CN113912075A - Preparation method of lithium tetrafluoroborate - Google Patents
Preparation method of lithium tetrafluoroborate Download PDFInfo
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- CN113912075A CN113912075A CN202111408170.XA CN202111408170A CN113912075A CN 113912075 A CN113912075 A CN 113912075A CN 202111408170 A CN202111408170 A CN 202111408170A CN 113912075 A CN113912075 A CN 113912075A
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- -1 lithium tetrafluoroborate Chemical compound 0.000 title claims abstract description 112
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 94
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000002156 mixing Methods 0.000 claims abstract description 44
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 38
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 43
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 43
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 16
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 12
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- URXNVXOMQQCBHS-UHFFFAOYSA-N naphthalene;sodium Chemical compound [Na].C1=CC=CC2=CC=CC=C21 URXNVXOMQQCBHS-UHFFFAOYSA-N 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 239000004342 Benzoyl peroxide Substances 0.000 claims description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 claims description 6
- 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 claims description 6
- BHELZAPQIKSEDF-UHFFFAOYSA-N allyl bromide Chemical compound BrCC=C BHELZAPQIKSEDF-UHFFFAOYSA-N 0.000 claims description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000009776 industrial production Methods 0.000 abstract description 4
- 238000007599 discharging Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 24
- 239000007789 gas Substances 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 231100000086 high toxicity Toxicity 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- KZMAWJRXKGLWGS-UHFFFAOYSA-N 2-chloro-n-[4-(4-methoxyphenyl)-1,3-thiazol-2-yl]-n-(3-methoxypropyl)acetamide Chemical compound S1C(N(C(=O)CCl)CCCOC)=NC(C=2C=CC(OC)=CC=2)=C1 KZMAWJRXKGLWGS-UHFFFAOYSA-N 0.000 description 1
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B35/00—Boron; Compounds thereof
- C01B35/06—Boron halogen compounds
- C01B35/063—Tetrafluoboric acid; Salts thereof
- C01B35/066—Alkali metal tetrafluoborates
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention provides a preparation method of lithium tetrafluoroborate, which comprises the following steps: 1) dissolving lithium fluoride in anhydrous hydrofluoric acid to obtain a lithium fluoride solution, and adjusting the temperature of the solution to 5-10 ℃; 2) and (2) at normal temperature, mixing the lithium fluoride solution and the boron trifluoride diethyl etherate solution according to the molar ratio of lithium fluoride to boron trifluoride of 1: 1 introducing the solution into a micro-reactor micro-channel for reaction to obtain a hydrogen fluoride solution of lithium tetrafluoroborate; 3) and separating the ether solution and the lithium tetrafluoroborate hydrogen fluoride solution, filtering the lithium tetrafluoroborate hydrogen fluoride through micropores, concentrating and crystallizing to obtain lithium tetrafluoroborate crystals, and drying to obtain the finished product. The preparation method can realize the continuous feeding and discharging of the reaction, and the raw materials can realize the molecular 1: 1, the contact reaction has high conversion rate, stable reaction and easy control, and can realize industrial production.
Description
Technical Field
The invention belongs to the technical field of chemical product preparation, and particularly relates to a preparation method of lithium tetrafluoroborate.
Background
Lithium tetrafluoroborate, LiBF4CAS: 14283-07-9, which is mainly used as an electrolyte additive of a lithium ion battery, and the lithium tetrafluoroborate has better chemical stability and thermal stability, is not sensitive to moisture, improves the cycle life and improves the performance of the lithium ion battery. Further, LiBF4The passivation capability to aluminum foil is quite excellent, so that the aluminum foil is widely applied to electrolyte as a film forming additive. And the lithium ion electrolyte is added with LiBF4And the working temperature range of the lithium ion battery can be widened, the high and low temperature discharge performance of the battery is improved, and the lithium ion battery is more suitable for being used in extreme environments (high temperature or low temperature). The excellent performance of the product is widely accepted by the industry, but the manufacturers for producing the product in quantity in the market are few, and a plurality of enterprises are prepared in the organic solvent in the production process,in the batch reaction, a large amount of repeated labor is required for workers, lithium fluoride is generally not compatible with organic solvents, and the used boron trifluoride raw materials are all gases, so that the reaction effect is poor, the yield is low, the product carbonate insoluble substance is very high, the quality cannot meet the battery grade requirement, and the boron trifluoride gas is stored by using a steel cylinder, so that the problems of high pressure, high toxicity, operation danger and the like are caused.
At present, for the preparation of lithium tetrafluoroborate, the common method is that lithium fluoride is suspended in an organic solvent, boron trifluoride gas is introduced, recrystallization and drying are carried out after the reaction is finished, the extraction process is troublesome, the lithium fluoride is generally not compatible with the organic solvent, the lithium fluoride is excessive in the reaction, so that the raw material waste is caused, the carbonate insoluble substance is very high, the quality cannot meet the requirement of a battery grade, the extraction yield of the crystal is low, the organic solvent often remains in the product more or less, the performance of the electrolyte fluctuates slightly, the storage pressure of the raw material boron trifluoride is 10Mpa at normal temperature, the transportation and the storage are difficult, the reaction process is influenced by the ventilation pressure fluctuation along with the normal pressure solution, and the like.
The lithium tetrafluoroborate can be obtained by a process method of directly introducing boron trifluoride gas, but the reaction control difficulty is very high, the boron trifluoride gas is easy to escape from a solvent to cause raw material waste, and the generation of three wastes is increased. And the material adopted for filtration is polytetrafluoroethylene, and after long-term use, the anhydrous hydrogen fluoride has reduced strength and is easy to deform to cause blockage, thereby affecting the product quality.
Disclosure of Invention
The invention mainly aims to provide a preparation method of lithium tetrafluoroborate, which has the advantages of simple raw materials, high conversion rate of the raw materials in a micro reaction channel, less byproducts, capability of realizing continuous feeding and discharging, stable and easily controlled reaction and capability of realizing industrial continuous production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of lithium tetrafluoroborate comprises the following steps:
s1, dissolving lithium fluoride in anhydrous hydrogen fluoride to obtain a lithium fluoride solution, and adjusting the temperature of the solution to be 5-10 ℃;
s2, at normal temperature, mixing a lithium fluoride solution and a boron trifluoride diethyl etherate solution according to the molar ratio of lithium fluoride to boron trifluoride of 1: 1-1.5 introducing the solution into a microchannel reactor for reaction to obtain a hydrogen fluoride solution of lithium tetrafluoroborate;
s3, standing and layering the reacted lithium tetrafluoroborate solution, and removing the ether solution;
s4, filtering the lithium tetrafluoroborate solution, cooling and crystallizing to obtain lithium tetrafluoroborate crystals, and separating and drying to obtain finished products;
s5, the filtered anhydrous hydrogen fluoride solution can be used as a solvent for the next reaction to be recycled.
As a further preference, in step 1), the solvent is an anhydrous hydrogen fluoride solution.
Further preferably, in the step 1), the concentration of the lithium fluoride in the solution is 20-25% (Wt%).
Further preferably, in the step 1), the concentration of the boron trifluoride diethyl etherate solution is 35 to 47% (Wt%).
Preferably, in the step 2), the feeding speed of the lithium fluoride solution is 10 to 20 Kg/min.
Preferably, in the step 2), the feeding speed of the boron trifluoride diethyl etherate solution is 12-22 Kg/min.
In step 4), a precision filter made of PP, PTFE or SUS316L is preferably used for the filtration, and the pore diameter of the precision filter is 0.1-1 um.
More preferably, in the step 4), a precision filter made of modified polytetrafluoroethylene is adopted for filtering,
the invention also provides a preparation method of the modified polytetrafluoroethylene, which comprises the following steps:
s1: adding polytetrafluoroethylene into a sodium-naphthalene treatment solution according to the mass ratio of 1: 1.2-1: 2 mixing, stirring at 50-70 ℃ for 5-10min, performing suction filtration, washing, and vacuum drying to obtain pre-modified polytetrafluoroethylene,
s2: mixing 10-20 parts of ferrocene methanol, 20-40 parts of allyl bromide and 2-5 parts of tetrabutylammonium bromide according to the mass parts, and reacting at 80-90 ℃ for 0.5-2 h; obtaining the allyl ether ferrocene.
S3: according to the mass portion, heating 150 portions of pre-modified polytetrafluoroethylene with 100 portions of organic silicon and 0.5-2 portions of allyl ether ferrocene to 50-75 ℃ in a high-speed mixer, mixing for 10-30min, adding 10-20 portions of graphite powder and 2-5 portions of benzoyl peroxide, heating to 90-105 ℃ and mixing for 10-30min, then adding into an internal mixer, controlling the temperature to be 110-120 ℃ and mixing for 5-15min, standing for 30-50min, and then continuing mixing for 5-15min at 70-90 ℃ to obtain the modified polytetrafluoroethylene.
The sodium-naphthalene treatment solution is prepared by mixing sodium, naphthalene and tetrahydrofuran in a mass ratio of 1: 1: 20-1: 1: 40 and mixing uniformly.
Further preferably, in step 4), the solid-liquid separation is centrifugal separation.
The reaction mechanism is as follows:
the invention uses anhydrous hydrogen fluoride as solvent, lithium fluoride has larger solubility in the solvent, boron trifluoride diethyl etherate solution replaces boron trifluoride gas, a micro reaction channel is used for continuous feeding reaction,
the invention has the beneficial effects that:
1. compared with the method of directly using boron trifluoride gas (normal storage pressure is 10MPa), the method has the advantages that boron trifluoride ether solution is used, the method is safe and easy to operate, and the safety of operators is greatly improved;
1. the reaction is carried out by using a microreactor, and the reaction conditions that the molecule 1: 1, continuous reaction can be realized by mixing, and the reaction effect is excellent;
3. the device is a silicon carbide micro-reaction device, and the flow of the two solutions is controlled according to the molar ratio of the reaction raw materials, so that continuous feeding and continuous reaction are realized.
4. Lithium fluoride has high solubility in anhydrous hydrogen fluoride, boron trifluoride ether replaces high-pressure and high-toxicity gas boron trifluoride, the full-contact conversion rate of micro-reaction channel molecules reaches over 99.0 percent, the reaction is stable and easy to control, and the anhydrous hydrogen fluoride solution after crystallization separation can be recycled.
5. The two solutions are fully mixed, reacted and contacted, and meanwhile, a micro reaction channel can be conveniently used on the basis of the two solutions, so that the aim of full and continuous reaction is achieved, and industrial production can be realized.
6. The boron trifluoride diethyl etherate solution is convenient to transport, and the transport cost and the storage risk are greatly reduced. The solvent can be recycled after the solution is separated, thereby avoiding the generation of waste liquid in the working section and ensuring that the industrial production process is more environment-friendly.
6. The ferrocene structure is introduced into the modified polytetrafluoroethylene, so that the bonding strength of graphite powder and the polytetrafluoroethylene can be enhanced, the graphite powder is not easy to peel off, the strength of the anhydrous hydrogen fluoride cannot be reduced after long-term use, and the corrosive resistance of hydrofluoric acid is improved under the combined action.
Drawings
Fig. 1 is a process flow chart of a method for preparing lithium tetrafluoroborate according to an embodiment of the present invention.
FIG. 2 is a chromatogram of the method for preparing lithium tetrafluoroborate according to the embodiment of the present invention.
Detailed Description
The embodiment of the invention provides a preparation method of lithium tetrafluoroborate, and solves several defects of the existing preparation method of lithium tetrafluoroborate.
In order to better understand the technical solutions, the technical solutions of the present application are described in detail with specific embodiments below, and it should be understood that the specific features in the embodiments and examples of the present application are detailed descriptions of the technical solutions of the present application, but not limitations of the technical solutions of the present application, and the technical features in the embodiments and examples of the present application may be combined with each other without conflict. It should be understood that the term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The present application is described in more detail by way of examples below. These examples are merely illustrative of the best mode of carrying out the present application and do not limit the scope of the present application in any way.
The detection method comprises the following steps:
example 1
The preparation method of lithium tetrafluoroborate of the embodiment comprises the following steps:
a preparation method of lithium tetrafluoroborate comprises the following steps:
1) dissolving lithium fluoride in anhydrous hydrogen fluoride to obtain a lithium fluoride solution, and adjusting the temperature of the solution to 5 ℃;
2) and (2) at normal temperature, mixing the lithium fluoride solution and the boron trifluoride diethyl etherate solution according to the molar ratio of lithium fluoride to boron trifluoride of 1: 1 introducing the solution into a microchannel reactor for reaction to obtain a hydrogen fluoride solution of lithium tetrafluoroborate;
3) standing and layering the reacted lithium tetrafluoroborate solution, and removing the ether solution;
4) filtering the lithium tetrafluoroborate solution, cooling and crystallizing to obtain lithium tetrafluoroborate crystals, separating and drying to obtain finished products;
5) the filtered anhydrous hydrogen fluoride solution can be used as the solvent for the next reaction for continuous recycling.
In the step 1), the solvent is an anhydrous hydrogen fluoride solution.
In step 1), the concentration of lithium fluoride in the solution is 20% (Wt%).
In step 1), the concentration of boron trifluoride etherate solution was 35% (Wt%).
In the step 2), the feeding speed of the lithium fluoride solution is 10 Kg/min.
In the step 2), the feeding speed of the boron trifluoride diethyl etherate solution is 12 Kg/min.
In the step 4), the aperture of the precision filter is 0.1 um.
In the step 4), the filtration adopts a precision filter made of modified polytetrafluoroethylene,
the invention also provides a preparation method of the modified polytetrafluoroethylene, which comprises the following steps:
s1: adding polytetrafluoroethylene into a sodium-naphthalene treatment solution according to the mass ratio of 1: 1.2 mixing, stirring at 50 ℃ for 5min, performing suction filtration, washing and vacuum drying to obtain pre-modified polytetrafluoroethylene,
s2: mixing 10kg of ferrocene methanol, 20kg of allyl bromide and 2kg of tetrabutylammonium bromide, and reacting for 0.5h at 80 ℃; obtaining the allyl ether ferrocene.
S3: heating 100kg of pre-modified polytetrafluoroethylene and 0.5kg of allyl ether ferrocene to 50 ℃ in a high-speed mixer, mixing for 10min, adding 10kg of graphite powder and 2kg of benzoyl peroxide, heating to 90 ℃, mixing for 10min, adding into an internal mixer, mixing for 5min at the temperature of 110 ℃, standing for 30min, and continuing mixing for 5min at 70 ℃ to obtain the modified polytetrafluoroethylene.
The sodium-naphthalene treatment solution is prepared by mixing sodium, naphthalene and tetrahydrofuran in a mass ratio of 1: 1: 20 and mixing uniformly.
In the step 4), the solid-liquid separation is centrifugal separation.
TABLE 1 detection data for lithium tetrafluoroborate finished products
Example 2
A preparation method of lithium tetrafluoroborate comprises the following steps:
1) dissolving lithium fluoride in anhydrous hydrogen fluoride to obtain a lithium fluoride solution, and adjusting the temperature of the solution to 7 ℃;
2) and (2) at normal temperature, mixing the lithium fluoride solution and the boron trifluoride diethyl etherate solution according to the molar ratio of lithium fluoride to boron trifluoride of 1: 1.2 introducing the solution into a microchannel reactor for reaction to obtain a hydrogen fluoride solution of lithium tetrafluoroborate;
3) standing and layering the reacted lithium tetrafluoroborate solution, and removing the ether solution;
4) filtering the lithium tetrafluoroborate solution, cooling and crystallizing to obtain lithium tetrafluoroborate crystals, separating and drying to obtain finished products;
5) the filtered anhydrous hydrogen fluoride solution can be used as the solvent for the next reaction for continuous recycling.
In the step 1), the solvent is an anhydrous hydrogen fluoride solution.
In step 1), the concentration of lithium fluoride in the solution is 22% (Wt%).
In step 1), the concentration of boron trifluoride etherate solution was 40% (Wt%).
In the step 2), the feeding speed of the lithium fluoride solution is 15 Kg/min.
In the step 2), the feeding speed of the boron trifluoride diethyl etherate solution is 17 Kg/min.
In the step 4), the aperture of the precision filter is 0.5 um.
In the step 4), the filtration adopts a precision filter made of modified polytetrafluoroethylene,
the invention also provides a preparation method of the modified polytetrafluoroethylene, which comprises the following steps:
s1: adding polytetrafluoroethylene into a sodium-naphthalene treatment solution according to the mass ratio of 1: 1.6, stirring for 7min at 60 ℃, then carrying out suction filtration, washing and vacuum drying to prepare pre-modified polytetrafluoroethylene,
s2: mixing 15kg of ferrocene methanol, 30kg of allyl bromide and 3kg of tetrabutylammonium bromide, and reacting for 1.2h at 85 ℃; obtaining the allyl ether ferrocene.
S3: 125kg of pre-modified polytetrafluoroethylene and 1.2kg of allyl ether ferrocene are heated to 62 ℃ in a high-speed mixer and mixed for 20min, 15kg of graphite powder and 3kg of benzoyl peroxide are added, the mixture is heated to 98 ℃ and mixed for 20min, then the mixture is added into an internal mixer and mixed for 10min under the temperature of 115 ℃, and after standing for 40min, the mixture is continuously mixed for 10min at 80 ℃ to obtain the modified polytetrafluoroethylene.
The sodium-naphthalene treatment solution is prepared by mixing sodium, naphthalene and tetrahydrofuran in a mass ratio of 1: 1: 30 are evenly mixed to obtain the product.
In the step 4), the solid-liquid separation is centrifugal separation.
The purity analysis results of the lithium tetrafluoroborate product are shown in table 2 below:
table 2 lithium tetrafluoroborate product detection data
Example 3
A preparation method of lithium tetrafluoroborate comprises the following steps:
1) dissolving lithium fluoride in anhydrous hydrogen fluoride to obtain a lithium fluoride solution, and adjusting the temperature of the solution to 7 ℃;
2) and (2) at normal temperature, mixing the lithium fluoride solution and the boron trifluoride diethyl etherate solution according to the molar ratio of lithium fluoride to boron trifluoride of 1: 1.2 introducing the solution into a microchannel reactor for reaction to obtain a hydrogen fluoride solution of lithium tetrafluoroborate;
3) standing and layering the reacted lithium tetrafluoroborate solution, and removing the ether solution;
4) filtering the lithium tetrafluoroborate solution, cooling and crystallizing to obtain lithium tetrafluoroborate crystals, separating and drying to obtain finished products;
5) the filtered anhydrous hydrogen fluoride solution can be used as the solvent for the next reaction for continuous recycling.
In the step 1), the solvent is an anhydrous hydrogen fluoride solution.
In step 1), the concentration of lithium fluoride in the solution is 22% (Wt%).
In step 1), the concentration of boron trifluoride etherate solution was 40% (Wt%).
In the step 2), the feeding speed of the lithium fluoride solution is 15 Kg/min.
In the step 2), the feeding speed of the boron trifluoride diethyl etherate solution is 17 Kg/min.
In the step 4), the aperture of the precision filter is 0.5 um.
In the step 4), the filtration adopts a precision filter made of modified polytetrafluoroethylene,
the invention also provides a preparation method of the modified polytetrafluoroethylene, which comprises the following steps:
s1: adding polytetrafluoroethylene into a sodium-naphthalene treatment solution according to the mass ratio of 1: 1.6, stirring for 7min at 60 ℃, then carrying out suction filtration, washing and vacuum drying to prepare pre-modified polytetrafluoroethylene,
s2: mixing 15kg of ferrocene methanol, 30kg of allyl bromide and 3kg of tetrabutylammonium bromide, and reacting for 1.2h at 85 ℃; obtaining the allyl ether ferrocene.
S3: 125kg of pre-modified polytetrafluoroethylene and 1.2kg of allyl ether ferrocene are heated to 62 ℃ in a high-speed mixer and mixed for 20min, 15kg of graphite powder and 3kg of benzoyl peroxide are added, the mixture is heated to 98 ℃ and mixed for 20min, then the mixture is added into an internal mixer and mixed for 10min under the temperature of 115 ℃, and after standing for 40min, the mixture is continuously mixed for 10min at 80 ℃ to obtain the modified polytetrafluoroethylene.
The sodium-naphthalene treatment solution is prepared by mixing sodium, naphthalene and tetrahydrofuran in a mass ratio of 1: 1: 30 are evenly mixed to obtain the product.
In the step 4), the solid-liquid separation is centrifugal separation.
The purity analysis results of the lithium tetrafluoroborate product are shown in table 3 below:
table 3 lithium tetrafluoroborate product detection data
Example 4
A preparation method of lithium tetrafluoroborate comprises the following steps:
1) dissolving lithium fluoride in anhydrous hydrogen fluoride to obtain a lithium fluoride solution, and adjusting the temperature of the solution to 10 ℃;
2) and (2) at normal temperature, mixing the lithium fluoride solution and the boron trifluoride diethyl etherate solution according to the molar ratio of lithium fluoride to boron trifluoride of 1: 1.5 introducing the solution into a microchannel reactor for reaction to obtain a hydrogen fluoride solution of lithium tetrafluoroborate;
3) standing and layering the reacted lithium tetrafluoroborate solution, and removing the ether solution;
4) filtering the lithium tetrafluoroborate solution, cooling and crystallizing to obtain lithium tetrafluoroborate crystals, separating and drying to obtain finished products;
5) the filtered anhydrous hydrogen fluoride solution can be used as the solvent for the next reaction for continuous recycling.
In the step 1), the solvent is an anhydrous hydrogen fluoride solution.
In step 1), the concentration of lithium fluoride in the solution is 25% (Wt%).
In step 1), the concentration of boron trifluoride etherate solution was 47% (Wt%).
In the step 2), the feeding speed of the lithium fluoride solution is 20 Kg/min.
In the step 2), the feeding speed of the boron trifluoride diethyl etherate solution is 22 Kg/min.
In the step 4), the aperture of the precision filter is 1 um.
In the step 4), the filtration adopts a precision filter made of modified polytetrafluoroethylene,
the invention also provides a preparation method of the modified polytetrafluoroethylene, which comprises the following steps:
s1: adding polytetrafluoroethylene into a sodium-naphthalene treatment solution according to the mass ratio of 1: 2 mixing, stirring for 10min at 70 ℃, performing suction filtration, washing and vacuum drying to obtain pre-modified polytetrafluoroethylene,
s2: mixing 20kg of ferrocene methanol, 40kg of allyl bromide and 5kg of tetrabutylammonium bromide, and reacting for 2 hours at 90 ℃; obtaining the allyl ether ferrocene.
S3: heating 150kg of pre-modified polytetrafluoroethylene and 2kg of allyl ether ferrocene to 75 ℃ in a high-speed mixer, mixing for 30min, adding 20kg of graphite powder and 5kg of benzoyl peroxide, heating to 105 ℃ and mixing for 30min, then adding into an internal mixer, mixing for 15min at the temperature of 120 ℃, standing for 50min, and continuing mixing for 15min at the temperature of 90 ℃ to obtain the modified polytetrafluoroethylene.
The sodium-naphthalene treatment solution is prepared by mixing sodium, naphthalene and tetrahydrofuran in a mass ratio of 1: 1: 40 and mixing uniformly.
In the step 4), the solid-liquid separation is centrifugal separation.
The purity analysis results of the lithium tetrafluoroborate product are shown in table 4 below:
table 4 lithium tetrafluoroborate product detection data
Comparative example 1
The procedure of example 1 was repeated except that polytetrafluoroethylene was used instead of the modified polytetrafluoroethylene.
The purity analysis results of the lithium tetrafluoroborate product are shown in table 5 below:
TABLE 5 detection data for lithium tetrafluoroborate finished products
Comparative example 2
A tubular reactor having a diameter of 20mm and an L of 1m was used in place of the silicon carbide micro-reactor, and the procedure was otherwise the same as in example 1.
The purity analysis results of the lithium tetrafluoroborate product are shown in table 6 below:
TABLE 6 detection data for lithium tetrafluoroborate finished products
The technical scheme in the embodiment of the application at least has the following technical effects or advantages:
the invention uses the anhydrous hydrofluoric acid solution of lithium fluoride and boron trifluoride ether solution in proportion to be led into a micro-reactor micro-channel for reaction to obtain the lithium tetrafluoroborate solution, the solvent can be recycled after the solution is separated, and finally, a plurality of favorable results are produced, including: the boron trifluoride diethyl etherate solution is convenient to transport, so that the transport cost and the storage risk are greatly reduced; the continuous feeding and discharging can be realized, the molecular contact reaction of the raw materials can be realized in the micro-reaction channel, the conversion rate is high, the reaction is stable and easy to control, and the conversion rate is improved to more than 99.5 percent; the solvent can be recycled after the solution is separated, thereby avoiding the generation of waste liquid in the working section and ensuring that the industrial production process is more environment-friendly.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (13)
1. A preparation method of lithium tetrafluoroborate is characterized by comprising the following steps:
s1, dissolving lithium fluoride in anhydrous hydrogen fluoride to obtain a lithium fluoride solution, and adjusting the temperature of the solution to be 5-10 ℃;
s2, at normal temperature, mixing a lithium fluoride solution and a boron trifluoride diethyl etherate solution according to the molar ratio of lithium fluoride to boron trifluoride of 1: 1-1.5 introducing the solution into a microchannel reactor for reaction to obtain a hydrogen fluoride solution of lithium tetrafluoroborate;
s3, standing and layering the reacted lithium tetrafluoroborate solution, and removing the ether solution;
and S4, filtering the lithium tetrafluoroborate solution, cooling and crystallizing to obtain lithium tetrafluoroborate crystals, and separating and drying to obtain the finished product.
2. The method for producing lithium tetrafluoroborate according to claim 1, wherein the concentration of lithium fluoride in said solution is 20-25% (Wt%).
3. The method for producing lithium tetrafluoroborate according to claim 1, wherein the concentration of boron trifluoride etherate solution is 35 to 47% (Wt%).
4. The method for preparing lithium tetrafluoroborate according to claim 1, wherein the feeding speed of the lithium fluoride solution is 10 to 20 Kg/min.
5. The method for preparing lithium tetrafluoroborate according to claim 1, wherein the feeding speed of the boron trifluoride diethyl etherate solution is 12 to 22 Kg/min.
6. The method for preparing lithium tetrafluoroborate according to claim 1, wherein the filtration is performed by using a precision filter made of PP, PTFE or SUS316L, and the pore size of the precision filter is 0.1-1 um.
7. The method for preparing lithium tetrafluoroborate according to claim 6, wherein the filtering is performed by using a precision filter made of modified polytetrafluoroethylene.
8. The method for producing lithium tetrafluoroborate according to claim 1, wherein said separation is a centrifugal separation.
9. The method for producing lithium tetrafluoroborate according to claim 8, wherein,
the centrifugal separation is realized, the air is isolated by the centrifugal machine, the rotating speed is more than 1000rpm, and the maximum separation factor is more than 700.
10. The method for producing lithium tetrafluoroborate according to claim 1, wherein,
in the step (4), the anhydrous hydrogen fluoride solution after centrifugal separation is directly used as the solvent for the next reaction and is continuously recycled.
11. A preparation method of modified polytetrafluoroethylene comprises the following steps: it is characterized in that the preparation method is characterized in that,
s1: adding polytetrafluoroethylene into a sodium-naphthalene treatment solution according to the mass ratio of 1: 1.2-1: 2, mixing, stirring at 50-70 ℃ for 5-10min, and then performing suction filtration, washing and vacuum drying to obtain pre-modified polytetrafluoroethylene;
s2: mixing 10-20 parts of ferrocene methanol, 20-40 parts of allyl bromide and 2-5 parts of tetrabutylammonium bromide according to the mass parts, and reacting at 80-90 ℃ for 0.5-2 h; obtaining allyl ether ferrocene;
s3: according to the mass portion, heating 150 portions of pre-modified polytetrafluoroethylene with 100 portions of organic silicon and 0.5-2 portions of allyl ether ferrocene to 50-75 ℃ in a high-speed mixer, mixing for 10-30min, adding 10-20 portions of graphite powder and 2-5 portions of benzoyl peroxide, heating to 90-105 ℃ and mixing for 10-30min, then adding into an internal mixer, controlling the temperature to be 110-120 ℃ and mixing for 5-15min, standing for 30-50min, and then continuing mixing for 5-15min at 70-90 ℃ to obtain the modified polytetrafluoroethylene.
12. The method for producing lithium tetrafluoroborate according to claim 11, wherein,
the sodium-naphthalene treatment solution is prepared by mixing sodium, naphthalene and tetrahydrofuran in a mass ratio of 1: 1: 20-1: 1: 40 and mixing uniformly.
13. The method for preparing lithium tetrafluoroborate according to claim 1, wherein the material of the inner wall of the microchannel reactor is silicon carbide.
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