METHOD FOR RECYCLING IRON PHOSPHATE WASTE AND USE THEREOF
20240021903 ยท 2024-01-18
Inventors
- Chunxia Tang (Foshan, CN)
- Changdong LI (Foshan, CN)
- Shenghe TANG (Foshan, CN)
- Yanchao Qiao (Foshan, CN)
- Dingshan Ruan (Foshan, CN)
Cpc classification
International classification
Abstract
The present disclosure discloses a method for recycling iron phosphate waste and use thereof. The method includes: mixing the iron phosphate waste with an acid liquid for dissolution to obtain an iron-phosphorus solution; taking a small portion of the iron-phosphorus solution to prepare an iron phosphate precipitating agent; adding the iron phosphate precipitating agent to a remaining portion of the iron-phosphorus solution to react to obtain an iron phosphate dihydrate precipitate; and keeping a portion of the iron phosphate dihydrate precipitate as a precipitating agent for a reaction in a subsequent batch, and preparing a remaining portion of the iron phosphate dihydrate precipitate into anhydrous iron phosphate. In the present disclosure, an iron phosphate precipitating agent is prepared and used for the subsequent preparation of iron phosphate, and iron phosphate obtained in each preparation can be used for the next preparation of iron phosphate.
Claims
1. A method for recycling iron phosphate waste, comprising the following steps: S1: mixing the iron phosphate waste with an acid liquid for dissolution, and filtering a resulting mixture to obtain an iron-phosphorus solution; S2: adding an alkali liquid to a portion of the iron-phosphorus solution for pH adjustment, stirring and heating to allow a reaction, and filtering a resulting product to obtain an iron phosphate precipitating agent; S3: washing the iron phosphate precipitating agent and adding the iron phosphate precipitating agent to a remaining portion of the iron-phosphorus solution; stirring and heating a resulting mixture to allow a reaction to obtain an iron phosphate dihydrate precipitate, and filtering out and washing the iron phosphate dihydrate precipitate; and keeping a portion of the iron phosphate dihydrate precipitate as a precipitating agent for a reaction in a subsequent batch, and drying and sintering a remaining portion of the iron phosphate dihydrate precipitate to obtain anhydrous iron phosphate; and S4: repeating S1 to S3 wherein the iron phosphate precipitating agent added to the iron-phosphorus solution in S3 is the portion of the iron phosphate dihydrate precipitate kept in S3 from a previous batch, in S3, a filtrate obtained after the filtering is used for the dissolution of the iron phosphate waste in S1; in S2, a filtrate obtained after the filtering is added to the remaining portion of the iron-phosphorus solution in S3.
2. The method for recycling iron phosphate waste according to claim 1, wherein the iron phosphate waste comprises one or more from the group consisting of an iron phosphate scrap, a waste obtained after subjecting lithium iron phosphate (LFP) to lithium extraction, an iron-phosphorus residue obtained after subjecting an LFP electrode sheet to lithium extraction, and an iron-phosphorus residue obtained after subjecting an LFP battery to disassembly and lithium extraction.
3. The method for recycling iron phosphate waste according to claim 1, wherein in S1, the acid liquid comprises one or more from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, and phosphoric acid; and a molar ratio of acid anions in the acid liquid to iron ions is (1.1-1.5):1.
4. The method for recycling iron phosphate waste according to claim 1, wherein in S1, the mixing of the iron phosphate waste with the acid liquid for dissolution comprises: adding the acid liquid with stirring, wherein the stirring is conducted at a speed of 100 r/min to 400 r/min for 3 h to 5 h.
5. The method for recycling iron phosphate waste according to claim 1, wherein in S2, the alkali liquid comprises one or more from the group consisting of ammonia water, sodium hydroxide, potassium hydroxide, sodium carbonate, diammonium phosphate (DAP), sodium bicarbonate, and potassium bicarbonate.
6. The method for recycling iron phosphate waste according to claim 1, wherein in S2, the pH is adjusted to 0.5 to 2.5.
7. The method for recycling iron phosphate waste according to claim 1, wherein in S2 and S3, the stirring is conducted at a speed of 200 rpm/min to 600 rpm/min, the heating is conducted at 80 C. to 100 C., and the reaction is conducted for 2 h to 8 h.
8. The method for recycling iron phosphate waste according to claim 1, wherein in S3, a mass of the portion of the iron phosphate dihydrate precipitate kept accounts for 5% to 40% of a total mass of the iron phosphate dihydrate precipitate produced.
Description
BRIEF DESCRIPTION OF DRAWINGS
[0027] The present disclosure is further described below with reference to accompanying drawings and examples.
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[0029]
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[0031]
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[0035]
DETAILED DESCRIPTION
[0036] The concepts and technical effects of the present disclosure are clearly and completely described below in conjunction with examples, so as to allow the objectives, features and effects of the present disclosure to be fully understood. Apparently, the described examples are merely some rather than all of the examples of the present disclosure. All other examples obtained by those skilled in the art based on the examples of the present disclosure without creative efforts should fall within the protection scope of the present disclosure.
Example 1
[0037] Iron phosphate was prepared in this example by a specific process including the following steps: [0038] S1: 20 kg of a waste obtained after LFP was subjected to lithium extraction was added to a reactor A, 150 L of water was added, 10.5 L of concentrated sulfuric acid was added under stirring at a speed of 180 r/min, and the stirring was continued until the waste was completely dissolved to obtain an iron-phosphorus solution with iron ions, phosphate ions, and sulfate ions, where a molar ratio of acid anions to iron ions was 1.5:1; [0039] S2: the iron-phosphorus solution in the reactor A obtained in S1 was passed through a filtration system to remove a small amount of impurities and then transferred to a reactor B and a reactor C through pipes, where 120 L of the iron-phosphorus solution entered the reactor C and 30 L of the iron-phosphorus solution entered the reactor B; [0040] S3: ammonia water was added to the reactor B at a speed controlled at 3 L/h, and when a pH of the solution was 3.0, the addition of ammonia water was stopped, and stirring was started at a speed controlled at 300 rpm/min; the reactor B was heated to 94 C. and kept at the temperature for 3 h; and a resulting precipitate was filtered out, washed, and dried by flash evaporation at 120 C. to obtain an iron phosphate precipitating agent, which would be used in S4; where a resulting filtrate of the reactor B was transferred into the reactor C; [0041] S4: the iron phosphate precipitating agent obtained in S3 was added to the reactor C, and the reactor C was heated to 88 C. and kept at the temperature for 6 h to obtain an iron phosphate dihydrate precipitate; the iron phosphate dihydrate precipitate was filtered out, washed until a conductivity was lower than 500 S/cm, and subjected to pressure filtration to obtain an iron phosphate dihydrate filter cake; and 6 kg of the iron phosphate dihydrate filter cake was kept as a precipitating agent for a reaction in a subsequent batch, and a remaining portion of the iron phosphate dihydrate filter cake was dried by flash evaporation and incubated at 500 C. for 10 h in a rotary kiln to obtain anhydrous iron phosphate; where a resulting filtrate of the reactor C was returned to the reactor A to participate in the dissolution of iron phosphate waste; and [0042] S5: S1 was repeated, and a resulting iron-phosphorus solution in the reactor A was filtered and added to the reactor C; then the iron phosphate dihydrate kept in S4 was added to the reactor C to achieve the preparation of iron phosphate in the next batch; after iron phosphate dihydrate was obtained, 1 kg to 8 kg of the iron phosphate dihydrate was kept; and anhydrous iron phosphate could be cyclically prepared in the reactor C according to the above steps.
Example 2
[0043] Iron phosphate was prepared in this example by a specific process including the following steps: [0044] S1: 40 kg of an iron phosphate scrap was added to a reactor A, 300 L of water was added, 13.5 L of concentrated nitric acid was added under stirring at a speed of 180 r/min, and the stirring was continued until the waste was completely dissolved to obtain an iron-phosphorus solution with iron ions, phosphate ions, and nitrate ions, where a molar ratio of acid anions to iron ions was 1.15:1; [0045] S2: the iron-phosphorus solution in the reactor A obtained in S1 was passed through a filtration system to remove a small amount of impurities and then transferred to a reactor B and a reactor C through pipes, where 240 L of the iron-phosphorus solution entered the reactor C and 60 L of the iron-phosphorus solution entered the reactor B; [0046] S3: sodium hydroxide was added to the reactor B at a speed controlled at 3.5 L/h, and when a pH of the solution was 3.2, the addition of sodium hydroxide was stopped, and stirring was started at a speed controlled at 400 rpm/min; the reactor B was heated to 92 C. and kept at the temperature for 4 h; and a resulting precipitate was filtered out, washed, and dried by flash evaporation at 120 C. to obtain an iron phosphate precipitating agent, which would be used in S4; where a resulting filtrate of the reactor B was transferred into the reactor C; [0047] S4: the iron phosphate precipitating agent obtained in S3 was added to the reactor C, and the reactor C was heated to 94 C. and kept at the temperature for 3 h to obtain an iron phosphate dihydrate precipitate; the iron phosphate dihydrate precipitate was filtered out, washed until a conductivity was lower than 500 S/cm, and subjected to pressure filtration to obtain an iron phosphate dihydrate filter cake; and 10 kg of the iron phosphate dihydrate filter cake was kept as a precipitating agent for a reaction in a subsequent batch, and a remaining portion of the iron phosphate dihydrate filter cake was rake-dried at 120 C. and incubated at 650 C. for 5 h in a rotary kiln to obtain anhydrous iron phosphate; where a resulting filtrate of the reactor C was returned to the reactor A to participate in the dissolution of iron phosphate waste; and [0048] S5: S1 was repeated, and a resulting iron-phosphorus solution in the reactor A was filtered and added to the reactor C; then the iron phosphate dihydrate kept in S4 was added to the reactor C to achieve the preparation of iron phosphate in the next batch; after iron phosphate dihydrate was obtained, 2 kg to 16 kg of the iron phosphate dihydrate was kept; and anhydrous iron phosphate could be cyclically prepared in the reactor C according to the above steps.
Example 3
[0049] Iron phosphate was prepared in this example by a specific process including the following steps: [0050] S1: 50 kg of an iron-phosphorus residue obtained after an LFP battery was subjected to disassembly and lithium extraction was added to a reactor A, 370 L of water was added, 10 L of 85% phosphoric acid and 10 L of concentrated hydrochloric acid were added under stirring at a speed of 180 r/min, and the stirring was continued until the waste was completely dissolved to obtain an iron-phosphorus solution with iron ions, phosphate ions, and chloride ions, where a molar ratio of acid anions to iron ions was 1.2:1; [0051] S2: the iron-phosphorus solution in the reactor A obtained in S1 was passed through a filtration system to remove a small amount of impurities and then transferred to a reactor B and a reactor C through pipes, where 300 L of the iron-phosphorus solution entered the reactor C and 70 L of the iron-phosphorus solution entered the reactor B; [0052] S3: 3 mol/L DAP was added to the reactor B at a speed controlled at 2 L/h, and when a pH of the solution was 2.9, the addition of DAP was stopped, and stirring was started at a speed controlled at 300 rpm/min; the reactor B was heated to 92 C. and kept at the temperature for 5 h; and a resulting precipitate was filtered out, washed, and dried by flash evaporation at 120 C. to obtain an iron phosphate precipitating agent, which would be used in S4; where a resulting filtrate of the reactor B was transferred into the reactor C; [0053] S4: the iron phosphate precipitating agent obtained in S3 was added to the reactor C, and the reactor C was heated to 90 C. and kept at the temperature for 5 h to obtain an iron phosphate dihydrate precipitate; the iron phosphate dihydrate precipitate was filtered out, washed until a conductivity was lower than 500 S/cm, and subjected to pressure filtration to obtain an iron phosphate dihydrate filter cake; and 4 kg of the iron phosphate dihydrate filter cake was kept as a precipitating agent for a reaction in a subsequent batch, and a remaining portion of the iron phosphate dihydrate filter cake was dried by flash evaporation at 120 C. and incubated at 550 C. for 10 h in a rotary kiln to obtain anhydrous iron phosphate; where a resulting filtrate of the reactor C was returned to the reactor A to participate in the dissolution of iron phosphate waste; and [0054] S5: S1 was repeated, and a resulting iron-phosphorus solution in the reactor A was filtered and added to the reactor C; then the iron phosphate dihydrate kept in S4 was added to the reactor C to achieve the preparation of iron phosphate in the next batch; after iron phosphate dihydrate was obtained, 2 kg to 20 kg of the iron phosphate dihydrate was kept; and anhydrous iron phosphate could be cyclically prepared in the reactor C according to the above steps.
Example 4
[0055] Iron phosphate was prepared in this example by a specific process including the following steps: [0056] S1: 30 kg of an iron-phosphorus residue obtained after an LFP electrode sheet was subjected to lithium extraction was added to a reactor A, 200 L of water was added, 6.5 L of phosphoric acid and 6 L of nitric acid were added under stirring at a speed of 150 r/min, and the stirring was continued until the waste was completely dissolved to obtain an iron-phosphorus solution with iron ions, phosphate ions, and nitrate ions, where a molar ratio of acid anions to iron ions was 1.3:1; [0057] S2: the iron-phosphorus solution in the reactor A obtained in S1 was passed through a filtration system to remove a small amount of insoluble residue in the electrode sheet and then transferred to a reactor B and a reactor C through pipes, where 160 L of the iron-phosphorus solution entered the reactor C and 40 L of the iron-phosphorus solution entered the reactor B; [0058] S3: 5 mol/L sodium carbonate was added to the reactor B at a speed controlled at 6 L/h, and when a pH of the solution was 2.5, the addition of sodium carbonate was stopped, and stirring was started at a speed controlled at 400 rpm/min; the reactor B was heated to 92 C. and kept at the temperature for 3 h; and a resulting precipitate was filtered out, washed, and rake-dried at 120 C. to obtain an iron phosphate precipitating agent, which would be used in S4; where a resulting filtrate of the reactor B was transferred into the reactor C; [0059] S4: the iron phosphate precipitating agent obtained in S3 was added to the reactor C, and the reactor C was heated to 96 C. and kept at the temperature for 3 h to obtain an iron phosphate dihydrate precipitate; the iron phosphate dihydrate precipitate was filtered out, washed until a conductivity was lower than 500 S/cm, and subjected to pressure filtration to obtain an iron phosphate dihydrate filter cake; and 3 kg of the iron phosphate dihydrate filter cake was kept as a precipitating agent for a reaction in a subsequent batch, and a remaining portion of the iron phosphate dihydrate filter cake was rake-dried at 120 C. and incubated at 600 C. for 5 h in a rotary kiln to obtain anhydrous iron phosphate; where a resulting filtrate of the reactor C was returned to the reactor A to participate in the dissolution of iron phosphate waste; and [0060] S5: S1 was repeated, and a resulting iron-phosphorus solution in the reactor A was filtered and added to the reactor C; then the iron phosphate dihydrate kept in S4 was added to the reactor C to achieve the preparation of iron phosphate in the next batch; after iron phosphate dihydrate was obtained, 1.5 kg to 12 kg of the iron phosphate dihydrate was kept; and anhydrous iron phosphate could be cyclically prepared in the reactor C according to the above steps.
Comparative Example 1
[0061] Iron phosphate was prepared in this Comparative Example by a specific process including the following steps: [0062] S1: 50 kg of an iron-phosphorus residue obtained after an LFP battery was subjected to disassembly and lithium extraction was added to a reactor A, 370 L of water was added, 27.0 L of 85% phosphoric acid was added under stirring at a speed of 180 r/min, and the stirring was continued until the waste was completely dissolved to obtain an iron-phosphorus solution with iron ions, phosphate ions, and chloride ions, where a molar ratio of acid anions to iron ions was 1.2:1; [0063] S2: the iron-phosphorus solution in the reactor A obtained in S1 was passed through a filtration system to remove a small amount of impurities and then transferred to a reactor B through a pipe; 75 L to 80 L of 6 mol/L DAP was added to the reactor B at a speed of 2 L/min, and when a pH of the solution was 2.9 to 3.0, stirring was started at a speed controlled at 300 rpm/min; the reactor B was heated to 92 C. and kept at the temperature for 5 h; and a resulting precipitate was filtered out, washed, and dried by flash evaporation at 120 C. to obtain iron phosphate; and [0064] S3: the iron phosphate obtained in S2 was incubated at 550 C. for 10 h in a rotary kiln to obtain anhydrous iron phosphate.
Experimental Example
[0065] The anhydrous iron phosphate initially prepared and the anhydrous iron phosphate obtained after 3 cycles in Examples 1 to 4 were tested for physical and chemical indexes, and the physical and chemical indexes of the anhydrous iron phosphate initially prepared were compared with that of the anhydrous iron phosphate obtained after 3 cycles. Results were shown in Table 1 below.
TABLE-US-00001 TABLE 1 Test results of physical and chemical indexes of the anhydrous iron phosphate prepared in Examples 1 to 4 Standards of iron phosphate for LFP cathode Example Example Example Example Item materials 1 2 3 4 Anhydrous iron phosphate initially prepared Fe/% 36.00 to 37.00 36.05 36.26 36.35 36.31 P/% 20.50 to 21.00 20.53 20.63 20.74 20.57 Fe/P 0.960 to 1.0 0.974 0.974 0.972 0.979 Com- 0.60 0.65 0.80 0.78 0.81 pacted density (g/cm.sup.3) Anhydrous iron phosphate obtained after 3 cycles Fe/% 36.00 to 37.00 36.07 36.03 36.31 36.21 P/% 20.50 to 21.00 20.62 20.56 20.57 20.70 Fe/P 0.960 to 1.0 0.970 0.972 0.976 0.978 Com- 0.60 0.67 0.79 0.82 0.81 pacted density (g/cm.sup.3)
[0066] It can be seen from Table 1 that, for both the anhydrous iron phosphate initially prepared and the anhydrous iron phosphate obtained after 3 cycles in the method of the present disclosure, various physical and chemical indexes are in line with the standards for LFP cathode materials, indicating that the anhydrous iron phosphate prepared by the cycle process has stable quality and the process is reliable.
[0067] The anhydrous iron phosphate initially prepared and the anhydrous iron phosphate obtained after 3 cycles in Example 3 and the commercially-available anhydrous iron phosphate (purchased from Langfang Nabo Chemical Technology Co., Ltd.) were used to prepare LFP according to the following method: 2,800 ml of water, 1,000 g of iron phosphate, 80 g of glucose, and 80 g of PEG dispersed in 200 g of hot water were mixed, where a final solid-to-liquid ratio was controlled at 35%; the mixture was dispersed with a high-speed disperser for 30 min and then poured into a sand mill for fine grinding, where a slurry D50 was controlled at 500 nm to 550 nm during the fine grinding; a resulting material was spray-dried at an air outlet temperature controlled at 100 C. to 110 C.; and the material was sintered at 750 C. for 10 h in a sagger introduced with nitrogen as an inert protective gas to obtain highly-compacted LFP. The prepared LFP was tested for performance indexes of all aspects, and results were shown in Table 2 below:
TABLE-US-00002 TABLE 2 Comparison of performance indexes of LFP LFP prepared LFP prepared LFP prepared from from anhydrous from anhydrous commercially- iron phosphate iron phosphate available initially obtained after iron obtained 3 cycles phosphate Item Example 3 Example 3 (Langfang Nabo) C/% 1.42 1.45 1.45 BET (m.sup.2/g) 16 13.2 12 Powder compacted 2.36 2.46 2.20 density (g/cc) Initial specific 162 161.3 161 charge capacity at 1 C (mAh/g) Initial specific 156 157.2 154 discharge capacity at 1 C (mAh/g) Initial coulombic 96.3 97.4 95.6 efficiency (%) Specific charge 136 137 134 capacity after 200 cycles at 1 C (mAh/g)
[0068] It can be seen from Table 2 that the compacted density and specific surface area (SSA) of the LFP powder synthesized from anhydrous iron phosphate in the examples of the present disclosure are higher than that of the LFP synthesized from the commercially-available iron phosphate, and the electrochemical performance of the LFP powder synthesized from anhydrous iron phosphate in the examples of the present disclosure is also slightly better than that of the LFP synthesized from the commercially-available iron phosphate, indicating that the anhydrous iron phosphate prepared by the present disclosure has reached the standards of iron phosphate used for LFP and shows further-optimized performance, and thus can be directly used as a precursor for the production of LFP. In addition, the anhydrous iron phosphate initially prepared has comparable properties to the anhydrous iron phosphate obtained after 3 cycles, indicating that the anhydrous iron phosphate prepared by the cycle process has stable quality and the process is very stable.
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[0076] The present disclosure also compares Example 3 with Comparative Example 1 in terms of alkali consumption, specifically as shown in Table 3.
TABLE-US-00003 TABLE 3 Cumulative amount of treated iron- phosphorus residue (kg)/Alkali Comparative consumption (L)/Treatment method Example 3 Example 1 50 20 to 25 75 to 80 100 20 to 25 150 to 160 150 20 to 25 225 to 240
[0077] It can be seen from Table 3 that, in Example 3, alkali liquid is used only in the initial preparation, and an alkali liquid consumption in the initial preparation only accounts for about of an alkali liquid consumption in Comparative Example 1; and in Example 3, after the iron phosphate precipitate is recycled, the subsequent process does not involve the use of alkali liquid, but in Comparative Example 1, the alkali liquid consumption will increase with the increase in the treatment capacity of iron-phosphorus residue, indicating that the method of the present disclosure is more environmentally friendly and more economical than the conventional method.
[0078] The examples of present disclosure are described in detail with reference to the accompanying drawings, but the present disclosure is not limited to the above examples. Within the scope of knowledge possessed by those of ordinary skill in the technical field, various changes can also be made without departing from the purpose of the present disclosure. In addition, the examples in the present disclosure and features in the examples may be combined with each other in a non-conflicting situation.