CN115432682A - Method for recycling and preparing battery-grade iron phosphate from sludge and battery-grade iron phosphate - Google Patents
Method for recycling and preparing battery-grade iron phosphate from sludge and battery-grade iron phosphate Download PDFInfo
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- CN115432682A CN115432682A CN202211194237.9A CN202211194237A CN115432682A CN 115432682 A CN115432682 A CN 115432682A CN 202211194237 A CN202211194237 A CN 202211194237A CN 115432682 A CN115432682 A CN 115432682A
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- phosphate
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- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 title claims abstract description 99
- 239000010802 sludge Substances 0.000 title claims abstract description 82
- 229910000398 iron phosphate Inorganic materials 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004064 recycling Methods 0.000 title claims description 19
- 239000010865 sewage Substances 0.000 claims abstract description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 29
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 29
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 29
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000012452 mother liquor Substances 0.000 claims abstract description 23
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011574 phosphorus Substances 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000000706 filtrate Substances 0.000 claims abstract description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 13
- 239000002131 composite material Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 8
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 6
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- 238000007873 sieving Methods 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 37
- 239000011572 manganese Substances 0.000 claims description 34
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 24
- 238000011084 recovery Methods 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 10
- DPTATFGPDCLUTF-UHFFFAOYSA-N phosphanylidyneiron Chemical compound [Fe]#P DPTATFGPDCLUTF-UHFFFAOYSA-N 0.000 claims description 10
- 238000004090 dissolution Methods 0.000 claims description 9
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical group [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- 239000006012 monoammonium phosphate Substances 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 25
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract 2
- 239000010413 mother solution Substances 0.000 abstract 1
- 150000002500 ions Chemical class 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 10
- 229910052748 manganese Inorganic materials 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 230000006872 improvement Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- 229910019142 PO4 Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000010452 phosphate Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- -1 dihydrate ferric phosphate Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011790 ferrous sulphate Substances 0.000 description 2
- 235000003891 ferrous sulphate Nutrition 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 1
- 235000019838 diammonium phosphate Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Primary Cells (AREA)
- Treatment Of Sludge (AREA)
Abstract
The invention discloses a method for recovering and preparing battery-grade iron phosphate from sludge and the battery-grade iron phosphate. The method comprises the following steps: taking sludge in an iron phosphate sewage treatment system, adding dilute sulfuric acid until the solid is completely dissolved, and filtering to obtain filtrate; adding FeSO 4 Adding a small amount of phosphorus source into the solution, adjusting the pH to 2-3 with a sodium hydroxide solution, carrying out precipitation reaction, removing Ca, mg, mn and Na, and carrying out centrifugal separation to obtain insoluble composite salt and primary mother liquor; stirring and dispersing insoluble composite salt with proper pure water, adding 85wt% phosphoric acid, heating for reaction, cooling, centrifugally separating, and washing to obtain ferric phosphate dihydrate and a secondary mother solution; sintering, crushing and sieving the ferric phosphate dihydrate to obtain the battery-grade ferric phosphate. According to the invention, by carrying out impurity removal and regeneration treatment on the sludge of the iron phosphate sewage treatment system, the battery-grade iron phosphate can be synthesized and reused in the production of the lithium iron phosphate, so that the cost is greatly reduced, and the economic benefit is obvious.
Description
Technical Field
The invention relates to a preparation method of iron phosphate, in particular to a recovery preparation method for recovering and preparing battery-grade iron phosphate from sludge and the battery-grade iron phosphate prepared by the recovery preparation method.
Background
With the rapid development of new energy industry, in the first half of 2022, the shipment of the lithium iron phosphate material in China increases rapidly, mainly for the following reasons: the method comprises the following steps that firstly, the shipment volume of the Chinese power battery exceeds 200GWh, and the increase of the shipment volume exceeds 150% on the same scale, wherein the shipment volume of the lithium iron phosphate power battery exceeds 110GWh, so that the shipment volume of a lithium iron phosphate positive electrode material is increased; secondly, the energy storage market in the first year is increased at a high speed, and the increase is more than 2 times in the same ratio, so that the demand of lithium iron phosphate materials of energy storage lithium batteries is driven to increase rapidly; thirdly, due to the improvement of the lithium iron phosphate battery technology and the improvement of a thermal management system, the performance of a new generation of blade battery is better, and the number of vehicles carrying the lithium iron phosphate battery is more; and fourthly, the price of the upstream raw materials is greatly increased, the cost reduction pressure of vehicle enterprises and power battery enterprises is increased, and the cost of the lithium iron phosphate battery has more advantages compared with that of a ternary battery. Under the premise that the current 'carbon peak reaching' and 'carbon neutralization' are clearly proposed, the demand of lithium iron phosphate is greatly increased, so that the supply of the lithium iron phosphate is seriously insufficient. Lithium iron phosphate is mainly prepared by anhydrous iron phosphate, the existing anhydrous iron phosphate is mainly produced by a sodium method, phosphorus sources are mostly phosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate and the like, the price is in a high-order running state, the phosphorus source is relatively single in type, and the influence of the upstream phosphate ore market is large, so that a new phosphorus source is developed, and a new technical problem to be solved urgently in the iron phosphate industry is solved.
In the preparation process of the ferric phosphate by the sodium method, the working procedures of filter pressing, multiple times of water washing of filter cakes and the like are involved, and a large amount of Fe is generated in the processes 3+ And PO 4 3- The wastewater flows into the sewage treatment system, so that the wastewater can be treated in a green way, and the pollution-free discharge standard is reached. Therefore, when the wastewater is treated, a large amount of Fe is produced 3+ And PO 4 3- And (4) sludge. The sludge contains rich iron elementAnd phosphorus element, the content of Fe can reach 12 percent, the content of P can reach 6 percent, and the phosphorus content is equivalent to that of lower-grade phosphate ore, thus being a potential phosphate ore resource to be excavated. At present, no relevant patent and research report exists at home and abroad on how to recover sludge of an iron phosphate sewage treatment system at low cost and high value.
Disclosure of Invention
Aiming at the technical problem that the prior art cannot solve the technical problem of recycling sludge in a low-cost high-value iron phosphate sewage treatment system, the invention provides a recycling preparation method for recycling battery-grade iron phosphate from sludge and battery-grade iron phosphate prepared by the recycling preparation method.
The invention is realized by adopting the following technical scheme: a recovery preparation method for recovering and preparing battery-grade iron phosphate from sludge is used for recovering the sludge in an iron phosphate sewage treatment system and preparing the battery-grade iron phosphate, and comprises the following steps:
taking sludge in an iron phosphate sewage treatment system, adding 10-30wt% of dilute sulfuric acid with the solid content of 30-45% to enable the mass ratio of the sludge to the dilute sulfuric acid to be 1.1-1.5:1, and filtering to obtain filtrate after the solid is completely dissolved;
step two, adding 5.0wt% of FeSO into the filtrate 4 Solution of, in which, feSO 4 The addition amount is according to FeSO 4 The amount of manganese element in the material, n (FeSO) 4 ) Determination of ratio n (Mn) = (1.05-1.20): 1, adding a small amount of phosphorus source, and adjusting the phosphorus-iron ratio of the solution to n (P): n (Fe) = (0.95-1.05): 1, adjusting the pH to 2-3 by using a sodium hydroxide solution, carrying out precipitation reaction to remove Ca, mg, mn and Na, carrying out centrifugal separation to obtain insoluble composite salt and primary mother liquor, and circulating the primary mother liquor in a sewage treatment system;
and step three, stirring and dispersing the insoluble complex salt by using proper pure water, wherein the mass ratio of the pure water to the insoluble complex salt is (1.5-3): 1, adding 85wt% of phosphoric acid, and adjusting the phosphorus-iron ratio of the solution to n (P): n (Fe) = 1.05: 1, heating for reaction, cooling, performing centrifugal separation, washing to obtain ferric phosphate dihydrate and secondary mother liquor, and allowing the secondary mother liquor to enter a sewage treatment system for circulation;
and step four, sintering the ferric phosphate dihydrate for 2 hours at 600 ℃ in the air atmosphere, and crushing and sieving to obtain the battery-grade ferric phosphate.
As a further improvement of the scheme, in the step one, stirring is carried out at normal temperature and 300rpm, the dissolution reaction lasts for a period of time until the solid is completely dissolved, and the filtration is carried out to obtain the filtrate with dark brown color.
Preferably, the dissolution reaction is 0.5h.
As a further improvement of the above scheme, in the second step, feSO 4 The addition amount is according to FeSO 4 The amount of manganese element in the material, n (FeSO) 4 ) And (n) = (1.05-1.20): 1, stirring at 300rpm at normal temperature, reacting for 0.5h, and adding a small amount of phosphorus source.
As a further improvement of the above scheme, in the second step, the phosphorus source is monoammonium phosphate or sodium phosphate.
As a further improvement of the scheme, in the third step, the reaction is carried out by heating at 95 ℃, when the solution turns white from light yellow, the heating reaction is stopped, and after cooling, centrifugal separation and washing are carried out to obtain the ferric phosphate dihydrate and the secondary mother liquor.
As a further improvement of the above scheme, the phosphoric acid is 85wt% phosphoric acid.
As a further improvement of the scheme, in the first step, sludge in the iron phosphate sewage treatment system is taken, the solid content of the sludge is 30-45%, and 20wt% of dilute sulfuric acid is added, so that the mass ratio of the sludge to the dilute sulfuric acid is 1.3: 1;
in step two, feSO 4 The addition amount is according to FeSO 4 The amount of manganese element in the material, n (FeSO) 4 ) And n (Mn) =1.10:1, and adjusting the solution ferrophosphorus ratio to n (P): n (Fe) = 0.95: 1, pH adjusted to 2 with sodium hydroxide solution;
in the third step, the mass ratio of the pure water to the insoluble complex salt is 2: 1.
As a further improvement of the scheme, in the first step, sludge in the iron phosphate sewage treatment system is taken, the solid content of the sludge is 30-45%, and 25wt% of dilute sulfuric acid is added, so that the mass ratio of the sludge to the dilute sulfuric acid is 1.5:1;
in step two, feSO 4 The addition amount is according to FeSO 4 The amount of manganese element in the material, n (FeSO) 4 ) And n (Mn) =1.20:1, and adjusting the solution ferrophosphorus ratio to n (P): n (Fe) = 1.0: 1, pH adjusted to 2.5 with sodium hydroxide solution;
in the third step, the mass ratio of the pure water to the insoluble complex salt is 2: 1.
The invention also provides battery-grade iron phosphate, which is prepared by adopting the recovery preparation method for recovering and preparing the battery-grade iron phosphate from the sludge.
Compared with the prior art, the invention has the beneficial effects that:
1. the sludge dissolution rate can almost reach 100 percent, and the leaching rate of iron and phosphorus elements can almost reach 100 percent;
2. by removing impurities and regenerating sludge of the iron phosphate sewage treatment system, battery-grade iron phosphate can be synthesized and reused in the production of lithium iron phosphate, so that the cost is greatly reduced, and the economic benefit is obvious;
3. with FePO 4 The recovery rate of Fe and P can reach more than 96%, and meanwhile, the removal rate of impurity ions such as Mn, mg and the like in sludge can reach more than 99%, so that the iron phosphate can meet the use requirement of the anode material;
4. no waste liquid and no waste residue, low recovery cost and high added value, and realizes the real cyclic recycling;
5. skillfully using FeSO 4 The manganese and the high valence state manganese are subjected to oxidation reduction reaction to reduce the manganese element to a lower valence state, so that impurities are removed by a water washing mode, and iron is oxidized to Fe 3+ In a state, no impurity is introduced, and an oxidant is not required to be supplemented;
6. compared with the traditional method for recovering the ferric phosphate from the sludge, the traditional sludge refers to a product in the sewage treatment process of municipal sewage treatment plants in China, and the phosphorus content in the sludge mainly comes from the enrichment of phosphorus element of washing products in municipal water. The sludge of the invention is the sludge finally obtained by the sewage generated in the ferric phosphate production process through the sewage station environmental protection treatment, and the sludge contains a certain amount of Fe, P and other impurities; in addition, the traditional method for recovering the iron phosphate from the sludge needs to burn solid residues, so that the working procedures are increased, the energy consumption is increased, waste gas is discharged, and the method is not environment-friendly;
7. and compare with traditional method that utilizes municipal sludge incineration ash to prepare iron phosphate, traditional recovery object is to retrieve the iron phosphate to municipal sludge incineration ash, and impurity is more, and the edulcoration step is many, and first step removes ferro-aluminium impurity ion, and the second step removes calcium magnesium impurity ion, and the heavy metal ion is removed to the third portion, and the impurity ion condition is complicated, and the edulcoration step is loaded down with trivial details.
Drawings
FIG. 1 is a flow chart of the recovery preparation method of battery grade iron phosphate recovered from sludge according to the present invention.
Fig. 2 is an XRD pattern of iron phosphate prepared by the recycling preparation method of fig. 1.
Fig. 3 is an SEM image of iron phosphate prepared by the recycling manufacturing method of fig. 1.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "or/and" includes any and all combinations of one or more of the associated listed items.
The invention recovers the sludge of the iron phosphate sewage treatment system and prepares the battery-grade iron phosphate. In the sodium method production process of the iron phosphate, more wastewater can be generated, and the wastewater is treated systematically by a sewage station and precipitates iron, phosphorus, metal impurities and the like in water in the form of sludge, so that the green pollution-free discharge standard is reached. The sludge was analyzed and the composition table is shown in table 1:
table 1 ingredient table of sludge in iron phosphate sewage treatment system
Fig. 1 is a flow chart of the recycling method for preparing battery-grade iron phosphate from sludge according to the present invention. The recovery preparation method of the battery grade iron phosphate comprises the following steps:
1. taking sludge of an iron phosphate sewage treatment system, wherein the solid content of the sludge is about 40% (generally within the range of 30-45%), adding 10-30wt% of dilute sulfuric acid, enabling the mass ratio of the sludge to the dilute sulfuric acid to be 1.1-1.5, stirring at normal temperature at 300rpm, carrying out dissolution reaction for 0.5h until the solid is completely dissolved, and filtering to obtain dark brown filtrate;
2. adding 5.0wt% of FeSO 4 Solution of, in which, feSO 4 The addition amount is according to FeSO 4 The amount of manganese element in the material, n (FeSO) 4 ) N (Mn) =1.05-1.20, the reaction is carried out for 0.5h under the condition of normal temperature and stirring at 300rpm, a small amount of phosphorus source is added, and the phosphorus-iron ratio of the solution is adjusted to n (P): n (Fe) =0.95-1.05, adjusting pH to 2-3 with sodium hydroxide solution, performing precipitation reaction, removing Ca, mg, mn and Na, performing centrifugal separation to obtain insoluble composite salt and primary mother liquor, and allowing the primary mother liquor to enter a sewage treatment system for circulation;
3. stirring and dispersing insoluble composite salt by proper pure water, wherein the mass ratio of the pure water to the insoluble composite salt is 1.5-3:1, adding 85wt% phosphoric acid, and adjusting the phosphorus-iron ratio of the solution to n (P): n (Fe) =1.05, heating at 95 ℃ for reaction, stopping heating reaction when the solution turns white from light yellow, cooling, performing centrifugal separation, washing to obtain ferric phosphate dihydrate and secondary mother liquor, and allowing the secondary mother liquor to enter a sewage treatment system for circulation;
4. and sintering the ferric phosphate dihydrate for 2 hours at 600 ℃ in the air atmosphere, and crushing and sieving to obtain the battery-grade anhydrous ferric phosphate.
The reaction mechanism is as follows:
1. in the process of preparing sludge by treating iron phosphate sewage, mn 2+ The slow oxidation reaction can occur when the catalyst contacts oxygen to generate Mn 3+ Which further undergoes a complexation reaction with phosphate radicals to give a deep purple [ Mn (PO) 4 ) 2 ] 3- The reaction equation is as follows:
4Mn 2+ +O 2 +4H + →4Mn 3+ +2H 2 O，
Mn 3+ +2PO 4 3- →[Mn(PO 4 ) 2 ] 3- ，
2. adding FeSO 4 Reacting FeSO 4 And [ Mn (PO) ] 4 ) 2 ] 3- Reaction, reduction of complex to obtain Mn 2+ So that impurities are removed by a water washing mode, and the Mn content can be reduced to below 50 ppm;
Fe 2+ +[Mn(PO 4 ) 2 ] 3- →Mn 2+ +Fe 3+ +2PO 4 3- 。
after filtration, a ferrous sulfate solution is added to the sludge leach liquor to achieve reduction of the manganese complex to Mn 2+ And in a state, washing and impurity removal are facilitated. If the reduction of Mn is insufficient, the complex of Mn can wrap or adsorb other impurity ions, and the washing impurity removal effect of other ions is further reduced. To find out the better demanganization effect, different experimental parameters need to be controlled to reduce the manganese complex into Mn 2+ The process was optimized and the experimental comparison results are shown in table 2 below.
Table 2 test comparison results table
As can be seen from the table data, no FeSO was added 4 Manganese element of [ Mn (PO) ] 4 ) 2 ] 3- The complex exists in a form which cannot be removed by washing with water, and FeSO is added 4 After that, the manganese element is obviously reduced to Mn 2+ And impurities can be removed through washing. FeSO 4 The manganese removal effect can be better achieved by 5 percent excess, the excess coefficient is continuously increased, the manganese removal rate is not changed greatly, and therefore, the FeSO is fully considered 4 Under the condition of air-exposed oxidation, the FeSO is optimized 4 The excess coefficient is 5-20%.
Example 1
1. Taking sludge of an iron phosphate sewage treatment system, wherein the solid content of the sludge is about 40%, adding 20wt% of dilute sulfuric acid to ensure that the mass ratio of the sludge to the dilute sulfuric acid is 1.3, stirring at 300rpm at normal temperature, carrying out dissolution reaction for 0.5h until the solid is completely dissolved, and filtering to obtain dark brown filtrate, wherein the main components of the filtrate are shown in the following table 2.
TABLE 2 composition Table of the filtrates
| Composition (I) | P | Fe | Fe/P ratio | Ca | Mg | Mn | Na |
| The content wt% | 2.87 | 6.03 | 1.16 | 0.01 | 0.03 | 0.2 | 1.8 |
2. Adding 5.0wt% of FeSO 4 Solution of, in which, feSO 4 The addition amount is according to FeSO 4 And the ratio of the amount of the manganese element to the amount of the manganese element, n (FeSO 4) =1.10, stirring at 300rpm at normal temperature, reacting for 0.5h, adding a small amount of 85wt% phosphoric acid, and adjusting the phosphorus-iron ratio of the solution to n (P): n (Fe) =0.95, adjusting pH to 2 with sodium hydroxide solution, performing precipitation reaction, removing Ca, mg, mn and Na, performing centrifugal separation to obtain insoluble composite salt and primary mother liquor, and allowing the primary mother liquor to enter a sewage treatment system for circulation.
3. Stirring and dispersing insoluble composite salt by using proper pure water, wherein the mass ratio of the pure water to the insoluble composite salt is 2:1, adding 85wt% phosphoric acid, and adjusting the phosphorus-iron ratio of the solution to n (P): n (Fe) =1.05, heating at 95 ℃ for reaction, stopping heating reaction when the solution turns white from light yellow, cooling, performing centrifugal separation, washing to obtain ferric phosphate dihydrate and secondary mother liquor, and allowing the secondary mother liquor to enter a sewage treatment system for circulation.
4. And sintering the dihydrate ferric phosphate for 2 hours at 600 ℃ in the air atmosphere, and crushing and sieving to obtain the battery-grade anhydrous ferric phosphate.
The XRD of the anhydrous iron phosphate obtained by sintering, i.e., the XRD pattern of the iron phosphate prepared in example 1, is shown in fig. 2, and it can be seen that pure anhydrous iron phosphate having high crystallinity is prepared.
The SEM of the anhydrous iron phosphate obtained by sintering is shown in fig. 3, and the SEM of the iron phosphate prepared in example 1 is shown in fig. 1, in which the primary particles of iron phosphate are in the form of particles, spheroids, and uniformly distributed in size.
Example 2:
1. taking sludge of an iron phosphate sewage treatment system, wherein the solid content of the sludge is about 40%, adding 25wt% of dilute sulfuric acid to ensure that the mass ratio of the sludge to the dilute sulfuric acid is 1.5, stirring at 300rpm at normal temperature, carrying out dissolution reaction for 0.5h until the solid is completely dissolved, and filtering to obtain dark brown filtrate, wherein the main components of the filtrate are shown in the following table 3.
TABLE 3 Main ingredient Table of the filtrate
| Composition (A) | P | Fe | Fe/P ratio | Ca | Mg | Mn | Na |
| The content wt% | 2.67 | 5.53 | 1.147 | 0.01 | 0.03 | 0.25 | 2.8 |
2. Adding 5.0wt% of FeSO 4 Solution of, in which, feSO 4 The addition amount is according to FeSO 4 The amount of substance of manganese element (FeSO) 4 ) N (Mn) =1.20, determining that stirring is carried out at normal temperature and 300rpm, reacting for 0.5h, adding a small amount of 85wt% phosphoric acid, and adjusting the phosphorus-iron ratio of the solution to n (P): n (Fe) =1.0, adjusting pH to 2.5 with sodium hydroxide solution, performing precipitation reaction, removing Ca, mg, mn and Na, performing centrifugal separation to obtain insoluble composite salt and primary mother liquor, and allowing the primary mother liquor to enter a sewage treatment system for circulation.
3. Stirring and dispersing insoluble composite salt by using proper pure water, wherein the mass ratio of the pure water to the insoluble composite salt is 2:1, adding 85wt% phosphoric acid, and adjusting the phosphorus-iron ratio of the solution to n (P): n (Fe) =1.05, heating at 95 ℃ for reaction, stopping heating reaction when the solution turns white from light yellow, cooling, performing centrifugal separation, washing to obtain ferric phosphate dihydrate and secondary mother liquor, and allowing the secondary mother liquor to enter a sewage treatment system for circulation.
4. And sintering the dihydrate ferric phosphate for 2 hours at 600 ℃ in the air atmosphere, and crushing and sieving to obtain the battery-grade anhydrous ferric phosphate.
In order to obtain the comparative effect, the invention adds the following examples and comparative examples:
example 3: step 2, relative to example 1, the phosphorus source was replaced with monoammonium phosphate;
example 4: step 2 the phosphorus source was replaced with sodium phosphate as compared to example 1;
example 5: step 2 was adjusted to pH 3 with sodium hydroxide solution relative to example 1;
example 6: relative to example 1, the mass ratio of pure water to insoluble complex salt in step 3 is 1.5;
comparative example 1: the ferrous sulfate solution is not added;
comparative example 2: step 2, relative to comparative example 1, was adjusted to pH 4 with sodium hydroxide solution;
comparative example 3: step 2 was adjusted to pH 1 with sodium hydroxide solution relative to comparative example 1.
The data of the finished anhydrous iron phosphate prepared in the examples of the present invention and the comparative examples are shown in table 4 below.
TABLE 4 data table of finished anhydrous ferric phosphate prepared in examples and comparative examples
Compared with the prior art, the invention has the beneficial effects that:
1. the sludge dissolution rate can almost reach 100 percent, and the leaching rate of iron and phosphorus elements can almost reach 100 percent;
2. through impurity removal and regeneration treatment of sludge of the iron phosphate sewage treatment system, battery-grade iron phosphate can be synthesized and reused in the production of lithium iron phosphate, so that the cost is greatly reduced, and the economic benefit is obvious;
3. with FePO 4 The recovery rate of Fe and P can reach more than 96%, and meanwhile, the removal rate of impurity ions such as Mn, mg and the like in sludge can reach more than 99%, so that the iron phosphate can meet the use requirement of the anode material;
4. no waste liquid and no waste residue, low recovery cost and high added value, and realizes the real cyclic recycling;
5. skillfully using FeSO 4 The manganese and the high-valence manganese are subjected to oxidation-reduction reaction to reduce the manganese element to a lower valence state, so that impurities are removed by a water washing mode, and iron is oxidized to Fe 3+ In a state, no impurity is introduced, and an oxidant is not required to be supplemented;
6. compared with the traditional method for recovering the iron phosphate from the sludge, the traditional sludge is a product in the sewage treatment process of municipal sewage treatment plants in China, and the phosphorus content in the sludge is mainly derived from the enrichment of phosphorus element of washing products in municipal water. The sludge of the invention is the sludge finally obtained by the sewage generated in the ferric phosphate production process through the sewage station environmental protection treatment, and the sludge contains a certain amount of Fe, P and other impurities; in addition, the traditional method for recovering the ferric phosphate from the sludge needs to burn solid residues, so that the working procedures are increased, the energy consumption is increased, waste gas emission is generated, and the method is not environment-friendly;
7. and compare with traditional method that utilizes municipal sludge incineration ash to prepare iron phosphate, traditional recovery object is to retrieve the iron phosphate to municipal sludge incineration ash, and impurity is more, and the edulcoration step is many, and first step removes ferro-aluminium impurity ion, and the second step removes calcium magnesium impurity ion, and the heavy metal ion is removed to the third portion, and the impurity ion condition is complicated, and the edulcoration step is loaded down with trivial details.
All possible combinations of the technical features of the above embodiments may not be described for the sake of brevity, but should be considered as within the scope of the present disclosure as long as there is no contradiction between the combinations of the technical features.
The above examples are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but not to be construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present invention should be subject to the appended claims.
Claims (10)
1. The recovery preparation method for recovering and preparing battery-grade iron phosphate from sludge is characterized by being used for recovering the sludge in an iron phosphate sewage treatment system and preparing the battery-grade iron phosphate, and the recovery preparation method comprises the following steps:
taking sludge in an iron phosphate sewage treatment system, adding 10-30wt% of dilute sulfuric acid with the solid content of 30-45% to enable the mass ratio of the sludge to the dilute sulfuric acid to be 1.1-1.5:1, and filtering to obtain filtrate after the solid is completely dissolved;
step two, adding 5.0wt% of FeSO into the filtrate 4 Solution of, in which, feSO 4 The addition amount is according to FeSO 4 The amount of manganese element in the material, n (FeSO) 4 ) Determination of ratio n (Mn) = (1.05-1.20): 1, adding a small amount of phosphorus source, and adjusting the phosphorus-iron ratio of the solution to n (P): n (Fe) = (0.95-1.05): 1, adjusting the pH to 2-3 by using a sodium hydroxide solution, carrying out precipitation reaction to remove Ca, mg, mn and Na, carrying out centrifugal separation to obtain insoluble composite salt and primary mother liquor, and circulating the primary mother liquor in a sewage treatment system;
and step three, stirring and dispersing the insoluble complex salt by using proper pure water, wherein the mass ratio of the pure water to the insoluble complex salt is (1.5-3): 1, adding 85wt% of phosphoric acid, and adjusting the phosphorus-iron ratio of the solution to n (P): n (Fe) = 1.05: 1, heating for reaction, cooling, performing centrifugal separation, washing to obtain ferric phosphate dihydrate and secondary mother liquor, and allowing the secondary mother liquor to enter a sewage treatment system for circulation;
and step four, sintering the ferric phosphate dihydrate for 2 hours at 600 ℃ in the air atmosphere, and crushing and sieving to obtain the battery-grade ferric phosphate.
2. The method for recycling and preparing battery-grade iron phosphate from sludge according to claim 1, wherein in the first step, stirring is carried out at normal temperature and 300rpm, the dissolution reaction is carried out for a period of time until the solid is completely dissolved, and the filtration is carried out to obtain the filtrate with dark brown color.
3. The recovery preparation method for battery grade iron phosphate from sludge according to claim 2, characterized in that the dissolution reaction is carried out for 0.5h.
4. The method for recycling battery-grade iron phosphate from sludge according to claim 1, wherein in step two, feSO 4 The addition amount is according to FeSO 4 The amount of manganese element in the material, n (FeSO) 4 ) And (n) = (1.05-1.20): 1, stirring at 300rpm at normal temperature, reacting for 0.5h, and adding a small amount of phosphorus source.
5. The method for recycling battery-grade ferric phosphate from sludge according to claim 1, wherein in the second step, the phosphorus source is monoammonium phosphate or sodium phosphate.
6. The method for recycling battery grade ferric phosphate from sludge according to claim 1, wherein in the third step, the reaction is carried out by heating at 95 ℃, when the solution turns from pale yellow to white, the heating reaction is stopped, and after cooling, centrifugal separation and washing are carried out to obtain the ferric phosphate dihydrate and the secondary mother liquor.
7. The method for recycling battery-grade iron phosphate from sludge according to claim 1, wherein the phosphoric acid is 85wt% phosphoric acid.
8. The recovery preparation method of battery grade ferric phosphate in sludge recovery according to claim 1,
in the first step, sludge in the iron phosphate sewage treatment system is taken, the solid content of the sludge is 30-45%, and 20wt% of dilute sulfuric acid is added, so that the mass ratio of the sludge to the dilute sulfuric acid is 1.3: 1;
in step two, feSO 4 The addition amount is according to FeSO 4 The amount of manganese element in the material, n (FeSO) 4 ) Determination of h (n) =1.10:1, and the solution ferrophosphorus ratio is adjusted by n (P): n (Fe) = 0.95: 1, pH adjusted to 2 with sodium hydroxide solution;
in the third step, the mass ratio of the pure water to the insoluble complex salt is 2: 1.
9. The recycling production method for battery grade iron phosphate in sludge recycling production according to claim 1,
in the first step, sludge in the iron phosphate sewage treatment system is taken, the solid content of the sludge is 30-45%, and 25wt% of dilute sulfuric acid is added, so that the mass ratio of the sludge to the dilute sulfuric acid is 1.5:1;
in step two, feSO 4 The addition amount is according to FeSO 4 The amount of substance of manganese element (FeSO) 4 ) And n (Mn) =1.20:1, and adjusting the solution ferrophosphorus ratio to n (P): n (Fe) = 1.0: 1, pH adjusted to 2.5 with sodium hydroxide solution;
in the third step, the mass ratio of the pure water to the insoluble complex salt is 2: 1.
10. Battery grade iron phosphate, characterized in that it is obtained with a recycling preparation method for battery grade iron phosphate in sludge according to any one of claims 1 to 9.
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| CN116143093A (en) * | 2022-12-27 | 2023-05-23 | 湖北锂宝新材料科技发展有限公司 | Method for preparing battery-grade anhydrous ferric phosphate by utilizing industrial waste iron mud |
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