CN115744934A - 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 214
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 title claims abstract description 172
- 229910000029 sodium carbonate Inorganic materials 0.000 title claims abstract description 97
- 239000011775 sodium fluoride Substances 0.000 title claims abstract description 83
- 235000013024 sodium fluoride Nutrition 0.000 title claims abstract description 82
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 57
- 238000001914 filtration Methods 0.000 claims abstract description 54
- 238000010438 heat treatment Methods 0.000 claims abstract description 38
- 150000003839 salts Chemical class 0.000 claims abstract description 31
- 239000013078 crystal Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000010521 absorption reaction Methods 0.000 claims abstract description 23
- 239000002253 acid Substances 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 22
- 239000012535 impurity Substances 0.000 claims abstract description 22
- 239000012452 mother liquor Substances 0.000 claims abstract description 22
- 239000011347 resin Substances 0.000 claims abstract description 22
- 229920005989 resin Polymers 0.000 claims abstract description 22
- 239000012528 membrane Substances 0.000 claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000010000 carbonizing Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001768 cations Chemical class 0.000 claims abstract description 10
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 182
- 235000017550 sodium carbonate Nutrition 0.000 claims description 90
- 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 35
- 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
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 13
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 13
- 238000011049 filling Methods 0.000 claims description 12
- 238000004781 supercooling Methods 0.000 claims description 10
- 238000007664 blowing Methods 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 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
- 239000012085 test solution Substances 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 13
- 239000002904 solvent Substances 0.000 abstract description 10
- 238000005406 washing Methods 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 9
- 238000000746 purification Methods 0.000 abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 abstract description 5
- 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
- 238000002791 soaking Methods 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000011734 sodium Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- 238000004090 dissolution Methods 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
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 238000000926 separation method Methods 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
- 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
- 238000009825 accumulation Methods 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004140 cleaning Methods 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
- 238000012856 packing Methods 0.000 description 2
- 238000001556 precipitation 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
- LXXKJGXDEZDJOM-UHFFFAOYSA-N [Fe].[Mg].[Ca] Chemical compound [Fe].[Mg].[Ca] LXXKJGXDEZDJOM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000004411 aluminium 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
- 238000003889 chemical engineering Methods 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
- 239000000470 constituent Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 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
- 230000001939 inductive effect Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000014759 maintenance of location Effects 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
- 230000003252 repetitive effect Effects 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
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) Treating with strong acid type cation resin absorption column, and treating with acid-washing column to obtain activated carbon absorption column; 3) Carbonizing a sodium carbonate solution, separating solids, filtering, drying and drying to obtain purified sodium carbonate solids; 4) Adding purified sodium carbonate into the mother liquor, filtering by a filter membrane, and feeding into a neutralization tank; 5) Introducing the purified soda solution into a salt pond for heating and concentrating; 6) And (4) 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 only needs to purify raw materials to obtain electronic-grade sodium fluoride; the industrial sodium carbonate product is mature and low in price, electrolysis is not needed in the purification process, the amount of solvent water after reaction is small, the evaporation amount is reduced, and the cost of raw materials and energy consumption 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 wide application, is a main source of fluoride ions in many fluorine compounds, and is widely used in various fields such as agriculture, light industry, building industry and the like, but the sodium fluoride product on the market at present has low purity and is not enough to be applied to the field of fine chemical engineering.
The existing main preparation method for producing sodium fluoride comprises the following steps:
the fluosilicic acid separation and sedimentation method (1) for producing sodium fluoride by reacting soda ash with sodium fluosilicate and the ammonium fluosilicate synthesis method (2) for reacting ammonia gas, fluosilicic acid and caustic soda are adopted, the two preparation methods have mature processes and large 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 step of introducing sodium fluoride gas (3) into a high-purity sodium hydroxide solution, wherein the raw material sodium hydroxide needs to be produced by a perfluorosulfonic acid ion membrane electrolysis salt water method, in addition, a large amount of water produced by reaction influences the yield of sodium fluoride, higher requirements on a subsequent extraction treatment process are needed, and the cost of raw materials and energy consumption of the whole process is high.
NaOH + HF NaF ↓ + H 2 O(3)
But the existing preparation method can not 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 sodium fluoride production products of the methods (1) and (2) have byproducts which are difficult to completely remove, and the byproducts, namely silicon dioxide and ammonia water, cannot be completely separated and removed, can only be used as fluorine additives in the fields of agriculture, light industry, building industry and the like, and are difficult to apply to fine chemical production; in the method (3), the sodium hydroxide produced by a method of electrolyzing salt water by a cation permeable membrane is required, a large amount of water is generated in the process of reacting with a fluorine source, the yield of the sodium fluoride is influenced by the increase of the water amount used as a solvent, and the reaction concentration of the sodium hydroxide used as a strong base is limited; high-purity sodium hydroxide produced by a perfluorosulfonic acid ion membrane electrolysis salt water method is used as a raw material, and a large amount of solvent water is generated by reaction and needs evaporation concentration treatment. Therefore, there is an urgent need to develop a production process with low energy consumption and low cost, which can improve the purity of sodium fluoride.
Disclosure of Invention
The present invention has been made in view of the above problems, and an object of the present invention is to provide a production method for producing electronic-grade sodium fluoride, which is capable of easily controlling the concentration of sodium fluoride by purifying a production raw material and producing sodium fluoride using sodium carbonate, and which is inexpensive and can reduce the cost of raw materials and energy consumption.
In order to achieve the purpose, the application provides a preparation 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 filtering membrane;
(2) Filling a strong acid type cation resin absorption column, controlling the flow rate of the solution in the step (1) at 10-15V column/h for column treatment, and then treating the solution by an acid-washed activated carbon absorption column;
(3) Carbonizing a sodium carbonate solution, stirring and introducing carbon dioxide, then separating the solution from solids, centrifuging and filtering the solids to dryness, adding the solids into an oven, and heating at 150 ℃ to obtain purified sodium carbonate solids;
(4) Adding purified sodium carbonate into the mother liquor, adjusting the temperature of the solution to 35 ℃, preparing a sodium carbonate solution with the concentration of 3-4mol/L, stirring and standing, leading out the solution, filtering by a filter membrane, and feeding the solution into a neutralization tank;
(5) Introducing the purified soda solution into a salt pond, heating and concentrating, and blowing hydrogen fluoride gas into the solution in an excessive amount to generate carbon dioxide gas, sodium fluoride crystals and a small amount of sodium fluoride; heating and concentrating the solution in the salt pond, adding a sodium carbonate purified solution to adjust the pH value of the solution to be 6.7-7.0, continuously stirring, and determining that the reaction is finished when the test solution is neutral;
(6) And cooling the salt pond to 15 ℃ to generate sodium fluoride crystals, filtering and dehydrating sodium fluoride solids, performing centrifugal dehydration, and drying under reduced pressure to obtain a high-purity sodium fluoride product.
In any embodiment mode, after the filtering in the step (1) is finished, the solution is naturally cooled to 25 ℃, then the solution is cooled to 10 ℃ in a supercooling mode with an external cold source of 3-6 ℃, sodium carbonate-water crystals are filtered out, and nitrate radicals, sulfate radicals and other strong acid radicals in the sodium carbonate are removed.
In any embodiment, in the step (2), the resin is washed and soaked by 0.01mol/L hydrochloric acid, soaked by 1mol/L sodium hydroxide solution for regeneration for 2-3 times, and finally washed by pure water for column packing.
In any embodiment, the length-to-diameter ratio of the absorption column in step (2) is controlled to be between 15 and 20.
In any embodiment, the sodium carbonate solution is heated to maintain a temperature of 31 ℃ to 35 ℃ during the carbonation in step (3).
In any embodiment, the carbonization of the sodium carbonate is completed in step (3) when the pH of the solution is detected to be less than or equal to 8.5 and the gas is stopped.
In any embodiment, the carbon dioxide gas is recovered in step (5) for carbonation of the sodium carbonate in step (3).
In any embodiment, the sodium fluoride mother liquor produced by filtration in step (6) is returned to step (4) for recycle.
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 the sodium battery can be produced;
2. the purity requirement of production raw materials is reduced, the requirements of an electrolysis process and high tower equipment required by a raw material purification process are avoided, and the production efficiency of sodium fluoride is improved;
3. the process links of temperature swing crystallization and evaporation concentration are replaced and optimized, the temperature control only needs to consider the adsorption effect of the ion exchange resin, the water quantity of evaporation concentration is reduced, the energy consumption is also reduced, and the cost advantage is achieved;
4. carbon dioxide gas, sodium carbonate mother liquor and sodium fluoride mother liquor in the link can be recycled, so that resources are saved, and the production concept of green and environment protection is met.
5. The sodium fluoride is produced by using industrial soda ash, and the electronic-grade sodium fluoride can be obtained only by purifying production raw materials. The production by using sodium carbonate can reduce the generation amount of water, and the sodium carbonate is used as a strong alkali and weak acid salt to facilitate concentration control. The industrial sodium carbonate product is mature, the price is low, the purification process does not need electrolysis, the amount of solvent water after the reaction is less, the evaporation amount is reduced, and the cost of raw materials and energy consumption is reduced.
Detailed Description
Hereinafter, embodiments of the present process for producing electronic grade sodium fluoride by purifying technical grade soda ash are specifically disclosed with appropriate reference to the detailed description. But detailed description thereof will be omitted unnecessarily. For example, detailed descriptions of already known matters and repetitive descriptions of actually the same configurations may be omitted. This is to avoid unnecessarily obscuring the following description, and to facilitate understanding by those skilled in the art. The following description is provided for those skilled in the art to fully understand the present application, and is not intended to limit the subject matter described in the claims.
As disclosed herein, a "range" is defined in terms of lower and upper limits, with a given range being defined by the selection of one lower limit and one upper limit, which define the boundaries of the particular range. Ranges defined in this manner may or may not include endpoints and may be arbitrarily combined, i.e., any lower limit may 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 stated, 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, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is only a shorthand representation of the combination of these numbers. In addition, when a parameter is an integer of 2 or more, it is equivalent to disclose 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, if not specifically stated.
All technical and optional features of the present application may be combined with each other to form new solutions, if not specifically mentioned.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, if not specifically stated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, and may also comprise steps (b) and (a) performed sequentially. For example, reference to the process further comprising step (c) means that step (c) may be added to the process in any order, for example, the process may comprise steps (a), (b) and (c), may also comprise steps (a), (c) and (b), may also comprise steps (c), (a) and (b), etc.
The terms "comprises" and "comprising" as used herein mean either open or closed unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that other components not listed may also be included or included, or that only listed components may be included or included.
In this application, the term "or" is inclusive, if not 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 not present); a is false (or not present) and B is true (or present); or both a and B are true (or present).
A 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 filtering membrane;
(2) Filling a strong acid type cation resin absorption column, controlling the flow rate of the solution in the step (1) at 10-15V column/h for column passing treatment, and then carrying out activated carbon absorption column treatment after acid cleaning;
(3) Carbonizing a sodium carbonate solution, stirring and introducing carbon dioxide, separating the solution from solids, centrifugally filtering the solids, adding the solids into an oven, and heating at 150 ℃ to obtain purified sodium carbonate solids;
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 liquor, adjusting the temperature of the solution to 35 ℃, preparing a sodium carbonate solution with the concentration of 3.5mol/L, stirring and standing, leading out the solution, filtering by a filter membrane, and entering a neutralization tank; the solution was allowed to stand until the appearance was clear.
(5) Introducing the purified soda solution into a salt pond, heating and concentrating, and blowing hydrogen fluoride gas into the solution in an excessive amount to generate carbon dioxide gas, sodium fluoride crystals and a small amount of sodium fluoride; heating and concentrating the solution in the salt pond, adding a purified sodium carbonate solution to adjust the pH value of the solution to 6.7-7.0, continuously stirring, and judging that the reaction is finished when the test solution maintains neutrality;
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, performing centrifugal dehydration, 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 30 ℃ saturated sodium carbonate solution under the temperature condition of 40-50 ℃. The saturated solubility of sodium carbonate in water at 30 ℃ is nearly 40g/100g, which is a readily accessible substance. However, the volume of the mass of the material is nearly half of the volume of water, the dissolution speed is slow under the dissolution condition of 30 ℃, the burden of stirring is heavy due to a large amount of stockpiles, and the material is easy to accumulate at the bottom.
And the heating is carried out at the temperature of between 40 and 50 ℃, so that the dissolving speed can be greatly improved, the material accumulation is avoided, the filtering speed is also increased, and the efficiency of the step is generally improved. Purified sodium carbonate was added to the mother liquor and the temperature of the solution 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 circulated subsequently, and more specifically, the mother liquor refers to a solvent which is used for dissolving the industrial grade solid alkali raw material in the step 1 and is prepared into a saturated sodium carbonate solution at 30 ℃. Pure water is used for starting the mother liquor of the first circulation; the subsequent circulating mother liquor is a solution with a certain proportion of sodium fluoride after the product is filtered out in the previous circulation, and a certain proportion of pure water is supplemented; circulating to a certain degree to discharge all mother liquor, cleaning the mother liquor pool, and then starting from the beginning, namely, the mother liquor is pure water.
Preparing a sodium carbonate solution with the concentration of 3.5 mol/L. This concentration is lower than the maximum solubility of sodium carbonate in step (1) by about 15%, and is chosen to ensure conditions in which solid crystals will only form during the precipitation step in the overall industrial process, which is a consideration for safe and smooth operation of the system. The method also aims to reserve space for condition fluctuation in the whole production process flow, and simultaneously, after crystallization is finally separated out, the mother liquor is finally recycled, and a dissolving space is reserved to prevent solid accumulation in the flow.
And cooling the salt pond to 15 ℃. One option is to select this temperature as judged by the dissolution profile of sodium fluoride. The temperature is higher, the dissolving amount in water is more, and the single-batch output is less; the temperature is low again, the increase amplitude change of the precipitation amount is small, and the comparison of cooling energy consumption is not cost-effective. A calculated value belonging to an efficiency curve; secondly, the key point of the production process is the crystallization purification caused by the change of ion exchange and poor solubility, namely, the impurities are treated by exchange absorption, separation and retention, and the purity of the product can be controlled within 20 ppm.
Meanwhile, in process equipment, the invisible requirements of replacement and purification regeneration exist, more substances can be separated out at 15 ℃, and the separation variation range of impurities in a reasonable range is relatively stable, so that the product quality is more stable, 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 mode, after the filtering in the step (1) is finished, the solution is naturally cooled to 25 ℃, then the solution is cooled to 10 ℃ by induced cooling crystallization in a supercooling mode with an external cold source of 3-6 ℃, sodium carbonate crystals are filtered out, and nitrate radicals, sulfate radicals and other strong acid radicals in the sodium carbonate are removed.
In the treatment process, energy consumption is saved by natural cooling; the external supercooling cooling is adopted because the impurities in the solution are reduced after the sodium carbonate is heated, filtered and cooled, the solution is uniform and difficult to form crystal nucleus crystals, and the supercooling inducing solution induces the crystals due to uneven temperature.
For cold source temperature selection, the supercooling temperature is zero when being too low, so that the water content in the crystal is too high, and a strong acid radical of about 5ppm can be included on average, and 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 washed and soaked by 0.01mol/L hydrochloric acid, soaked by 1mol/L sodium hydroxide solution for regeneration for 2 to 3 times, and finally washed by pure water for column packing.
In any embodiment, the length-to-diameter ratio of the absorption column in step (2) is controlled to be between 15 and 20.
For the selection of the length-diameter ratio of the absorption column, the filtrate and the filter column need a certain exchange time to complete the exchange adsorption of ions, and the larger the length-diameter ratio is, the longer the contact time is. Long diameter less than 15K + The absorption rate of (2) is low, 10-20 ppm of residue is averagely left, and the content of metal impurities is greatly increased; the major-diameter ratio is higher than 20, and the filter tube is too long, and the phenomenon of filter tube filling unevenness is easy to appear at first, leads to the regional stagnation that flows of intraductal, appears solution and soaks the problem of ion exchange resin for a long time, leads to the high valence ion back-out such as calcium magnesium iron aluminium that absorbs.
In any embodiment, the sodium carbonate solution is heated to maintain a temperature of 31 ℃ to 35 ℃ during the carbonation in step (3).
In any embodiment, the carbonization of the sodium carbonate is completed in step (3) when the pH of the solution is detected to be less than or equal to 8.5 and the gas is stopped.
In any embodiment, the carbon dioxide gas water wash recovers the sodium carbonate used in step (3) in step (5) by carbonization.
In any embodiment, the saturated sodium fluoride solution produced in step (6) is filtered back to step (4) as the solvent. Namely, the solution after the sodium fluoride crystallization is filtered out, and the saturated sodium fluoride solution at 15 ℃ is the main part of the mother liquor of the next circulation.
Examples
Hereinafter, examples of the present application will be described. The following description of the embodiments is merely exemplary in nature and is in no way intended to limit the present disclosure. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
A 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; after filtering, naturally cooling the solution to 25 ℃, then cooling the solution to 10 ℃ in a supercooling mode of an external cold source at 3-6 ℃, filtering out sodium carbonate-water crystals, and removing nitrate radicals, sulfate radicals and other strong acid radicals in the sodium carbonate;
(2) Filling strong acid type cation resin absorption column, washing and soaking resin with 0.01mol/L hydrochloric acid, soaking and regenerating with 1mol/L sodium hydroxide solution for 2-3 times, and finally washing with pure water and filling column. The length-diameter ratio of the absorption column is controlled to be 15;
(3) Carbonizing a sodium carbonate solution, heating the sodium carbonate solution to maintain the temperature of 31-35 ℃, stirring and introducing carbon dioxide, stopping introducing gas when the PH is detected to be less than or equal to 8.5, separating the solution from a solid, centrifuging and filtering the solid to dry, adding the solid into an oven, and heating at 150 ℃ to obtain a purified sodium carbonate solid;
(4) Adding purified sodium carbonate into the mother liquor, adjusting the temperature of the solution to 35 ℃, preparing a sodium carbonate solution with the concentration of 3.5mol/L, stirring and standing, leading out the solution, filtering by a filter membrane, and feeding the solution into a neutralization tank;
(5) Introducing the purified soda solution into a salt pond, heating and concentrating, blowing hydrogen fluoride gas into the solution and enabling the hydrogen fluoride gas to be excessive to generate carbon dioxide gas, sodium fluoride crystals and a small amount of sodium fluoride, and recovering the carbon dioxide gas for sodium carbonate carbonization; heating and concentrating the solution in the salt pond, adjusting the pH of the solution, adding a purified solution of sodium carbonate, continuously stirring, and testing the pH = 6.7-7.0 of the solution to judge that the reaction is finished;
(6) And (3) cooling the salt pond to the room temperature of 15 ℃ to generate sodium fluoride crystals, filtering and dehydrating sodium fluoride solids, performing centrifugal dehydration, and drying under reduced pressure to obtain a high-purity sodium fluoride product, wherein the saturated sodium fluoride solution generated by filtering is returned to the step (4) to be used 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 filtering membrane; after filtering, naturally cooling the solution to 25 ℃, then cooling the solution to 10 ℃ in a supercooling mode of an external cold source at 3-6 ℃, filtering out sodium carbonate-water crystals, and removing strong acid radicals such as nitrate radicals, sulfate radicals and the like in the sodium carbonate;
(2) Filling strong acid type cation resin absorption columns, washing and soaking the resin by 0.01mol/L hydrochloric acid, soaking and regenerating the resin for 2-3 times by using 1mol/L sodium hydroxide solution, and finally washing the resin by using pure water to be clean and filling the resin into the columns. The length-diameter ratio of the absorption column is controlled to be 18;
(3) Carbonizing a sodium carbonate solution, heating the sodium carbonate solution to maintain the temperature of 31-35 ℃, stirring and introducing carbon dioxide, stopping introducing gas when the PH is detected to be less than or equal to 8.5, separating the solution from a solid, centrifuging and filtering the solid to dry, adding the solid into an oven, and heating at 150 ℃ to obtain a purified sodium carbonate solid;
(4) Adding purified sodium carbonate into the mother liquor, adjusting the temperature of the solution to 35 ℃, preparing a sodium carbonate solution with the concentration of 3.3mol/L, stirring and standing, leading out the solution, filtering by a filter membrane, and feeding the solution into a neutralization tank;
(5) Introducing the purified soda solution into a salt pond, heating and concentrating, blowing hydrogen fluoride gas into the solution and excessively adding the hydrogen fluoride gas to generate carbon dioxide gas, sodium fluoride crystals and a small amount of sodium fluoride, wherein the carbon dioxide gas is recovered and used for carbonizing sodium carbonate; heating and concentrating the solution in the salt pond, adjusting the pH of the solution, adding a purified solution of sodium carbonate, continuously stirring, and testing the pH = 6.7-7.0 of the solution to judge that the reaction is finished;
(6) And (3) cooling the salt pond to the room temperature of 15 ℃ to generate sodium fluoride crystals, filtering and dehydrating sodium fluoride solids, performing centrifugal dehydration, and drying under reduced pressure to obtain a high-purity sodium fluoride product, wherein the saturated sodium fluoride solution generated by filtering is returned to the step (4) to be used 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; after filtering, naturally cooling the solution to 25 ℃, then cooling the solution to 10 ℃ in a supercooling mode of an external cold source at 3-6 ℃, filtering out sodium carbonate-water crystals, and removing nitrate radicals, sulfate radicals and other strong acid radicals in the sodium carbonate;
(2) Filling strong acid type cation resin absorption column, washing and soaking resin with 0.01mol/L hydrochloric acid, soaking and regenerating with 1mol/L sodium hydroxide solution for 2-3 times, and finally washing with pure water and filling column. The length-diameter ratio of the absorption column is controlled to be 19;
(3) Carbonizing a sodium carbonate solution, heating the sodium carbonate solution to maintain the temperature of between 31 and 35 ℃, stirring, introducing carbon dioxide, detecting the pH value of less than or equal to 8.5, stopping introducing gas, separating the solution from solids, centrifugally filtering the solids, adding the solids into an oven, and heating at the temperature of 150 ℃ to obtain purified sodium carbonate solids;
(4) Adding purified sodium carbonate into the mother liquor, adjusting the temperature of the solution to 35 ℃, preparing a sodium carbonate solution with the concentration of 3.0mol/L, stirring and standing, leading out the solution, filtering by a filter membrane, and feeding the solution into a neutralization tank;
(5) Introducing the purified soda solution into a salt pond, heating and concentrating, blowing hydrogen fluoride gas into the solution and excessively adding the hydrogen fluoride gas to generate carbon dioxide gas, sodium fluoride crystals and a small amount of sodium fluoride, wherein the carbon dioxide gas is recovered and used for carbonizing sodium carbonate; heating and concentrating the solution in the salt pond, adjusting the pH of the solution, adding a purified solution of sodium carbonate, continuously stirring, and testing the pH = 6.7-7.0 of the solution to judge that the reaction is finished;
(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 drying under reduced pressure to obtain a high-purity sodium fluoride product, wherein the saturated sodium fluoride solution generated by filtering is returned to the step (4) to be used 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; after filtering, naturally cooling the solution to 25 ℃, then cooling the solution to 10 ℃ in a supercooling mode of an external cold source at 3-6 ℃, filtering out sodium carbonate-water crystals, and removing strong acid radicals such as nitrate radicals, sulfate radicals and the like in the sodium carbonate;
(2) Filling strong acid type cation resin absorption columns, washing and soaking the resin by 0.01mol/L hydrochloric acid, soaking and regenerating the resin for 2-3 times by using 1mol/L sodium hydroxide solution, and finally washing the resin by using pure water to be clean and filling the resin into the columns. The length-diameter ratio of the absorption column is controlled between 15 and 18, the flow rate of the solution passing through the column is controlled between 10 and 15V column/h, and the solution passes through the activated carbon absorption column after being treated by the acid washing column;
(3) Carbonizing a sodium carbonate solution, heating the sodium carbonate solution to maintain the temperature of between 31 and 35 ℃, stirring, introducing carbon dioxide, detecting the pH value of less than or equal to 8.5, stopping introducing gas, separating the solution from solids, centrifugally filtering the solids, adding the solids into an oven, and heating at the temperature of 150 ℃ to obtain purified sodium carbonate solids;
(4) Adding purified sodium carbonate into the mother liquor, adjusting the temperature of the solution to 35 ℃, preparing a sodium carbonate solution with the concentration of 3.7mol/L, stirring and standing, leading out the solution, filtering by a filter membrane, and feeding the solution into a neutralization tank;
(5) Introducing the purified soda solution into a salt pond, heating and concentrating, blowing hydrogen fluoride gas into the solution and enabling the hydrogen fluoride gas to be excessive to generate carbon dioxide gas, sodium fluoride crystals and a small amount of sodium fluoride, and recovering the carbon dioxide gas for sodium carbonate carbonization; heating and concentrating the solution in the salt pond, adjusting the pH of the solution, adding a purified solution of sodium carbonate, continuously stirring, and testing the pH = 6.7-7.0 of the solution to judge that the reaction is finished;
(6) And (3) cooling the salt pond to the room temperature of 15 ℃ to generate sodium fluoride crystals, filtering and dehydrating sodium fluoride solids, performing centrifugal dehydration, and drying under reduced pressure to obtain a high-purity sodium fluoride product, wherein the saturated sodium fluoride solution generated by filtering is returned to the step (4) to be used as a solvent.
The preparation method has the following test effects:
| item | 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 embodiments. The above embodiments are merely examples, and embodiments having substantially the same configuration as the technical idea and exhibiting the same operation and effect within the technical scope of the present application are included in the technical scope of the present application. In addition, various modifications that can be conceived by those skilled in the art are applied to the embodiments and other embodiments are also included in the scope of the present application, in which some of the constituent elements in the embodiments are combined and constructed, without departing from the scope of the present application.
Claims (8)
1. A preparation method for producing electronic-grade sodium fluoride by purifying industrial-grade sodium carbonate is characterized by comprising the following steps:
(1) Preparing saturated sodium carbonate solution, heating the solution to 40-50 ℃ to remove impurities;
(2) Strong acid type cation resin absorption column treatment;
(3) Carbonizing a sodium carbonate solution, separating the solution from solids, and drying to obtain purified sodium carbonate solids;
(4) Adding purified sodium carbonate into the mother liquor, preparing a sodium carbonate solution with the concentration of 3-4mol/L, filtering, and entering a neutralization tank; standing the solution until the appearance is clear;
(5) Introducing the purified soda solution into a salt pond, heating and concentrating, and blowing hydrogen fluoride gas into the solution; heating and concentrating the solution in the salt pond, and simultaneously adding a purified sodium carbonate solution to adjust the pH of the solution until the reaction is finished;
(6) And cooling the salt pond to 15 ℃ to generate sodium fluoride crystals, filtering and drying the sodium fluoride solids to obtain the high-purity sodium fluoride product.
2. The preparation method for producing electronic-grade sodium fluoride by purifying industrial-grade sodium carbonate according to claim 1, which is characterized by comprising the following steps:
(1) Preparing a 25-35 ℃ 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 500-1000 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) at 10-15V column/h for column treatment, and then treating the solution by an acid-washed activated carbon absorption column;
(3) Carbonizing a sodium carbonate solution, stirring and introducing carbon dioxide, then separating the solution from solids, centrifuging and filtering the solids to dryness, adding the solids into an oven, and heating at 150 ℃ to obtain purified sodium carbonate solids;
(4) Adding purified sodium carbonate into the mother liquor, adjusting the temperature of the solution to 35 ℃, preparing a sodium carbonate solution with the concentration of 3-4mol/L, stirring and standing, leading out the solution, filtering by a filter membrane, and feeding the solution into a neutralization tank; standing the solution until the appearance is clear;
(5) Introducing the purified sodium carbonate solution into a salt pond, heating and concentrating, blowing hydrogen fluoride gas into the solution and excessively adding the hydrogen fluoride gas to generate carbon dioxide gas, sodium fluoride crystals and a small amount of sodium fluoride; heating and concentrating the solution in the salt pond, adding a purified sodium carbonate solution to adjust the pH value of the solution to 6.7-7.0, continuously stirring, and judging that the reaction is finished when the test solution is kept neutral;
(6) And cooling the salt pond to 15 ℃ to generate sodium fluoride crystals, filtering and dehydrating sodium fluoride solids, performing centrifugal dehydration, and drying under reduced pressure to obtain a high-purity sodium fluoride product.
3. The preparation method for producing the electronic-grade sodium fluoride by purifying the industrial-grade sodium carbonate is characterized in that after the filtration in the step (1) is finished, the solution is naturally cooled to 25 ℃, then is cooled to 10 ℃ in a supercooling mode through an external cold source at the temperature of 3-6 ℃, and sodium carbonate-water crystals are filtered out to remove nitrate radicals, sulfate radicals and other strong acid radicals in the sodium carbonate.
4. The preparation method for producing electronic grade sodium fluoride according to claim 1 or 2, characterized in that in the step (2), the resin is washed and soaked with 0.01mol/L hydrochloric acid, then soaked and regenerated with 1mol/L sodium hydroxide solution for 2-3 times, and finally washed clean with pure water and packed into a column.
5. The process according to claim 1 or 2, wherein the sodium carbonate solution is heated to maintain a temperature of 31-35 ℃ during the carbonization step (3).
6. The method as claimed in claim 5, wherein the carbonization of sodium carbonate is completed when pH of the solution is detected to be less than or equal to 8.5 in step (3).
7. The process according to claim 2, wherein in step (5) carbon dioxide gas is recovered for carbonization of sodium carbonate in step (3).
8. The process for preparing sodium fluoride in electronic grade by purifying technical grade soda ash according to claim 1 or 2, characterized in that the saturated sodium fluoride solution produced by filtering in step (6) is returned to step (4).
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