CN115744934B - Preparation method for producing electronic grade sodium fluoride by purifying industrial grade sodium carbonate - Google Patents
Preparation method for producing electronic grade sodium fluoride by purifying industrial grade sodium carbonate Download PDFInfo
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- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 title claims abstract description 210
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 title claims abstract description 149
- 229910000029 sodium carbonate Inorganic materials 0.000 title claims abstract description 99
- 239000011775 sodium fluoride Substances 0.000 title claims abstract description 72
- 235000013024 sodium fluoride Nutrition 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 178
- 238000001914 filtration Methods 0.000 claims abstract description 55
- 239000007787 solid Substances 0.000 claims abstract description 54
- 238000010438 heat treatment Methods 0.000 claims abstract description 29
- 239000002253 acid Substances 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 238000001816 cooling Methods 0.000 claims abstract description 26
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000012535 impurity Substances 0.000 claims abstract description 22
- 238000010521 absorption reaction Methods 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 21
- 239000012528 membrane Substances 0.000 claims abstract description 19
- 239000013078 crystal Substances 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000010413 mother solution Substances 0.000 claims abstract description 13
- 150000001768 cations Chemical class 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000010000 carbonizing Methods 0.000 claims abstract description 8
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 44
- 239000007789 gas Substances 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 28
- 239000001569 carbon dioxide Substances 0.000 claims description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 22
- 238000002425 crystallisation Methods 0.000 claims description 15
- 230000008025 crystallization Effects 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000003763 carbonization Methods 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 11
- 238000004781 supercooling Methods 0.000 claims description 9
- 238000011049 filling Methods 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 7
- 238000007664 blowing Methods 0.000 claims description 7
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 7
- 238000012856 packing Methods 0.000 claims description 7
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 claims description 7
- MQRJBSHKWOFOGF-UHFFFAOYSA-L disodium;carbonate;hydrate Chemical compound O.[Na+].[Na+].[O-]C([O-])=O MQRJBSHKWOFOGF-UHFFFAOYSA-L 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000012085 test solution Substances 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 7
- 238000000746 purification Methods 0.000 abstract description 7
- 238000001704 evaporation Methods 0.000 abstract description 5
- 230000008020 evaporation Effects 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 15
- 235000011121 sodium hydroxide Nutrition 0.000 description 14
- 239000012452 mother liquor Substances 0.000 description 9
- 238000002791 soaking Methods 0.000 description 8
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical compound [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005868 electrolysis reaction Methods 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- 239000012267 brine Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- -1 fluoride ions Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910017855 NH 4 F Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The application provides a preparation method for producing electronic grade sodium fluoride by purifying industrial grade sodium carbonate, which comprises the following production steps: 1) Preparing saturated sodium carbonate solution, and removing impurities through a screen and a filtering membrane; 2) A strong acid type cation resin absorption column is treated, and then an activated carbon absorption column is treated by an acid washing column; 3) Carbonizing the sodium carbonate solution, and separating, filtering and drying the solid to obtain a purified sodium carbonate solid; 4) Adding purified sodium carbonate into the mother solution, filtering the mother solution by a filter membrane, and entering a neutralization tank; 5) Introducing the purified sodium carbonate solution into a salt pond for heating and concentrating; 6) And cooling the salt pond to generate sodium fluoride crystals, and drying under reduced pressure to obtain a high-purity sodium fluoride product. The preparation method uses industrial sodium carbonate to produce sodium fluoride, and electronic grade sodium fluoride can be obtained only by purifying raw materials; the industrial sodium carbonate product is mature, the price is low, the purification process is unnecessary to electrolyze, the water content of the solvent after the reaction is small, the evaporation capacity is reduced, and the raw material and energy consumption cost is reduced.
Description
Technical Field
The application belongs to the technical field of materials, and particularly relates to a preparation method for producing electronic grade sodium fluoride by purifying industrial grade sodium carbonate.
Background
Sodium fluoride is an important chemical raw material, has very wide application, is a main source of fluoride ions in many fluorine compounds, and has wide application in various fields such as agriculture, light industry, building industry and the like, but the sodium fluoride product on the market is low in purity and is not suitable for the field of fine chemical industry.
The existing preparation method for producing sodium fluoride mainly comprises the following steps:
the fluosilicic acid separation sedimentation method (1) for producing sodium fluoride by utilizing the reaction of sodium carbonate and sodium fluosilicate and the ammonium fluosilicate synthesis method (2) by utilizing the reaction of ammonia gas, fluosilicic acid and caustic soda are mature in process and high in yield, but byproducts which are difficult to completely separate exist in the reaction, the product purity is insufficient and the process is difficult to improve:
Na 2 SiF 6 + 2Na 2 CO 3 → 6NaF + SiO 2 +2CO 2 ↑ (1)
H 2 SiF 6 +6NH 3 +2H 2 o-6 NH 4 F+SiO 2 ↓；
NH 4 F+NaOH-NaF ∈+NH 3 +H 2 O(2)
The production of high-purity electronic grade sodium fluoride generally adopts the method of introducing sodium fluoride gas (3) into high-purity sodium hydroxide solution, wherein raw material sodium hydroxide is produced by a perfluorosulfonic acid ion membrane electrolysis brine method, and in addition, the reaction produces a large amount of water to influence the yield of sodium fluoride, so that the subsequent extraction treatment process has higher requirements, and the overall process has high raw material and energy consumption cost.
NaOH+HF-NaF ∈+H 2 O(3)
However, the existing preparation method cannot meet the requirement of high purity, and has the problems of high raw material requirement, high production cost, high energy consumption and the like. The byproducts which are difficult to completely remove are contained in the sodium fluoride production products of the methods (1) and (2), and the byproducts silicon dioxide and ammonia water cannot be completely separated and removed, so that the method can be used as fluorine additives in the fields of agriculture, light industry, building industry and the like, and is difficult to apply to fine chemical production; in the method (3), sodium hydroxide produced by a cation permeable membrane electrolysis brine method is required to be generated along with a large amount of water in the reaction process with a fluorine source, the increase of the water amount serving as a solvent tends to influence the yield of sodium fluoride, and in addition, the sodium hydroxide serving as a strong base has limited reaction concentration; the high-purity sodium hydroxide produced by the perfluorosulfonic acid ion membrane electrolysis brine method is used as a raw material, and a large amount of solvent water is produced by the reaction, so that evaporation and concentration treatment are needed. Therefore, it is highly demanded to develop a production process capable of improving the purity of sodium fluoride, which consumes less energy and has a low cost.
Disclosure of Invention
The present invention has been made in view of the above problems, and an object thereof is to provide a method for producing electronic grade sodium fluoride, which can produce sodium carbonate by purifying production raw materials, can control the concentration easily, can reduce the raw materials and energy costs, and can produce electronic grade sodium fluoride at a low cost.
In order to achieve the above purpose, the present application provides a method for producing electronic grade sodium fluoride by purifying industrial grade sodium carbonate.
The first aspect of the application provides a preparation method for producing electronic grade sodium fluoride by purifying industrial grade sodium carbonate, which specifically comprises the following steps:
(1) Preparing a 30 ℃ saturated sodium carbonate solution, heating the solution to 40-50 ℃, stirring until the solution is uniform and stable, filtering obvious solid impurities in the solution through a 1000-mesh screen, and further removing the solid impurities through a filter membrane;
(2) Filling a strong acid type cation resin absorption column, controlling the flow rate of the solution in the step (1) to be 10-15V/h, carrying out column treatment, and then carrying out acid washing on the activated carbon absorption column;
(3) Carbonizing a sodium carbonate solution, stirring and introducing carbon dioxide, separating the solution from the solid, centrifugally filtering the solid, and adding the solid into an oven to heat at 150 ℃ to obtain a purified sodium carbonate solid;
(4) Adding purified sodium carbonate into the mother solution, regulating the temperature of the solution to 35 ℃, preparing sodium carbonate solution with the concentration of 3-4mol/L, stirring and standing, leading out the solution, filtering the solution by a filter membrane, and entering a neutralization tank;
(5) Introducing the purified sodium carbonate solution into a salt pond, heating and concentrating, and then blowing hydrogen fluoride gas into the solution and generating carbon dioxide gas, sodium fluoride crystals and a small amount of sodium bifluoride; heating the solution in the concentrated salt pond, adding the purified sodium carbonate solution to adjust the pH value of the solution to 6.7-7.0, continuously stirring, and taking the reaction as the end when the test solution is maintained neutral;
(6) And cooling the salt pond to 15 ℃ to generate sodium fluoride crystals, filtering and dehydrating sodium fluoride solids, centrifugally dehydrating, and drying under reduced pressure to obtain a high-purity sodium fluoride product.
In any embodiment, after the filtration in the step (1), naturally cooling the solution to 25 ℃, cooling the solution to 10 ℃ through a supercooled form of an external cold source of 3-6 ℃, filtering out sodium carbonate-water crystallization, and removing strong acid radicals such as nitrate radical, sulfate radical and the like carried in sodium carbonate.
In any embodiment, in the step (2), the resin is firstly soaked by 0.01mol/L hydrochloric acid washing, then soaked and regenerated for 2-3 times by using 1mol/L sodium hydroxide solution, and finally washed cleanly by pure water for column packing.
In any embodiment, the aspect ratio of the absorber column in step (2) is controlled between 15:1 and 20:1.
In any embodiment, the sodium carbonate solution is heated during the carbonization process in step (3) to maintain 31 ℃ to 35 ℃.
In any embodiment, in the step (3), when the PH of the solution is detected to be less than or equal to 8.5, stopping introducing gas, and completing carbonization of sodium carbonate.
In any embodiment, the carbon dioxide gas is recovered in step (5) for carbonization of sodium carbonate in step (3).
In any embodiment, the sodium fluoride mother liquor generated by filtering in the step (6) is returned to the step (4) for recycling.
The invention has the beneficial effects that:
1. the metal impurity content of the sodium fluoride is less than 25ppm, and the electronic grade sodium fluoride for sodium battery use can be produced;
2. the purity requirement of the production raw materials is reduced, the requirements of an electrolysis process and high tower equipment required by the raw material purification process are avoided, and the sodium fluoride production efficiency is improved;
3. the process links of variable-temperature crystallization and evaporation concentration are replaced and optimized, only the adsorption effect of the ion exchange resin is considered in temperature control, the water quantity of evaporation concentration is reduced, the energy consumption is also reduced, and the method has the advantage of cost;
4. the carbon dioxide gas, the sodium carbonate mother solution and the sodium fluoride mother solution in the link can be recycled, so that the resources are saved, and the production concept of green and environment protection is met.
5. The industrial sodium carbonate is used for producing the sodium fluoride, and the electronic grade sodium fluoride can be obtained only by purifying production raw materials. The sodium carbonate is used for production, so that the generation amount of water can be reduced, and the sodium carbonate can be used as a strong alkali weak acid salt to facilitate concentration control. The industrial sodium carbonate product is mature, the price is low, the purification process is unnecessary to electrolyze, the water content of the solvent after the reaction is small, the evaporation capacity is reduced, and the raw material and energy consumption cost is reduced.
Detailed Description
Hereinafter, embodiments of a method for producing electronic grade sodium fluoride by purifying technical grade soda of the present application are specifically disclosed with reference to the detailed description as appropriate. However, unnecessary detailed description may be omitted. For example, detailed descriptions of well-known matters and repeated descriptions of the actual same structure may be omitted. This is to avoid that the following description becomes unnecessarily lengthy, facilitating the understanding of those skilled in the art. Furthermore, the following description is provided for a thorough understanding of the present application by those skilled in the art, and is not intended to limit the subject matter recited in the claims.
The "range" disclosed herein is defined in terms of lower and upper limits, with a given range being defined by the selection of a lower and an upper limit, the selected lower and upper limits defining the boundaries of the particular range. Ranges that are defined in this way can be inclusive or exclusive of the endpoints, and any combination can be made, i.e., any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4 and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise indicated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0-5" means that all real numbers between "0-5" have been listed throughout, and "0-5" is simply a shorthand representation of a combination of these values. When a certain parameter is expressed as an integer of 2 or more, it is disclosed that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12 or the like.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, unless specifically stated otherwise.
All technical features and optional technical features of the present application may be combined with each other to form new technical solutions, unless specified otherwise.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, unless otherwise indicated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, or may comprise steps (b) and (a) performed sequentially. For example, the method may further include step (c), which means that step (c) may be added to the method in any order, for example, the method may include steps (a), (b) and (c), may include steps (a), (c) and (b), may include steps (c), (a) and (b), and the like.
Reference herein to "comprising" and "including" means open ended, as well as closed ended, unless otherwise noted. For example, the terms "comprising" and "comprises" may mean that other components not listed may be included or included, or that only listed components may be included or included.
The term "or" is inclusive in this application, unless otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or absent); a is false (or absent) and B is true (or present); or both A and B are true (or present).
The preparation method for producing electronic grade sodium fluoride by purifying industrial grade sodium carbonate specifically comprises the following steps:
(1) Preparing a 30 ℃ saturated sodium carbonate solution, heating the solution to 40-50 ℃, stirring until the solution is uniform and stable, filtering obvious solid impurities in the solution through a 1000-mesh screen, and further removing the solid impurities through a filter membrane;
(2) Filling a strong acid type cation resin absorption column, controlling the flow rate of the solution in the step (1) to be 10-15V/h, carrying out column treatment, and then carrying out acid washing on the activated carbon absorption column;
(3) Carbonizing a sodium carbonate solution, stirring and introducing carbon dioxide, separating the solution from the solid, centrifugally filtering the solid, and adding the solid into an oven to heat at 150 ℃ to obtain a purified sodium carbonate solid;
Na 2 CO 3 +H 2 O+CO 2 →NaHCO 3 ↓
2NaHCO 3 →2Na 2 CO 3 +H 2 O↑+CO 2 ↑
(4) Adding purified sodium carbonate into the mother solution, regulating the temperature of the solution to 35 ℃, preparing sodium carbonate solution with the concentration of 3.5mol/L, stirring and standing, leading out the solution, filtering the solution by a filter membrane, and entering a neutralization tank; the solution was allowed to stand until apparent clear.
(5) Introducing the purified sodium carbonate solution into a salt pond, heating and concentrating, and then blowing hydrogen fluoride gas into the solution and generating carbon dioxide gas, sodium fluoride crystals and a small amount of sodium bifluoride; heating the solution in the concentrated salt pond, adding the purified sodium carbonate solution to adjust the pH value of the solution to 6.7-7.0, continuously stirring, and taking the reaction as the end when the test solution is maintained neutral;
Na 2 CO 3 +2HF→2NaF+H 2 O+CO 2 ↑
NaF+HF→NaHF 2
NaHF 2 +NaOH→2NaF+H 2 O
(6) And cooling the salt pond to 15 ℃ to generate sodium fluoride crystals, filtering and dehydrating sodium fluoride solids, centrifugally dehydrating, and drying under reduced pressure to obtain a high-purity sodium fluoride product.
Preparing a saturated sodium carbonate solution at 30 ℃, and heating the solution to 40-50 ℃. The method is to prepare a saturated sodium carbonate solution at the temperature of 40-50 ℃ and the temperature of 30 ℃. The saturated solubility of sodium carbonate in water at 30 ℃ is approximately 40g/100g, which belongs to the easily-contained substances. However, the volume of the material is nearly half of the volume of the water, the dissolution speed is low under the dissolution condition of 30 ℃, the burden of stirring by a large amount of piled materials is heavy, and the piled materials are easy to accumulate at the bottom.
The heating is carried out at 40-50 ℃, so that the dissolution speed can be greatly improved, the occurrence of accumulated materials is avoided, the filtration speed is increased, and the efficiency of the step is generally improved. Purified sodium carbonate was added to the mother liquor and the solution temperature was adjusted to 35 ℃.35 ℃ is the maximum solubility temperature of sodium carbonate in water.
The mother liquor refers to pure water or a solution which is recycled later, more specifically, the mother liquor refers to a solvent which is used for dissolving industrial-grade solid alkali raw materials in the step 1 and is used for preparing a 30 ℃ saturated sodium carbonate solution. Pure water is used for the initial first circulating mother liquor; the mother solution in the subsequent circulation is a solution with a certain proportion of sodium fluoride after filtering out the product in the previous circulation, and the solution is supplemented with a certain proportion of pure water; and (3) circulating to a certain extent to discharge all the mother liquor, cleaning the mother liquor pond, and then starting from the beginning, namely, the mother liquor is pure water.
A sodium carbonate solution was prepared at a concentration of 3.5 mol/L. This concentration is about 15% lower than the maximum solubility of sodium carbonate in step (1) and is chosen to ensure that solid crystallization only occurs during the precipitation step throughout the industrial process, which is a safety and smooth operation of the system. The method is also used for reserving space for condition fluctuation in the whole production process flow, and simultaneously, after crystallization is finally precipitated, the mother solution is recycled, so that a dissolving space is reserved, and solid accumulation in the flow is prevented.
The salt pond is cooled to 15 ℃. The temperature is selected based on the dissolution profile of sodium fluoride. The temperature is higher, the amount of dissolution in water is more, and the single batch output is less; the temperature is further low, the increase amplitude change of the precipitation amount is small, and the energy consumption is not cost-effective in comparison with the cooling. A calculated value belonging to an efficiency curve; the key point of the production process is that the crystallization and purification caused by ion exchange and the change of poor solubility, namely the impurity treatment is that the impurities are absorbed by exchange and separated and remain, and the purity of the product can be controlled within 20 ppm.
Meanwhile, in the process equipment, the invisible requirements of replacement, purification and regeneration exist, more substances can be separated out at 15 ℃, and meanwhile, the separation change range of impurities in a reasonable range is relatively stable, so that the product quality is more stable, in addition, the circulating solution is cleaner, the purification pressure of the whole system can be reduced, and the service life of the system is prolonged.
In any embodiment, after the filtration in the step (1), naturally cooling the solution to 25 ℃, cooling the solution to 10 ℃ through supercooling form induced cooling crystallization of an external cold source at 3-6 ℃, filtering out sodium carbonate crystals, and removing strong acid radicals such as nitrate radical, sulfate radical and the like carried in the sodium carbonate.
The energy consumption is saved in the treatment process of natural cooling; the external supercooling cooling is adopted because the impurity of the solution is reduced after the sodium carbonate is heated, filtered and cooled, the solution is uniform, the crystallization of crystal nucleus is difficult to form, the supercooling induces the uneven temperature of the solution, and the crystallization is induced.
For the selection of the cold source temperature, the supercooling temperature is too low to be zero, so that the water content in the crystal is easily too high, and strong acid roots about 5ppm can be included on average, so that the purification effect is reduced; the temperature is too high, the crystallization efficiency is low, and the temperature change induction is not obvious.
In any embodiment, in the step (2), the resin is firstly soaked by 0.01mol/L hydrochloric acid washing, then soaked and regenerated for 2-3 times by using 1mol/L sodium hydroxide solution, and finally washed cleanly by pure water for column packing.
In any embodiment, the aspect ratio of the absorber column in step (2) is controlled between 15:1 and 20:1.
For the selection of the length-diameter ratio of the absorption column, the filtrate and the filtration column need a certain exchange time to finish the exchange adsorption of ions, and the larger the length-diameter ratio isThe longer the contact time. The long diameter is lower than 15:1, the exchange is insufficient, and the low-valence metal ions K are + The absorptivity is low, and the average residual content is 10-20 ppm, so that the metal impurity content is greatly increased; the length-diameter ratio is higher than 20:1, the filter tube is too long, the phenomenon of uneven filling of the filter tube is easy to occur, the regional flow in the tube is stopped, the problem that the solution soaks the ion exchange resin for a long time occurs, and the absorbed high-valence ions such as calcium, magnesium, iron, aluminum and the like are reversely separated out.
In any embodiment, the sodium carbonate solution is heated during the carbonization process in step (3) to maintain 31 ℃ to 35 ℃.
In any embodiment, in the step (3), when the PH of the solution is detected to be less than or equal to 8.5, stopping introducing gas, and completing carbonization of sodium carbonate.
In any embodiment, in step (5), the carbon dioxide gas is washed with water to recover sodium carbonate for carbonization in step (3).
In any embodiment, the saturated sodium fluoride solution produced by filtration in step (6) is returned to step (4) as solvent. I.e. the solution after crystallization of sodium fluoride is filtered off, a saturated sodium fluoride solution at 15 ℃ being the main part of the mother liquor for the next cycle.
Examples
Hereinafter, embodiments of the present application are described. The embodiments described below are exemplary only for the purpose of illustrating the present application and are not to be construed as limiting the present application. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The preparation method for producing electronic grade sodium fluoride by purifying industrial grade sodium carbonate specifically comprises the following steps:
(1) Preparing a 30 ℃ saturated sodium carbonate solution, heating the solution to 40-50 ℃, stirring until the solution is uniform and stable, filtering obvious solid impurities in the solution through a 1000-mesh screen, and further removing the solid impurities through a filter membrane; naturally cooling the solution to 25 ℃ after the filtration is completed, cooling the solution to 10 ℃ through a supercooling mode of an external cold source at 3-6 ℃, filtering out sodium carbonate-water crystallization, and removing strong acid roots such as nitrate radical, sulfate radical and the like carried in sodium carbonate;
(2) Filling a strong acid type cation resin absorption column, washing and soaking the resin by 0.01mol/L hydrochloric acid, then soaking and regenerating the resin for 2 to 3 times by using 1mol/L sodium hydroxide solution, and finally washing the resin by using pure water to clean the resin for column packing. The length-diameter ratio of the absorption column is controlled to be 15:1, the flow rate of the solution passing through the column is controlled to be 10.5V/h, and then the activated carbon absorption column is treated by the acid washing column;
(3) Carbonizing sodium carbonate solution, heating the sodium carbonate solution to maintain the temperature of 31-35 ℃, stirring and introducing carbon dioxide, detecting the pH value to be less than or equal to 8.5, stopping introducing gas, separating the solution from solid, centrifugally filtering the solid, and adding the solid into an oven to heat at 150 ℃ to obtain purified sodium carbonate solid;
(4) Adding purified sodium carbonate into the mother solution, regulating the temperature of the solution to 35 ℃, preparing sodium carbonate solution with the concentration of 3.5mol/L, stirring and standing, leading out the solution, filtering the solution by a filter membrane, and entering a neutralization tank;
(5) Introducing the purified sodium carbonate solution into a salt pond, heating and concentrating, and then blowing hydrogen fluoride gas into the solution and generating carbon dioxide gas, sodium fluoride crystals and a small amount of sodium bifluoride, wherein the carbon dioxide gas is recycled for carbonization of sodium carbonate; heating the solution in the concentrated salt pond, regulating the PH of the solution, adding the purified sodium carbonate solution, continuously stirring and testing the PH of the solution to be between 6.7 and 7.0, and finishing the reaction;
(6) And (3) cooling the salt pond to room temperature of 15 ℃ to generate sodium fluoride crystals, filtering and dehydrating sodium fluoride solids, performing centrifugal dehydration, and then performing reduced pressure drying to obtain a high-purity sodium fluoride product, wherein a saturated sodium fluoride solution generated by filtering returns to the step (4) to serve as a solvent.
Example 2
(1) Preparing a 30 ℃ saturated sodium carbonate solution, heating the solution to 40-50 ℃, stirring until the solution is uniform and stable, filtering obvious solid impurities in the solution through a 1000-mesh screen, and further removing the solid impurities through a filter membrane; naturally cooling the solution to 25 ℃ after the filtration is completed, cooling the solution to 10 ℃ through a supercooling mode of an external cold source at 3-6 ℃, filtering out sodium carbonate-water crystallization, and removing strong acid roots such as nitrate radical, sulfate radical and the like carried in sodium carbonate;
(2) Filling a strong acid type cation resin absorption column, washing and soaking the resin by 0.01mol/L hydrochloric acid, then soaking and regenerating the resin for 2 to 3 times by using 1mol/L sodium hydroxide solution, and finally washing the resin by using pure water to clean the resin for column packing. The length-diameter ratio of the absorption column is controlled to be 18:1, the flow rate of the solution passing through the column is controlled to be 13V/h, and then the activated carbon absorption column is treated by the acid washing column;
(3) Carbonizing sodium carbonate solution, heating the sodium carbonate solution to maintain the temperature of 31-35 ℃, stirring and introducing carbon dioxide, detecting the pH value to be less than or equal to 8.5, stopping introducing gas, separating the solution from solid, centrifugally filtering the solid, and adding the solid into an oven to heat at 150 ℃ to obtain purified sodium carbonate solid;
(4) Adding purified sodium carbonate into the mother solution, regulating the temperature of the solution to 35 ℃, preparing sodium carbonate solution with the concentration of 3.3mol/L, stirring and standing, leading out the solution, filtering the solution by a filter membrane, and entering a neutralization tank;
(5) Introducing the purified sodium carbonate solution into a salt pond, heating and concentrating, and then blowing hydrogen fluoride gas into the solution and generating carbon dioxide gas, sodium fluoride crystals and a small amount of sodium bifluoride, wherein the carbon dioxide gas is recycled for carbonization of sodium carbonate; heating the solution in the concentrated salt pond, regulating the PH of the solution, adding the purified sodium carbonate solution, continuously stirring and testing the PH of the solution to be between 6.7 and 7.0, and finishing the reaction;
(6) And (3) cooling the salt pond to room temperature of 15 ℃ to generate sodium fluoride crystals, filtering and dehydrating sodium fluoride solids, performing centrifugal dehydration, and then performing reduced pressure drying to obtain a high-purity sodium fluoride product, wherein a saturated sodium fluoride solution generated by filtering returns to the step (4) to serve as a solvent.
Example 3
(1) Preparing a 30 ℃ saturated sodium carbonate solution, heating the solution to 40-50 ℃, stirring until the solution is uniform and stable, filtering obvious solid impurities in the solution through a 1000-mesh screen, and further removing the solid impurities through a filter membrane; naturally cooling the solution to 25 ℃ after the filtration is completed, cooling the solution to 10 ℃ through a supercooling mode of an external cold source at 3-6 ℃, filtering out sodium carbonate-water crystallization, and removing strong acid roots such as nitrate radical, sulfate radical and the like carried in sodium carbonate;
(2) Filling a strong acid type cation resin absorption column, washing and soaking the resin by 0.01mol/L hydrochloric acid, then soaking and regenerating the resin for 2 to 3 times by using 1mol/L sodium hydroxide solution, and finally washing the resin by using pure water to clean the resin for column packing. The length-diameter ratio of the absorption column is controlled between 19:1, the flow rate of the solution passing through the column is controlled at 11V column/h, and the activated carbon absorption column is treated by the acid washing column;
(3) Carbonizing sodium carbonate solution, heating the sodium carbonate solution to maintain the temperature of 31-35 ℃, stirring and introducing carbon dioxide, detecting the pH value to be less than or equal to 8.5, stopping introducing gas, separating the solution from solid, centrifugally filtering the solid, and adding the solid into an oven to heat at 150 ℃ to obtain purified sodium carbonate solid;
(4) Adding purified sodium carbonate into the mother solution, regulating the temperature of the solution to 35 ℃, preparing sodium carbonate solution with the concentration of 3.0mol/L, stirring and standing, leading out the solution, filtering the solution by a filter membrane, and entering a neutralization tank;
(5) Introducing the purified sodium carbonate solution into a salt pond, heating and concentrating, and then blowing hydrogen fluoride gas into the solution and generating carbon dioxide gas, sodium fluoride crystals and a small amount of sodium bifluoride, wherein the carbon dioxide gas is recycled for carbonization of sodium carbonate; heating the solution in the concentrated salt pond, regulating the PH of the solution, adding the purified sodium carbonate solution, continuously stirring and testing the PH of the solution to be between 6.7 and 7.0, and finishing the reaction;
(6) And (3) cooling the salt pond to room temperature of 15 ℃ to generate sodium fluoride crystals, filtering and dehydrating sodium fluoride solids, performing centrifugal dehydration, and then performing reduced pressure drying to obtain a high-purity sodium fluoride product, wherein a saturated sodium fluoride solution generated by filtering returns to the step (4) to serve as a solvent.
Example 4
(1) Preparing a 30 ℃ saturated sodium carbonate solution, heating the solution to 40-50 ℃, stirring until the solution is uniform and stable, filtering obvious solid impurities in the solution through a 1000-mesh screen, and further removing the solid impurities through a filter membrane; naturally cooling the solution to 25 ℃ after the filtration is completed, cooling the solution to 10 ℃ through a supercooling mode of an external cold source at 3-6 ℃, filtering out sodium carbonate-water crystallization, and removing strong acid roots such as nitrate radical, sulfate radical and the like carried in sodium carbonate;
(2) Filling a strong acid type cation resin absorption column, washing and soaking the resin by 0.01mol/L hydrochloric acid, then soaking and regenerating the resin for 2 to 3 times by using 1mol/L sodium hydroxide solution, and finally washing the resin by using pure water to clean the resin for column packing. The length-diameter ratio of the absorption column is controlled between 15:1 and 18:1, the flow rate of the solution passing through the column is controlled between 10 and 15V column/h, and the activated carbon absorption column is treated by the acid washing column;
(3) Carbonizing sodium carbonate solution, heating the sodium carbonate solution to maintain the temperature of 31-35 ℃, stirring and introducing carbon dioxide, detecting the pH value to be less than or equal to 8.5, stopping introducing gas, separating the solution from solid, centrifugally filtering the solid, and adding the solid into an oven to heat at 150 ℃ to obtain purified sodium carbonate solid;
(4) Adding purified sodium carbonate into the mother solution, regulating the temperature of the solution to 35 ℃, preparing sodium carbonate solution with the concentration of 3.7mol/L, stirring and standing, leading out the solution, filtering the solution by a filter membrane, and entering a neutralization tank;
(5) Introducing the purified sodium carbonate solution into a salt pond, heating and concentrating, and then blowing hydrogen fluoride gas into the solution and generating carbon dioxide gas, sodium fluoride crystals and a small amount of sodium bifluoride, wherein the carbon dioxide gas is recycled for carbonization of sodium carbonate; heating the solution in the concentrated salt pond, regulating the PH of the solution, adding the purified sodium carbonate solution, continuously stirring and testing the PH of the solution to be between 6.7 and 7.0, and finishing the reaction;
(6) And (3) cooling the salt pond to room temperature of 15 ℃ to generate sodium fluoride crystals, filtering and dehydrating sodium fluoride solids, performing centrifugal dehydration, and then performing reduced pressure drying to obtain a high-purity sodium fluoride product, wherein a saturated sodium fluoride solution generated by filtering returns to the step (4) to serve as a solvent.
Test effects of each embodiment of the preparation method:
| project | Filtrate metal impurities (ppm) | Sodium fluoride yield (%) | Purity (%) |
| Example 1 | 3.84 | 76.5 | ≥99.995 |
| Example 2 | 4.29 | 75.5 | ≥99.995 |
| Example 3 | 4.13 | 76.1 | ≥99.995 |
| Example 4 | 3.77 | 76.9 | ≥99.995 |
The present application is not limited to the above embodiment. The above embodiments are merely examples, and embodiments having substantially the same configuration and the same effects as those of the technical idea within the scope of the present application are included in the technical scope of the present application. Further, various modifications that can be made to the embodiments and other modes of combining some of the constituent elements in the embodiments, which are conceivable to those skilled in the art, are also included in the scope of the present application within the scope not departing from the gist of the present application.
Claims (5)
1. The preparation method for producing electronic grade sodium fluoride by purifying industrial grade sodium carbonate is characterized by comprising the following steps of:
(1) Preparing a saturated sodium carbonate solution at 25-35 ℃, heating the solution to 40-50 ℃, stirring the solution uniformly and stably, filtering obvious solid impurities in the solution through a 500-1000 mesh screen, and further removing the solid impurities through a filter membrane; naturally cooling the solution to 25 ℃ after the filtration is completed, cooling the solution to 10 ℃ through a supercooling mode of an external cold source of 3-6 ℃, filtering out sodium carbonate-water crystallization, and removing strong acid roots with nitrate and sulfate radicals in the sodium carbonate;
(2) Filling a strong acid type cation resin absorption column, controlling the flow rate of the solution in the step (1) to be 10-15V columns/h, performing column treatment, and performing acid washing on the activated carbon absorption column;
(3) Carbonizing a sodium carbonate solution, stirring and introducing carbon dioxide, heating the sodium carbonate solution in the carbonization process to maintain the temperature of 31-35 ℃, separating the solution from solid, centrifugally filtering the solid, and adding the solid into an oven to heat at 150 ℃ to obtain purified sodium carbonate solid;
(4) Adding purified sodium carbonate into the mother solution, regulating the temperature of the solution to 35 ℃, preparing sodium carbonate solution with the concentration of 3-4mol/L, stirring and standing, leading out the solution, filtering the solution by a filter membrane, and entering a neutralization tank; standing the solution until the solution is apparent clear;
(5) Introducing the purified sodium carbonate solution into a salt pond, heating and concentrating, and then blowing hydrogen fluoride gas into the solution and generating carbon dioxide gas, sodium fluoride crystals and a small amount of sodium bifluoride; heating the solution in the concentrated salt pond, adding the purified sodium carbonate solution to adjust the pH value of the solution to 6.7-7.0, continuously stirring, and taking the reaction as the end when the test solution is maintained neutral;
(6) And cooling the salt pond to 15 ℃ to generate sodium fluoride crystals, filtering and dehydrating sodium fluoride solids, centrifugally dehydrating, and drying under reduced pressure to obtain a high-purity sodium fluoride product.
2. The method for producing electronic grade sodium fluoride by using purified technical grade sodium carbonate according to claim 1, wherein in the step (2), resin is soaked by hydrochloric acid of 0.01mol/L, then soaked and regenerated for 2-3 times by using 1mol/L sodium hydroxide solution, and finally washed cleanly by pure water for column packing.
3. The method for producing electronic grade sodium fluoride from purified technical grade sodium carbonate according to claim 1, wherein in the step (3), when the pH of the solution is detected to be less than or equal to 8.5, the gas is stopped to complete carbonization of sodium carbonate.
4. The method for producing electronic grade sodium fluoride from purified technical grade sodium carbonate according to claim 1, wherein carbon dioxide gas is recovered in step (5) for carbonization of sodium carbonate in step (3).
5. The method for producing electronic grade sodium fluoride from purified technical grade sodium carbonate according to claim 1, wherein the saturated sodium fluoride solution produced by filtration in step (6) is returned to step (4).
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| CN117105246B (en) * | 2023-09-26 | 2024-03-29 | 福建省龙德新能源有限公司 | Synthesis process of electronic grade sodium carbonate |
| CN117361573A (en) * | 2023-11-13 | 2024-01-09 | 山东立中新能源材料有限公司 | Method for directly preparing battery-grade sodium fluoride from industrial-grade sodium carbonate |
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