CN113104827A - Method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear solution or industrial ammonium phosphate mother solution - Google Patents
Method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear solution or industrial ammonium phosphate mother solution Download PDFInfo
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Abstract
The invention discloses a method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear liquid or industrial ammonium phosphate mother liquid, which comprises the following steps: s1, fluorine removal: adding diatomite and sodium carbonate into the clear industrial ammonium phosphate solution or the mother solution of the industrial ammonium phosphate to remove fluorine; s2, refining: adjusting the pH value of the phosphorus-containing solution obtained in the step S1 to remove impurities such as calcium, magnesium, manganese, aluminum and the like; s3, removing heavy metals: adding a heavy metal precipitator into the phosphorus-containing solution with low impurity ion content in the step S2 to remove heavy metal impurities; s4, synthesizing ferric phosphate dihydrate: fully reacting the refined phosphate solution obtained in the step S3 with ferrous sulfate under the action of an oxidant to prepare ferric phosphate dihydrate; s5, preparing battery-grade anhydrous iron phosphate: and (4) calcining the ferric phosphate dihydrate prepared in the step (S4) to prepare the battery-grade anhydrous ferric phosphate. The method provided by the invention has the advantages of simple process, low overall cost and higher industrial application value and economic value.
Description
Technical Field
The invention belongs to the technical field of new energy battery material preparation, and particularly relates to a method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear solution or industrial ammonium phosphate mother solution.
Background
The lithium iron phosphate anode material with the orthorhombic olivine structure is a hot material in the field of new energy batteries at present. The material integrates the advantages of lithium cobaltate, lithium nickelate, lithium manganate and the positive electrode material of the derivative thereof: the raw materials are cheap and the resources are very rich; stable structure, excellent safety performance and LiFePO4The O and the P in the material are firmly combined by a strong covalent bond, so that the material is difficult to decompose by oxygen evolution; the high-temperature performance and the thermal stability are obviously superior to other known cathode materials; the cycle performance is good; the volume is reduced during charging, and the volume effect is good when the carbon cathode material is matched; the electrolyte has good compatibility with most electrolyte systems and good storage performance; is nontoxic and is a real green material. The electrode material can be prepared by taking iron phosphate as a raw material.
The existing iron phosphate uses battery-grade or industrial-grade monoammonium phosphate, diammonium phosphate or purified phosphoric acid as a phosphorus source. The phosphate solution required by iron phosphate synthesis is prepared by the procedures of dissolving with pure water, adjusting pH and the like, and then battery-grade iron phosphate is prepared by taking a divalent or trivalent iron salt as an iron source through a chemical reaction mode, wherein the process flow diagram is shown in figure 1.
For example, the publication No. CN106629644A entitled method for producing industrial primary and battery grade monoammonium phosphate from fertilizer grade monoammonium phosphate discloses a production process for producing industrial primary or battery grade monoammonium phosphate from agricultural grade monoammonium phosphate.
The Chinese patent with the publication number of CN103825024A and the invention name of battery-grade iron phosphate and the preparation method thereof discloses a preparation process for preparing the battery-grade iron phosphate by adopting diammonium phosphate and ferric salt.
Generally, in the traditional production process, high-purity monoammonium phosphate or diammonium phosphate crystals are used as raw materials, the preparation process is complex, the raw material cost is high, and the overall production cost of the iron phosphate is extremely high.
The domestic traditional production method of agricultural grade monoammonium phosphate is mainly prepared by carrying out neutralization reaction on wet-process phosphoric acid and ammonia, and carrying out spraying granulation and drying. The method has low production cost, and each index of the production can better meet the production requirement of the traditional compound fertilizer, and the method is widely used in the last years and achieves better effect. The method specifically adopts the following process: firstly, crushing phosphate ore by a crusher, adding water into the crushed phosphate ore, and further crushing the phosphate ore in a ball mill to obtain phosphate ore pulp; then, primarily filtering the ore pulp, adding sulfuric acid to extract phosphoric acid, and filtering impurities to obtain finished phosphoric acid; and finally, introducing gas ammonia to perform neutralization reaction to obtain slurry, concentrating the slurry, and performing spray granulation to obtain granular ammonium phosphate, namely the finished product of the monoammonium phosphate.
The production method of industrial monoammonium phosphate comprises the steps of preparing phosphoric acid, introducing ammonia gas to prepare an industrial monoammonium phosphate clear solution, crystallizing the industrial monoammonium phosphate clear solution to obtain crystals, namely industrial monoammonium phosphate, and crystallizing the residual phosphorus-containing solution to obtain the industrial monoammonium phosphate mother solution.
In the preparation process, clear liquid and mother liquid in the preparation process of industrial grade monoammonium phosphate belong to semi-finished products and byproducts in the preparation process. The existing disposal mode is to recycle the mother liquor and continue to be used for preparing industrial-grade monoammonium phosphate.
Currently, there are also improved processes for the preparation of battery grade anhydrous iron phosphate in the prior art.
For example, chinese patent publication No. CN102491302A entitled "battery-grade anhydrous iron phosphate and method for preparing same" discloses a method for preparing battery-grade anhydrous iron phosphate, which comprises adding a mixture aqueous solution of ferrous salt and phosphoric acid or phosphate into a pH regulator solution to control pH, introducing air, stirring, reacting to generate a crystalline complex containing ammonium, hydroxyl and crystal water, performing solid-liquid separation, washing, and drying to obtain NH4Fe2(OH)(PO4)2·2H2O powder; the powder is roasted in the air atmosphere, and ammonium, hydroxyl and crystal water are decomposed and removed, so that the battery grade anhydrous iron phosphate with the orthorhombic crystal form is obtained. However, the method has complicated process, adopts air as an oxidant, and has process linksThe control is difficult, the cost is high, and the industrialization is difficult to realize.
Disclosure of Invention
The invention provides a method for preparing battery-grade anhydrous iron phosphate by using industrial ammonium phosphate clear liquid or industrial ammonium phosphate mother liquid, aiming at least one technical problem in the prior art, the battery-grade anhydrous iron phosphate meeting the quality requirement can be prepared by using the industrial ammonium phosphate clear liquid or the industrial ammonium phosphate mother liquid as a raw material and through simple process control, and the production cost of the battery-grade anhydrous iron phosphate can be greatly reduced.
In order to solve the above problems, the present invention provides a method for preparing battery grade anhydrous iron phosphate from industrial ammonium phosphate clear solution or industrial ammonium phosphate mother solution, the process flow of which is shown in fig. 2, and the method comprises the following steps:
s1, fluorine removal: adding diatomite and a sodium carbonate solution into the clear industrial ammonium phosphate solution or the mother solution of the industrial ammonium phosphate to react, and then filtering to prepare a phosphorus-containing solution after defluorination;
s2, refining: adjusting the pH value of the phosphorus-containing solution prepared in the step S1, and removing impurities such as calcium, magnesium, manganese, aluminum and the like through precipitation reaction to obtain the phosphorus-containing solution with low impurity ion content;
s3, removing heavy metals: adding a heavy metal precipitator into the phosphorus-containing solution with low impurity ion content prepared in the step S2 to remove heavy metal impurities to obtain a refined phosphate solution;
s4, synthesizing ferric phosphate dihydrate: fully reacting the refined phosphate solution obtained in the step S3 with a ferrous sulfate solution under the action of an oxidant, filtering, washing and drying a filter cake to obtain ferric phosphate dihydrate;
s5, preparing battery-grade anhydrous iron phosphate: and (4) calcining the ferric phosphate dihydrate prepared in the step (S4), and removing crystal water to prepare the battery-grade anhydrous ferric phosphate.
The technical scheme of the invention has the beneficial effects that: the method adopts the industrial ammonium phosphate clear solution or the industrial ammonium phosphate mother solution as the raw material, and can prepare the phosphate solution meeting the preparation requirement of the battery-grade ferric phosphate after simple fluorine removal, impurity removal and heavy metal removal treatment; according to the invention, the battery-grade anhydrous iron phosphate is prepared by directly taking the prepared phosphate solution as a phosphorus source, so that the production cost of the battery-grade anhydrous iron phosphate can be greatly reduced; the process is simple, the process links are easy to control, and the method is very suitable for industrial mass production; the invention changes the phosphorus source of the prior battery-grade iron phosphate from industrial-grade monoammonium phosphate, diammonium phosphate or purified phosphoric acid into industrial-grade monoammonium phosphate clear liquid (semi-finished product) or mother liquid (by-product), simplifies the production process of the iron phosphate, saves raw materials and energy, and can greatly reduce the production cost of the battery-grade iron phosphate.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in the step S1, the reaction pH is 3-5, the reaction temperature is 55-85 ℃, the addition amount of the diatomite is 1-4%, the addition amount of the sodium carbonate is 1-4%, and the reaction time is 1-5 hours; preferably, the addition amount of the diatomite is 1.5-2%, the addition amount of the sodium carbonate is 2-2.5%, and the reaction time is 2-3 h.
In step S2, the pH adjuster is one or a combination of more than one of ammonia water, sodium (bi) carbonate, caustic soda flakes, ammonium (bi) carbonate, and potassium (bi) carbonate.
Preferably, in the step S2, the pH is adjusted to 6.8 to 7.2, and the reaction is stopped until no precipitate is formed.
Further, in the step S3, the precipitating agent is one or a combination of more than one of sodium sulfide, ammonium sulfide and potassium sulfide.
Further, in the step S4, the ferrous sulfate solution is refined from ferrous sulfate, which is a byproduct in titanium dioxide production.
Preferably, the step S4 includes the steps of:
a. diluting the refined phosphate solution obtained in the step S3 with pure water, and adjusting the pH value to obtain a phosphate solution required by the synthesis reaction;
b. dissolving ferrous sulfate as a titanium dioxide byproduct in water, and refining to obtain a synthetic refined iron-smelted sulfate solution;
c. slowly adding the phosphate solution required by the reaction obtained in the step a into the ferrous sulfate solution obtained in the step b, synchronously adding an oxidant, and fully reacting to obtain synthetic slurry;
d. and c, filter-pressing the synthetic slurry obtained in the step c, and washing and drying a filter cake to obtain the ferric phosphate dihydrate.
Preferably, in the step b, a pH regulator is added into the ferrous sulfate solution in the refining process, the pH value is regulated to 4-4.5, and then impurities are filtered; the pH regulator is one or more of ammonia water, sodium bicarbonate, caustic soda flakes, ammonium bicarbonate and potassium bicarbonate.
Further, in step S4, the oxidizing agent is hydrogen peroxide or sodium peroxide.
Further, the step S2 includes an operation step of collecting and reusing the reaction precipitate.
The invention has the following overall beneficial effects: the method adopts the clear industrial ammonium phosphate solution or the mother liquor of the industrial ammonium phosphate as a phosphorus source, takes the ferrous sulfate heptahydrate solid as an iron source, and adopts two main raw materials which are respectively from the by-product of titanium dioxide production and the by-product of industrial ammonium, thereby really realizing changing waste into valuable; the battery-grade ferric phosphate dihydrate is prepared through a simple synthesis reaction, so that the battery-grade anhydrous ferric phosphate is prepared, the production cost is far lower than that of the existing preparation method of the battery-grade anhydrous ferric phosphate, and the method has considerable economic benefit; the precipitate in the impurity removal treatment process of the industrial ammonium phosphate clear liquid or the industrial ammonium phosphate mother liquid contains certain phosphorus elements, and can be collected and provided for secondary utilization of phosphorus chemical enterprises, so that the cost can be further reduced, the emission can be further reduced, and the environmental pollution is avoided; the invention adopts the additive which is easy to obtain and has lower cost, and the reaction condition of the whole process is simple and easy to control, thereby being very suitable for industrialized mass production.
Drawings
FIG. 1 is a flow diagram of a conventional process for making iron phosphate;
fig. 2 is a process flow diagram of the iron phosphate of the present invention.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
In the invention, no special description or definition is provided, and all percentage contents are mass percentages.
The invention relates to a method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear solution or industrial ammonium phosphate mother solution, which comprises the following steps:
s1, fluorine removal: adding diatomite and a sodium carbonate solution into the clear industrial ammonium phosphate solution or the mother solution of the industrial ammonium phosphate to react, and then filtering to prepare a phosphorus-containing solution after defluorination;
s2, refining: adjusting the pH value of the phosphorus-containing solution prepared in the step S1, and removing impurities such as calcium, magnesium, manganese, aluminum and the like through precipitation reaction to obtain the phosphorus-containing solution with low impurity ion content;
s3, removing heavy metals: adding a heavy metal precipitator into the phosphorus-containing solution with low impurity ion content prepared in the step S2 to remove heavy metal impurities to obtain a refined phosphate solution;
s4, synthesizing ferric phosphate dihydrate: fully reacting the refined phosphate solution obtained in the step S3 with a ferrous sulfate solution under the action of an oxidant, filtering, washing and drying a filter cake to obtain ferric phosphate dihydrate;
s5, preparing battery-grade anhydrous iron phosphate: and (4) calcining the ferric phosphate dihydrate prepared in the step (S4), and removing crystal water to prepare the battery-grade anhydrous ferric phosphate.
Before the invention, in the new energy industry and the industrial production process, the battery-grade anhydrous iron phosphate mainly adopts battery-grade or industrial-grade monoammonium phosphate, diammonium phosphate and purified phosphoric acid as phosphorus sources, and phosphate solution required by iron phosphate synthesis is prepared by the working procedures of dissolving with pure water, adjusting pH and the like. Although the method is technically mature and adopted by most of anhydrous iron phosphate production enterprises, the price of the used battery-grade or industrial-grade monoammonium phosphate, diammonium phosphate and purified phosphoric acid is high, and dissolving equipment needs to be added and pure water is consumed, so that the production cost of the anhydrous iron phosphate is high.
In the production process of industrial monoammonium phosphate or diammonium phosphate, a semi-finished product of industrial ammonium phosphate clear liquid is prepared, and then industrial grade ammonium phosphate salt solid and industrial ammonium phosphate mother liquor are obtained by crystallizing the industrial ammonium phosphate clear liquid, and the industrial ammonium phosphate mother liquor is recycled. There is no prior art disclosure of battery grade anhydrous ferric phosphate preparation using industrial ammonium phosphate clear solution or industrial ammonium phosphate mother liquor as the phosphorus source. The composition of the prior industrial ammonium phosphate clear solution or industrial ammonium phosphate mother solution is shown in the following table 1.
TABLE 1 ingredient table of the existing industrial ammonium phosphate clear solution or industrial ammonium phosphate mother liquor
As can be seen from the data in Table 1, the currently available clear industrial ammonium phosphate solution or mother industrial ammonium phosphate solution contains a certain amount of fluorine, and also contains a large amount of impurities such as calcium, magnesium, manganese, aluminum ions and the like, and also contains a certain amount of heavy metal impurities. Because the existing ammonium phosphate process is to prepare the monoammonium phosphate after directly treating phosphate ore, the content of impurities completely depends on the quality of the ore, and the industrial ammonium phosphate clear solution or the industrial ammonium phosphate mother solution has higher content of impurities on the whole, particularly higher content of fluorine, and is completely not suitable for being used as a phosphorus source to produce battery-grade anhydrous iron phosphate with higher requirements on quality.
The inventor discovers that the adverse impurities in the industrial ammonium phosphate clear liquid or the industrial ammonium phosphate mother liquid can be effectively removed through a reasonable and simple process after carrying out component analysis and a large amount of research on the conventional industrial ammonium phosphate clear liquid or the industrial ammonium phosphate mother liquid, the phosphorus element content in the industrial ammonium phosphate clear liquid or the industrial ammonium phosphate mother liquid can completely meet the requirement of battery-grade anhydrous iron phosphate preparation, and the battery-grade anhydrous iron phosphate can be produced by taking the industrial ammonium phosphate clear liquid or the industrial ammonium phosphate mother liquid as a phosphorus source as long as the adverse impurities can be effectively removed. The core of the invention lies in cost control, and the cost of impurity removal needs to be effectively controlled so as to ensure that the overall cost of the process can be lower than that of the existing process, and meanwhile, the quality can meet the requirement of battery-grade anhydrous iron phosphate.
The method comprises the steps of firstly precipitating and removing fluorine by diatomite and sodium carbonate under specific process conditions, then removing harmful impurities by adopting a precipitation mode through pH value control, and finally removing heavy metals by a precipitator. Through the process design, the sediment generated in the fluorine removal link and the harmful impurity removal link contains lost phosphorus elements, and can be supplied to phosphorus chemical enterprises for secondary utilization. The cost is effectively controlled.
At present, the price of the ferro-phosphorus ore is more than 3000 yuan/ton, the selling price of the high-quality ferro-phosphorus ore of the product phase is multiplied, the price of the raw materials of phosphoric acid and nitric acid, the requirements of the production process of high temperature and high pressure and the cost required by the subsequent waste liquid treatment are added, and the cost for producing the battery-grade anhydrous iron phosphate by using the ferro-phosphorus ore as the raw material and adopting a hydrothermal method is more than 8000 yuan/ton at present.
And the material cost is more than 6000 yuan/ton by adopting the patented technology in the background technology. By integrating the factors such as reaction conditions, process parameters and the like required by the technical scheme of the background technology, the whole production cost is more than 8000 yuan/ton.
The invention adopts diatomite and sodium carbonate to remove fluorine, has little dosage, removes impurities by adjusting the pH value, and has extremely low dosage of precipitator used for removing heavy metals. The industrial ammonium phosphate clear liquid or the industrial ammonium phosphate mother liquid belongs to industrial byproducts, the price is below 1300 yuan/ton, the whole process does not need conditions of high temperature, high pressure and the like, and the production cost can be reduced by 20-30% compared with the prior art.
In a more preferred embodiment of the present invention, in the step S1, the reaction pH is 3 to 5, the reaction temperature is 55 to 85 ℃, the addition amount of the diatomaceous earth is 1 to 4%, the addition amount of the sodium carbonate is 1 to 4%, and the reaction time is 1 to 5 hours; preferably, the addition amount of the diatomite is 1.5-2%, the addition amount of the sodium carbonate is 2-2.5%, and the reaction time is 2-3 h.
Most preferably, in the step S1, the reaction pH is 3.5 to 4, the addition amount of the diatomite is 1.5%, the addition amount of the sodium carbonate is 2.2%, the reaction time is 2.5 hours, and the reaction temperature is 65 to 70 ℃.
By adopting the additive amount, the additive amounts of the diatomite and the sodium carbonate can be accurately controlled, and the additive amount can be saved as much as possible on the premise of ensuring the optimal defluorination effect, thereby reducing the cost. The inventor tests the defluorination effect through the defluorination experiment, and the specific experimental result is shown in table 2.
TABLE 2 defluorination experiment test results table
| Numbering | Fluorine content of the original solution | pH value of reaction | Sodium carbonate | Diatomite | Time | Reaction temperature | Fluorine content after defluorination | Fluorine removal rate |
| Unit of | ppm | Numerical value | ％ | ％ | h | ℃ | ppm | ％ |
| 1 | 820 | 3.5-4 | 2.2 | 1.5 | 2.5 | 65-70 | 166 | 79.76 |
| 2 | 820 | 3.5-4 | 3 | 3 | 2.5 | 65-70 | 174 | 78.78 |
| 3 | 1580 | 3.5-4 | 2.2 | 1.5 | 2.5 | 70-80 | 340 | 78.48 |
| 4 | 1580 | 5.5-6 | 2.2 | 1.5 | 2 | 65-70 | 775 | 50.95 |
| 5 | 1580 | 4.5-5 | 2.2 | 3 | 2 | 65-70 | 474 | 70.00 |
| 6 | 2260 | 3.5-4 | 2.2 | 1.5 | 2 | 65-70 | 477 | 78.89 |
In a more preferred embodiment of the present invention, in step S2, the pH adjusting agent is one or a combination of more than one of ammonia water, sodium bicarbonate, caustic soda flakes, ammonium bicarbonate and potassium bicarbonate.
Preferably, in the step S2, the pH is adjusted to 6.8 to 7.2, and the reaction is stopped until no precipitate is formed.
Most preferably, in the step S2, the pH value is adjusted to 7.05-7.10, and the reaction is stopped until no precipitate is generated.
Another core of the invention is the removal of harmful impurities from the industrial ammonium phosphate clear solution or the industrial ammonium phosphate mother solution. The inventor carries out component analysis and research on a large amount of existing industrial ammonium phosphate clear liquid or industrial ammonium phosphate mother liquid, and in the industrial ammonium phosphate clear liquid or the industrial ammonium phosphate mother liquid, the harmful impurities for preparing the battery-grade anhydrous iron phosphate are calcium, magnesium and manganese ions. Although other impurities are limited by the influence of factors such as ore quality, based on the industrial ammonium phosphate production process, a certain impurity removal treatment is carried out in a pretreatment ring, so that the content of other impurities in the industrial ammonium phosphate clear liquid or the industrial ammonium phosphate mother liquid is low, and the finally prepared anhydrous iron phosphate cannot meet the requirement of a battery grade. Through experimental research, the inventor finds that calcium, magnesium and manganese ions can be better removed when the pH value is adjusted to 6.8-7.2, and the removal rate is higher. When the pH value is adjusted to 7.05-7.10, the removal rate is optimal. The inventor tests the impurity removal, and the specific impurity removal effect is tested, and the specific result is shown in table 3.
Table 3 table of test results of impurity removal test
| Element(s) | Mn | Mg | Ca | Al |
| Unit of | ppm | ppm | ppm | ppm |
| Defluorination filtrate (before ammonia introduction) | 260.86 | 2375.9 | 177.32 | 429.53 |
| Ammonia-introducing filtrate with pH value of 5.02 | 319.87 | 1769.65 | 273.61 | 78.22 |
| Ammonia-passing filtrate with pH 5.5 | 159.17 | 876.59 | 118.96 | 25.05 |
| Ammonia-passing filtrate with pH 7.09 | 21.9 | 60.73 | 18.92 | 3.32 |
In a more preferred embodiment of the present invention, in step S3, the precipitating agent is one or a combination of more than one of sodium sulfide, ammonium sulfide and potassium sulfide.
The precipitator has good heavy metal removal effect and low cost. The inventors prefer to use sodium sulfide as the precipitating agent. The inventor artificially verifies the effect of removing the heavy metals and experimentally verifies the part for removing the heavy metals, and specific results are shown in table 4.
Table 4 heavy metal removal test results table
In a more preferred embodiment of the present invention, in step S4, the ferrous sulfate is ferrous sulfate crystal produced as a byproduct of titanium dioxide production.
The production cost can be further reduced by adopting the byproduct ferrous sulfate crystal produced by titanium dioxide.
In a preferred embodiment of the present invention, the step S4 includes the following steps:
a. diluting the refined phosphate solution obtained in the step S3 with pure water, and adjusting the pH value to obtain a phosphate solution required by the synthesis reaction;
b. adding water to dissolve ferrous sulfate crystals as a titanium dioxide byproduct to obtain a sulfate solution required by a synthesis reaction;
c. slowly adding the phosphate solution required by the reaction obtained in the step a into the sulfate solution obtained in the step b, synchronously adding an oxidant, and fully reacting to obtain synthetic slurry;
d. and c, filter-pressing the synthetic slurry obtained in the step c, and washing and drying a filter cake to obtain the ferric phosphate dihydrate.
Preferably, in the step b, a pH regulator is added into the ferrous sulfate solution in the refining process, the pH value is regulated to 4-4.5, and then impurities are filtered; the pH regulator is one or more of ammonia water, sodium bicarbonate, caustic soda flakes, ammonium bicarbonate and potassium bicarbonate.
The overall yield, the quality of the prepared anhydrous iron phosphate and the overall process cost of the synthesis process are all better. In particular, the impurity content can be further reduced by purifying the iron salt solution. Therefore, the inventor selects to prepare the battery-grade anhydrous iron phosphate by adopting the process subsequently.
In a more preferred embodiment of the present invention, in step S4, the oxidizing agent is hydrogen peroxide.
The following are specific examples of the present invention.
Example 1
S1, fluorine removal: adding 1 percent of diatomite and 1 percent of sodium carbonate solution into the clear industrial ammonium phosphate solution to react for 5 hours, and then filtering to obtain the phosphorus-containing solution after fluorine removal.
S2, refining: and (4) introducing ammonia gas into the phosphorus-containing solution prepared in the step (S1) to adjust the pH value, adjusting the pH value to 6.8, and removing impurities such as calcium, magnesium, manganese, aluminum and the like through a precipitation reaction to obtain the phosphorus-containing solution with low impurity ion content.
S3, removing heavy metals: and (4) adding a proper amount of sodium sulfide into the phosphorus-containing solution with low impurity ion content prepared in the step (S2), and removing heavy metal impurities to obtain a refined phosphate solution.
S4, synthesizing ferric phosphate dihydrate: diluting the refined phosphate solution obtained in the step S3 with pure water, and adjusting the pH value to obtain a phosphate solution required by the synthesis reaction; dissolving ferrous sulfate crystals as a titanium dioxide byproduct in water, then introducing ammonia gas, adjusting the pH value to 4, and filtering impurities to obtain a sulfate solution required by a synthesis reaction; slowly adding phosphate solution required by the reaction into the sulfate solution obtained in the step, synchronously adding hydrogen peroxide, and fully reacting to obtain synthetic slurry; and (3) carrying out filter pressing on the synthetic slurry, and washing and drying a filter cake to obtain the ferric phosphate dihydrate.
S5, preparing battery-grade anhydrous iron phosphate: and (4) calcining the ferric phosphate dihydrate prepared in the step (S4), and removing crystal water to prepare the battery-grade anhydrous ferric phosphate powder.
Example 2
S1, fluorine removal: adding 2 percent of diatomite and 2.5 percent of sodium carbonate solution into the industrial ammonium phosphate mother liquor to react for 3 hours, and then filtering to obtain the phosphorus-containing solution after defluorination.
S2, refining: and (4) introducing ammonia gas into the phosphorus-containing solution prepared in the step (S1) to adjust the pH value, adjusting the pH value to 7.05, and removing impurities such as calcium, magnesium, manganese, aluminum and the like through a precipitation reaction to obtain the phosphorus-containing solution with low impurity ion content.
S3, removing heavy metals: and (4) adding a proper amount of sodium sulfide into the phosphorus-containing solution with low impurity ion content prepared in the step (S2), and removing heavy metal impurities to obtain a refined phosphate solution.
S4, synthesizing ferric phosphate dihydrate: diluting the refined phosphate solution obtained in the step S3 with pure water, and adjusting the pH value to obtain a phosphate solution required by the synthesis reaction; dissolving ferrous sulfate crystals as a titanium dioxide byproduct in water, then introducing ammonia gas, adjusting the pH value to 4.5, and filtering impurities to obtain a sulfate solution required by a synthesis reaction; slowly adding phosphate solution required by the reaction into the sulfate solution obtained in the step, synchronously adding hydrogen peroxide, and fully reacting to obtain synthetic slurry; and (3) carrying out filter pressing on the synthetic slurry, and washing and drying a filter cake to obtain the ferric phosphate dihydrate.
S5, preparing battery-grade anhydrous iron phosphate: and (4) calcining the ferric phosphate dihydrate prepared in the step (S4), and removing crystal water to prepare the battery-grade anhydrous ferric phosphate powder.
Example 3
S1, fluorine removal: 1.5 percent of diatomite and 2.2 percent of sodium carbonate solution are added into the clear industrial ammonium phosphate solution to react for 2 hours, and then the solution is filtered to obtain the phosphorus-containing solution after the fluorine is removed.
S2, refining: and (4) introducing ammonia gas into the phosphorus-containing solution prepared in the step (S1) to adjust the pH value, adjusting the pH value to 7.10, and removing impurities such as calcium, magnesium, manganese, aluminum and the like through a precipitation reaction to obtain the phosphorus-containing solution with low impurity ion content.
S3, removing heavy metals: and (4) adding a proper amount of sodium sulfide into the phosphorus-containing solution with low impurity ion content prepared in the step (S2), and removing heavy metal impurities to obtain a refined phosphate solution.
S4, synthesizing ferric phosphate dihydrate: diluting the refined phosphate solution obtained in the step S3 with pure water, and adjusting the pH value to obtain a phosphate solution required by the synthesis reaction; dissolving ferrous sulfate crystals as a titanium dioxide byproduct in water, then introducing ammonia gas, adjusting the pH value to 4.4, and filtering impurities to obtain a sulfate solution required by a synthesis reaction; slowly adding phosphate solution required by the reaction into the sulfate solution obtained in the step, synchronously adding hydrogen peroxide, and fully reacting to obtain synthetic slurry; and (3) carrying out filter pressing on the synthetic slurry, and washing and drying a filter cake to obtain the ferric phosphate dihydrate.
S5, preparing battery-grade anhydrous iron phosphate: and (4) calcining the ferric phosphate dihydrate prepared in the step (S4), and removing crystal water to prepare the battery-grade anhydrous ferric phosphate powder.
Example 4
S1, fluorine removal: adding 4 percent of diatomite and 4 percent of sodium carbonate solution into the industrial ammonium phosphate mother liquor to react for 1 hour, and then filtering to prepare the phosphorus-containing solution after defluorination.
S2, refining: and (4) introducing ammonia gas into the phosphorus-containing solution prepared in the step (S1) to adjust the pH value, adjusting the pH value to 7.2, and removing impurities such as calcium, magnesium, manganese, aluminum and the like through a precipitation reaction to obtain the phosphorus-containing solution with low impurity ion content.
S3, removing heavy metals: and (4) adding a proper amount of sodium sulfide into the phosphorus-containing solution with low impurity ion content prepared in the step (S2), and removing heavy metal impurities to obtain a refined phosphate solution.
S4, synthesizing ferric phosphate dihydrate: diluting the refined phosphate solution obtained in the step S3 with pure water, and adjusting the pH value to obtain a phosphate solution required by the synthesis reaction; dissolving ferrous sulfate crystals as a titanium dioxide byproduct in water, then introducing ammonia gas, adjusting the pH value to 4.2, and filtering impurities to obtain a sulfate solution required by a synthesis reaction; slowly adding phosphate solution required by the reaction into the sulfate solution obtained in the step, synchronously adding hydrogen peroxide, and fully reacting to obtain synthetic slurry; and (3) carrying out filter pressing on the synthetic slurry, and washing and drying a filter cake to obtain the ferric phosphate dihydrate.
S5, preparing battery-grade anhydrous iron phosphate: and (4) calcining the ferric phosphate dihydrate prepared in the step (S4), and removing crystal water to prepare the battery-grade anhydrous ferric phosphate powder.
Example 5
S1, fluorine removal: 1.8 percent of diatomite and 2 percent of sodium carbonate solution are added into the industrial ammonium phosphate mother liquor to react for 2.5 hours, and then the phosphorus-containing solution after defluorination is prepared by filtration.
S2, refining: and (4) introducing ammonia gas into the phosphorus-containing solution prepared in the step (S1) to adjust the pH value, adjusting the pH value to 6.9, and removing impurities such as calcium, magnesium, manganese, aluminum and the like through a precipitation reaction to obtain the phosphorus-containing solution with low impurity ion content.
S3, removing heavy metals: and (4) adding a proper amount of sodium sulfide into the phosphorus-containing solution with low impurity ion content prepared in the step (S2), and removing heavy metal impurities to obtain a refined phosphate solution.
S4, synthesizing ferric phosphate dihydrate: diluting the refined phosphate solution obtained in the step S3 with pure water, and adjusting the pH value to obtain a phosphate solution required by the synthesis reaction; dissolving ferrous sulfate crystals as a titanium dioxide byproduct in water, then introducing ammonia gas, adjusting the pH value to 4.1, and filtering impurities to obtain a sulfate solution required by a synthesis reaction; slowly adding phosphate solution required by the reaction into the sulfate solution obtained in the step, synchronously adding hydrogen peroxide, and fully reacting to obtain synthetic slurry; and (3) carrying out filter pressing on the synthetic slurry, and washing and drying a filter cake to obtain the ferric phosphate dihydrate.
The components of the anhydrous iron phosphate prepared in the examples 1 to 5 are detected, and the quality of the anhydrous iron phosphate powder prepared in the examples 1 to 5 meets the quality requirement of the battery-grade anhydrous iron phosphate through detection, and the content of each element is basically the same as that of the element in the patent technology in the background technology. The results of the tests of examples 1 to 5 are shown in tables 5 to 9.
Table 5 table of measured data of anhydrous iron phosphate prepared in example 1
Table 6 table of data for detection of anhydrous iron phosphate prepared in example 2
Table 7 table of data for testing anhydrous iron phosphate prepared in example 3
Table 8 table of data for testing anhydrous iron phosphate prepared in example 4
Table 9 table of data for testing anhydrous iron phosphate prepared in example 5
From tables 5 to 9, it can be seen that the battery grade anhydrous iron phosphate prepared by the process of the present invention has a good quality, and the quality completely meets the quality requirements of the existing battery grade anhydrous iron phosphate. The cost and the process difficulty of the process are combined, and the overall cost is far lower than that of the existing preparation process of the battery-grade anhydrous iron phosphate.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear liquid or industrial ammonium phosphate mother liquid is characterized by comprising the following steps:
s1, fluorine removal: adding diatomite and a sodium carbonate solution into the clear industrial ammonium phosphate solution or the mother solution of the industrial ammonium phosphate to react, and then filtering to prepare a phosphorus-containing solution after defluorination;
s2, refining: adjusting the pH value of the phosphorus-containing solution prepared in the step S1, and removing impurities such as calcium, magnesium, manganese, aluminum and the like through precipitation reaction to obtain the phosphorus-containing solution with low impurity ion content;
s3, removing heavy metals: adding a heavy metal precipitator into the phosphorus-containing solution with low impurity ion content prepared in the step S2 to remove heavy metal impurities to obtain a refined phosphate solution;
s4, synthesizing ferric phosphate dihydrate: fully reacting the refined phosphate solution obtained in the step S3 with a ferrous sulfate solution under the action of an oxidant, filtering, washing and drying a filter cake to obtain ferric phosphate dihydrate;
s5, preparing battery-grade anhydrous iron phosphate: and (4) calcining the ferric phosphate dihydrate prepared in the step (S4), and removing crystal water to prepare the battery-grade anhydrous ferric phosphate.
2. The method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear liquid or industrial ammonium phosphate mother liquid according to claim 1, wherein in the step S1, the reaction pH is 3-5, the reaction temperature is 55-85 ℃, the addition amount of the diatomite is 1-4%, the addition amount of the sodium carbonate is 1-4%, and the reaction time is 1-5 hours; preferably, the addition amount of the diatomite is 1.5-2%, the addition amount of the sodium carbonate is 2-2.5%, and the reaction time is 2-3 h.
3. The method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear liquid or industrial ammonium phosphate mother liquid according to claim 1, wherein in the step S2, the pH regulator is one or more of ammonia water, sodium (hydrogen) carbonate, caustic soda flakes, ammonium (hydrogen) carbonate and potassium (hydrogen) carbonate.
4. The method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear liquid or industrial ammonium phosphate mother liquid according to claim 4, wherein in the step S2, the pH value is adjusted to 6.8-7.2, and the reaction is stopped until no precipitate is generated.
5. The method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear liquid or industrial ammonium phosphate mother liquid according to claim 1, wherein in the step S3, the precipitating agent is one or more of sodium sulfide, ammonium sulfide or potassium sulfide.
6. The method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear solution or industrial ammonium phosphate mother solution according to claim 1, wherein in the step S4, the ferrous sulfate solution is obtained by refining ferrous sulfate which is a byproduct in titanium dioxide production.
7. The method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear solution or industrial ammonium phosphate mother solution according to claim 6, wherein the step S4 comprises the following steps:
a. diluting the refined phosphate solution obtained in the step S3 with pure water, and adjusting the pH value to obtain a phosphate solution required by the synthesis reaction;
b. dissolving ferrous sulfate as a titanium dioxide byproduct in water, and refining to obtain a synthetic refined iron-smelted sulfate solution;
c. slowly adding the phosphate solution required by the reaction obtained in the step a into the ferrous sulfate solution obtained in the step b, synchronously adding an oxidant, and fully reacting to obtain synthetic slurry;
d. and c, filter-pressing the synthetic slurry obtained in the step c, and washing and drying a filter cake to obtain the ferric phosphate dihydrate.
8. The method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear solution or industrial ammonium phosphate mother solution according to claim 7, wherein in the step b, the refining process comprises adding a pH regulator into a ferrous sulfate solution, regulating the pH value to 4-4.5, and then filtering impurities; the pH regulator is one or more of ammonia water, sodium (hydrogen) carbonate, caustic soda flakes, ammonium (hydrogen) carbonate and potassium (hydrogen) carbonate.
9. The method for preparing battery-grade anhydrous iron phosphate from the industrial ammonium phosphate clear solution or the industrial ammonium phosphate mother solution according to claim 1 or 8, wherein in the step S4, the oxidant is hydrogen peroxide or sodium peroxide.
10. The method for preparing battery-grade anhydrous iron phosphate from industrial ammonium phosphate clear liquid or industrial ammonium phosphate mother liquid according to claim 1, wherein the step S2 further comprises an operation step of collecting and reusing the reaction precipitate.
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| CN114314680A (en) * | 2022-03-02 | 2022-04-12 | 湖北虹润高科新材料有限公司 | Method for preparing low-impurity iron phosphate by using monocalcium phosphate and application |
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