CN111646447B - Method for recovering iron phosphate from iron-phosphorus slag after lithium extraction of lithium iron phosphate lithium battery - Google Patents
Method for recovering iron phosphate from iron-phosphorus slag after lithium extraction of lithium iron phosphate lithium battery Download PDFInfo
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Abstract
The invention provides a method for recovering iron phosphate from iron-phosphorus slag after lithium extraction of a lithium iron phosphate battery. Mixing iron-phosphorus slag obtained after lithium extraction of a lithium iron phosphate battery with water, mixing the mixture with acid, reacting the mixture with acid, performing solid-liquid separation to obtain leachate containing iron-phosphorus ions, performing iron addition replacement to remove copper, and removing aluminum by using resin to obtain purified liquid, adding iron phosphate heptahydrate or phosphoric acid to adjust the phosphorus-iron ratio to obtain a synthetic stock solution with a certain ratio of P to Fe, adding hydrogen peroxide and ammonia water, adjusting the pH value to obtain an iron phosphate precursor precipitate, and performing post-treatment to obtain a battery-grade iron phosphate precursor product. The recovery method provided by the invention can be used for recovering the iron phosphorus slag after lithium extraction of the waste lithium iron phosphate battery, has good raw material adaptability, can realize recovery no matter whether the iron phosphorus slag contains anode and cathode carbon powder and copper and aluminum impurities or not, has high recovery rate of iron and phosphorus, and is high in purity of the obtained iron phosphate precursor material.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a method for recovering iron phosphate from iron phosphate slag after lithium extraction of a lithium iron phosphate battery.
Background
The lithium iron phosphate power battery has stable chemical property, good safety performance and longer service life, and simultaneously still occupies a half-wall river mountain of the power battery due to low price of raw materials; in recent years, the energy storage device is widely applied to various electric automobiles and energy storage fields. The back of mass production, application means that a large number of discarded lithium iron phosphate batteries are produced each year. The market reserve of the lithium iron phosphate battery is calculated according to the production and sales data of the medium-steam-assisted new energy vehicle, and 20.31GWh and 18.47 ten thousand tons of retired lithium iron phosphate batteries in 2020 are calculated. 33.96GWh and 21.23 ten thousand tons of retired lithium iron phosphate batteries in 2025, so that the retired dynamic lithium iron phosphate batteries have wide development prospects in the aspect of recycling markets. Meanwhile, from the environmental point of view, although the lithium ion battery is called a green battery, the lithium ion battery is also classified as a toxic and harmful battery with flammability, leaching toxicity, corrosiveness and the like, and therefore, the recycling and reusing of the waste lithium iron phosphate battery are not slow.
The waste lithium iron phosphate batteries have low Li content and high Fe and P contents, but have high Li recovery value and low Fe and P recovery value. The waste lithium iron phosphate battery recovery part process is oxidation recovery, and lithium is recovered into a high-value lithium carbonate or lithium hydroxide product, but carbon powder and iron phosphate basically exist in a waste residue form, so that certain pollution is caused to the environment, and the values of Fe and P are not maximized.
The patent application CN110835683A discloses a method for selectively extracting lithium from waste lithium ion battery materials, which takes waste lithium ion batteries as raw materials, obtains a lithium iron phosphate anode material through battery splitting, crushing and screening, obtains a lithium-containing solution and transformation slag through oxidizing roasting, water size mixing, adding calcium chloride or lime milk solution for reaction transformation, filtering and separating, and the lithium solution can be further processed into lithium products, but the method for recovering the transformation slag is not explained.
The patent CN106785166B discloses a method for preparing battery-grade lithium carbonate by recovering lithium from lithium iron phosphate waste batteries, which takes the lithium iron phosphate waste batteries as raw materials, and obtains a battery-grade lithium carbonate product through the steps of battery disassembly, disc granulation, high-temperature roasting, acidification leaching, deep transformation, alkalization impurity removal, soda lithium precipitation and the like, but the method for recovering acid leaching residues, namely iron phosphorus residues, is not explained.
Patent application CN109534372A discloses a method for preparing lithium carbonate by using lithium iron phosphate waste, aiming at the lithium iron phosphate waste, the method obtains a lithium carbonate product by sodium hypomixing, acid addition oxidation reaction, filtration and leaching, concentration and impurity removal, alkalization and impurity removal and sodium carbonate lithium precipitation, but does not make a description on a recovery method for iron phosphorus slag obtained by leaching.
Although documents such as patent applications, periodicals and the like disclose or report various waste lithium iron phosphate battery recovery methods, most of the prior art does not consider the full recovery of lithium iron phosphate battery resources, only recovers Li with low value and content, and does not recover Fe and P with relatively low value and high content, so that the Fe and P resources are wasted, and meanwhile, certain influence is caused on the environment. In addition, in some prior arts, for example, CN110683528 relates to recovery of iron phosphorus slag after lithium extraction from waste lithium iron phosphate batteries, but the recovery method has poor raw material adaptability, and only aims at pure waste iron phosphate, the method needs to completely remove and separate positive and negative carbon powders and other impurities of the waste batteries in advance, and does not study the recovery process of carbon-containing iron phosphorus slag after lithium extraction from waste lithium iron phosphate batteries, and meanwhile, the recovery effect is poor.
Disclosure of Invention
In view of the above, the present invention aims to provide a method for recovering iron phosphate from iron-phosphorus slag after lithium extraction from a lithium iron phosphate battery. The recovery method provided by the invention can be used for efficiently recovering the iron phosphate precursor from the iron phosphate slag after lithium extraction of the waste lithium iron phosphate battery.
The invention provides a method for recovering iron phosphate from iron-phosphorus slag after lithium extraction of a lithium iron phosphate battery, which comprises the following steps:
s1) mixing the iron phosphorus slag after lithium extraction of the lithium iron phosphate battery with water for size mixing to obtain size mixing liquid;
s2) mixing and reacting the size mixing liquid with acid liquor, and then carrying out solid-liquid separation to obtain a separation liquid A;
s3) mixing and reacting the separation liquid A with iron powder, and then carrying out solid-liquid separation to obtain a separation liquid B;
s4) carrying out ion exchange aluminum removal on the separation liquid B by adopting ion exchange resin, and then adding FeSO4·7H2O or H3PO4Adjusting the molar ratio of phosphorus to iron in the system to (1-2) to 1 to obtain a raw material solution;
s5) mixing the raw material liquid with hydrogen peroxide and ammonia water for reaction to form iron phosphate.
Preferably, in step S2), the acid solution is concentrated sulfuric acid or concentrated phosphoric acid.
Preferably, in step S2), the addition amount of the acid solution is: acidic compound in acid liquor and FePO in size mixing liquor40.9 to 2 times the stoichiometric ratio of (A).
Preferably, in step S3), the addition amount of the iron powder is: the molar weight of the iron is Cu in the separation liquid A2+1 to 5 times of the molar weight.
Preferably, in step S5):
the addition amount of the hydrogen peroxide is as follows: hydrogen in hydrogen peroxide2O2With the stock solutionMiddle Fe2+1 to 2 times of the stoichiometric ratio of (A);
the addition amount of the ammonia water is such that the pH value of the mixed system is 2.5-3;
the reaction temperature is 40-70 ℃.
Preferably, in step S1):
the solid-liquid mass ratio of the iron-phosphorus slag to water is 1: 1-4;
the mixing and size mixing time is 10-30 min.
Preferably, in step S5):
the mixing mode is as follows: simultaneously dropwise adding the raw material liquid, hydrogen peroxide and ammonia water;
the mixing time is 1.5-3 h;
aging after mixing; the aging time is 1.5-3 h.
Preferably, in step S4):
the ion exchange resin is strong-acid cation exchange resin;
the particle size of the particles in the ion exchange resin is 0.42-1.2 mm;
and controlling the flow speed of adsorption in the ion exchange to be 1-5 BV/h.
Preferably, in the step S2), the reaction time is 0.5-2.5 h;
in the step S3), the reaction time is 0.5-2.5 h.
Preferably, the step S5), after the reaction, further includes: solid-liquid separation, washing and drying.
The invention provides a method for recovering iron phosphate from iron phosphorus slag after lithium extraction of a lithium iron phosphate battery, which comprises the steps of mixing the iron phosphorus slag after lithium extraction of the lithium iron phosphate battery with water, carrying out size mixing, reacting with acid, carrying out solid-liquid separation to obtain leachate containing iron phosphorus ions, carrying out iron addition replacement to remove copper, carrying out resin dealuminization to obtain purified liquid, adding iron phosphate heptahydrate or phosphoric acid to adjust the phosphorus-iron ratio to obtain a synthetic stock solution with a certain ratio of P to Fe, adding hydrogen peroxide and ammonia water, adjusting pH to obtain an iron phosphate precursor precipitate, and carrying out post-treatment to obtain a battery-grade iron phosphate precursor product. The recovery method provided by the invention can be used for recovering the iron phosphorus slag (containing carbon or not) after lithium extraction of the waste lithium iron phosphate batteries, has good raw material adaptability, can realize recovery no matter whether the iron phosphorus slag contains anode and cathode carbon powder and copper and aluminum impurities, and has high recovery rate of iron and phosphorus.
Test results show that the recovery method provided by the invention has strong adaptability to raw materials and can efficiently recover the iron-phosphorus slag containing carbon or not containing carbon; meanwhile, the recovery rate of iron and phosphorus is high, wherein the recovery rate of iron is more than 98.5%, and the recovery rate of phosphorus is more than 98.3%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is a schematic flow diagram of a recovery process provided by the present invention;
figure 2 is the XRD spectrum of the iron phosphate product obtained in example 1.
Detailed Description
The invention provides a method for recovering iron phosphate from iron-phosphorus slag after lithium extraction of a lithium iron phosphate battery, which comprises the following steps:
s1) mixing the iron phosphorus slag after lithium extraction of the lithium iron phosphate battery with water for size mixing to obtain size mixing liquid;
s2) mixing and reacting the size mixing liquid with acid liquor, and then carrying out solid-liquid separation to obtain a separation liquid A;
s3) mixing and reacting the separation liquid A with iron powder, and then carrying out solid-liquid separation to obtain a separation liquid B;
s4) carrying out ion exchange aluminum removal on the separation liquid B by adopting ion exchange resin, and then adding FeSO4·7H2O or H3PO4Adjusting the molar ratio of phosphorus to iron in the system to (1-2) to 1 to obtain a raw material solution;
s5) mixing the raw material liquid with hydrogen peroxide and ammonia water for reaction to form iron phosphate.
Mixing iron-phosphorus slag obtained after lithium extraction of a lithium iron phosphate battery with water, carrying out size mixing, reacting with acid, carrying out solid-liquid separation to obtain leachate containing iron-phosphorus ions, adding iron to replace copper and removing aluminum by resin to obtain purified liquid, adding iron phosphate heptahydrate and phosphoric acid to adjust the phosphorus-iron ratio to obtain a synthetic stock solution with a certain ratio of P to Fe, adding hydrogen peroxide and ammonia water, adjusting the pH value to obtain an iron phosphate precursor precipitate, and carrying out post-treatment to obtain a battery-grade iron phosphate precursor product. The recovery method provided by the invention can be used for recovering the iron phosphorus slag (containing carbon or not) after lithium extraction of the waste lithium iron phosphate battery, has good raw material adaptability, can realize recovery no matter whether the iron phosphorus slag contains positive and negative carbon powder and copper and aluminum impurities, has high recovery rate of iron and phosphorus, and is high in purity of the obtained iron phosphate precursor material.
With respect to step S1): and mixing the iron-phosphorus slag obtained after lithium extraction of the lithium iron phosphate battery with water for size mixing to obtain size mixing liquid.
In the invention, the obtaining mode of the iron phosphorus slag after lithium extraction of the lithium iron phosphate battery is not particularly limited, and the iron phosphorus slag is the iron phosphorus slag left after conventional lithium extraction treatment of the waste lithium iron phosphate battery or the commercially available iron phosphorus slag after conventional lithium extraction, which is well known to those skilled in the art. In the prior art, before the lithium extraction treatment, the waste lithium iron phosphate batteries are usually pretreated, including discharging the batteries, disassembling, roasting, crushing and screening positive and negative electrode plates, and the like, and the obtained positive and negative electrode powders are subjected to the lithium extraction treatment, so that iron phosphorus slag is generated in the lithium extraction process. Lithium iron phosphate batteries generally use aluminum foils as positive current collectors, copper foils as negative current collectors, lithium iron phosphate as a positive electrode material, and graphite as a negative electrode material; therefore, the disassembled positive and negative electrode plates comprise copper, aluminum materials, lithium iron phosphate materials and carbon materials. Although individual prior art such as CN110683528 relates to recycling of iron phosphorus slag after lithium extraction from waste lithium iron phosphate batteries, the recycling method has poor raw material adaptability, only aims at pure iron phosphate waste, and needs to remove and separate positive and negative carbon powder and other impurities of the waste batteries completely in advance, and meanwhile, the recycling effect is not good, and in addition, the recycling method cannot effectively recycle carbon-containing iron phosphorus slag (i.e., iron phosphorus slag without separating positive and negative carbon powder and even copper and aluminum impurities) after lithium extraction from waste lithium iron phosphate batteries, and has great limitation on recycling of iron phosphorus slag. The recovery method provided by the invention has good adaptability to iron-phosphorus slag raw materials, wherein the iron-phosphorus slag raw materials not only contain iron phosphate waste materials, but also can contain cathode carbon powder, copper-aluminum impurities and the like, and can realize high-efficiency recovery of carbon-containing or carbon-free iron-phosphorus slag.
In the present invention, the water is preferably pure water. According to the invention, the solid-liquid mass ratio of the iron-phosphorus slag to water is preferably 1: 1-4, if the solid-liquid ratio is too low, the concentration of iron and phosphorus in the leachate is influenced, so that the concentration of iron and phosphorus is too low, further the synthesis efficiency is low when the iron phosphate product is synthesized subsequently, if the solid-liquid ratio is too high, the leaching rate of iron and phosphorus in the iron-phosphorus slag is influenced, the leaching rate of iron and phosphorus is low, and meanwhile, the solid content of the slurry is too high, so that the stirring, mixing and transferring in the working procedure are not facilitated. In some embodiments of the invention, the solid-liquid mass ratio is 1: 1, 1: 2 or 1: 4.
In the present invention, the mixing and size mixing manner is not particularly limited, and may be performed according to a conventional size mixing operation well known to those skilled in the art, such as mixing and stirring solid and liquid uniformly. In the invention, the temperature of the mixing and size mixing is not particularly limited, and the mixing and size mixing can be carried out at room temperature, and specifically can be 10-35 ℃. In the invention, the mixing and size mixing time is preferably 10-30 min. After mixing and size mixing, a uniform size system, namely size mixing liquid, is formed.
With respect to step S2): after the size mixing liquid is obtained, mixing the size mixing liquid with acid liquor for reaction, and then carrying out solid-liquid separation to obtain a separation liquid A.
In the invention, the size mixing liquid is mixed with acid liquid to react, so that the iron-phosphorus slag reacts with the acid, iron and phosphorus become soluble forms, and the ferro-phosphorus component is separated from other solid impurities. In the invention, the acid solution is preferably concentrated sulfuric acid or concentrated phosphoric acid; wherein, concentrated sulfuric acid is sulfuric acid solution with mass fraction more than or equal to 70%, and concentrated phosphoric acid is phosphoric acid solution with mass fraction of 85%. The chemical reactions of the two acids with the iron-phosphorus slag are respectively shown as the following formulas S2-1 and S2-2:
2FePO4+6H++3SO4 2-＝2Fe3++3SO4 2-+2H2PO4 -+2HPO4 2-formula S2-1;
FePO4+3H++PO4 3-＝Fe3++H2PO4 -+HPO4 2-formula S2-2.
In the invention, the addition amount of the acid liquor is preferably 0.9-2 times of the theoretical amount; the theoretical amount refers to the stoichiometric amount in the chemical reaction according to the formulas S2-1 and S2-2, and 0.9-2 times of the theoretical amount refers to the acid compound in the acid liquor and FePO in the size mixing liquid40.9 to 2 times the stoichiometric ratio of (A); for example H in sulphuric acid liquors2SO4With FePO in the iron-phosphorus slag4When the theoretical amount of the chemical equilibrium molar ratio of (A) to (B) is 3: 2 (i.e. 1.5), the addition amount of concentrated sulfuric acid is controlled to be 0.9-2 times of the theoretical amount, i.e. H in the sulfuric acid solution is controlled2SO4With FePO in the iron-phosphorus slag4The molar ratio of (1) to (2) is (0.9) x 1.5. In some embodiments of the invention, the acid is added in an amount of 1, 1.5 or 2 times the theoretical amount.
In the invention, the mixing mode of the size mixing liquid and the acid liquid is as follows: and dropwise adding concentrated acid into the prepared slurry. In the invention, the mixture is kept stand for a period of time for full reaction, and the temperature in the mixing process and the standing reaction process is preferably 10-35 ℃; in some embodiments of the invention, the temperature is 25 ℃. In the invention, the reaction time is preferably 0.5-2.5 h; in some embodiments of the invention, the reaction time is 0.5h, 1.5h, or 2.5 h.
In the invention, after the reaction, solid-liquid separation is carried out to separate the liquid containing the soluble ferrophosphorus component from other solid impurities. The solid-liquid separation method is not particularly limited in the present invention, and may be a conventional separation operation known to those skilled in the art, such as filtration. After separation, a separation liquid A is obtained.
With respect to step S3): after the separated liquid A is obtained, the separated liquid A and iron powder are mixed and reacted, and then solid-liquid separation is carried out, so that separated liquid B is obtained.
In the invention, the separation liquid A is mixed with iron powder for reaction, and the iron simple substance and Cu in the separation liquid A2+A displacement reaction occurs to change the copper ions in the solution into elemental copper (as shown in the following formula S3-1) to achieve the effect of copper removal.
Fe+Cu2+＝Fe2++ Cu is of formula S3-1.
In the present invention, the amount of the iron powder added is preferably 1 to 5 times of the theoretical amount. The theoretical amount is consistent with the meaning of the theoretical amount in the previous text, specifically, the theoretical amount in the step is the stoichiometric amount in the chemical reaction according to the formula S3-1, and 1-5 times of the theoretical amount refers to the molar amount of iron and the Cu in the separation liquid A2+1 to 5 times of the molar weight ratio (i.e. 1: 1); the molar amount of iron was Cu in the separated liquid A because the theoretical molar ratio was 12+1 to 5 times of the molar weight. Cu in the separated liquid A was measured in advance before the iron powder was added2+The content of the iron powder is controlled based on the content. In some embodiments of the invention, the iron powder is added in an amount of 1.5, 2 or 5 times the theoretical amount.
In the invention, the temperature for mixing and reacting the separation liquid A and the iron powder is preferably 25-40 ℃; in some embodiments of the invention, the temperature is 25 ℃. The reaction time is preferably 0.5-2.5 h; in some embodiments of the invention, the reaction time is 0.5h, 1h, or 2.5 h. Through the reaction, the dissolved Cu in the solution system2+And converting into an insoluble Cu simple substance to separate Cu impurities from the solution.
In the invention, after the reaction, solid-liquid separation is carried out, so that the liquid containing the dissolved ferrophosphorus is separated from the Cu simple substance. The solid-liquid separation method is not particularly limited in the present invention, and may be a conventional separation operation known to those skilled in the art, such as filtration. Separating to obtain separated liquid B.
With respect to step S4): after separation liquid B is obtained, ion exchange resin is adopted to carry out ion exchange aluminum removal on the separation liquid B, and FeSO is added4·7H2O or H3PO4And adjusting the molar ratio of phosphorus to iron in the system to (1-2) to 1 to obtain a raw material solution.
In the present invention, the ion exchange resin is a strong acid cation exchange resin, preferably a macroporous strong acid cation exchange resin, more preferably a catalyst-grade macroporous strong acid cation exchange resin. The particle size of the particles in the ion exchange resin is preferably 0.42-1.2 mm. In the invention, when the separation liquid B is subjected to ion exchange aluminum removal by using the ion exchange resin, the flow rate is preferably controlled to be 1-5 BV/h during adsorption, and within the flow rate range, the aluminum removal effect can be ensured, and the treatment efficiency is higher. The Al content in the effluent is below 0.005g/L through the adsorption treatment. In the invention, after the preorder treatment, the aluminum removal rate of the step is more than 99 percent, the loss of iron and phosphorus is less than 1 percent, and the recovery rate of iron and phosphorus can be improved.
In the invention, after the aluminum is removed by ion exchange, the ion exchange resin can be regenerated and then recycled. The regeneration treatment is particularly preferably: 3 to 10 percent (mass fraction) of sulfuric acid solution is adopted to carry out elution at the flow rate of 3BV/h, the amount of the sulfuric acid solution is shared to be 6BV, and then the resin is washed by water until the pH value is more than 6, so that the resin can be regenerated and recycled.
In the invention, after the aluminum removal solution is obtained through the treatment, FeSO is added4·7H2O or H3PO4The proportion of phosphorus and iron in the system is adjusted. The invention preferably adjusts the molar ratio of phosphorus to iron in the system to (1-2) to 1 to form a synthetic raw material solution. The "molar ratio of phosphorus to iron" refers to the molar ratio of phosphorus ions to iron ions in the solution system. In some embodiments of the invention, the ferrophosphorus molar ratio is adjusted to 1: 1, 1.5: 1, or 2: 1.
With respect to step S5): and after a raw material liquid is obtained, mixing the raw material liquid with hydrogen peroxide and ammonia water for reaction to form the iron phosphate.
In the invention, the raw material liquid is mixed with hydrogen peroxide and ammonia water, wherein the hydrogen peroxide and H in the raw material liquid3PO4And FeSO4A chemical reaction occurs, as shown in formula S5-1:
2H3PO4+2FeSO4+H2O2＝FePO4+2H2SO4+2H2o is S5-1.
In the invention, the addition amount of the hydrogen peroxide is preferably 1-2 times of the theoretical amount. The theoretical amount is consistent with the meaning of the theoretical amount in the previous text, the theoretical amount in the step specifically refers to the stoichiometric usage amount in the chemical reaction according to the formula S5-1, and 1-2 times of the theoretical amount refers to H in hydrogen peroxide2O2With FeSO in the feed solution41-2 times the stoichiometric ratio of the reaction according to the formula S5-1 (i.e., Fe)2+1-2 times of theoretical amount). E.g. H2O2With FeSO in the feed solution4The theoretical amount of the chemical equilibrium molar ratio of (1: 2) (i.e. 0.5) is controlled, and then H in the hydrogen peroxide is controlled2O2The dosage of (A) is 1-2 times of the theoretical amount, namely H in the hydrogen peroxide is controlled2O2With FeSO in the feed solution4The molar ratio of (1-2) × 0.5. Fe in the raw materials was measured in advance before the addition2+And controlling the addition of hydrogen peroxide by taking the content as a reference. In some embodiments of the invention, the amount of hydrogen peroxide added is 1, 1.3 or 2 times the theoretical amount. In the present invention, the mass concentration of the hydrogen peroxide is preferably 30%.
In the invention, the adding amount of the ammonia water is controlled by taking the pH value of a mixed system of the raw material liquid, hydrogen peroxide and the ammonia water as an index, the pH value of the system is preferably 2.5-3, and if the pH value deviates from the pH range, a high-quality iron phosphate precursor cannot be synthesized. In some embodiments of the invention, the pH is 2.5, 2.8, or 3.0.
In the invention, the mixing and feeding mode is as follows: and dropwise adding the raw material liquid, hydrogen peroxide and ammonia water, and dropwise adding the raw material liquid, the hydrogen peroxide and the ammonia water simultaneously. In the invention, the feeding time is preferably 1.5-3 h; in some embodiments of the invention, the addition time is 1.5h, 2h, or 3 h. In the invention, after the feeding is finished, the ageing is carried out; the aging time is preferably 1.5-3 h; in some embodiments of the invention, the aging time is 1.5h, 2h, or 3 h. In the feeding process and the aging process, materials react with each other; in the invention, the reaction temperature is preferably 40-70 ℃, namely the temperature of the feeding and aging process is controlled to be 40-70 ℃; in some embodiments of the invention, the temperature is 40 ℃, 50 ℃ or 70 ℃. And generating an iron phosphate precursor after the reaction.
In the present invention, after the reaction, it is preferable to further include: solid-liquid separation, washing and drying. After the reaction, iron phosphate precursor precipitate is formed, and the iron phosphate is separated out through solid-liquid separation. The solid-liquid separation method is not particularly limited in the present invention, and may be a conventional separation operation known to those skilled in the art, such as filtration. After solid-liquid separation, washing and drying; the drying temperature is preferably 100-150 ℃. And drying to obtain the iron phosphate product.
The process flow of the recovery method provided by the invention is shown in fig. 1, and fig. 1 is a schematic flow chart of the recovery method provided by the invention.
The recovery method provided by the invention has the following beneficial effects: 1. the recovery rate of iron and phosphorus is high; 2. the prepared iron phosphate material has high purity, narrow particle size distribution and uniform mixing; 3. the used raw materials are iron phosphorus slag after lithium extraction of the lithium iron phosphate battery, and the iron phosphorus slag has good adaptability and can be carbon-containing iron phosphorus slag or carbon-free iron phosphorus slag; 4. the recovery process flow is simple, the production cost is low, and the environment is friendly.
For a further understanding of the invention, reference will now be made to the preferred embodiments of the invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the invention, and not to limit the scope of the claims. In the following examples, the macroporous, strongly acidic cation exchange resin used was Tulsion-62MP, available from Beijing technology, Inc., Kaihsi.
Example 1
1. Recovery and preparation of iron phosphate
1.1 iron-phosphorus slag without negative carbon
The raw material is iron-phosphorus waste residue without a graphite cathode, which is produced by a lithium iron phosphate recovery enterprise, and the component analysis of the iron-phosphorus waste residue is shown in table 1:
TABLE 1 analysis of composition of raw iron-phosphorus slag of examples 1 to 3
| Li2O,％ | Fe,％ | P,％ | SO4 2-,％ | Na,％ | K,％ | Ca,％ | Mg,％ | Al,％ | Cu,％ | Zn,％ | Ni,％ | C,％ | |
| Example 1 | 0.051 | 36.36 | 20.13 | 0.11 | 0.0087 | 0.00084 | ND | 0.00042 | 0.96 | 0.005 | 0.00088 | 0.021 | - |
| Example 2 | 0.059 | 24.22 | 13.41 | 0.21 | 0.012 | 0.00093 | ND | 0.00037 | 0.98 | 0.067 | 0.00057 | 0.0023 | 33.1 |
| Example 3 | 0.061 | 23.38 | 12.94 | 0.14 | 0.0087 | 0.00076 | ND | 0.00052 | 0.84 | 0.045 | 0.00052 | 0.004 | 35.2 |
1.2 recovery of iron phosphate from iron-phosphorus slag
S1, mixing the iron phosphorus slag and pure water according to the solid-to-liquid ratio of 1: 1, and carrying out slurry mixing and reaction for 30min to obtain slurry mixing liquid.
S2, adding concentrated phosphoric acid (the mass fraction is 85%) of which the amount is 1 time of the theoretical amount into the size mixing liquid, reacting for 2.5 hours at the temperature of 25 ℃, and filtering to obtain filtrate A.
S3, adding iron powder 2 times of the theoretical amount into the filtrate A, reacting for 2.5h at 25 ℃, and filtering to obtain filtrate B.
And S4, passing the filtrate B through a macroporous strong-acid cation exchange resin at the flow rate of 1BV/h, wherein the treatment capacity is 10BV when the Al content in effluent is less than 0.005g/L, and obtaining the purified liquid after Al removal. After the resin is adsorbed and saturated, sulfuric acid solution (with the concentration of 3%) is used for desorption, the flow rate is 3BV/h, the sulfuric acid solution is used for 6BV, and then the resin is washed by water until the pH value is 6.5, so that regenerated resin can be obtained and can be recycled.
S5, adding FeSO into the purified liquid after Al removal4·7H2And O, adjusting the ratio of phosphorus to iron in the solution to be 1: 1, and taking the solution as a synthetic raw material solution.
S6, simultaneously dropwise adding a synthetic raw material liquid, hydrogen peroxide (with the mass concentration of 30%) and ammonia water into the reaction kettle, wherein the addition amount of the hydrogen peroxide is Fe2+Controlling the pH to be 3.0 and the temperature to be 40 ℃ according to 2 times of the theoretical amount, feeding for 3h, aging for 1.5h, reacting to generate iron phosphate precipitate, filtering, washing and drying the iron phosphate precipitate to obtain the battery-grade iron phosphate precursor.
2. Characterization and testing of the product
(1) The X-ray diffraction test of the obtained iron phosphate product shows that the result is shown in fig. 2, fig. 2 is the XRD spectrogram of the iron phosphate product obtained in example 1, and it can be seen that the obtained iron phosphate product and FePO4The characteristic peaks of the standard substance correspond to each other, and the obtained product is proved to be ferric phosphate.
(2) The iron phosphate product was subjected to composition analysis and physical property test, and the results are shown in table 2.
TABLE 2 Properties of the products of examples 1 to 3
Note: in table 2, "iron to phosphorus ratio" means the molar ratio of iron to phosphorus; "Density" is tap density; "ND" is not detected.
The test results in table 2 show that the iron phosphate product prepared by the method disclosed by the invention has the characteristics of component distribution, iron-phosphorus ratio, particle size, tap density, moisture content and the like which all meet the industrial standards of the iron phosphate for batteries.
(3) Yield of
The yields of iron and phosphorus were measured separately, and the results showed that the yield of iron was 98.5% and the yield of phosphorus was 98.3%.
The test method is as follows:
testing of iron: sodium tungstate is used as an indicator of a sample, a small amount of ferric iron is reduced into ferrous iron by titanium trichloride until tungsten blue is generated, excessive ferric titanium is naturally oxidized in the air, sodium diphenylamine sulfonate is used as the indicator in a sulfuric acid-phosphoric acid medium, and the ferrous iron is titrated by a potassium dichromate standard solution.
Testing of phosphorus: in an acid medium, orthophosphate radicals react with a quinomolybdic citranone precipitator to generate yellow phosphomolybdic quinoline precipitates, and the yellow phosphomolybdic quinoline precipitates are filtered, washed, dried and weighed to obtain the phosphorus content.
The calculation method comprises the following steps:
the iron yield is as follows:
in steps 1 and 2:
in the step 3:
in the step 4:
in the step 6:
total iron yield: cFe＝CFe1×CFe2×CFe3×CFe4×100％
Yield of phosphorus:
in steps 1 and 2:
in the step 3:
in the step 4:
in the step 6:
total phosphorus yield: cP＝CP1×CP2×CP3×CP4×100％。
Example 2
1. Recovery and preparation of iron phosphate
1.1 iron-phosphorus slag containing negative carbon
The raw material is iron-phosphorus waste residue without a graphite cathode produced by a lithium iron phosphate recovery enterprise, and the composition analysis of the iron-phosphorus waste residue is shown in table 1.
1.2 recovery of iron phosphate from iron-phosphorus slag
S1, mixing the iron phosphorus slag and pure water according to the solid-to-liquid ratio of 1: 2, and carrying out slurry mixing and reaction for 10min to obtain slurry mixing liquid.
S2, adding concentrated sulfuric acid (mass fraction is 98%) of which the theoretical amount is 1.5 times of that of the mixed slurry, reacting at 25 ℃ for 1.5h, and filtering to obtain filtrate A.
S3, adding iron powder with the amount being 3 times of the theoretical amount into the filtrate A, reacting for 1h at 25 ℃, and filtering to obtain filtrate B.
S4, enabling the filtrate B to pass through a macroporous strong-acid cation exchange resin at the flow rate of 2BV/h, wherein the treatment capacity is 8BV when the Al content in effluent is below 0.005g/L, and forming the purified liquid after Al removal. After the resin is adsorbed and saturated, a sulfuric acid solution (with the concentration of 5%) is used for desorption, the flow rate is 3BV/h, the sulfuric acid solution is used for 6BV, and then the resin is washed by water until the pH value is 6.2, so that the regenerated resin can be obtained and can be recycled.
S5, adding H into the purified liquid after Al removal3PO4And regulating the ratio of phosphorus to iron in the solution to be 1.5: 1 to obtain the synthetic raw material solution.
S6, simultaneously dropwise adding a synthetic raw material liquid, hydrogen peroxide (with the mass concentration of 30%) and ammonia water into the reaction kettle, wherein the addition amount of the hydrogen peroxide is Fe2+Controlling the pH to be 2.8 and the temperature to be 50 ℃, feeding for 2h, aging for 2h, reacting to generate iron phosphate precipitate, filtering, washing and drying the iron phosphate precipitate to obtain the battery-grade iron phosphate precursor, wherein the theoretical amount of the precursor is 1.3 times that of the battery-grade iron phosphate precursor.
2. Characterization and testing of the product
(1) The obtained ferric phosphate product is subjected to X-ray diffraction test, and the result shows that the obtained ferric phosphate product and FePO are obtained4The characteristic peaks of the standard substance correspond to each other, and the obtained product is proved to be ferric phosphate.
(2) The iron phosphate product was subjected to composition analysis and physical property test, and the results are shown in table 2. The test results in table 2 show that the iron phosphate product prepared by the method disclosed by the invention has the characteristics of component distribution, iron-phosphorus ratio, particle size, tap density, moisture content and the like which all meet the industrial standards of the iron phosphate for batteries.
(3) Yield the recovery rates were measured according to the test methods in example 1, respectively, and the results showed that the yield of iron was 98.7% and the yield of phosphorus was 98.5%.
Example 3
1. Recovery and preparation of iron phosphate
1.1 iron-phosphorus slag containing negative carbon
The raw material is iron-phosphorus waste residue containing a graphite cathode produced by a lithium iron phosphate recovery enterprise, and the composition analysis of the iron-phosphorus waste residue is shown in table 1.
1.2 recovery of iron phosphate from iron-phosphorus slag
S1, mixing the iron phosphorus slag and pure water according to the solid-to-liquid ratio of 1: 4, and carrying out slurry mixing and reaction for 20min to obtain slurry mixing liquid.
S2, adding concentrated sulfuric acid (mass fraction is 98%) of which the theoretical amount is 2 times of that of the mixed slurry, reacting at 25 ℃ for 0.5h, and filtering to obtain filtrate A.
S3, adding iron powder 5 times of the theoretical amount into the filtrate A, reacting at 25 ℃ for 0.5h, and filtering to obtain filtrate B.
S4, passing the filtrate B through a macroporous strong-acid cation exchange resin at a flow rate of 5BV/h, wherein the treatment capacity is 7BV when the Al content in effluent is below 0.005g/L, and forming a purified liquid after Al removal. After the resin is adsorbed and saturated, sulfuric acid solution (with the concentration of 3%) is used for desorption, the flow rate is 3BV/h, the sulfuric acid solution is used for 6BV, and then the resin is washed by water until the pH value is 6.5, so that regenerated resin can be obtained and can be recycled.
S5, adding H into the purified liquid after Al removal3PO4And regulating the ratio of phosphorus to iron in the solution to be 2: 1 to obtain the synthetic raw material solution.
S6, simultaneously dropwise adding a synthetic raw material liquid, hydrogen peroxide (with the mass concentration of 30%) and ammonia water into the reaction kettle, wherein the addition amount of the hydrogen peroxide is Fe2+Controlling the pH value to be 2.5 and the temperature to be 70 ℃ according to 1 time of the theoretical amount, feeding for 1.5h, aging for 3h, reacting to generate iron phosphate precipitate, filtering, washing and drying the iron phosphate precipitate to obtain the battery-grade iron phosphate precursor.
2. Characterization and testing of the product
(1) The obtained ferric phosphate product is subjected to X-ray diffraction test, and the result shows that the obtained ferric phosphate product and FePO are obtained4The characteristic peaks of the standard substance correspond to each other, and the obtained product is proved to be ferric phosphate.
(2) The iron phosphate product was subjected to composition analysis and physical property test, and the results are shown in table 2. The test results in table 2 show that the iron phosphate product prepared by the method disclosed by the invention has the characteristics of component distribution, iron-phosphorus ratio, particle size, tap density, moisture content and the like which all meet the industrial standards of the iron phosphate for batteries.
(3) Yield of
The recovery rates were measured according to the test methods in example 1, respectively, and the results showed that the yield of iron was 98.9% and the yield of phosphorus was 98.5%.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A method for recovering iron phosphate from iron-phosphorus slag after lithium extraction of a lithium iron phosphate battery is characterized by comprising the following steps of:
s1) mixing the iron phosphorus slag after lithium extraction of the lithium iron phosphate battery with water for size mixing to obtain size mixing liquid;
s2) mixing and reacting the size mixing liquid with acid liquor, and then carrying out solid-liquid separation to obtain a separation liquid A;
the addition amount of the acid liquor is as follows: acidic compound in acid liquor and FePO in size mixing liquor40.9 to 2 times the stoichiometric ratio of (A);
s3) mixing and reacting the separation liquid A with iron powder, and then carrying out solid-liquid separation to obtain a separation liquid B;
s4) carrying out ion exchange aluminum removal on the separation liquid B by adopting ion exchange resin, and then adding FeSO4·7H2O or H3PO4Adjusting the molar ratio of phosphorus to iron in the system to (1-2) to 1 to obtain a raw material solution;
the ion exchange resin is strong-acid cation exchange resin;
the particle size of the particles in the ion exchange resin is 0.42-1.2 mm;
controlling the flow rate of adsorption in the ion exchange to be 1-5 BV/h;
s5) mixing the raw material liquid with hydrogen peroxide and ammonia water for reaction to form iron phosphate;
the addition amount of the ammonia water is such that the pH value of the mixed system is 2.5-3.
2. The method according to claim 1, wherein in the step S2), the acid solution is concentrated sulfuric acid or concentrated phosphoric acid.
3. The method as claimed in claim 1, wherein in the step S3), the iron powder is added in an amount of: the molar weight of the iron is Cu in the separation liquid A2+1 to 5 times of the molar weight.
4. The method according to claim 1, wherein in step S5):
the addition amount of the hydrogen peroxide is as follows: hydrogen in hydrogen peroxide2O2With Fe in the feed solution2+1 to 2 times of the stoichiometric ratio of (A);
the reaction temperature is 40-70 ℃.
5. The method according to claim 1, wherein in step S1):
the solid-liquid mass ratio of the iron-phosphorus slag to water is 1: 1-4;
the mixing and size mixing time is 10-30 min.
6. Method according to claim 1 or 3, characterized in that in step S5):
the mixing mode is as follows: simultaneously dropwise adding the raw material liquid, hydrogen peroxide and ammonia water;
the mixing time is 1.5-3 h;
aging after mixing; the aging time is 1.5-3 h.
7. The method according to claim 1, wherein in the step S2), the reaction time is 0.5-2.5 h;
in the step S3), the reaction time is 0.5-2.5 h.
8. The method according to claim 1, wherein in step S5), after the reaction, the method further comprises: solid-liquid separation, washing and drying.
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| CN112357899B (en) | 2020-11-23 | 2022-04-22 | 湖南金源新材料股份有限公司 | Comprehensive recycling method of waste lithium iron phosphate batteries |
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