CN116002655A - Process for co-producing hexafluorophosphate and byproduct light calcium carbonate by taking fluorite as raw material - Google Patents
Process for co-producing hexafluorophosphate and byproduct light calcium carbonate by taking fluorite as raw material Download PDFInfo
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- CN116002655A CN116002655A CN202211725166.0A CN202211725166A CN116002655A CN 116002655 A CN116002655 A CN 116002655A CN 202211725166 A CN202211725166 A CN 202211725166A CN 116002655 A CN116002655 A CN 116002655A
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- hexafluorophosphate
- gas
- fluorite
- calcium carbonate
- light calcium
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 80
- -1 hexafluorophosphate Chemical compound 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 62
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 40
- 239000006227 byproduct Substances 0.000 title claims abstract description 37
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 title claims abstract description 37
- 230000008569 process Effects 0.000 title claims abstract description 36
- 239000010436 fluorite Substances 0.000 title claims abstract description 35
- 239000002994 raw material Substances 0.000 title claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 101
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000000047 product Substances 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 150000004673 fluoride salts Chemical class 0.000 claims abstract description 11
- 238000000746 purification Methods 0.000 claims abstract description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 230000003068 static effect Effects 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 24
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 22
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 20
- 229910052731 fluorine Inorganic materials 0.000 claims description 20
- 239000011737 fluorine Substances 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 238000000354 decomposition reaction Methods 0.000 claims description 15
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- 238000010000 carbonizing Methods 0.000 claims description 10
- 229910052717 sulfur Inorganic materials 0.000 claims description 10
- 239000011593 sulfur Substances 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 238000007710 freezing Methods 0.000 claims description 9
- 230000008014 freezing Effects 0.000 claims description 9
- 239000010440 gypsum Substances 0.000 claims description 9
- 229910052602 gypsum Inorganic materials 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 239000003638 chemical reducing agent Substances 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 7
- 230000003197 catalytic effect Effects 0.000 claims description 7
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002028 Biomass Substances 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000012141 concentrate Substances 0.000 claims description 5
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 4
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 3
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 claims description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 3
- 239000003610 charcoal Substances 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 claims description 3
- 229940017219 methyl propionate Drugs 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 3
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 35
- 239000010419 fine particle Substances 0.000 description 12
- 239000011362 coarse particle Substances 0.000 description 11
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- OBCUTHMOOONNBS-UHFFFAOYSA-N phosphorus pentafluoride Chemical compound FP(F)(F)(F)F OBCUTHMOOONNBS-UHFFFAOYSA-N 0.000 description 8
- 229910013870 LiPF 6 Inorganic materials 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- 238000005243 fluidization Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 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 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a process for co-producing hexafluorophosphate and byproduct light calcium carbonate by taking fluorite as a raw material, belonging to the technical field of hexafluorophosphate production. The invention solves the technical problem of providing a process for co-producing hexafluorophosphate and byproduct light calcium carbonate by taking fluorite as a raw material. The process comprises the following steps: a. fluorite reacts with fuming sulfuric acid to generate crude hydrogen fluoride gas; b. conversion of crude hydrogen fluoride gas to PF 5 A gas; c. PF (physical filter) 5 The gas reacts with fluoride salt, the temperature is controlled below 15 ℃ in the reaction process, the product is extracted by adding a solvent of lithium battery electrolyte, and the liquid hexafluorophosphate is obtained through static layering and filtering. According to the invention, through material substitution and process innovation, the transverse development of multi-product coupling is realized, and simultaneously, a three-dimensional industrial structure for recycling byproducts and wastes is realized, so that the resource and energy consumption in the production process is reduced. The process production process is safe, and the reverse reaction is avoidedThe method has good dangers and purification effects, and can be used for preparing high-purity hexafluorophosphate.
Description
Technical Field
The invention relates to a process for co-producing hexafluorophosphate and byproduct light calcium carbonate by taking fluorite as a raw material, belonging to the technical field of hexafluorophosphate production.
Background
Hexafluorophosphates, including lithium hexafluorophosphate (LiPF) 6 ) And sodium hexafluorophosphate (NaPF) 6 ) Is a common electrolyte material for preparing lithium ion batteries or sodium ion batteries. LiPF is manufactured by increasingly steering to make all-electric or hybrid electric vehicles 6 The demand for (c) has increased dramatically over the last few years. However, lithium reserves are limited and unevenly distributed, which limits the large-scale application of lithium ion batteries in energy storage. Sodium with similar physical and chemical properties to lithium has abundant reserves, wide distribution and low cost, so that the sodium ion battery has wide application prospect in large-scale power grid energy storage.
Compared with other electrolytes, hexafluorophosphate has advantages of good stability, high compatibility, high solubility, good conductivity and high ion mobility, and thus is widely used for preparing secondary batteries. At present, the main preparation method of hexafluorophosphate comprises the following steps: a gas-solid reaction method, an HF solvent method, an organic solvent method, an ion exchange method and a liquid phase method.
The invention patent with publication number of CN101570326A discloses a preparation method of lithium hexafluorophosphate, which comprises the following steps:
(1) Reacting anhydrous hydrogen fluoride with concentrated phosphoric acid under the protection of inert gas to prepare hexafluorophosphoric acid; (2) Adding fuming sulfuric acid into the hexafluorophosphoric acid prepared in the step (1) under cooling and stirring to prepare phosphorus pentafluoride gas; (3) Dissolving high-purity lithium fluoride in anhydrous hydrogen fluoride solution to form anhydrous hydrogen fluoride solution of lithium fluoride; (4) After cooling the phosphorus pentafluoride gas, introducing the phosphorus pentafluoride gas into an anhydrous hydrogen fluoride solution containing lithium fluoride, and obtaining a pure lithium hexafluorophosphate product through reaction, crystallization, separation and drying; (5) And continuously introducing unreacted cooled phosphorus pentafluoride gas into an anhydrous hydrogen fluoride solution containing lithium fluoride, and continuously reacting to obtain a lithium hexafluorophosphate finished product. The process adopts an HF solution method, the crystallization is not easy to control, the HF remained in the product exists in the product in the form of a complex, and the mass fraction of the HF is extremely difficult to be reduced to 1 multiplied by 10 by a common method -5 The purity of the product is greatly affected; residual HF corrodes battery materials, thereby affecting the battery electrical performance; the reaction is severe, and a large amount of heat is released during the reaction. The process has high requirements on equipment materials, anti-corrosion measures and production safety measures, and increases capital investment; the process is a cryogenic process, and has the advantages of high energy consumption and high production cost.
The invention patent publication No. CN101353161A discloses a process for producing phosphorus pentafluoride gas and a process for producing lithium hexafluorophosphate using the gas, wherein the process for producing lithium hexafluorophosphate comprises a contact reaction of solid lithium fluoride with phosphorus pentafluoride gas in the presence of a solvent selected from one or more of ether, acetonitrile, carbonate and ethyl acetate. The method is mainly an organic solvent method, and the solubility of raw material solids in the organic solvent is low, so that the reaction efficiency and the yield are low; the reaction raw materials react with the organic solvent to cause polymerization and decomposition, so that a high-purity product is difficult to obtain, and the method is only suitable for preparing liquid lithium hexafluorophosphate.
Disclosure of Invention
Aiming at the defects, the invention solves the technical problem of providing a process for co-producing hexafluorophosphate and byproduct light calcium carbonate by taking fluorite as a raw material.
The invention relates to a process for co-producing hexafluorophosphate and byproduct light calcium carbonate by taking fluorite as a raw material, which comprises the following steps:
a. fluorite reacts with fuming sulfuric acid to generate crude hydrogen fluoride gas;
b. conversion of crude hydrogen fluoride gas to PF using Process 1 or Process 2 5 A gas;
c、PF 5 the gas reacts with fluoride salt, the temperature is controlled below 15 ℃ in the reaction process, the product is extracted by adding a solvent of lithium battery electrolyte, and liquid hexafluorophosphate is obtained through static layering and filtering, wherein the fluoride salt is LiF or NaF;
wherein the method 1 comprises the following steps:
1.1, purifying crude hydrogen fluoride gas to obtain anhydrous hydrogen fluoride gas; by-product content in the purification processThe fluorogypsum is heated and decomposed into CaO and SO 2 Emulsifying CaO, filtering to obtain saturated lime water, and mixing with CO 2 Carbonizing, filtering and drying to obtain light calcium carbonate;
1.2, reacting anhydrous hydrogen fluoride with a phosphorus-containing substance to generate hexafluorophosphoric acid or hexafluorophosphate; the phosphorus-containing material is polyphosphoric acid or P 2 O 5 ；
1.3 decomposition of hexafluorophosphoric acid or hexafluorophosphate to give PF 5 A gas;
the method 2 comprises the following steps:
2.1, reacting the crude hydrogen fluoride gas with a phosphorus-containing substance to generate crude hexafluorophosphoric acid or hexafluorophosphate;
2.2 decomposition of crude hexafluorophosphoric acid or hexafluorophosphate to give crude PF 5 A gas; byproduct CaSO of the reaction 4 Reduction to SO by addition of a reducing agent 2 Gas and CaO, SO 2 SO formed by catalytic oxidation of gas 3 C, returning the gas to the step a; emulsifying CaO, filtering, drying filter residue, and returning to step a, wherein the filtrate and CO 2 Carbonizing, filtering and drying to obtain light calcium carbonate;
2.3 coarse PF 5 Purifying the gas to obtain PF 5 And (3) gas.
In one embodiment of the invention, in step c, the liquid hexafluorophosphate is concentrated and crystallized and filtered to give solid hexafluorophosphate.
In one embodiment of the invention, in step 1.1, the crude hydrogen fluoride gas is purified by washing, cooling, condensing, rectifying and degassing in sequence.
In one embodiment of the present invention, the decomposition temperature is controlled to be-20 to 30 ℃ in step 1.3 and step 2.2.
In one embodiment of the invention, step 1.3 is carried out in a reaction vessel with anhydrous hydrogen fluoride accompanying the hexafluorophosphate salt entering the reaction vessel thermally decomposing the SO generated by the fluorine-containing gypsum of step 1.1 2 Reacting at 25-35 ℃ to generate fluorine-containing phosphoric acid, and returning the fluorine-containing phosphoric acid to the step a.
In one embodiment of the present invention, in step 2.2, the reducing agent is sulfur, carbon, sulfur concentrate, or biomass char.
In one embodiment of the present invention, in step 2.3, the crude PF 5 The PF is obtained by the gas through the freeze purification 5 The freezing temperature of the gas is-40 to 15 ℃ and the pressure is 0.0 to 0.5MPa.
In one embodiment of the invention, in the step c, the fluoride salt is in the form of particles, the particles with the particle size of 250-380 mu m account for 25-35 wt% and the rest are particles with the particle size of 100-200 mu m; preferably, the particles having a particle size of 250 to 380 μm account for 30wt%.
In the step c, the solvent of the lithium battery electrolyte is at least one of ethylene glycol dimethyl ether, isopropyl ether, anisole, propylene carbonate, methyl ethyl carbonate, ethylene carbonate, vinylene carbonate and methyl propionate.
Compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, through material substitution and process innovation, the transverse development of multi-product coupling is realized, and simultaneously, a three-dimensional industrial structure for recycling byproducts and wastes is realized, so that the resource and energy consumption in the production process is reduced.
2. The method has the advantages of safe production process, avoidance of reaction danger and good purification effect, and can be used for preparing high-purity hexafluorophosphate.
3. The hexafluorophosphate obtained by the process has the purity of 99.99 percent, the moisture content of less than 2ppm and the free acid (calculated by HF) content of less than 6ppm. The whiteness of the byproduct light calcium carbonate of the process is more than or equal to 97 percent, the content is more than or equal to 98.5 percent, and the settled body (i.e. settled volume) is 2.8 to 3.2.
Drawings
FIG. 1 is a flow chart of the process for co-producing hexafluorophosphate and by-product light calcium carbonate by using fluorite as raw material in examples 1 and 2 of the present invention.
FIG. 2 is a flow chart of the process for co-producing hexafluorophosphate and by-product light calcium carbonate by using fluorite as raw material in examples 3 and 4 of the present invention.
Detailed Description
The invention relates to a process for co-producing hexafluorophosphate and byproduct light calcium carbonate by taking fluorite as a raw material, which comprises the following steps:
a. fluorite reacts with fuming sulfuric acid to generate crude hydrogen fluoride gas;
b. conversion of crude hydrogen fluoride gas to PF using Process 1 or Process 2 5 A gas;
c、PF 5 the gas reacts with fluoride salt, the temperature is controlled below 15 ℃ in the reaction process, the product is extracted by adding solution of lithium battery electrolyte, and liquid hexafluorophosphate is obtained through static layering filtration, wherein the fluoride salt is LiF or NaF;
wherein the method 1 comprises the following steps:
1.1, purifying crude hydrogen fluoride gas to obtain anhydrous hydrogen fluoride gas; the by-product fluorine-containing gypsum in the purification process is decomposed into CaO and SO by heating 2 Emulsifying CaO, filtering to obtain saturated lime water, and mixing with CO 2 Carbonizing, filtering and drying to obtain light calcium carbonate;
1.2, reacting anhydrous hydrogen fluoride with a phosphorus-containing substance to generate hexafluorophosphoric acid or hexafluorophosphate; the phosphorus-containing material is polyphosphoric acid or P 2 O 5 ；
1.3 decomposition of hexafluorophosphoric acid or hexafluorophosphate to give PF 5 A gas;
the method 2 comprises the following steps:
2.1, reacting the crude hydrogen fluoride gas with a phosphorus-containing substance to generate crude hexafluorophosphoric acid or hexafluorophosphate;
2.2 decomposition of crude hexafluorophosphoric acid or hexafluorophosphate to give crude PF 5 A gas; byproduct CaSO of the reaction 4 Reduction to SO by addition of a reducing agent 2 Gas and CaO, SO 2 SO formed by catalytic oxidation of gas 3 C, returning the gas to the step a; the CaO is emulsified and filtered, the filter residue is unreacted fluorite, and the residue is dried and returned to the step a, and the filtrate and CO 2 Carbonizing, filtering and drying to obtain light calcium carbonate;
2.3 coarse PF 5 Purifying the gas to obtain PF 5 And (3) gas.
According to the invention, from the viewpoints of reducing the cost, energy demand and environmental impact of producing hexafluorophosphate, the fluorite is used as a raw material to produce phosphorus pentafluoride, so that hexafluorophosphate is prepared, the transverse development of multi-product coupling is realized through material substitution and process innovation, the three-dimensional industrial structure of recycling byproducts and wastes is realized, and the resource and energy consumption in the production process is reduced. The method has the advantages of safe production process, avoidance of reaction danger and good purification effect, and can be used for preparing high-purity hexafluorophosphate.
In one embodiment of the invention, in step c, the liquid hexafluorophosphate is concentrated and crystallized and filtered to give solid hexafluorophosphate. By adopting the method, hexafluorophosphate solid can be further obtained, so that the method is suitable for more complex electrolyte, such as DC/MC and the like.
In one embodiment of the invention, in step 1.1, the crude hydrogen fluoride gas is purified by washing, cooling, condensing, rectifying and degassing in sequence. By the purification method, the hydrogen fluoride gas with higher purity can be obtained.
In one embodiment of the present invention, the decomposition temperature is controlled to be-20 to 30 ℃ in step 1.3 and step 2.2. At this decomposition temperature, hexafluorophosphate can be decomposed with high efficiency to obtain phosphorus pentafluoride gas.
In one embodiment of the invention, step 1.3 is carried out in a reaction vessel with anhydrous hydrogen fluoride accompanying the hexafluorophosphate salt entering the reaction vessel thermally decomposing the SO generated by the fluorine-containing gypsum of step 1.1 2 Reacting at 25-35 ℃ to generate fluorine-containing phosphoric acid, and returning the fluorine-containing phosphoric acid to the step a. Therefore, materials can be recycled, and the cost is reduced.
In one embodiment of the present invention, in step 2.2, the reducing agent is sulfur or carbon or sulfur concentrate or biomass char.
In one embodiment of the present invention, in step 2.3, the crude PF 5 The PF is obtained by the gas through the freeze purification 5 The freezing temperature of the gas is-40 to 15 ℃ and the pressure is 0.0 to 0.5MPa.
In one embodiment of the invention, step c is carried out in a fluidized bed reactor. Preferably, in the step c, the fluoride salt is granular, the proportion of the granules with the grain diameter of 250-380 mu m is 25-35 wt%, and the rest is the granules with the grain diameter of 100-200 mu m; preferably, the particles having a particle size of 250 to 380 μm account for 30wt%. The coarse particles can play a role in crushing the fine particles, so that acting force among the fine particles is reduced. Through the configuration of different particles, the agglomeration of fluoride salt particles is effectively reduced, good fluidization is realized, and the generated hexafluorophosphate is prevented from completely coating solid particles, so that the further progress of the reaction is prevented, and the yield and purity are improved.
In step c, the extraction may employ a solvent commonly used in the art for lithium battery electrolyte in which hexafluorophosphate is dissolved, including but not limited to at least one of ethylene glycol dimethyl ether, isopropyl ether, anisole, propylene carbonate, methyl ethyl carbonate, ethylene carbonate, vinylene carbonate and methyl propionate.
The following describes the invention in more detail with reference to examples, which are not intended to limit the invention thereto.
Example 1
As shown in fig. 1, the following method is adopted to co-produce lithium hexafluorophosphate and byproduct light calcium carbonate by taking fluorite as raw materials:
(1) Heating fluorite and fuming sulfuric acid in a rotary furnace to react to generate crude hydrogen fluoride gas;
(2) The crude hydrogen fluoride gas is washed, cooled, condensed, rectified and degassed to obtain anhydrous hydrogen fluoride gas.
By-product fluorine-containing gypsum (slag CaSO) 4 ) The CaO and the SO are generated through heating decomposition 2 And (3) gas.
And (3) performing emulsification filtration on CaO to obtain saturated lime water, drying filter residues which contain calcium fluoride, returning to the step (1), and performing heating reaction on the filter residues with fuming sulfuric acid again in a rotary furnace. Saturated lime water and CO 2 Carbonizing, filtering and drying to finally obtain the light calcium carbonate product. The whiteness of the light calcium carbonate is more than or equal to 97%, the content is more than or equal to 98.5%, and the sediment is 2.8-3.2.
SO 2 SO formed by catalytic oxidation of gas 3 The gas is returned to the step (1), or the gas is reacted with anhydrous hydrogen fluoride at 25-35 ℃ to generate fluorine-containing phosphoric acid, and the gas is returned to the step (1)In a converter.
(3) The anhydrous hydrogen fluoride gas is slowly introduced into the reaction kettle to react with polyphosphoric acid or P 2 O 5 The reaction produces hexafluorophosphoric acid or hexafluorophosphate.
(4) Decomposition of hexafluorophosphoric acid or hexafluorophosphate to PF at-25 DEG C 5 And (3) gas.
SO generated by thermal decomposition of anhydrous hydrogen fluoride and fluorine-containing gypsum along with phosphate entering reaction kettle 2 Reacting at 25-35 ℃ to generate fluorine-containing phosphoric acid, and returning to the rotary furnace in the step (1).
(5)PF 5 The gas reacts with the LiF in the fluidized bed reactor.
To the fluidized bed, 30wt% of coarse LiF particles of 250-380 μm and the balance of fine LiF particles of 100-200 μm were added. The coarse particles can break up the fine particles, and reduce the acting force among the fine particles. The addition of coarse particles can effectively reduce the agglomeration of LiF particles and realize good fluidization.
The temperature is controlled below 15 ℃ in the reaction process. Extracting the product with ethylene glycol dimethyl ether (DME), standing, and filtering to obtain liquid LiPF 6 Concentrating and crystallizing to obtain solid LiPF 6 The product, insoluble LiF, is returned to the fluidized bed reactor.
The solid LiPF 6 The purity of the product was 99.99%, the moisture content was less than 2ppm, and the free acid (as HF) content was less than 6ppm.
Example 2
As shown in fig. 1, the following method is adopted to co-produce sodium hexafluorophosphate and byproduct light calcium carbonate by using fluorite as raw materials:
(1) Heating fluorite and fuming sulfuric acid in a rotary furnace to react to generate crude hydrogen fluoride gas;
(2) The crude hydrogen fluoride gas is washed, cooled, condensed, rectified and degassed to obtain anhydrous hydrogen fluoride gas.
By-product fluorine-containing gypsum (slag CaSO) 4 ) The CaO and the SO are generated through heating decomposition 2 And (3) gas.
The CaO is emulsified and filtered to obtain saturated lime water, filter residues are dried by calcium fluoride, and then returned to the step (1) to enter a rotary furnaceAnd the mixture is heated and reacted with fuming sulfuric acid again. Saturated lime water and CO 2 Carbonizing, filtering and drying to finally obtain the light calcium carbonate product. The whiteness of the light calcium carbonate is more than or equal to 97%, the content is more than or equal to 98.5%, and the sediment is 2.8-3.2.
SO 2 SO formed by catalytic oxidation of gas 3 The gas is returned to the step (1), or the gas is reacted with anhydrous hydrogen fluoride at 25-35 ℃ to generate fluorine-containing phosphoric acid, and the fluorine-containing phosphoric acid is returned to the rotary furnace in the step (1).
(3) The anhydrous hydrogen fluoride gas is slowly introduced into the reaction kettle to react with polyphosphoric acid or P 2 O 5 The reaction produces hexafluorophosphoric acid or hexafluorophosphate.
(4) Decomposition of hexafluorophosphoric acid or hexafluorophosphate to PF at-25 DEG C 5 And (3) gas.
SO generated by thermal decomposition of anhydrous hydrogen fluoride and fluorine-containing gypsum along with phosphate entering reaction kettle 2 Reacting at 25-35 ℃ to generate fluorine-containing phosphoric acid, and returning to the rotary furnace in the step (1).
(5)PF 5 The gas reacts with the NaF in the fluidized bed reactor.
30wt% of NaF coarse particles with the diameter of 250-380 mu m and the balance of fine particles with the diameter of 100-200 mu m are added into the fluidized bed. The coarse particles can break up the fine particles, and reduce the acting force among the fine particles. The addition of coarse particles can effectively reduce the agglomeration of NaF particles and realize good fluidization.
The temperature is controlled below 15 ℃ in the reaction process. Extracting the product with ethylene glycol dimethyl ether (DME), standing, and filtering to obtain liquid NaPF 6 Concentrating and crystallizing to obtain solid NaPF 6 The product, insoluble NaF, is returned to the fluidized bed reactor.
The solid NaPF 6 The purity of the product was 99.99%, the moisture content was less than 2ppm, and the free acid (as HF) content was less than 6ppm.
Example 3
As shown in fig. 2, the following method is adopted to co-produce lithium hexafluorophosphate and byproduct light calcium carbonate by using fluorite as raw materials:
(1) Fluorite and oleum or SO 3 Heating the reaction product in a rotary furnaceForming crude hydrogen fluoride gas.
(2) The crude hydrogen fluoride gas is then mixed with polyphosphoric acid or P 2 O 5 The reaction produces crude hexafluorophosphoric acid or hexafluorophosphate.
(3) Decomposing crude hexafluorophosphoric acid or hexafluorophosphate to obtain crude PF 5 And (3) gas.
CaSO, a by-product formed after the reaction 4 By adding reducing agent (sulfur or carbon or sulfur concentrate or biomass charcoal) to decompose into SO 2 Gas, and SO generated by catalytic oxidation 3 The gas is returned to the rotary kiln in the step (1).
At the same time CaSO 4 Reducing and decomposing into CaO, emulsifying, filtering, drying unreacted fluorite in filter residues, returning to the rotary furnace in the step (1), and mixing the filtrate with CO 2 Carbonizing, filtering and drying to finally obtain a light calcium carbonate product, wherein the whiteness of the light calcium carbonate product is more than or equal to 97%, the content of the light calcium carbonate product is more than or equal to 98.5%, and the sediment is 2.8-3.2).
(4) Coarse PF generated by rotary kiln 5 Introducing gas into a freezing bubble tower, wherein the operating temperature is-40-15 ℃, the operating pressure of the freezing bubble tower is 0.0-0.5 MPa, and separating H by freezing 2 O, obtain PF 5 And (3) gas.
(5)PF 5 The gas reacts with the LiF in the fluidized bed reactor.
To the fluidized bed, 30wt% of coarse LiF particles of 250-380 μm and the balance of fine LiF particles of 100-200 μm were added. The coarse particles can break up the fine particles, and reduce the acting force among the fine particles. The addition of coarse particles can effectively reduce the agglomeration of LiF particles and realize good fluidization.
The temperature is controlled below 15 ℃ in the reaction process. Extracting the product with ethylene glycol dimethyl ether (DME), standing, and filtering to obtain liquid LiPF 6 Concentrating and crystallizing to obtain solid LiPF 6 The product, insoluble LiF, is returned to the fluidized bed reactor.
The solid LiPF 6 The product purity was 99.99%, the moisture content was less than 2ppm, and the free acid (as HF) content was less than 6ppm.
Example 4
As shown in fig. 2, the following method is adopted to co-produce sodium hexafluorophosphate and byproduct light calcium carbonate by using fluorite as raw materials:
(1) Fluorite and oleum or SO 3 Heating and reacting in a rotary furnace to generate crude hydrogen fluoride gas.
(2) The crude hydrogen fluoride gas is then mixed with polyphosphoric acid or P 2 O 5 The reaction produces crude hexafluorophosphoric acid or hexafluorophosphate.
(3) Decomposing crude hexafluorophosphoric acid or hexafluorophosphate to obtain crude PF 5 And (3) gas.
CaSO, a by-product formed after the reaction 4 By adding reducing agent (sulfur or carbon or sulfur concentrate or biomass charcoal) to decompose into SO 2 Gas, and SO generated by catalytic oxidation 3 The gas is returned to the rotary kiln in the step (1).
At the same time CaSO 4 Reducing and decomposing into CaO, emulsifying, filtering, drying unreacted fluorite in filter residues, returning to the rotary furnace in the step (1), and mixing the filtrate with CO 2 Carbonizing, filtering and drying to finally obtain a light calcium carbonate product, wherein the whiteness of the light calcium carbonate product is more than or equal to 97%, the content of the light calcium carbonate product is more than or equal to 98.5%, and the sediment is 2.8-3.2).
(4) Coarse PF generated by rotary kiln 5 Introducing gas into a freezing bubble tower, wherein the operating temperature is-40-15 ℃, the operating pressure of the freezing bubble tower is 0.0-0.5 MPa, and separating H by freezing 2 O, obtain PF 5 And (3) gas.
(5)PF 5 The gas reacts with the NaF in the fluidized bed reactor.
30wt% of NaF coarse particles with the diameter of 250-380 mu m and the balance of fine particles with the diameter of 100-200 mu m are added into the fluidized bed. The coarse particles can break up the fine particles, and reduce the acting force among the fine particles. The addition of coarse particles can effectively reduce the agglomeration of NaF particles and realize good fluidization.
The temperature is controlled below 15 ℃ in the reaction process. Extracting the product with ethylene glycol dimethyl ether (DME), standing, and filtering to obtain liquid NaPF 6 Concentrating and crystallizing to obtain solid NaPF 6 The product, insoluble NaF, is returned to the fluidized bed reactor.
The solid NaPF 6 The purity of the product was 99.99%, the moisture content was less than 2ppm, and the free acid (as HF) content was less than 6ppm.
Claims (9)
1. The process for co-producing hexafluorophosphate and byproduct light calcium carbonate by taking fluorite as raw material is characterized by comprising the following steps:
a. fluorite reacts with fuming sulfuric acid to generate crude hydrogen fluoride gas;
b. conversion of crude hydrogen fluoride gas to PF using Process 1 or Process 2 5 A gas;
c、PF 5 the gas reacts with fluoride salt, the temperature is controlled below 15 ℃ in the reaction process, the product is extracted by adding a solvent of lithium battery electrolyte, and liquid hexafluorophosphate is obtained through static layering and filtering, wherein the fluoride salt is LiF or NaF;
wherein the method 1 comprises the following steps:
1.1, purifying crude hydrogen fluoride gas to obtain anhydrous hydrogen fluoride gas; the by-product fluorine-containing gypsum in the purification process is decomposed into CaO and SO by heating 2 Emulsifying CaO, filtering to obtain saturated lime water, and mixing with CO 2 Carbonizing, filtering and drying to obtain light calcium carbonate;
1.2, reacting anhydrous hydrogen fluoride with a phosphorus-containing substance to generate hexafluorophosphoric acid or hexafluorophosphate; the phosphorus-containing material is polyphosphoric acid or P 2 O 5 ；
1.3 decomposition of hexafluorophosphoric acid or hexafluorophosphate to give PF 5 A gas;
the method 2 comprises the following steps:
2.1, reacting the crude hydrogen fluoride gas with a phosphorus-containing substance to generate crude hexafluorophosphoric acid or hexafluorophosphate;
2.2 decomposition of crude hexafluorophosphoric acid or hexafluorophosphate to give crude PF 5 A gas; byproduct CaSO of the reaction 4 Reduction to SO by addition of a reducing agent 2 Gas and CaO, SO 2 SO formed by catalytic oxidation of gas 3 C, returning the gas to the step a; emulsifying CaO, filtering, drying filter residue, and returning to step a, wherein the filtrate and CO 2 Carbonizing, filtering and drying to obtain light calcium carbonate;
2.3 coarse PF 5 Purifying the gas to obtain PF 5 And (3) gas.
2. The process for co-producing hexafluorophosphate and byproduct light calcium carbonate by using fluorite as raw material according to claim 1, which is characterized in that: in the step c, the liquid hexafluorophosphate is concentrated and crystallized and filtered to obtain solid hexafluorophosphate.
3. The process for co-producing hexafluorophosphate and byproduct light calcium carbonate by using fluorite as raw material according to claim 1, which is characterized in that: in step 1.1, the crude hydrogen fluoride gas is purified to be washed, cooled, condensed, rectified and degassed sequentially.
4. The process for co-producing hexafluorophosphate and byproduct light calcium carbonate by using fluorite as raw material according to claim 1, which is characterized in that: in the step 1.3 and the step 2.2, the decomposition temperature is controlled to be-20-30 ℃.
5. The process for co-producing hexafluorophosphate and byproduct light calcium carbonate by using fluorite as raw material according to claim 1, which is characterized in that: step 1.3 is carried out in a reaction kettle, and anhydrous hydrogen fluoride with hexafluorophosphate entering the reaction kettle is thermally decomposed with SO generated by the fluorine-containing gypsum of step 1.1 2 Reacting at 25-35 ℃ to generate fluorine-containing phosphoric acid, and returning the fluorine-containing phosphoric acid to the step a.
6. The process for co-producing hexafluorophosphate and byproduct light calcium carbonate by using fluorite as raw material according to claim 1, which is characterized in that: in the step 2.2, the reducing agent is sulfur, carbon, sulfur concentrate or biomass charcoal.
7. The process for co-producing hexafluorophosphate and byproduct light calcium carbonate by using fluorite as raw material according to claim 1, which is characterized in that: in step 2.3, crude PF 5 The PF is obtained by the gas through the freeze purification 5 Gas, freezing temperature is-40-15 deg.C, pressingThe force is 0.0-0.5 MPa.
8. The process for co-producing hexafluorophosphate and byproduct light calcium carbonate by using fluorite as raw material according to claim 1, which is characterized in that: in the step c, the fluoride salt is granular, the proportion of the granules with the grain diameter of 250-380 mu m is 25-35 wt%, and the rest is the granules with the grain diameter of 100-200 mu m; preferably, the particles having a particle size of 250 to 380 μm account for 30wt%.
9. The process for co-producing hexafluorophosphate and byproduct light calcium carbonate by using fluorite as raw material according to claim 1, which is characterized in that: in the step c, the solvent of the lithium battery electrolyte is at least one of ethylene glycol dimethyl ether, isopropyl ether, anisole, propylene carbonate, methyl ethyl carbonate, ethylene carbonate, vinylene carbonate and methyl propionate.
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