirring 2h at a temperature of 120rpm speeds of agitator and 60 DEG C,
Through centrifugal filtration, addition 0.5g activated carbons are cleaned and decolourized suspension in gained filtrate, are prepared N235 volume fractions and are
15% N235- kerosene mixing organic liquor 300mL, takes the 100mL mixing organic liquors to add to through activated carbon and cleans and decolouring, mistake
In clear filtrate obtained by filter, 30min is stirred under 120rpm rotating speeds, standing separation, obtains extract and raffinate, repeated
The extraction process is twice.Finally the dilute sulfuric acid that the extract mass concentration of gained is 15% is stripped, the extractant of recovery 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.Weigh
0.15g cetyl trimethylammonium bromide（That is CTAB）With 10.0g Fe(NO3)39H2O【Fe(NO3) 3·9H2O】Prepare
Into 200 mL mixed solution, the mixed solution is added drop-wise in above-mentioned raffinate at 90rpm speeds of agitator and 60 DEG C, it is extremely 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, that is, obtains phosphate dihydrate iron product.Through analysis measure and calculate, product quality reaches《Battery ferric phosphate（HG/T
4701-2014）》Standard requires that the overall recovery of phosphate radical is 81.4% in phosphatization slag.
Embodiment 4
20.0 g are taken to contain PO4 3-Be placed in for 51.8% phosphatization slag in beaker, add thereto 200mL mass concentrations be 1.5% it is dilute
HNO3Solution, the heating stirring 45min at a temperature of 80rpm speeds of agitator and 60 DEG C, suspension is through centrifugal filtration, in gained filter residue
It is middle to add the NaOH solution that 100 mL mass concentrations are 15%, after heating stirring 2h at a temperature of 80rpm speeds of agitator and 60 DEG C,
Through centrifugal filtration, addition 1.0g activated carbons are cleaned and decolourized suspension in gained filtrate, are prepared P507 volume fractions and are
20% P507- toluene mixing organic liquor 300mL, takes the 100mL mixing organic liquors to add to through activated carbon and cleans and decolouring, mistake
In clear filtrate obtained by filter, 30min is stirred under 120rpm rotating speeds, standing separation, obtains extract and raffinate, repeated
The extraction process is twice.Finally the dilute sulfuric acid that the extract mass concentration of gained is 15% is stripped, the extractant of recovery 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.Weigh
0.25g hexadecyltrimethylammonium chloride（That is CTAC, or 1631）With 18.0g Fe(NO3)39H2O【Fe(NO3) 3·
9H2O】200 mL mixed solution is configured to, the mixed solution is added drop-wise to above-mentioned raffinate at 90rpm speeds of agitator and 60 DEG C
In liquid, stop being added dropwise when reaching 2.0 to the pH of suspension system, continue to stir 120min, suspension is filtered, filter residue is through water
Wash, 4h is dried at 120 DEG C, that is, obtain phosphate dihydrate iron product.Through analysis measure and calculate, product quality reaches《Battery phosphorus
Sour iron（HG/T 4701-2014）》Standard requires that the overall recovery of phosphate radical is 75.1% in phosphatization slag.
Embodiment 5
10.0 g are taken to contain PO4 3-Be placed in for 51.8% phosphatization slag in beaker, add thereto 100mL mass concentrations be 1.0% it is dilute
HNO3Solution, the heating stirring 30min at a temperature of 80rpm speeds of agitator and 70 DEG C, suspension is through centrifugal filtration, in gained filter residue
It is middle to add the NaOH solution that 65 mL mass concentrations are 10%, after heating stirring 2h at a temperature of 80rpm speeds of agitator and 70 DEG C,
Through centrifugal filtration, addition 0.5g activated carbons are cleaned and decolourized suspension in gained filtrate, are prepared P507 volume fractions and are
15% P507- benzene mixing organic liquor 300mL, takes the 100mL mixing organic liquors to add to through activated carbon and cleans with decolourizing, filtering
In resulting clear filtrate, 30min is stirred under 120rpm rotating speeds, standing separation, obtains extract and raffinate, repeating should
Extraction process is twice.Finally the dilute sulfuric acid that the extract mass concentration of gained is 15% is stripped, the extractant of recovery repeats to use
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.Weigh 0.15g
Hexadecyltrimethylammonium chloride（That is CTAC, or 1631）With 10.0g Fe(NO3)39H2O【Fe(NO3) 3·9H2O】Match somebody with somebody
100 mL mixed solution is made, the mixed solution is added drop-wise in above-mentioned raffinate at 90rpm speeds of agitator and 60 DEG C, extremely
The pH of suspension system stops being added dropwise when reaching 2.0, continues to stir 120min, suspension is filtered, and filter residue is through washing, 120 DEG C
Lower dry 4h, that is, obtain phosphate dihydrate iron product.Through analysis measure and calculate, product quality reaches《Battery ferric phosphate（HG/T
4701-2014）》Standard requires that the overall recovery of phosphate radical is 79.8% in phosphatization slag.
Embodiment 6
10.0 g are taken to contain PO4 3-Be placed in for 51.8% phosphatization slag in beaker, add thereto 100mL mass concentrations be 1.5% it is dilute
HNO3Solution, the heating stirring 40min at a temperature of 80rpm speeds of agitator and 50 DEG C, suspension is through centrifugal filtration, in gained filter residue
It is middle to add the KOH solution that 60 mL mass concentrations are 15%, after heating stirring 2h at a temperature of 80rpm speeds of agitator and 50 DEG C, hang
Supernatant liquid is through centrifugal filtration, and addition 0.5g activated carbons are cleaned and decolourized in gained filtrate, and it is 20% to prepare N235 volume fractions
N235- kerosene mixing organic liquor 240mL, take the 80mL mixing organic liquors add to through activated carbon clean with decolourize, filtering institute
In obtained clear filtrate, 30min is stirred under 120rpm rotating speeds, standing separation, obtains extract and raffinate, repeats the extraction
Take process twice.Finally the dilute sulfuric acid that the extract mass concentration of gained is 15% is stripped, the extractant of recovery is 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.Weigh 0.10g's
Hexadecyltrimethylammonium chloride（That is CTAC, or 1631）With 10.0g Fe(NO3)39H2O【Fe(NO3) 3·9H2O】Prepare
Into 100 mL mixed solution, the mixed solution is added drop-wise in above-mentioned raffinate at 90rpm speeds of agitator and 60 DEG C, it is extremely outstanding
The pH of supernatant liquid system stops being added dropwise when reaching 2.5, continues to stir 120min, suspension is filtered, filter residue is through at washing, 120 DEG C
4h is dried, that is, obtains phosphate dihydrate iron product.Through analysis measure and calculate, product quality reaches《Battery ferric phosphate（HG/T
4701-2014）》Standard requires that the overall recovery of phosphate radical is 80.6% in phosphatization slag.
Claims (10)
- A kind of 1. method for preparing battery ferric phosphate using phosphatization slag for raw material, it is characterised in that including pickling, alkali leaching, take off Color, extraction, precipitation reaction, specifically comprise the following steps：1. pickling：Dilute HNO is added into phosphatization slag3, pickling is carried out under agitation, then suspension is filtered, water Wash, 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 suspending Liquid is filtered, and collects filtrate；3. decolourize：Activated carbon is added into step 2. gained filtrate, is adsorbed, suspension is entered under agitation then Row filtering, collects filtrate；4. extract：Extractant and organic solvent are added into step 3. gained filtrate, is extracted under agitation, then Separating and extracting liquid and raffinate, gained extract extractant of gained after diluted acid is stripped are recycled and reused for extraction process, gained extraction It is used to after its pH value prepare ferric phosphate by the way that phosphoric acid is added dropwise and adjusts in extraction raffinate；5. precipitation reaction：Under agitation, surfactant is added into step 4. gained raffinate, then nitre is added dropwise to it Precipitation reaction occurs for sour ferrous solution, and when the pH value of suspension reaches 1.5 ~ 3.5, suspension is filtered, gained solid warp Washing, dry, that is, obtain ferric phosphate product.
- 2. the method according to claim 1 for preparing battery ferric phosphate using phosphatization slag for raw material, it is characterised 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, it is characterised in that step Suddenly 2. in, described strong base solution is NaOH solution or/and KOH solution；The mass concentration of strong base solution is 10 ~ 30%；Highly basic is molten The dosage of liquid meets that alkali/iron mol ratio is (2.7 ~ 4.5)/1.0；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, it is characterised in that step Suddenly 3. in, the dosage of activated carbon is the 0.5 ~ 5% of filtrate quality；Adsorption time is 15 ~ 40min；Adsorption temp is normal temperature.
- 5. the method according to claim 1 for preparing battery ferric phosphate using phosphatization slag for raw material, it is characterised in that step Suddenly 4. in, described extractant is more than one or both of P204, P507 or N235；Described organic solvent is benzene, first It is more than one or both of benzene or kerosene.
- 6. the method according to claim 1 for preparing battery ferric phosphate using phosphatization slag for raw material, it is characterised 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, it is characterised in that step Suddenly 4. in, be added dropwise phosphoric acid regulation suspension pH value scope be 5.0 ~ 8.0.
- 8. the method according to claim 1 for preparing battery ferric phosphate using phosphatization slag for raw material, it is characterised in that step Suddenly 5. in, described surfactant is hexadecyltrimethylammonium chloride or/and cetyl trimethylammonium bromide；Live on surface 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, it is characterised 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, it is characterised in that Step 5. in, step 5. in, the pH value of suspension is 2.0 ~ 2.5.
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| 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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