CN110817913A - Preparation method of high-purity sodium tetrachloroaluminate for sodium salt battery - Google Patents
Preparation method of high-purity sodium tetrachloroaluminate for sodium salt battery Download PDFInfo
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- -1 sodium tetrachloroaluminate Chemical compound 0.000 title claims abstract description 47
- 229910001538 sodium tetrachloroaluminate Inorganic materials 0.000 title claims abstract description 47
- 159000000000 sodium salts Chemical class 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 108
- 238000006243 chemical reaction Methods 0.000 claims abstract description 101
- 239000011780 sodium chloride Substances 0.000 claims abstract description 54
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 51
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 50
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 37
- 238000003860 storage Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000000047 product Substances 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 22
- 239000002184 metal Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 239000011261 inert gas Substances 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 10
- 239000006228 supernatant Substances 0.000 claims abstract description 10
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 239000003792 electrolyte Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 238000007789 sealing Methods 0.000 claims abstract description 4
- 238000005303 weighing Methods 0.000 claims description 11
- 238000004321 preservation Methods 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 3
- 239000012450 pharmaceutical intermediate Substances 0.000 claims 1
- 238000005580 one pot reaction Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000873 Beta-alumina solid electrolyte Inorganic materials 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000005501 phase interface Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
- H01M10/39—Accumulators not provided for in groups H01M10/05-H01M10/34 working at high temperature
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/78—Compounds containing aluminium, with or without oxygen or hydrogen, and containing two or more other elements
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a preparation method of high-purity sodium tetrachloroaluminate of a second electrolyte of a sodium salt battery, which comprises the following steps of uniformly mixing anhydrous aluminum trichloride, anhydrous sodium chloride and metal aluminum; adding the uniformly mixed anhydrous aluminum trichloride, anhydrous sodium chloride and metallic aluminum into a reaction kettle, and adding high-purity nitrogen for heating; after all the materials are liquefied, opening the top cover of the reaction kettle, continuously stirring, covering the top cover of the reaction kettle, and continuously preserving heat; after the reaction is finished, transferring the supernatant in the reaction kettle into a storage tank heated to 170-250 ℃ in advance; putting the material storage tank with the temperature of 170-250 ℃ into a vacuum purification device, and purifying the product for 0.5-2 h; and cooling the storage tank, and introducing inert gas for sealing and storing to obtain the final high-purity sodium tetrachloroaluminate crystal product. The purity of the sodium tetrachloroaluminate prepared by the method can reach more than 99.5 percent, and the requirement of sodium salt batteries on the purity of the electrolyte can be met.
Description
Technical Field
The invention relates to the field of sodium salt batteries.
Background
Nowadays, lithium ion batteries are rapidly developed and expanded, and sodium salt batteries are more and more valued by enterprises and scientific research institutions due to the characteristics of high safety, long service life, environmental protection and the like.
The sodium salt battery is a high-temperature battery, the working temperature is 250-325 ℃, under the condition, a second electrolyte sodium tetrachloroaluminate exists in a liquid state, the sodium tetrachloroaluminate has the function of transporting sodium ions to a first electrolyte β -solid phase interface of an alumina ceramic tube in the charging process, the sodium ions exchange with original sodium ions in the ceramic tube, electrons obtained at a battery cathode are reduced, in the discharging process, the sodium simple substance loses electrons at the cathode and is oxidized, the sodium simple substance is conducted to an anode interface through a first electrolyte β -alumina ceramic tube, then the sodium tetrachloroaluminate transports the sodium ions to a nickel chloride interface, the chlorine ions are captured to produce sodium chloride solids, the nickel ions obtain electrons and are reduced to produce metallic nickel, and therefore, the function of the sodium tetrachloroaluminate as a sodium ion conduction medium in the sodium salt battery is important, the purity, the chemical structural integrity, the sodium ion conductivity and the like of the sodium tetrachloroaluminate directly influence the performance of the sodium salt battery.
At present, the price of the high-purity sodium tetrachloroaluminate reagent sold on the market is generally 5000-100000 yuan/kg, the price is high, and the price difference is very large. The reason for this is due to the preparation methods which are currently popular. At present, the common preparation method of high-purity sodium tetrachloroaluminate is that high-purity aluminum is melted at high temperature, then high-purity chlorine gas is introduced to generate high-purity aluminum trichloride steam, then the steam is introduced into a container of high-purity sodium chloride to be subjected to contact reaction, then the product is cooled and heated again to be melted, and redundant sodium chloride is filtered out, so that the high-purity sodium tetrachloroaluminate is obtained. It can be seen from the synthesis process that the generation process is very complex, the required equipment and environmental protection measures (chlorine + aluminum trichloride steam) are very harsh, and melting aluminum and melting sodium tetrachloroaluminate after cooling in the process are very energy consuming, so the method produces high-price sodium tetrachloroaluminate.
In order to promote the development of the sodium salt battery industry and reduce the production cost of the sodium salt battery, all people with sodium salt have urgent needs, and the production method of sodium tetrachloroaluminate is convenient, environment-friendly and low in cost.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of high-purity sodium tetrachloroaluminate as a second electrolyte of a sodium salt battery, which comprises the following steps,
(1) weighing anhydrous aluminum trichloride and anhydrous sodium chloride according to the molar ratio of the anhydrous aluminum trichloride to the anhydrous sodium chloride, and then weighing metal aluminum according to the mass ratio of the sum of the anhydrous aluminum trichloride and the anhydrous sodium chloride to the metal aluminum;
(2) uniformly mixing anhydrous aluminum trichloride, anhydrous sodium chloride and metal aluminum;
(3) adding the uniformly mixed anhydrous aluminum trichloride, anhydrous sodium chloride and metallic aluminum into a reaction kettle, and adding high-purity nitrogen for heating; after all the materials are liquefied, opening the top cover of the reaction kettle, continuously stirring, covering the top cover of the reaction kettle, and continuously preserving heat;
(4) after the reaction is finished, transferring the supernatant in the reaction kettle into a storage tank heated to 170-250 ℃ in advance;
(5) putting the material storage tank with the temperature of 170-250 ℃ into a vacuum purification device, and purifying the product for 0.5-2 h;
(6) and cooling the storage tank, and introducing inert gas for sealing and storing to obtain the final high-purity sodium tetrachloroaluminate crystal product.
Further, a gas inlet of the top cover of the reaction kettle is connected with high-purity nitrogen for purging, and a gas outlet of the top cover of the reaction kettle is connected into an alkali liquor pool tail gas absorption device; setting the heating temperature of the reaction kettle to be 170-250 ℃, starting a heating switch of the reaction kettle, and heating the reaction kettle to the set temperature within 0.5-2 h.
Further, opening a top cover of the reaction kettle, and continuously stirring for 1-5 min; and then covering a top cover of the reaction kettle, and continuing to perform heat preservation reaction for 24-72 hours.
Furthermore, the reaction temperature is 170-250 ℃, and the temperature rise speed is 0.5-2 h.
Further, anhydrous aluminum trichloride: the molar ratio of the anhydrous sodium chloride is 1: 0.950-1.500.
Furthermore, the purity of the anhydrous aluminum trichloride is 90-99.900%, the purity of the anhydrous sodium chloride is 95-99.900%, and the metal aluminum can be aluminum powder, aluminum scraps, aluminum foil or aluminum blocks.
Further, the high-purity sodium tetrachloroaluminate is applied to sodium salt batteries or medical intermediates in the medical industry.
The invention has the advantages that: the method takes anhydrous aluminum trichloride, anhydrous sodium chloride and metallic aluminum as raw materials, prepares the high-purity sodium tetrachloroaluminate by a simple one-step reaction method, omits the complex processes of firstly preparing gaseous aluminum trichloride, repeatedly melting metal and sodium tetrachloroaluminate products, filtering strong corrosive substances, treating chlorine and the like in the conventional preparation method of the sodium tetrachloroaluminate, and has the advantages of simple equipment, controllable process, environmental protection and low energy consumption in the whole preparation process. The method for preparing the sodium tetrachloroaluminate can reduce the cost of the sodium tetrachloroaluminate, and is beneficial to promoting the development of the sodium salt battery industry or the related industry requiring the sodium tetrachloroaluminate product.
Detailed Description
The following specific examples further describe the invention.
The preparation method of the sodium salt battery high-purity sodium tetrachloroaluminate comprises the following steps,
(1) weighing anhydrous aluminum trichloride (with the purity of 90-99.900%) and anhydrous sodium chloride (with the purity of 95-99.900%) according to the molar ratio of the anhydrous aluminum trichloride to the anhydrous sodium chloride of 1: 0.950-1.500, and then weighing metal aluminum according to the mass ratio of the total mass of the anhydrous aluminum trichloride and the anhydrous sodium chloride to the metal aluminum (aluminum scrap or aluminum powder or aluminum foil or aluminum block) of 1000: 1-10;
(2) uniformly mixing anhydrous aluminum trichloride, anhydrous sodium chloride and metal aluminum;
(3) adding the uniformly mixed anhydrous aluminum trichloride, anhydrous sodium chloride and metallic aluminum into a reaction kettle, and adding high-purity nitrogen for heating; after all the materials are liquefied, opening the top cover of the reaction kettle, continuously stirring, covering the top cover of the reaction kettle, and continuously preserving heat;
(4) after the reaction is finished, transferring the supernatant in the reaction kettle into a storage tank heated to 170-250 ℃ in advance;
(5) putting the material storage tank with the temperature of 170-250 ℃ into a vacuum purification device, and purifying the product for 0.5-2 h;
(6) and cooling the storage tank, and introducing inert gas for sealing and storing to obtain the final high-purity sodium tetrachloroaluminate crystal product.
Implementation mode one
Firstly, according to the weight ratio of anhydrous aluminum trichloride: anhydrous sodium chloride molar ratio 1:0.985 anhydrous aluminum trichloride (purity 98.500%) and anhydrous sodium chloride (purity 99.200%) are weighed, and then the mass sum of the anhydrous aluminum trichloride and the anhydrous sodium chloride is as follows: weighing metal aluminum according to the aluminum scrap mass ratio of 1000: 1.5;
then, uniformly mixing anhydrous aluminum trichloride, anhydrous sodium chloride and metal aluminum;
the one-step reaction method comprises the following steps: adding the uniformly mixed anhydrous aluminum trichloride, anhydrous sodium chloride and metallic aluminum into a reaction kettle; the air inlet of the top cover of the reaction kettle is connected with high-purity nitrogen for purging, and the air outlet of the top cover of the reaction kettle is connected into the tail gas absorption device of the alkali liquor pool; setting the heating temperature of the reaction kettle to 190 ℃, starting a heating switch of the reaction kettle, and heating the reaction kettle to the set temperature within 1 h; after all the materials are liquefied, opening the top cover of the reaction kettle, and continuously stirring for 2 min; then covering a top cover of the reaction kettle, and continuing to perform heat preservation reaction for 48 hours;
after the reaction is finished, transferring the supernatant in the reaction kettle into a material storage tank heated to 190 ℃ in advance through a special tool;
then, a material storage tank with the temperature of 190 ℃ is connected into a vacuum purification device, and the product is purified for 0.5 h;
finally, cooling the storage tank and introducing inert gas for sealed preservation to obtain the final high-purity sodium tetrachloroaluminate crystal product with the purity of 98.200 percent
Second embodiment
Firstly, according to the weight ratio of anhydrous aluminum trichloride: anhydrous sodium chloride (purity 98.500%) and anhydrous sodium chloride (purity 99.200%) are weighed according to the molar ratio of the anhydrous sodium chloride being 1:1, and then the mass sum of the anhydrous aluminum chloride and the anhydrous sodium chloride is as follows: weighing metal aluminum according to the aluminum scrap mass ratio of 1000: 2.2;
then, uniformly mixing anhydrous aluminum trichloride, anhydrous sodium chloride and metal aluminum;
the one-step reaction method comprises the following steps: adding the uniformly mixed anhydrous aluminum trichloride, anhydrous sodium chloride and metallic aluminum into a reaction kettle; the air inlet of the top cover of the reaction kettle is connected with high-purity nitrogen for purging, and the air outlet of the top cover of the reaction kettle is connected into the tail gas absorption device of the alkali liquor pool; setting the heating temperature of the reaction kettle to 210 ℃, starting a heating switch of the reaction kettle, and heating the reaction kettle to the set temperature within 1 h; after all the materials are liquefied, opening the top cover of the reaction kettle, and continuously stirring for 3 min; then covering a top cover of the reaction kettle, and continuing to perform heat preservation reaction for 60 hours;
after the reaction is finished, transferring the supernatant in the reaction kettle into a storage tank heated to 210 ℃ in advance through a special tool;
then, a material storage tank with the temperature of 210 ℃ kept is connected into a vacuum purification device, and a product is purified for 1 h;
and finally, cooling the storage tank and introducing inert gas for sealed storage to obtain the final high-purity sodium tetrachloroaluminate crystal product with the product purity of 99.500%.
Third embodiment
Firstly, according to the weight ratio of anhydrous aluminum trichloride: anhydrous sodium chloride (purity 98.500%) and anhydrous sodium chloride (purity 99.200%) are weighed according to the molar ratio of the anhydrous sodium chloride of 1:1.050, and then the mass sum of the anhydrous aluminum trichloride and the anhydrous sodium chloride is as follows: weighing metal aluminum according to the aluminum scrap mass ratio of 1000: 2.5;
then, uniformly mixing anhydrous aluminum trichloride, anhydrous sodium chloride and metal aluminum;
the one-step reaction method comprises the following steps: adding the uniformly mixed anhydrous aluminum trichloride, anhydrous sodium chloride and metallic aluminum into a reaction kettle; the air inlet of the top cover of the reaction kettle is connected with high-purity nitrogen for purging, and the air outlet of the top cover of the reaction kettle is connected into the tail gas absorption device of the alkali liquor pool; setting the heating temperature of the reaction kettle to 220 ℃, starting a heating switch of the reaction kettle, and heating the reaction kettle to the set temperature within 1 h; after all the materials are liquefied, opening the top cover of the reaction kettle, and continuously stirring for 3 min; then covering a top cover of the reaction kettle, and continuing to perform heat preservation reaction for 72 hours;
after the reaction is finished, transferring the supernatant in the reaction kettle into a storage tank heated to 220 ℃ in advance through a special tool;
then, a material storage tank with the temperature of 220 ℃ kept is connected into a vacuum purification device, and a product is purified for 1.5 h;
finally, cooling the storage tank and introducing inert gas for sealed preservation to obtain the final high-purity sodium tetrachloroaluminate crystal product with the purity of 99.200 percent
Embodiment IV
Firstly, according to the weight ratio of anhydrous aluminum trichloride: anhydrous sodium chloride (purity 98.500%) and anhydrous sodium chloride (purity 99.200%) are weighed according to the molar ratio of the anhydrous sodium chloride of 1:1.200, and then the mass sum of the anhydrous aluminum trichloride and the anhydrous sodium chloride is as follows: weighing metal aluminum according to the aluminum scrap mass ratio of 1000: 2.5;
then, uniformly mixing anhydrous aluminum trichloride, anhydrous sodium chloride and metal aluminum;
the one-step reaction method comprises the following steps: adding the uniformly mixed anhydrous aluminum trichloride, anhydrous sodium chloride and metallic aluminum into a reaction kettle; the air inlet of the top cover of the reaction kettle is connected with high-purity nitrogen for purging, and the air outlet of the top cover of the reaction kettle is connected into the tail gas absorption device of the alkali liquor pool; setting the heating temperature of the reaction kettle to be 200 ℃, starting a heating switch of the reaction kettle, and heating the reaction kettle to the set temperature within 1 h; after all the materials are liquefied, opening the top cover of the reaction kettle, and continuously stirring for 3 min; then covering a top cover of the reaction kettle, and continuing to perform heat preservation reaction for 72 hours;
after the reaction is finished, transferring the supernatant in the reaction kettle into a storage tank heated to 200 ℃ in advance through a special tool;
then, a material storage tank with the temperature kept at 200 ℃ is connected into a vacuum purification device, and a product is purified for 1 h;
finally, cooling the storage tank and introducing inert gas for sealed preservation to obtain the final high-purity sodium tetrachloroaluminate crystal product with the purity of 99.600 percent
Fifth embodiment
Firstly, according to the weight ratio of anhydrous aluminum trichloride: anhydrous sodium chloride molar ratio 1:1.500 anhydrous aluminum trichloride (purity 98.500%) and anhydrous sodium chloride (purity 99.200%) are weighed, and then the mass sum of the anhydrous aluminum trichloride and the anhydrous sodium chloride is as follows: weighing metal aluminum according to the aluminum scrap mass ratio of 1000: 2.2;
then, uniformly mixing anhydrous aluminum trichloride, anhydrous sodium chloride and metal aluminum;
the one-step reaction method comprises the following steps: adding the uniformly mixed anhydrous aluminum trichloride, anhydrous sodium chloride and metallic aluminum into a reaction kettle; the air inlet of the top cover of the reaction kettle is connected with high-purity nitrogen for purging, and the air outlet of the top cover of the reaction kettle is connected into the tail gas absorption device of the alkali liquor pool; setting the heating temperature of the reaction kettle to 220 ℃, starting a heating switch of the reaction kettle, and heating the reaction kettle to the set temperature within 1 h; after all the materials are liquefied, opening the top cover of the reaction kettle, and continuously stirring for 3 min; then covering a top cover of the reaction kettle, and continuing to perform heat preservation reaction for 72 hours;
after the reaction is finished, transferring the supernatant in the reaction kettle into a storage tank heated to 220 ℃ in advance through a special tool;
then, a material storage tank with the temperature of 220 ℃ kept is connected into a vacuum purification device, and a product is purified for 1.5 h;
and finally, cooling the storage tank and introducing inert gas for sealed storage to obtain the final high-purity sodium tetrachloroaluminate crystal product with the product purity of 98.800%.
According to the invention, the raw materials are uniformly mixed in advance, so that the contact area between the materials is increased, and the reaction speed is increased.
The synthesis steps of all the embodiments of the invention are one-step reaction methods, solid raw materials are added into a reaction kettle, and after a period of reaction, liquid products are directly obtained, the process is simple, and complex operation is not needed.
Specifically, the reaction equation of the one-step reaction method of the invention is as follows: AlCl3+ NaCl NaAlCl4
Specifically, the stirring is only needed to be carried out for 1-3 min in the reaction process, and in the rest reaction processes, the materials or the products are always protected by inert gas, so that the contact time of the materials and air or moisture is reduced to the maximum extent, and the appearance and the purity of the products are favorably improved.
Specifically, in the reaction process, the temperature is kept continuously after stirring, the product can be vertically layered, and the supernatant is liquid sodium tetrachloroaluminate with high purity.
In addition, the purpose of vacuum purification of the liquid product in the embodiment of the invention is to further improve the purity of the product, and the purity of the product can reach more than 99%.
Further, the high purity sodium tetrachloroaluminate prepared in the example of the present invention is used as a second electrolyte in a sodium salt battery. The purity of the sodium tetrachloroaluminate prepared by the method can reach more than 99.5 percent, the requirement of sodium salt batteries on the purity of electrolyte can be met, and the high-purity sodium tetrachloroaluminate prepared by the method can also meet the requirement of related pharmaceutical industries on the purity of the sodium tetrachloroaluminate.
The above description is only exemplary of the present invention and should not be construed as limiting the scope of the present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (7)
1. A preparation method of high-purity sodium tetrachloroaluminate as a second electrolyte of a sodium salt battery comprises the following steps,
(1) weighing anhydrous aluminum trichloride and anhydrous sodium chloride according to the molar ratio of the anhydrous aluminum trichloride to the anhydrous sodium chloride, and then weighing metal aluminum according to the mass ratio of the sum of the anhydrous aluminum trichloride and the anhydrous sodium chloride to the metal aluminum;
(2) uniformly mixing anhydrous aluminum trichloride, anhydrous sodium chloride and metal aluminum;
(3) adding the uniformly mixed anhydrous aluminum trichloride, anhydrous sodium chloride and metallic aluminum into a reaction kettle, and adding high-purity nitrogen for heating; after all the materials are liquefied, opening the top cover of the reaction kettle, continuously stirring, covering the top cover of the reaction kettle, and continuously preserving heat;
(4) after the reaction is finished, transferring the supernatant in the reaction kettle into a storage tank heated to 170-250 ℃ in advance;
(5) putting the material storage tank with the temperature of 170-250 ℃ into a vacuum purification device, and purifying the product for 0.5-2 h;
(6) and cooling the storage tank, and introducing inert gas for sealing and storing to obtain the final high-purity sodium tetrachloroaluminate crystal product.
2. The method for preparing high-purity sodium tetrachloroaluminate according to claim 1, wherein in step 3, the inlet of the top cover of the reaction kettle is connected to a high-purity nitrogen purge, and the outlet of the top cover of the reaction kettle is connected to an alkali pool tail gas absorption device; setting the heating temperature of the reaction kettle to be 170-250 ℃, starting a heating switch of the reaction kettle, and heating the reaction kettle to the set temperature within 0.5-2 h.
3. The method for preparing high-purity sodium tetrachloroaluminate according to claim 2, wherein the top cover of the reaction kettle is opened, and the reaction is continuously stirred for 1-5 min; and then covering a top cover of the reaction kettle, and continuing to perform heat preservation reaction for 24-72 hours.
4. The method for preparing high-purity sodium tetrachloroaluminate according to claim 5, wherein the reaction temperature is 170-250 ℃ and the temperature rise rate is 0.5-2 h.
5. The method for preparing high purity sodium tetrachloroaluminate according to claim 1, wherein the ratio of anhydrous aluminum trichloride: the molar ratio of the anhydrous sodium chloride is 1: 0.950-1.500.
6. The method for preparing high-purity sodium tetrachloroaluminate according to claim 1, wherein the purity of anhydrous aluminum trichloride is 90-99.900%, the purity of anhydrous sodium chloride is 95-99.900%, and the metallic aluminum can be aluminum powder, aluminum scrap, aluminum foil or aluminum block.
7. The method for preparing high-purity sodium tetrachloroaluminate according to any one of claims 1 to 6, wherein the high-purity sodium tetrachloroaluminate is applied to sodium salt batteries or pharmaceutical intermediates in pharmaceutical industry.
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|---|---|---|---|---|
| CN119018921A (en) * | 2024-10-29 | 2024-11-26 | 内蒙古默锐能源材料有限公司 | A production method of sodium tetrachloroaluminate and a production system of sodium tetrachloroaluminate |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000073209A1 (en) * | 1999-05-28 | 2000-12-07 | Merck Patent Gmbh | METHOD AND DEVICE FOR THE CONTINUOUS PRODUCTION OF NaAlCl4 OR NaFeCl¿4? |
| CN1347390A (en) * | 1999-03-24 | 2002-05-01 | 默克专利股份有限公司 | Device and method for producing molten salts and use thereof |
| CN101049954A (en) * | 2006-04-06 | 2007-10-10 | 杨风春 | Method for preparing tetrachloro - lithium aluminate |
| CN101805000A (en) * | 2009-02-12 | 2010-08-18 | 比亚迪股份有限公司 | Production method of lithium terachloroaluminate |
| CN107140664A (en) * | 2017-05-27 | 2017-09-08 | 上海中锂实业有限公司 | A kind of preparation method of tetrachloro-lithium aluminate |
| CN107311213A (en) * | 2017-07-13 | 2017-11-03 | 中国恩菲工程技术有限公司 | The preparation method of high-purity water aluminium chloride of nothing three |
-
2019
- 2019-09-29 CN CN201910935104.4A patent/CN110817913A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1347390A (en) * | 1999-03-24 | 2002-05-01 | 默克专利股份有限公司 | Device and method for producing molten salts and use thereof |
| WO2000073209A1 (en) * | 1999-05-28 | 2000-12-07 | Merck Patent Gmbh | METHOD AND DEVICE FOR THE CONTINUOUS PRODUCTION OF NaAlCl4 OR NaFeCl¿4? |
| CN101049954A (en) * | 2006-04-06 | 2007-10-10 | 杨风春 | Method for preparing tetrachloro - lithium aluminate |
| CN101805000A (en) * | 2009-02-12 | 2010-08-18 | 比亚迪股份有限公司 | Production method of lithium terachloroaluminate |
| CN107140664A (en) * | 2017-05-27 | 2017-09-08 | 上海中锂实业有限公司 | A kind of preparation method of tetrachloro-lithium aluminate |
| CN107311213A (en) * | 2017-07-13 | 2017-11-03 | 中国恩菲工程技术有限公司 | The preparation method of high-purity water aluminium chloride of nothing three |
Non-Patent Citations (2)
| Title |
|---|
| 李国欣: "《新型化学电源技术概论》", 31 May 2007 * |
| 窦青山: "四氯铝酸锂制备工艺方法探讨", 《新疆有色金属》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN119018921A (en) * | 2024-10-29 | 2024-11-26 | 内蒙古默锐能源材料有限公司 | A production method of sodium tetrachloroaluminate and a production system of sodium tetrachloroaluminate |
| CN119018921B (en) * | 2024-10-29 | 2025-01-03 | 内蒙古默锐能源材料有限公司 | A kind of production method of sodium tetrachloroaluminate |
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