CN116692795A - Potassium removal method for fertilizer grade monoammonium phosphate and application of product thereof - Google Patents
Potassium removal method for fertilizer grade monoammonium phosphate and application of product thereof Download PDFInfo
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- CN116692795A CN116692795A CN202310642043.9A CN202310642043A CN116692795A CN 116692795 A CN116692795 A CN 116692795A CN 202310642043 A CN202310642043 A CN 202310642043A CN 116692795 A CN116692795 A CN 116692795A
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- monoammonium phosphate
- groups
- potassium
- fertilizer grade
- solution
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- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 title claims abstract description 168
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 title claims abstract description 168
- 239000006012 monoammonium phosphate Substances 0.000 title claims abstract description 168
- 235000019837 monoammonium phosphate Nutrition 0.000 title claims abstract description 168
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 239000011591 potassium Substances 0.000 title claims abstract description 94
- 229910052700 potassium Inorganic materials 0.000 title claims abstract description 94
- 239000003337 fertilizer Substances 0.000 title claims abstract description 71
- 238000000034 method Methods 0.000 title claims abstract description 56
- 239000000243 solution Substances 0.000 claims abstract description 72
- 239000007788 liquid Substances 0.000 claims abstract description 46
- 239000011259 mixed solution Substances 0.000 claims abstract description 43
- 239000002253 acid Substances 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 30
- 238000001556 precipitation Methods 0.000 claims description 24
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 20
- 150000001553 barium compounds Chemical class 0.000 claims description 19
- 238000011282 treatment Methods 0.000 claims description 19
- 239000000411 inducer Substances 0.000 claims description 17
- 239000002270 dispersing agent Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 13
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 10
- 238000001694 spray drying Methods 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 229920004890 Triton X-100 Polymers 0.000 claims description 6
- 239000013504 Triton X-100 Substances 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 6
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 6
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 5
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 229960003638 dopamine Drugs 0.000 claims description 5
- 235000002906 tartaric acid Nutrition 0.000 claims description 5
- 239000011975 tartaric acid Substances 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims description 4
- 229910001626 barium chloride Inorganic materials 0.000 claims description 4
- AYJRCSIUFZENHW-DEQYMQKBSA-L barium(2+);oxomethanediolate Chemical compound [Ba+2].[O-][14C]([O-])=O AYJRCSIUFZENHW-DEQYMQKBSA-L 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000005396 acrylic acid ester group Chemical group 0.000 claims 1
- 239000002244 precipitate Substances 0.000 abstract description 30
- 229910001414 potassium ion Inorganic materials 0.000 abstract description 18
- 239000000047 product Substances 0.000 abstract description 12
- 238000009776 industrial production Methods 0.000 abstract description 3
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 20
- 239000002994 raw material Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 10
- -1 ammonium ions Chemical class 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 7
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000012065 filter cake Substances 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229940104869 fluorosilicate Drugs 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 2
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000000909 electrodialysis Methods 0.000 description 2
- 150000002191 fatty alcohols Chemical class 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000002686 phosphate fertilizer Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- YWJVFBOUPMWANA-UHFFFAOYSA-H [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Li+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O YWJVFBOUPMWANA-UHFFFAOYSA-H 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- INQZXVMNJLSCGI-UHFFFAOYSA-M azanium;potassium;hydrogen phosphate Chemical compound [NH4+].[K+].OP([O-])([O-])=O INQZXVMNJLSCGI-UHFFFAOYSA-M 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 229910001422 barium ion Inorganic materials 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005536 corrosion prevention Methods 0.000 description 1
- 150000003983 crown ethers Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location 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
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
- C01B25/28—Ammonium phosphates
-
- 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
- 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
Abstract
The application provides a potassium removing method of fertilizer grade monoammonium phosphate and application of a product thereof, wherein the potassium removing method comprises the following steps: dissolving fertilizer grade monoammonium phosphate into water to obtain monoammonium phosphate solution; adding fluosilicic acid and/or fluosilicate into monoammonium phosphate solution, adjusting the pH value, and reacting to obtain mixed solution; carrying out solid-liquid separation on the mixed solution, and keeping clear liquid; and drying the clear liquid to obtain purified monoammonium phosphate. According to the technical scheme, fluosilicic acid and/or fluosilicate can react with potassium ions to generate potassium fluosilicate precipitate, and the potassium fluosilicate precipitate is separated by a solid-liquid separation method to obtain monoammonium phosphate with low potassium content, so that the product purity is high, the preparation method is reasonable and effective, the operability is strong, and the method is suitable for industrial production.
Description
Technical Field
The application belongs to the technical field of phosphate materials, and particularly relates to a method for removing potassium from fertilizer-grade monoammonium phosphate and application of a product thereof.
Background
With the development of lithium power batteries, the demand of new energy industries for lithium iron phosphate positive electrode materials is continuously increasing, and monoammonium phosphate is one of the most important phosphorus sources for synthesizing the lithium iron phosphate positive electrode materials. Since the higher the purity requirements of the lithium power battery on the raw materials, the lower the content of each impurity is limited, the fertilizer grade monoammonium phosphate cannot meet the production requirements of the cathode material because the fertilizer grade monoammonium phosphate raw materials contain part of potassium which is difficult to remove.
The lithium iron phosphate anode material contains a proper amount of potassium ions, so that the formation of non-conductive compounds deposited on the surface of metal lithium can be relieved, the transmission of the potassium ions is prevented in the charge and discharge process of the battery, and the growth of lithium dendrites is finally limited, thereby improving the cycle performance of the potassium ion battery. However, too high a potassium content reduces battery capacity retention and tends to cause instability of the lithium iron phosphate lattice, thereby shortening battery life, and thus it is necessary to remove potassium from the monoammonium phosphate of fertilizer grade.
The potassium ions have the ion radius and physical properties very close to those of ammonium ions, so that the difficulty of not losing ammonium in the phosphate fertilizer in the potassium removal process is high, and the research of the industry on monoammonium phosphate potassium removal of a phosphate fertilizer system is less. The method for removing potassium from monoammonium phosphate commonly used at present comprises the following steps:
1. the crystallization method is a separation and purification method with low energy consumption and high purity, and is characterized in that after a salt solution is cooled, seed crystals are placed in the salt solution, and crystals are waited to separate from an original solution, so that the purification is realized. However, due to the similar nature of potassium ions and ammonium ions, similar crystal lattices will encapsulate potassium during crystallization, and thus multiple crystallization is often required to obtain monoammonium phosphate of higher purity, and the time cost and efficiency are not suitable for large-scale industrial production.
2. The selective reaction of the complexing agent on potassium ions and further removal of potassium chelate by electrodialysis seems feasible, but other potassium chelates are easily dissociated in the electrodialysis process except for expensive crown ether due to the small complexing constant of potassium ions and instability.
Disclosure of Invention
Based on the above, an object of the present application is to provide a method for removing potassium from monoammonium phosphate at a fertilizer level, so as to solve the technical problems of the prior art that the method for removing potassium from monoammonium phosphate at a fertilizer level is difficult and is not suitable for large-scale industrial application.
The application also aims to provide an application of the purified monoammonium phosphate obtained by the potassium removal method of the fertilizer-grade monoammonium phosphate in preparing a battery positive electrode material, so as to reduce the production cost of the positive electrode material.
In order to achieve the above purpose, the application adopts the following technical scheme:
in a first aspect, a method for removing potassium from fertilizer grade monoammonium phosphate is provided, comprising the steps of:
dissolving fertilizer grade monoammonium phosphate into water to obtain monoammonium phosphate solution;
adding fluosilicic acid and/or fluosilicate into monoammonium phosphate solution, adjusting the pH value, and reacting to obtain mixed solution;
carrying out solid-liquid separation on the mixed solution, and keeping clear liquid;
and drying the clear liquid to obtain purified monoammonium phosphate.
Optionally, the solid-to-liquid ratio of the fertilizer grade monoammonium phosphate to water is 1:3-1:5; and/or the number of the groups of groups,
the potassium content of the fertilizer grade monoammonium phosphate is less than or equal to 5000ppm; and/or the number of the groups of groups,
the potassium content in the purified monoammonium phosphate is less than or equal to 50ppm.
Optionally, the fluosilicic acid and/or fluorosilicate is/are added into the monoammonium phosphate solution in a slow dropwise manner, and the dropwise speed is 8-12 mL/min; and/or the number of the groups of groups,
the addition amount of the fluosilicic acid and/or the fluosilicate is 3-9% of the mass of the fertilizer grade monoammonium phosphate; and/or the number of the groups of groups,
the step of adjusting the pH value comprises; adding ammonia water, and adjusting the pH value to be more than or equal to 4; and/or the number of the groups of groups,
the drying treatment includes spray drying.
Optionally, after the step of adjusting the pH value, the method further comprises the steps of:
under heating, an inducer is added to the monoammonium phosphate solution, and then the solution is treated at a low temperature.
Optionally, the addition amount of the inducer is 0.02-5% of the mass of the fertilizer grade monoammonium phosphate; and/or the number of the groups of groups,
the inducer comprises at least one of polyacrylamide, ferric chloride, polymeric ferric sulfate, small molecular alcohols and hydrocarbon sulphonates; and/or the number of the groups of groups,
the temperature of the heating condition is 40-50 ℃, and the time of the heating condition is 30-40 min; and/or the number of the groups of groups,
the temperature of the low-temperature treatment is 1-5 ℃, and the time of the low-temperature treatment is 3-5 h.
After the step of low temperature treatment, the method further comprises the following steps: adding a dispersing agent into the monoammonium phosphate solution and stirring;
preferably, the addition amount of the dispersing agent is 0.05-0.1% of the mass of the fertilizer grade monoammonium phosphate;
preferably, the dispersing agent includes at least one of polyethylene glycol (PEG-200, PEG-600), triton X-100, sodium Dodecyl Sulfate (SDS), cetyltrimethylammonium bromide (CTAB), tributyl phosphate (TBP) and fatty alcohol polyoxyethylene ether (AEO).
Optionally, after the step of low temperature treatment or after the step of adding a dispersant and stirring, the method further comprises the steps of:
and adding a barium compound and sulfate into the monoammonium phosphate solution at room temperature to perform a reaction.
Optionally, the addition amount of the barium compound is 1-5% of the mass of the fertilizer grade monoammonium phosphate; and/or the number of the groups of groups,
the molar ratio of the barium compound to the sulfate is 0.95-1.1:0.45-0.55; and/or the number of the groups of groups,
the barium compound includes at least one of barium chloride, barium carbonate, and barium hydroxide; and/or the number of the groups of groups,
the sulfate salt includes ammonium sulfate and/or ammonium bisulfate.
Optionally, before the step of adding the barium compound and the sulfate, the method further comprises the steps of: adding a precipitation auxiliary agent into monoammonium phosphate solution and uniformly stirring;
preferably, the addition amount of the precipitation auxiliary agent is 0.06% -0.1% of the mass of the fertilizer grade monoammonium phosphate;
preferably, the precipitation aid comprises at least one of polyacrylic acid (PAA), acrylate, aminoethanol, tartaric Acid (TA), dopamine (DOPA), ethylenediamine tetraacetic acid (EDTA).
In a second aspect, the application of the purified monoammonium phosphate obtained by the potassium removal method of the fertilizer-grade monoammonium phosphate in preparing a battery positive electrode material is provided
The application has the beneficial effects that:
according to the potassium removing method for the fertilizer-grade monoammonium phosphate, fluosilicic acid and/or fluosilicate can react with potassium ions in the fertilizer-grade monoammonium phosphate to generate potassium fluosilicate precipitate, and the potassium fluosilicate precipitate is separated by a solid-liquid separation method to obtain monoammonium phosphate solution with low potassium content; compared with the prior art, the potassium removal method of the fertilizer grade monoammonium phosphate utilizes the chemical property difference of potassium ions and ammonium ions, the potassium ions can react with fluosilicic acid and/or fluosilicate to generate precipitate, and the ammonium ions and fluosilicic acid and/or fluosilicate do not react, so that the potassium is removed from the fertilizer grade monoammonium phosphate, the monoammonium phosphate is purified, the loss of ammonium is small, the preparation method is reasonable and effective, the operability is strong, and the method is suitable for industrial production;
the purified monoammonium phosphate obtained by the method for removing potassium from the fertilizer-grade monoammonium phosphate provided by the application has low potassium content, can meet the production requirements of raw materials of lithium ion battery materials, and can be applied to preparing battery anode materials.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear, the application is further described in detail in the following examples. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
The potassium removing method of the fertilizer grade monoammonium phosphate provided by the embodiment of the application comprises the following steps:
s1: providing fertilizer grade monoammonium phosphate, and dissolving the fertilizer grade monoammonium phosphate in water to obtain monoammonium phosphate solution.
The fertilizer grade monoammonium phosphate is used as a solid raw material, and the solution is prepared for subsequent reactions.
In some embodiments, the solid-to-liquid ratio of the fertilizer grade monoammonium phosphate to water is 1:3-1:5, and the dissolution ratio can obtain better solution concentration, so that subsequent potassium ions react with fluosilicic acid and/or fluorosilicate to generate precipitate, if the concentration of the monoammonium phosphate solution is too small, for example, the solid-to-liquid ratio of the fertilizer grade monoammonium phosphate to water is less than 1:5, the content of potassium ions is lower, the reaction rate is lower, and the potassium removal to a larger extent is unfavorable; if the concentration of monoammonium phosphate solution is too high, for example, the solid-to-liquid ratio of fertilizer grade monoammonium phosphate to water is greater than 1:3, the concentration of monoammonium phosphate approaches the saturation concentration, crystals of monoammonium phosphate may precipitate during the reaction, and ammonium is lost. So the solid-to-liquid ratio of the fertilizer grade monoammonium phosphate to the water can be selected to be 1:3-1:5.
The potassium content of the fertilizer grade monoammonium phosphate is less than or equal to 5000ppm, and the potassium removing method provided by the application can be used for treating the fertilizer grade monoammonium phosphate, so that a good potassium removing effect can be obtained.
S2: and (3) adding fluosilicic acid and/or fluosilicate into monoammonium phosphate solution, adjusting the pH value, and reacting to obtain mixed solution.
The fluosilicic acid and/or fluosilicate reacts with potassium ions in the monoammonium phosphate solution to generate potassium fluosilicate precipitate, and the monoammonium phosphate does not react with the fluosilicic acid and/or fluosilicate, so that the potassium can be separated and removed by a solid-liquid separation method.
In some embodiments, the method of adding fluosilicic acid and/or fluosilicate into monoammonium phosphate solution is slow dripping, obvious turbidity of the solution can be observed in the dripping process, the dripping speed is 8-12 mL/min, the concentration and the reaction rate of fluosilicic acid and/or fluosilicate in the mixed solution are controlled by controlling the dripping speed, the problem that the local concentration of the solution is too high, the generated precipitate is clustered, monoammonium phosphate is coated in the precipitate, and the monoammonium phosphate loss is caused is avoided.
In some embodiments, the pH of the reaction solution is greater than or equal to 4, and potassium fluosilicate precipitates are maximized by adjusting the pH of the solution.
Generally, the fertilizer grade monoammonium phosphate is an acidic mixture, so in some embodiments, the pH of the solution can be adjusted by adding ammonia water, and the ammonia water is used as an adjusting agent, so that the condition of adding other impurities can be avoided while adjusting the pH of the solution.
S3: and (3) carrying out solid-liquid separation on the mixed solution, and retaining clear liquid.
Most of potassium is contained in potassium fluosilicate precipitate, and monoammonium phosphate is in clear liquid, so that the potassium fluosilicate precipitate and the monoammonium phosphate can be separated by a solid-liquid separation method, and the aim of purifying the monoammonium phosphate is fulfilled.
In some embodiments, after the fluorosilicic acid and/or fluorosilicate is added, the reaction produces flocculent precipitate, which is smaller in size and is not conducive to solid-liquid separation.
Therefore, in some embodiments, before subjecting the a-mixed liquid to solid-liquid separation, the method further comprises the steps of:
under the conditions of heating and stirring, an inducer is added into the mixed solution to promote the precipitation of potassium fluosilicate, and then the mixed solution is obtained after low-temperature treatment.
After fluosilicic acid and/or fluosilicate are added, the reaction is carried out to generate precipitate, and then under the condition of heating and stirring, an inducer is added into the mixed solution to promote the precipitation of potassium fluosilicate. After heating reaction for a period of time, the reaction system is placed in a low-temperature environment for continuous reaction, and a proper amount of inducer is added to induce generation of potassium fluosilicate crystal nucleus, so that precipitation is promoted, the reaction is complete by heating, and the solubility of potassium fluosilicate in the solution can be reduced by the low-temperature environment, so that the potassium fluosilicate is completely precipitated.
It is understood that the low temperature treatment is carried out under the condition of maintaining stirring, so as to avoid the generated sediment from agglomerating and on the other hand, avoid the sediment from adhering to the bottom of the reaction kettle to form scale.
In some embodiments, the inducer is 0.02% -5% of the mass of the fertilizer grade monoammonium phosphate, and if the inducer is added in an amount that is too small, for example, less than 0.02% of the mass of the fertilizer grade monoammonium phosphate, the inducer induces little effect and may not achieve the promoting effect; if the mass of the inducer added is too large, for example, more than 5% of the mass of the fertilizer grade monoammonium phosphate, the introduction of a large amount of inducer may affect the performance of the product or cause precipitation of monoammonium phosphate crystals and loss.
In some embodiments, the inducer comprises at least one of Polyacrylamide (PAM), ferric chloride, polymeric ferric sulfate, small-molecule alcohols, and hydrocarbon sulfonate, and the inducer has good effect of promoting precipitation and is not reacted with monoammonium phosphate.
In some embodiments, the step of cryogenically treating further comprises the steps of:
a dispersant is added to the monoammonium phosphate solution and stirred.
The method comprises the steps of adding an inducer, heating, reacting for a period of time under stirring, cooling, continuing to react, and then adding a small amount of dispersing agent, namely surfactant, into the monoammonium phosphate solution, wherein the dispersing agent reduces the surface adsorption of potassium fluosilicate crystals by increasing the interfacial energy of potassium fluosilicate and the solution and the interfacial energy of potassium fluosilicate and a container, thereby preventing the initial deposition of scale and the scale blockage of a solid-liquid separation system and a transmission pipeline.
In some embodiments, the dispersant is 0.05% to 0.1% by mass of the fertilizer grade monoammonium phosphate.
In some embodiments, the dispersant comprises at least one of polyethylene glycol (PEG-200, PEG-600), triton X-100, sodium Dodecyl Sulfate (SDS), cetyltrimethylammonium bromide (CTAB), tributyl phosphate (TBP), and fatty alcohol polyoxyethylene ether (AEO).
In some embodiments, the heating conditions are at a temperature of 40 ℃ to 50 ℃ and the heating conditions are for a time of 30min to 40min to provide sufficient energy for the potassium ions to react with the fluorosilicic acid and/or fluorosilicate to form a precipitate that promotes the reaction to a maximum extent.
In some embodiments, the temperature of the low-temperature treatment is 1-5 ℃, the time of the low-temperature treatment is 3-5 h, and the solubility of the potassium fluosilicate in the solution is low in the temperature range, so that the potassium fluosilicate is completely precipitated.
In some embodiments, the step of cryogenic treatment is followed by or after the step of adding the dispersant and stirring, further comprising the steps of:
and adding a barium compound and sulfate into the monoammonium phosphate solution at room temperature to perform a reaction.
Before solid-liquid separation, adding proper amount of barium compound and sulfate, and reacting the barium compound and sulfate to form barium sulfate precipitate, and coprecipitating with suspended potassium fluosilicate to form large particle crystal, so as to increase the filtering performance and separation effect of the precipitate. In addition, since the particle size of potassium fluosilicate particles becomes small due to the dispersing and emulsifying effects of the dispersing agent, and the difficulty of filtration increases, it is preferable to add the barium compound and the sulfate to the monoammonium phosphate solution after the step of adding the dispersing agent and stirring.
In some embodiments, the mass of the barium compound is 1-5% of the mass of the fertilizer grade monoammonium phosphate, the generation amount of barium sulfate precipitation is controlled by controlling the addition amount of the barium compound, the potassium fluosilicate-barium sulfate coprecipitation effect is adjusted, excessive generation amount of barium sulfate precipitation is avoided, the workload of solid-liquid separation is increased, and the working efficiency is reduced.
In some embodiments, the molar ratio of barium compound to sulfate is (0.95-1.1): (0.45-0.55), and the molar ratio of barium to sulfate is 1, depending on the presence of 0.24% -0.25% sulfur impurities in the feedstock and the nature of the reaction of barium ions to sulfate: 0.5, so that the molar ratio of reactants charged is preferably about 1:0.5.
in some embodiments, the barium compound includes at least one of barium chloride, barium carbonate, and barium hydroxide.
In some embodiments, the sulfate salt comprises ammonium sulfate and/or ammonium bisulfate, the introduction of other cations is reduced, and the sulfate salt is capable of reacting with barium chloride, barium carbonate, and barium hydroxide to produce barium sulfate precipitate.
In some embodiments, prior to the step of adding the barium compound and the sulfate, the method further comprises the steps of:
adding precipitation auxiliary agent into monoammonium phosphate solution and stirring uniformly.
The barium sulfate precipitation has the defect of amorphous and easy agglomeration in the production process, and in order to quickly form the potassium fluosilicate-barium sulfate large particle uniform precipitation, a proper amount of precipitation auxiliary agent is added into the mixed solution to promote the growth of barium sulfate crystals, improve the crystal morphology and form uniform spherical large particle precipitation in a system so as to improve the separation effect.
In some embodiments, the precipitation aid is 0.06% -0.1% by mass of the fertilizer grade monoammonium phosphate.
In some embodiments, the precipitation aid comprises at least one of polyacrylic acid (PAA), acrylate, aminoethanol, tartaric Acid (TA), dopamine (DOPA), ethylenediamine tetraacetic acid (EDTA), which can promote barium sulfate crystal growth and can be removed during subsequent drying treatments, avoiding affecting the purity and properties of monoammonium phosphate.
It can be understood that after the solid-liquid separation treatment, besides clear liquid, solid slag is obtained, and the solid slag contains potassium fluosilicate and can be recycled in the processes of wood corrosion prevention, ceramic manufacturing and the like, so that no solid waste is generated and no environmental pollution is caused.
S4: and drying the clear liquid to obtain purified monoammonium phosphate.
In some embodiments, the drying process comprises spray drying, and the filtered monoammonium phosphate solution is spray dried to obtain a solid product, and the excess fluorosilicic acid in the solution is decomposed into hydrogen fluoride and silicon tetrafluoride gas under the high temperature condition of spray drying so as to be removed.
In some embodiments, after the mixed solution is subjected to solid-liquid separation treatment, the obtained solid slag may be washed with a small amount of cold water to collect monoammonium phosphate remaining on the solid slag, the washed liquid is retained, and the obtained liquid is mixed with a clear solution obtained by the solid-liquid separation treatment, and dried together.
According to the potassium removing method for the fertilizer-grade monoammonium phosphate, fluosilicic acid and/or fluosilicate can react with potassium ions in the fertilizer-grade monoammonium phosphate to generate potassium fluosilicate precipitate, and the potassium fluosilicate precipitate is separated by a solid-liquid separation method to obtain monoammonium phosphate solution with low potassium content.
Compared with the prior art, the potassium removing method for the fertilizer grade monoammonium phosphate provided by the embodiment of the application utilizes the chemical property difference of potassium ions and ammonium ions, the potassium ions can react with fluosilicic acid and/or fluosilicate to generate precipitate, and the ammonium ions do not react with fluosilicic acid and/or fluosilicate, so that the potassium is removed from the fertilizer grade monoammonium phosphate, the monoammonium phosphate is purified, the loss of the ammonium is small, the preparation method is reasonable and effective, the flow is simple, the operability is strong, the dosage of the agent is less, the selectivity to potassium precipitate is high, the overall cost is lower, and the industrialization is easy to realize.
According to the potassium removing method for the fertilizer-grade monoammonium phosphate, the potassium content of the obtained purified monoammonium phosphate is lower than 50ppm, the product purity reaches 99%, the yield of the monoammonium phosphate can reach more than 99% under the condition of continuous feeding production, the product performance is close to the raw material production requirement of lithium ion battery materials, and the method can be applied to preparing the positive electrode materials of batteries, such as the positive electrode materials of phosphate batteries, such as lithium iron phosphate batteries, lithium manganese iron phosphate batteries, vanadium lithium phosphate batteries and the like.
The lithium iron phosphate positive electrode material prepared from the monoammonium phosphate has the advantages of less impurity brought by monoammonium phosphate and proper potassium content, and improves the lattice stability of the lithium iron phosphate positive electrode material and the cycle performance of a lithium ion battery.
The following is exemplified by a number of examples.
Example 1
The potassium removing method of the fertilizer grade monoammonium phosphate comprises the following steps:
s1: 15g of fertilizer grade monoammonium phosphate is completely dissolved in deionized water according to a solid-to-liquid ratio of 1:3, so as to obtain monoammonium phosphate solution.
S2: slowly dripping 3% fluosilicic acid and ammonium fluosilicate into monoammonium phosphate solution at a dripping speed of 10mL/min, and adjusting the pH value of the reaction solution to 4.0 by using ammonia water while stirring to generate potassium fluosilicate precipitate to obtain a mixed solution A.
S3: adding 0.02% of DNSK into the mixed solution A, stirring at 50 ℃ for 30min, cooling the reaction solution at 1 ℃ to separate out for 3h, adding 0.05% of AEO, and stirring to obtain mixed solution B.
S4: adding 0.06% of PAA into the mixed solution B, stirring uniformly, adding 5% of barium hydroxide and sulfate with 0.5 time of molar mass, and reacting for 2 hours at room temperature to obtain the mixed solution C.
S5: and (3) filtering and separating the mixed solution C, and flushing a filter cake with a small amount of cold water to obtain clear liquid.
S6: spray drying the clear solution to obtain purified monoammonium phosphate solid.
The analysis of the components of the fertilizer grade monoammonium phosphate raw material and the purified monoammonium phosphate product in this example is shown in table 1.
TABLE 1
Example 2
The potassium removing method of the fertilizer grade monoammonium phosphate comprises the following steps:
s1: 15g of fertilizer grade monoammonium phosphate is completely dissolved in deionized water according to a solid-to-liquid ratio of 1:3, so as to obtain monoammonium phosphate solution.
S2: slowly dripping 3% fluosilicic acid/ammonium fluosilicate into monoammonium phosphate solution at the dripping speed of 10mL/min, and adjusting the pH value of the reaction solution to 4.0 by using ammonia water while stirring to generate potassium fluosilicate precipitate to obtain the mixed solution A.
S3: adding 5% ethanol into the mixed solution A, stirring at 50deg.C for 10min, cooling the reaction solution at 5deg.C for precipitation for 5h, adding 0.05% triton X-100, and stirring to obtain mixed solution B.
S4: and adding 0.06% of EDTA into the mixed solution B, uniformly stirring, adding 3% of barium carbonate and 0.5 time of sulfate with the molar mass, and reacting for 2 hours at room temperature to obtain the mixed solution C.
S5: and (3) filtering and separating the mixed solution C, and flushing a filter cake with a small amount of cold water to obtain clear liquid.
S6: spray drying the clear solution to obtain purified monoammonium phosphate solid.
The analysis of the components of the fertilizer grade monoammonium phosphate raw material and the purified monoammonium phosphate product in this example is shown in table 2.
TABLE 2
Example 3
The potassium removing method of the fertilizer grade monoammonium phosphate comprises the following steps:
s1: 15g of fertilizer grade monoammonium phosphate is completely dissolved in deionized water according to a solid-to-liquid ratio of 1:4, so as to obtain monoammonium phosphate solution.
S2: adding 5% ammonium fluosilicate into monoammonium phosphate solution, stirring and adjusting the pH value of the reaction solution to 4.0 while stirring after dissolving the solid, so as to generate potassium fluosilicate precipitate, and obtaining the mixed solution A.
S3: adding 5% ethanol into the mixed solution A, stirring at 50 ℃ for 30min, cooling the reaction solution at 1 ℃ to separate out for 3h, adding 0.075% SDS, and stirring to obtain mixed solution B.
S4: adding 0.06% of PAA into the mixed solution B, stirring uniformly, adding 5% of barium hydroxide and sulfate with 0.5 time of molar mass, and reacting for 2 hours at room temperature to obtain the mixed solution C.
S5: and (3) filtering and separating the mixed solution C, and flushing a filter cake with a small amount of cold water to obtain clear liquid.
S6: spray drying the clear solution to obtain purified monoammonium phosphate solid.
The analysis of the components of the fertilizer grade monoammonium phosphate raw material and the purified monoammonium phosphate product in this example is shown in table 3.
TABLE 3 Table 3
Example 4
The potassium removing method of the fertilizer grade monoammonium phosphate comprises the following steps:
s1: 15g of fertilizer grade monoammonium phosphate is completely dissolved in deionized water according to a solid-to-liquid ratio of 1:3, so as to obtain monoammonium phosphate solution.
S2: slowly dripping 3% fluosilicic acid into monoammonium phosphate solution at a dripping speed of 10mL/min, and adjusting the pH value of the reaction solution to 4.0 by using ammonia water while stirring to generate potassium fluosilicate precipitate to obtain a mixed solution A.
S3: adding 0.02% naphthalene sulfonic acid into the mixed solution A, stirring at 50 ℃ for 10min, cooling the reaction solution at 5 ℃ for precipitation for 5h, then adding 0.05% triton X-100, and stirring uniformly to obtain mixed solution B.
S4: and adding 0.06% of EDTA into the mixed solution B, uniformly stirring, adding 3% of barium carbonate and 0.5 time of sulfate with the molar mass, and reacting for 2 hours at room temperature to obtain the mixed solution C.
S5: and (3) filtering and separating the mixed solution C, and flushing a filter cake with a small amount of cold water to obtain clear liquid.
S6: spray drying the clear solution to obtain purified monoammonium phosphate solid.
The analysis of the components of the fertilizer grade monoammonium phosphate raw material and the purified monoammonium phosphate product in this example is shown in Table 4.
TABLE 4 Table 4
Comparative example 1
The potassium removing method of the fertilizer grade monoammonium phosphate of the comparative example comprises the following steps:
s1: 15g of fertilizer grade monoammonium phosphate is completely dissolved in deionized water according to a solid-to-liquid ratio of 1:3, so as to obtain monoammonium phosphate solution.
S2: slowly dripping 1% fluosilicic acid/ammonium fluosilicate into monoammonium phosphate solution, and adjusting the pH value of the reaction solution to 4.0 by using ammonia water while stirring to generate potassium fluosilicate precipitate to obtain a mixed solution A.
S3: adding 5% ethanol into the solution, stirring at 50deg.C for 10min, cooling the reaction solution at 1deg.C for precipitation for 5 hr, adding 0.05% triton X-100, and stirring to obtain mixed solution B.
S4: and adding 0.06% of EDTA into the mixed solution B, uniformly stirring, adding 3% of barium carbonate and 0.5 time of sulfate with the molar mass, and reacting for 2 hours at room temperature to obtain the mixed solution C.
S5: and (3) filtering and separating the mixed solution C, and flushing a filter cake with a small amount of cold water to obtain clear liquid.
S6: spray drying the clear solution to obtain purified monoammonium phosphate solid.
The monoammonium phosphate raw material and the purified monoammonium phosphate product composition analysis in this comparative example 1 are shown in Table 5.
TABLE 5
As can be seen from tables 1 to 4, in examples 1 to 4, by using the technical scheme of the application to remove the impurity potassium in the fertilizer-grade monoammonium phosphate, the potassium content of the purified monoammonium phosphate is lower than 50ppm, the content of the impurity potassium is greatly reduced, and the purified monoammonium phosphate has high purity and meets the requirement of being used as a raw material for preparing the battery anode material. In addition, a small amount of calcium and magnesium impurities in the raw materials are removed by reacting with hydrogen fluoride generated by the decomposition of fluosilicic acid/ammonium fluosilicate to generate a precipitate, and a small amount of sulfur impurities in the raw materials are removed by forming a barium sulfate precipitate with soluble barium salt, so that the purity of the purified monoammonium phosphate is further improved.
As can be seen from the data in table 5, compared with example 2, the comparative example maintains the liquid-solid ratio and the reaction temperature unchanged, and the potassium precipitation reaction is insufficient, the purification degree is reduced, the residual potassium content is high, and the production requirement of the raw materials of the battery anode material is not met after the precipitant fluosilicic acid/ammonium fluosilicate is reduced to be less than 1% of the mass of the monoammonium phosphate raw materials.
The foregoing description of the preferred embodiments of the application is not intended to limit the application to the particular embodiments disclosed, but on the contrary, the intention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the application.
Claims (10)
1. A method for removing potassium from fertilizer grade monoammonium phosphate is characterized by comprising the following steps: the method comprises the following steps:
dissolving fertilizer grade monoammonium phosphate into water to obtain monoammonium phosphate solution;
adding fluosilicic acid and/or fluosilicate into the monoammonium phosphate solution, adjusting the pH value, and reacting to obtain a mixed solution;
carrying out solid-liquid separation on the mixed solution, and keeping clear liquid;
and drying the clear liquid to obtain purified monoammonium phosphate.
2. The method for removing potassium from a fertilizer grade monoammonium phosphate according to claim 1, wherein: the solid-to-liquid ratio of the fertilizer grade monoammonium phosphate to water is 1:3-1:5; and/or the number of the groups of groups,
the potassium content in the fertilizer grade monoammonium phosphate is less than or equal to 5000ppm; and/or the number of the groups of groups,
the potassium content in the purified monoammonium phosphate is less than or equal to 50ppm.
3. The method for removing potassium from a fertilizer grade monoammonium phosphate according to claim 1, wherein: the fluosilicic acid and/or the fluosilicate are/is added into the monoammonium phosphate solution in a slow dropwise adding mode, and the dropwise adding speed is 8-12 mL/min; and/or the number of the groups of groups,
the addition amount of the fluosilicic acid and/or the fluosilicate is 3-9% of the mass of the fertilizer grade monoammonium phosphate; and/or the number of the groups of groups,
the step of adjusting the pH value comprises the following steps of; adding ammonia water, and adjusting the pH value to be more than or equal to 4; and/or the number of the groups of groups,
the drying treatment comprises spray drying.
4. The method for removing potassium from a fertilizer grade monoammonium phosphate according to claim 1, wherein: after the step of adjusting the pH value, the method further comprises the steps of:
an inducer is added to the monoammonium phosphate solution under heating, and then the solution is treated at a low temperature.
5. The method for removing potassium from a fertilizer grade monoammonium phosphate according to claim 4, wherein: the addition amount of the inducer is 0.02-5% of the mass of the fertilizer grade monoammonium phosphate; and/or the number of the groups of groups,
the inducer comprises at least one of polyacrylamide, ferric chloride, polymeric ferric sulfate, micromolecular alcohols and hydrocarbon sulphonates; and/or the number of the groups of groups,
the temperature of the heating condition is 40-50 ℃, and the time of the heating condition is 30-40 min; and/or the number of the groups of groups,
the temperature of the low-temperature treatment is 1-5 ℃, and the time of the low-temperature treatment is 3-5 h.
6. The method for removing potassium from a fertilizer grade monoammonium phosphate according to claim 4, wherein: after the step of low temperature treatment, the method further comprises the steps of: adding a dispersing agent into the monoammonium phosphate solution and stirring;
preferably, the addition amount of the dispersing agent is 0.05-0.1% of the mass of the fertilizer grade monoammonium phosphate;
preferably, the dispersing agent comprises at least one of polyethylene glycol, triton X-100, sodium dodecyl sulfate, cetyltrimethylammonium bromide, tributyl phosphate and fatty alcohol-polyoxyethylene ether.
7. The method for removing potassium from a fertilizer grade monoammonium phosphate according to claim 5 or 6, characterized by: after the step of low temperature treatment or after the step of adding a dispersant and stirring, the method further comprises the steps of:
and adding a barium compound and sulfate into the monoammonium phosphate solution at room temperature to perform a reaction.
8. The method for removing potassium from a fertilizer grade monoammonium phosphate according to claim 7, wherein: the addition amount of the barium compound is 1-5% of the mass of the fertilizer grade monoammonium phosphate; and/or the number of the groups of groups,
the molar ratio of the barium compound to the sulfate is (0.95-1.1): 0.45-0.55; and/or the number of the groups of groups,
the barium compound includes at least one of barium chloride, barium carbonate, and barium hydroxide; and/or the number of the groups of groups,
the sulfate comprises ammonium sulfate and/or ammonium bisulfate.
9. The method for removing potassium from a fertilizer grade monoammonium phosphate according to claim 7, wherein: before the step of adding the barium compound and the sulfate, the method further comprises the following steps: adding a precipitation auxiliary agent into the monoammonium phosphate solution and uniformly stirring;
preferably, the addition amount of the precipitation auxiliary agent is 0.06% -0.1% of the mass of the fertilizer grade monoammonium phosphate;
preferably, the precipitation aid includes at least one of polyacrylic acid, acrylic acid ester, amino ethanol, tartaric acid, dopamine and ethylenediamine tetraacetic acid.
10. Use of the purified monoammonium phosphate obtained by the potassium removal method of fertilizer grade monoammonium phosphate according to any one of claims 1-9 for the preparation of a battery positive electrode material.
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