CN116022756A - Method for preparing battery-grade ferric phosphate from pyrite cinder and wet-process phosphoric acid - Google Patents
Method for preparing battery-grade ferric phosphate from pyrite cinder and wet-process phosphoric acid Download PDFInfo
- Publication number
- CN116022756A CN116022756A CN202211441585.1A CN202211441585A CN116022756A CN 116022756 A CN116022756 A CN 116022756A CN 202211441585 A CN202211441585 A CN 202211441585A CN 116022756 A CN116022756 A CN 116022756A
- Authority
- CN
- China
- Prior art keywords
- phosphoric acid
- iron
- wet
- ferric phosphate
- pyrite cinder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Compounds Of Iron (AREA)
Abstract
The invention discloses a method for preparing battery-grade ferric phosphate from pyrite cinder and wet-process phosphoric acid, which comprises the following steps: (1) Reducing and roasting pyrite cinder in a tubular atmosphere furnace; (2) Leaching the roasted product with sulfur-phosphorus mixed acid, and filtering; (3) Adding iron powder into the filtrate, reducing part of ferric iron into bivalent iron, adding sodium sulfide solution to remove heavy metal, adding ammonia water to adjust pH after reaction, adding ammonium bicarbonate, and filtering after reaction; (4) Adding sulfuric acid into the filtrate to adjust the pH, then slowly adding hydrogen peroxide, heating, reacting and filtering; (6) And washing, drying, roasting and crushing the filter cake to obtain the battery-grade anhydrous ferric phosphate. The invention adopts low-value pyrite cinder as an iron source, adopts fertilizer-grade wet-process phosphoric acid as a phosphorus source, fully utilizes the synergistic effect among raw materials, adopts a mixed impurity removal process to obtain ferrous phosphate purifying liquid, and then adopts a one-step method to prepare ferric phosphate, thereby greatly reducing the cost of the iron source and the phosphorus source.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a method for extracting/purifying a low-value iron source and a phosphorus source in the preparation process of battery-grade anhydrous iron phosphate.
Background
The development of iron phosphate preparation technology is mature so far, and the main flow process comprises an ammonia process route and a sodium process route. Wherein, the ammonia process route adopts industrial monoammonium phosphate/diammonium phosphate as a phosphorus source, the sodium process route adopts industrial phosphoric acid as a phosphorus source, and most of iron sources of the two routes adopt titanium dioxide byproduct ferrous sulfate heptahydrate. Along with the great development of new energy industry in China, iron phosphate is also brought to better development opportunities as a precursor of the lithium iron phosphate positive electrode material, however, along with the dispute layout of industries such as phosphorus chemical industry, titanium dioxide and the like, iron phosphate is subjected to surplus productivity, and in order to improve market competitiveness, the reduction of the production cost of the iron phosphate is particularly important. At present, 2.2 to 2.5 tons of titanium white slag (the purity of ferrous sulfate heptahydrate is not less than 85%) is needed for producing 1 ton of anhydrous ferric phosphate, the cost accounts for about 7 percent of the total production cost of the ferric phosphate, and the cost is higher when the ferric phosphate is required to be delivered from the outside of the province. For ferric phosphate production enterprises with less titanium dioxide enterprises in provinces, the cost of the iron source is higher, and when the productivity of ferric phosphate is improved, the supply of the iron source is difficult to ensure, so that the source approach of the iron is widened, and the method has important significance for the production of the ferric phosphate.
Pyrite cinder is a byproduct of sulfuric acid production from pyrite, and the iron content is generally 45% -55%, and is usually sold at a low price of 100-200 yuan/ton. According to the calculation that 1 ton of sulfuric acid needs 1 ton of pyrite, 0.6-0.8 ton of cinder generated by 1 ton of pyrite is calculated, the yield of pyrite cinder in China in 2021 year is 1110-1480 ten thousand tons, and the yield can be matched with more than 1500 ten thousand tons of anhydrous ferric phosphate. Related researches on extracting iron from pyrite cinder and preparing iron phosphate exist, however, the existing patent has one or more problems of low iron leaching rate, long iron leaching time, low iron phosphate purity, complex preparation process, high cost and the like, chinese patent CN102730659A (green tomb chemical industry, 2011) discloses a method for preparing battery grade iron phosphate by using pyrite cinder, and the method adopts organic-non materialsLeaching pyrite cinder by using organic acid, adding an organic solvent for extraction, and having large organic acid and organic solvent consumption and high cost; chinese patent CN108706562A (university of light industry, 2018) discloses a method for preparing ferric phosphate by utilizing pyrite cinder, wherein sulfuric acid is adopted to leach pyrite cinder at high temperature for 6-12 hours, then pickle liquor is directly used for preparing ferric phosphate, and the purity of the obtained ferric phosphate is only 90-91%, and the product value is low. Chinese patent CN109368610a (city, 2018) discloses a method for preparing high iron phosphorus ratio ferric phosphate from pyrite cinder, which uses alkali washing method to remove silicon and aluminum, the alkali liquor amount is large and the waste water is difficult to be treated, in addition, the inventor finds that sulfuric acid and Fe are directly mixed by many experimental researches 2 O 3 The reaction has low iron leaching rate (less than 30 percent) and needs to be subjected to reduction treatment. According to the invention, the pyrite cinder is pretreated by adopting reduction roasting, and then is subjected to acid leaching by using sulfur-phosphorus mixed acid, so that the iron leaching rate is high, and in addition, the battery-grade anhydrous iron phosphate product is prepared by combining various impurity removing modes.
Disclosure of Invention
The core technical problems to be solved by the invention are as follows: firstly, preprocessing pyrite cinder, and improving the leaching rate of iron as much as possible during acid leaching; secondly, impurities affecting the subsequent ferric phosphate products (including impurities brought by fertilizer-grade wet-process phosphoric acid) in the pickle liquor are removed to the maximum extent; thirdly, preparing qualified battery-grade anhydrous ferric phosphate products by a process flow as short as possible.
The technical scheme of the invention relates to a method for preparing battery-grade ferric phosphate by pyrite cinder and wet-process phosphoric acid, which mainly comprises the following steps:
(1) Reducing and roasting pyrite cinder in a tubular atmosphere furnace;
(2) Leaching the roasted product with sulfur-phosphorus mixed acid, and filtering;
(3) Adding iron powder into the filtrate, reducing part of ferric iron into bivalent, then adding sodium sulfide solution, adding ammonia water into the filtrate to adjust pH after reacting for a period of time, then adding ammonium bicarbonate, adding flocculating agent polyacrylamide after reacting for a period of time, stirring, and filtering;
(4) Adding sulfuric acid into the filtrate to adjust the pH, then slowly adding hydrogen peroxide, heating after the addition, and filtering after the reaction;
(5) And washing, drying, roasting and crushing the filter cake to obtain the battery-grade anhydrous ferric phosphate.
According to the preparation method of the battery-grade ferric phosphate, the reducing agent adopted in the reduction roasting in the step (1) is one of graphite, coal powder, sucrose, glucose, carbon monoxide and hydrogen, wherein when the reducing agent is one of graphite, coal powder, sucrose and glucose, the molar ratio of the folded pure carbon to iron in pyrite cinder is 0.5-1:1, the roasting temperature is 800-1000 ℃, preferably, the molar ratio of the folded pure carbon to iron is 0.7-0.8, and the roasting temperature is 850-900 ℃; when one of carbon monoxide and hydrogen is used as a reducing agent, the roasting temperature is 600-900 ℃, preferably 600-650 ℃. The reduction roasting time is 0.5 to 3 hours, preferably 1 to 1.5 hours.
According to the preparation method of the battery-level ferric phosphate, the phosphoric acid in the step (2) is fertilizer-level wet phosphoric acid, the phosphoric acid consumption is 1.39-1.40:1, and the phosphoric acid concentration is 20% -25%. The molar ratio of sulfuric acid to iron is 0.3-0.4:1, and the concentration of sulfuric acid is 20% -25%. The acid leaching temperature is 60-90 ℃, the acid leaching time is 0.5-3 h, and the preferable temperature is 75-80 ℃ and the time is 1.5-2 h.
According to the preparation method of the battery-grade ferric phosphate, in the step (3), the adding amount of the ferric powder is controlled in such a way that the sodium sulfide is added in a concentration of 13% until bubbles begin to appear in the solution, and the using amount of the sodium sulfide solution is 4% -6% of the mass of the pickle liquor. The concentration of ammonia water is 10% -20%, and the end point of the pH value is 3.5-4.1. The addition amount of the ammonium bicarbonate is 0.3 to 1 percent of the mass of the solution, and preferably, 0.5 to 0.7 percent.
In the above method for producing battery grade ferric phosphate, in the step (4), the pH is adjusted to 1.5 to 2.1, preferably 1.70 to 1.80 with sulfuric acid. The concentration of the hydrogen peroxide is 5% -8%. The molar ratio of the hydrogen peroxide to the iron is 0.6-0.65:1, the hydrogen peroxide is added for 10-15 min, the temperature is raised to 90-95 ℃ after the addition, and the reaction time is 2.5-3 h.
According to the preparation method of the battery-grade ferric phosphate, a three-stage repulping countercurrent washing mode is adopted in the step (5), and the volume flow ratio of the washing water consumption to the slurry is 1-1.1:1. Drying temperature is 200-250 ℃, drying time is 1-2 h, roasting temperature is 600-700 ℃ and roasting time is 1.5-2 h.
The invention adopts a reduction roasting mode to reduce high-valence iron in pyrite cinder into low-valence iron (FeO is the main component and a small amount of Fe is the main component) 3 O 4 ) When the roasting product is subjected to acid leaching, the leaching rate of iron is over 96 percent by controlling the technological parameters. The key point of the invention is the removal of impurities (impurities carried by wet phosphoric acid containing fertilizer) in pickle liquor. First, fe is treated with iron powder 3+ All are reduced to Fe 2+ In Fe 2+ The impurity removal is performed under the system because of Fe 3+ Precipitation starts at a pH > 1.5, while Fe 2+ The precipitation is started only when the pH is more than 6.5, and the other purpose of adding the iron powder is to remove inert metal impurities such as copper. The purpose of adding sodium sulfide is to remove heavy metal impurities such as arsenic, lead and the like in the pickle liquor, and the sodium sulfide also has a certain effect on the removal of manganese. The purpose of the step (3) is to adjust the pH to 3.5-4.1 by ammonia water to remove impurities such as aluminum and titanium, al 3+ The precipitation starts when the pH is more than 3.3, and the titanium is removed by the adsorption of ferrous phosphate colloid and Ti 4+ The removal effect is obvious because of more positive charges. The purpose of adding ammonium bicarbonate is to remove Ca in the pickle liquor 2+ 。
Compared with the existing preparation method of the battery-grade anhydrous ferric phosphate, the preparation method has the following advantages:
(1) The pyrite cinder is used as an iron source, so that the iron source cost is low. At present, the iron content of the pyrite cinder of the Guizhou phosphorization group (the occurrence form is Fe 2 O 3 ) 45% -50% and the selling price is 80-100 yuan/ton. The leaching rate of the iron is not less than 96%, and the comprehensive yield of the iron is not less than 92% when the iron is prepared into the iron phosphate.
(2) And the wet-process phosphoric acid is adopted as a phosphorus source, so that the cost of the phosphorus source is low. The existing technology adopts industrial grade phosphoric acid or industrial grade monoammonium phosphate as a phosphorus source, and 1 ton of anhydrous ferric phosphate consumes about 0.85 ton of industrial grade phosphoric acid or industrial grade monoammonium phosphate, and the fertilizer grade wet-process phosphoric acid has a larger cost advantage compared with the phosphorus source.
(3) The iron source and phosphorus source mixed impurity removing process is adopted, so that the problem that the process flow is too long due to independent impurity removing is avoided. The phosphoric acid is taken as a phosphorus source, plays a role of leaching iron, and impurities such as copper, aluminum, titanium, calcium, manganese, arsenic, lead and the like in the phosphorus source of the iron source can be removed by the combined impurity removing process, and other impurities such as sodium, sulfate radical, potassium, magnesium and the like can be removed by multistage repulping and washing of an iron phosphate filter cake, so that a qualified battery grade iron phosphate product is finally obtained.
(4) Wet phosphoric acid (P) 2 O 5 The concentration of the iron in the wet-process phosphoric acid is 25-30 percent, and the content of the iron in the wet-process phosphoric acid is generally 0.2-0.6 percent, so that the method can remove harmful impurities (aluminum, calcium, manganese, arsenic, lead and the like) of subsequent iron phosphate products, retain beneficial elemental iron, and realize the maximization of the wet-process phosphoric acid value through a selective impurity removal process.
Drawings
FIG. 1 is a block diagram of the process flow of the present invention.
Detailed Description
The main chemical compositions of the pyrite cinder used in the invention are shown in table 1,
TABLE 1 main chemical compositions (unit:%)
| Name of the name | Fe 2 O 3 | SiO 2 | SO 3 | CaO | Al 2 O 3 | MgO | TiO 2 | K 2 O | P 2 O 5 |
| Content of | 67.30 | 13.50 | 5.04 | 2.38 | 2.35 | 0.64 | 0.17 | 0.47 | 0.10 |
The main chemical compositions of the wet-process phosphoric acid used in the invention are shown in table 2,
TABLE 2 Main chemical composition of phosphoric acid by wet process (unit:%)
| Name of the name | P 2 O 5 | Fe 2 O 3 | Al 2 O 3 | MgO | SiO 2 | CaO | SO 4 2- | K 2 O | As |
| Content of | 48.10 | 0.58 | 0.95 | 1.85 | 0.21 | 0.28 | 4.36 | 0.083 | 0.0045 |
Example 1
200g of pyrite cinder powder is weighed, 14.1g of graphite powder is placed in a small high-speed universal crusher to be mixed and crushed, then the mixture is transferred into a square corundum crucible, the corundum crucible is placed in a tubular atmosphere furnace (phi 100 mm), nitrogen is continuously introduced after vacuumizing, then the temperature is raised (10 ℃/min) at the beginning, the end point temperature is set to 850 ℃, the constant temperature period is 1.5h, and the mixture is taken out for natural cooling after being cooled to 200 ℃. The roasted product is placed in a 2L glass jacketed reaction kettle, 345.1g of wet phosphoric acid, 483.1g of pure water and 263.2g of 20% sulfuric acid are added, the reaction kettle is heated by jacket circulating water, the temperature is 80 ℃, the reaction time is 1.5h, and the filtration is carried out after the reaction is finished.
Transferring the filtrate into a 2000ml beaker, placing the beaker in a constant-temperature water bath at 45 ℃, adding 23g of reduced iron powder (added for 5 min) into the beaker, changing the color of the solution from light red to green, then adding 53g of 13% sodium sulfide solution (added for 5 min), adding 12% ammonia water after 15min of reaction, adjusting the pH end point to 3.6, adding 3.6g of ammonium bicarbonate, continuing to react for 0.5h, adding 15g of 0.1% polyacrylamide after stirring for 2min, and filtering.
Transferring the filtered filtrate into a 2L glass jacketed reaction kettle, starting stirring, reversely regulating the pH to 1.82 by using industrial grade sulfuric acid, slowly adding 664.7g of 6% hydrogen peroxide for 12min, starting jacket circulating water, setting the temperature of an external constant temperature tank to 90 ℃, aging for 2h and 26min to observe that the color of slurry changes from yellow to white, continuing aging for 0.5h, filtering, reslurrying a filter cake with pure water (keeping the added pure water volume to be similar to the volume of the filtrate), filtering, and repeating the above process for three times (washing water gradient utilization). Transferring the filter cake into a tray, uniformly spreading, drying in a 200 ℃ oven for 2 hours, taking out, cooling, crushing, transferring into a square corundum crucible, placing the crucible into a 680 ℃ box-type resistance furnace (with an exhaust port at the top) for calcining for 2 hours, taking out, and cooling to obtain 295.5g of battery-grade anhydrous ferric phosphate. The comprehensive recovery rate of iron is 92.03%, the recovery rate of phosphorus is 84.98%, and the index of anhydrous ferric phosphate products is shown in Table 3.
Example 2
200g of pyrite cinder powder is weighed, 45.3g of glucose is placed in a small high-speed universal crusher to be mixed and crushed, then the mixture is transferred into a square corundum crucible, the corundum crucible is placed in a tubular atmosphere furnace (phi 100 mm), nitrogen is continuously introduced after vacuumizing, then the temperature is raised (10 ℃/min) at the beginning, the end point temperature is set to 1000 ℃, the constant temperature is kept for 1h, and the mixture is cooled to 200 ℃ and then taken out for natural cooling. The roasted product is placed in a 2L glass jacketed reaction kettle, 346.6g of wet phosphoric acid, 318.8g of pure water and 263.2g of 25% sulfuric acid are added, the reaction kettle is heated by jacket circulating water, the temperature is 90 ℃, the reaction time is 0.5h, and the filtration is carried out after the reaction is finished.
Transferring the filtrate into a 2000ml beaker, placing the beaker in a constant-temperature water bath at 45 ℃, adding 21.6g of reduced iron powder into the beaker (adding time is 5 min), changing the color of the solution from light red to green, then adding 46g of 13% sodium sulfide solution (adding time is 5 min), adding 17% ammonia water after 15min of reaction, adjusting the pH end point to 3.9, adding 5.2g of ammonium bicarbonate, continuing to react for 0.5h, adding 15g of 0.1% polyacrylamide, stirring for 2min, and filtering.
Transferring the filtered filtrate into a 2L glass jacketed reaction kettle, starting stirring, reversely regulating the pH to 1.71 by using industrial grade sulfuric acid, slowly adding 526.9g of 8% hydrogen peroxide for 10min, starting jacket circulating water, setting the temperature of an external constant temperature tank to 95 ℃, aging for 2h and 3min to observe that the color of slurry changes from yellow to white, continuing aging for 45min, filtering, reslurrying a filter cake with pure water (keeping the added pure water volume to be similar to the volume of the filtrate), and then filtering, and repeating the process for three times (washing water echelon utilization). Transferring the filter cake into a tray, uniformly spreading, drying in a 250 ℃ oven for 1 hour, taking out, cooling, crushing, transferring into a square corundum crucible, placing the crucible into a 700 ℃ box-type resistance furnace (with an exhaust port at the top) for calcining for 1.5 hours, taking out, and cooling to obtain 294.0g of battery-grade anhydrous ferric phosphate. The comprehensive recovery rate of iron is 92.27%, the recovery rate of phosphorus is 84.20%, and the index of anhydrous ferric phosphate products is shown in Table 3.
Example 3
200g of pyrite cinder powder is weighed into a square corundum crucible, the corundum crucible is placed into a tubular atmosphere furnace (phi 100 mm), carbon monoxide is introduced to normal pressure after vacuumizing, then carbon monoxide is continuously introduced at a rate of 6mL/min (the outlet gas of the tubular furnace is discharged to the outside through a fume hood), then the temperature is raised (10 ℃/min), the end point temperature is set to 650 ℃, the constant temperature is kept for 1h, and the corundum crucible is taken out for natural cooling after being cooled to 200 ℃. The roasted product is placed in a 2L glass jacketed reaction kettle, 345.8g of wet phosphoric acid, 4815 g of pure water and 269.2g of 25% sulfuric acid are added, the reaction kettle is heated by jacket circulating water, the temperature is 75 ℃, the reaction time is 2h, and the filtration is carried out after the reaction is finished.
Transferring the filtrate into a 2000ml beaker, placing the beaker in a constant-temperature water bath at 45 ℃, adding 23g of reduced iron powder (added for 5 min) into the beaker, changing the color of the solution from light red to green, then adding 55g of 13% sodium sulfide solution (added for 5 min), adding 15% ammonia water after 15min of reaction, adjusting the pH end point to 4.0, adding 6.9g of ammonium bicarbonate, continuing to react for 0.5h, adding 15g of 0.1% polyacrylamide after stirring for 2min, and filtering.
Transferring the filtered filtrate into a 2L glass jacketed reaction kettle, starting stirring, reversely regulating the pH to 1.92 by using industrial grade sulfuric acid, slowly adding 824.2g of 5% hydrogen peroxide for 15min, starting jacket circulating water, setting the temperature of an external constant temperature tank to 94 ℃, aging for 2h and 37min to observe that the color of the slurry changes from yellow to white, continuing aging for 0.5h, filtering, reslurrying a filter cake with pure water (keeping the added pure water volume to be similar to the volume of the filtrate), filtering, and repeating the process for three times (washing water gradient utilization). Transferring the filter cake into a tray, uniformly spreading, drying in a 220 ℃ oven for 2 hours, taking out, cooling, crushing, transferring into a square corundum crucible, placing the crucible into a 630 ℃ box-type resistance furnace (with an exhaust port at the top) for calcining for 2 hours, taking out, and cooling to obtain 295.7g of battery-grade anhydrous ferric phosphate. The comprehensive recovery rate of iron is 92.13%, the recovery rate of phosphorus is 85.15%, and the index of the anhydrous ferric phosphate product is shown in Table 3.
TABLE 3 iron phosphate product index of examples 1-3
| Name of the name | Example 1 | Example 2 | Example 3 | Index of some downstream customer |
| Fe (%) | 36.30 | 36.14 | 36.31 | 36.0～36.6 |
| P (%) | 20.80 | 20.8 | 20.87 | 20.6～21.0 |
| Fe/P | 0.968 | 0.963 | 0.965 | 0.960～0.980 |
| Na（ppm） | 17 | 19 | 25 | ≤50 |
| Mg（ppm） | 22 | 23 | 23 | ≤250 |
| K（ppm） | 9 | 11 | 8 | ≤50 |
| Ca（ppm） | 26 | 25 | 29 | ≤50 |
| Zn（ppm） | 23 | 22 | 26 | ≤30 |
| Cu（ppm） | Not detected | Not detected | Not detected | ≤20 |
| Al（ppm） | 27 | 35 | 32 | ≤150 |
| Mn（ppm） | 3 | 5 | 5 | ≤200 |
| Ni（ppm） | Not detected | Not detected | Not detected | ≤10 |
| Pb （ppm） | 25 | 25 | 23 | ≤30 |
| S（ppm） | 292 | 339 | 230 | ≤350 |
| Ti（ppm） | 2 | 2 | 3 | ≤150 |
| Moisture (ppm) | 2306 | 2664 | 2289 | ≤5000 |
| pH | 2.98 | 3.07 | 3.14 | 2.7～3.6 |
| Particle size D 50 μm | 3.52 | 3.27 | 3.23 | ≤5 |
| Specific surface area m 2 /g | 4.47 | 4.82 | 4.35 | 4～8 |
| Tap density g/cm 3 | 0.816 | 0.831 | 0.802 | ≥0.6 |
Claims (7)
1. The method for preparing the battery-grade ferric phosphate by using pyrite cinder and wet-process phosphoric acid is characterized by comprising the following steps of:
(1) Reducing and roasting pyrite cinder in a tubular atmosphere furnace;
(2) Leaching the roasted product with sulfur-phosphorus mixed acid, and filtering;
(3) Adding iron powder into the filtrate, reducing part of ferric iron into bivalent, then adding sodium sulfide solution, adding ammonia water into the filtrate to adjust pH after reacting for a period of time, then adding ammonium bicarbonate, adding flocculating agent polyacrylamide after reacting for a period of time, stirring, and filtering;
(4) Adding sulfuric acid into the filtrate to adjust the pH, then slowly adding hydrogen peroxide, heating after the addition, and filtering after the reaction;
(5) And washing, drying, roasting and crushing the filter cake to obtain the battery-grade anhydrous ferric phosphate.
2. The method for preparing battery grade ferric phosphate by using pyrite cinder and wet-process phosphoric acid as claimed in claim 1, wherein the reducing agent adopted in the reduction roasting in the step (1) is one of graphite, coal powder, sucrose, glucose, carbon monoxide and hydrogen, and when the reducing agent is one of graphite, coal powder, sucrose and glucose, the molar ratio of the folded carbon to the iron in the pyrite cinder is 0.5-1:1, and the roasting temperature is 800-1000 ℃; when one of carbon monoxide and hydrogen is used as a reducing agent, the roasting temperature is 600-900 ℃, and the reduction roasting time is 0.5-3 h.
3. The method for preparing battery grade ferric phosphate from pyrite cinder and wet-process phosphoric acid according to claim 1, wherein in the step (2), the phosphoric acid adopts fertilizer grade wet-process phosphoric acid, the phosphoric acid dosage is 1.39-1.40:1 of the molar ratio of the ferrophosphorus, and the phosphoric acid concentration is 20% -25%; the molar ratio of sulfuric acid to iron is 0.3-0.4:1, and the concentration of sulfuric acid is 20% -25%; the acid leaching temperature is 60-90 ℃ and the acid leaching time is 0.5-3 h.
4. The method for preparing battery grade ferric phosphate by using pyrite cinder and wet-process phosphoric acid as claimed in claim 1, wherein the adding amount of the ferric powder in the step (3) is controlled in such a way that sodium sulfide is added to a concentration of 13% until bubbles begin to appear in the solution, and the using amount of the sodium sulfide solution is 4% -6% of the mass of the pickling solution.
5. The method for preparing battery grade ferric phosphate by using pyrite cinder and wet-process phosphoric acid according to claim 1, wherein the concentration of ammonia water in the step (3) is 10% -20%, and the end point of the pH value is adjusted to be 3.5-4.1 by using ammonia water; the addition amount of the ammonium bicarbonate is 0.3-1% of the mass of the solution.
6. The method for preparing battery grade ferric phosphate from pyrite cinder and wet-process phosphoric acid according to claim 1, wherein in the step (4), sulfuric acid is used for adjusting the pH to 1.5-2.1, the concentration of hydrogen peroxide is 5% -8%, the molar ratio of hydrogen peroxide to iron is 0.6-0.65:1, the hydrogen peroxide is added for 10-15 min, the temperature is raised to 90-95 ℃ after the addition, and the reaction time is 2.5-3 h.
7. The method for preparing battery-grade ferric phosphate from pyrite cinder and wet-process phosphoric acid according to claim 1, wherein in the step (5), a three-stage repulping countercurrent washing mode is adopted, the volume flow ratio of the washing water consumption to the slurry is 1-1.1:1, the drying temperature is 200-250 ℃, the drying time is 1-2 h, the roasting temperature is 600-700 ℃, and the roasting time is 1.5-2 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211441585.1A CN116022756A (en) | 2022-11-17 | 2022-11-17 | Method for preparing battery-grade ferric phosphate from pyrite cinder and wet-process phosphoric acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211441585.1A CN116022756A (en) | 2022-11-17 | 2022-11-17 | Method for preparing battery-grade ferric phosphate from pyrite cinder and wet-process phosphoric acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116022756A true CN116022756A (en) | 2023-04-28 |
Family
ID=86074772
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211441585.1A Pending CN116022756A (en) | 2022-11-17 | 2022-11-17 | Method for preparing battery-grade ferric phosphate from pyrite cinder and wet-process phosphoric acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116022756A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116443835A (en) * | 2023-05-25 | 2023-07-18 | 河南佰利新能源材料有限公司 | Ferric phosphate and preparation method and application thereof |
-
2022
- 2022-11-17 CN CN202211441585.1A patent/CN116022756A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116443835A (en) * | 2023-05-25 | 2023-07-18 | 河南佰利新能源材料有限公司 | Ferric phosphate and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102002585B (en) | Method for producing vanadium iron with stone-like coal pickle liquor | |
| CN113277489A (en) | Method for preparing high-purity iron phosphate by using ferrophosphorus waste | |
| CN115583641A (en) | Method for preparing battery-grade iron phosphate by cooperation of pyrite cinder and waste lithium iron phosphate cores | |
| CN102337409A (en) | Method for recovering vanadium from dephosphorization bottom flow residues | |
| CN101723461A (en) | Neutralization aluminum removing method for sodium chromate alkali solution | |
| CN103833156B (en) | A kind for the treatment of process of cold rolling chlorohydric acid pickling spent acid | |
| US20150240327A1 (en) | Method for Producing a High-purity Nanometer Zinc Oxide from Low-grade Zinc Oxide Ore by Ammonia Decarburization | |
| CN116022756A (en) | Method for preparing battery-grade ferric phosphate from pyrite cinder and wet-process phosphoric acid | |
| CN110963515A (en) | Method for recovering alumina from fly ash | |
| CN113955733B (en) | Method for preparing ferric phosphate by utilizing waste hydrochloric acid containing iron | |
| CN110218861A (en) | A kind of method of calcification tailings in vanadium extraction desulfurization | |
| CN101705377B (en) | Method for extracting vanadium from stone coal by wet-process enrichment and pyrogenic-process conversion | |
| CN110331297B (en) | Method for preparing vanadium pentoxide from vanadium slag in short process | |
| CN114572954B (en) | Method for preparing battery grade ferric phosphate by using pyrite cinder | |
| CN116588909A (en) | Method for preparing ferric phosphate from ferrophosphorus slag after lithium extraction of waste lithium iron phosphate | |
| CN111041243A (en) | Method for extracting vanadium from acidic high-phosphorus vanadium solution | |
| CN103466583A (en) | Method of preparing iron phosphate by using phosphor-iron oxidizing slag | |
| CN112662866B (en) | Method for reducing sulfate radical content in rare earth oxide by carbonization roasting | |
| CN114976337A (en) | Comprehensive recovery method of scrapped lithium iron phosphate | |
| CN110357164B (en) | Method for green purification of manganese oxide ore slurry by coupling circulating efficient flue gas desulfurization with manganese sulfate | |
| CN108147437B (en) | Method for producing high-purity magnesium oxide by taking magnesium arsenate as raw material | |
| CN113753952A (en) | Method for preparing ammonium polyvanadate from sodium vanadium solution with low ammonium content | |
| CN112126784A (en) | Method for recovering vanadium and chromium resources from vanadium and chromium sludge | |
| CN114477257B (en) | Method for preparing low-sodium low-iron aluminum hydroxide flame retardant and co-producing ammonium chloride by using circulating fluidized bed fly ash | |
| CN105543506A (en) | Method for producing high-purity chromium metal |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |