CN114645287B - Method for preparing electronic grade sodium hydroxide, hydrochloric acid, hydrogen and chlorine by one-step electrolysis of sodium chloride - Google Patents
Method for preparing electronic grade sodium hydroxide, hydrochloric acid, hydrogen and chlorine by one-step electrolysis of sodium chloride Download PDFInfo
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- CN114645287B CN114645287B CN202210272985.8A CN202210272985A CN114645287B CN 114645287 B CN114645287 B CN 114645287B CN 202210272985 A CN202210272985 A CN 202210272985A CN 114645287 B CN114645287 B CN 114645287B
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- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 title claims abstract description 102
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 title claims abstract description 98
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 239000011780 sodium chloride Substances 0.000 title claims abstract description 49
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000000460 chlorine Substances 0.000 title claims abstract description 41
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 41
- 239000001257 hydrogen Substances 0.000 title claims abstract description 35
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 35
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 32
- 238000005868 electrolysis reaction Methods 0.000 title claims description 3
- 239000000706 filtrate Substances 0.000 claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 37
- 238000001914 filtration Methods 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 239000012498 ultrapure water Substances 0.000 claims abstract description 22
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 20
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 18
- -1 iron ions Chemical class 0.000 claims abstract description 14
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 12
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052742 iron Inorganic materials 0.000 claims abstract description 11
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229910001626 barium chloride Inorganic materials 0.000 claims abstract description 10
- 239000011575 calcium Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001422 barium ion Inorganic materials 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 239000011777 magnesium Substances 0.000 claims abstract description 9
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 9
- 239000000084 colloidal system Substances 0.000 claims abstract description 8
- 230000001105 regulatory effect Effects 0.000 claims abstract description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 5
- 239000010935 stainless steel Substances 0.000 claims abstract description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 17
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 16
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 16
- 230000002194 synthesizing effect Effects 0.000 claims description 9
- 229920006395 saturated elastomer Polymers 0.000 claims description 7
- 229910001424 calcium ion Inorganic materials 0.000 claims description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 claims 1
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 13
- 239000000047 product Substances 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 description 9
- 238000003860 storage Methods 0.000 description 8
- 238000000926 separation method Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 4
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/34—Simultaneous production of alkali metal hydroxides and chlorine, oxyacids or salts of chlorine, e.g. by chlor-alkali electrolysis
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B7/00—Halogens; Halogen acids
- C01B7/01—Chlorine; Hydrogen chloride
- C01B7/012—Preparation of hydrogen chloride from the elements
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D3/00—Halides of sodium, potassium or alkali metals in general
- C01D3/14—Purification
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/50—Processes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses a method for preparing electronic-grade sodium hydroxide, hydrochloric acid, hydrogen and chlorine by electrolyzing sodium chloride by a one-step method, belonging to the technical field of chemical products. Comprising the following steps: step 1, preparing an aqueous solution of sodium chloride from industrial sodium chloride by using ultrapure water, and filtering to remove colloid and solid particle impurities; step 2, collecting the filtrate in the step 1, adding excessive barium chloride solution for reaction, and filtering to remove sulfate ions after the reaction is completed; step 3, collecting the filtrate in the step 2, adding sodium carbonate solution for reaction, and filtering to remove calcium and magnesium and excessive barium ions after the reaction is completed; and 4, collecting the filtrate in the step 3, regulating the pH value to be in a range of 10-12 by using a NaOH solution, filtering to remove residual magnesium ions, recrystallizing the obtained filtrate, and removing iron ions to obtain the high-purity sodium chloride solid. The equipment and the pipeline used in the scheme are all stainless steel lined polytetrafluoroethylene, so that the pollution of foreign impurities is avoided, and various electronic chemicals can be obtained simultaneously by using the method.
Description
Technical Field
The invention relates to the technical field of chemical products, in particular to a method for preparing electronic-grade sodium hydroxide, hydrochloric acid, hydrogen and chlorine by electrolyzing sodium chloride through a one-step method.
Background
With the increasing development of technology, the demand for semiconductor materials is increasing, and the amount of electronic chemicals used in the production process is increasing year by year. The electronic chemical, also called ultra-clean high-purity reagent or process chemical, refers to chemical whose main component purity is greater than 99.99%, and impurity ions and particle number meet strict requirements. Is an indispensable liquid chemical material in the process of microelectronic and optoelectronic wet processes.
The current preparation process of electronic grade sodium hydroxide and hydrochloric acid is to remove metal ions from industrial grade sodium hydroxide and hydrochloric acid by multistage filtration, distillation, purification and other processes, so as to improve the purity and meet the requirements of electronic grade chemicals. The process flow is long, the operation is complex, the equipment requirement is high, and the productivity is low.
Disclosure of Invention
The invention aims at the problems and provides a method for preparing electronic-grade sodium hydroxide, hydrochloric acid, hydrogen and chlorine by electrolyzing sodium chloride by a one-step method.
The invention adopts the technical scheme that: a method for preparing electronic grade sodium hydroxide, hydrochloric acid, hydrogen and chlorine by electrolyzing sodium chloride by a one-step method, which comprises the following steps:
step 1, preparing an aqueous solution of sodium chloride from industrial sodium chloride by using ultrapure water, and then filtering to remove impurities such as colloid, solid particles and the like;
step 2, collecting the filtrate in the step 1, adding excessive barium chloride solution, stirring, naturally settling, and removing sulfate ions by adopting filtration;
step 3, collecting the filtrate in the step 2, adding sodium carbonate solution, and then filtering to remove calcium and magnesium and excessive barium ions;
step 4, collecting the filtrate in the step 3, regulating the pH value to be in a pH=10-12 range by using NaOH solution, removing residual magnesium ions, and removing iron ions from the filtrate through multiple recrystallization to obtain sodium chloride with the purity of 99.99%;
step 5, preparing the pure sodium chloride in the step 4 into an aqueous solution, pumping the aqueous solution into an electrolytic tank, introducing current, purifying and separating the electrolyzed chlorine and hydrogen by a chlorine separation device, and respectively storing the purified and separated chlorine and hydrogen in corresponding storage tanks;
and 6, synthesizing hydrogen chloride gas from high-purity chlorine and hydrogen through a tubular reactor, and then absorbing the hydrogen chloride gas by the high-purity water to generate electronic-grade hydrochloric acid.
Further, in the step 1, the aqueous solution of sodium chloride is a saturated aqueous solution.
Further, in the step 2, the barium chloride solution is 25-35% by mass, and the addition amount is 1.1 times of the sulfate ions.
Further, in the step 3, the mass fraction of the sodium carbonate solution is 15% -25% of the aqueous solution.
Further, in the step 5, the purified sodium chloride solid is prepared into a 20% -30% aqueous solution, and the electrolytic tank is stainless steel lined polytetrafluoroethylene.
Further, in the step 5, after the current is introduced, the voltage is controlled to be 5V-15V.
Further, in the step 6, the remaining electrolyte meets the requirement of electronic grade sodium hydroxide by measuring the content and metal ions.
Further, in the step 4, the pH of the prepared solution is=11.
Further, in the step 5, after the current is introduced, the voltage is controlled to be 8V-12V.
Furthermore, the equipment, the pipeline and the storage tank used in the method are all stainless steel lined with tetrafluoro.
The invention has the beneficial effects that:
1. the invention purifies sodium hydroxide and hydrochloric acid from the source, shortens the process flow, can obtain various electronic chemicals at the same time, and opens up a new path for the production of the electronic chemicals.
2. The scheme has simple operation, simple process, low operation energy consumption and high safety coefficient, meets the requirement of preparing the electronic grade sodium hydroxide and the hydrochloric acid by electrolyzing the sodium chloride in one step, and provides a new production path for the production of the electronic grade sodium hydroxide and the hydrochloric acid.
3. The storage tank, the pipeline and the filtering device used in the process are made of stainless steel, the inner wall of the container is specially treated and lined with the polytetrafluoroethylene anti-corrosion layer, so that chemical reaction with the reaction device is avoided in the preparation process, foreign impurities and metal ions are not brought in the whole process flow, and the purity requirement of the product is further ensured.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 is a schematic illustration of the operation of an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The whole scheme is as follows:
the main points of the present invention are as follows: firstly, the content of industrial sodium chloride is generally more than 98%, wherein the iodized content is 0.001%, the bromide content is 0.005%, the phosphate content is 0.005%, the heavy metal lead content is 0.0005%, the potassium content is 0.01%, the requirements of electronic chemicals are basically met, the sulfate content of high-content impurities is about 0.5%, the calcium ions are 0.2%, the magnesium ions are 0.008%, and the iron ions are 0.0004%, the requirements of reducing the calcium, magnesium, iron and sulfate ions to 500ppb are met, the purity of industrial sodium hydroxide and hydrochloric acid is improved through multistage filtration, purification, distillation and other processes, and the metal ions are removed, so that the requirements of the electronic chemicals are met;
the method comprises the steps of preparing electronic-grade sodium hydroxide, hydrochloric acid, hydrogen and chlorine from raw materials, separating the electrolyzed gas into the chlorine and the hydrogen through a chlorine separation device to be used as raw materials for synthesizing the hydrochloric acid, synthesizing the high-purity chlorine and the hydrogen into hydrogen chloride gas through a tubular reactor, and absorbing the hydrogen chloride gas through the high-purity water to obtain the electronic-grade hydrochloric acid, wherein iron ions, calcium ions, magnesium ions and sulfate ions can be controlled within 50ppb, and compared with the operation process of preparing the electronic-grade sodium hydroxide, the hydrochloric acid, the hydrogen and the chlorine from the industrial-grade sodium chloride in the prior art, the method is simpler, more convenient and more efficient.
Example 1
Referring to fig. 1, as shown in fig. 1, a method for preparing electronic grade sodium hydroxide, hydrochloric acid, hydrogen and chlorine by electrolyzing sodium chloride by a one-step method comprises the following steps:
step 1, preparing saturated aqueous sodium chloride solution from industrial sodium chloride by using ultrapure water, and filtering to remove colloid and solid particle impurities;
step 2, collecting the filtrate in the step 1, adding an excessive barium chloride solution with the mass fraction of 25% and the addition amount of 1.1 times of sulfate ions in the filtrate, stirring, naturally settling, and removing the sulfate ions by adopting filtration;
step 3, collecting the filtrate in the step 2, adding a sodium carbonate solution with the mass fraction of 15%, and then filtering to remove calcium and magnesium and excessive barium ions;
step 4, collecting the filtrate in the step 3, regulating the pH value to be pH=10 by using NaOH solution, removing residual magnesium ions, and removing iron ions from the filtrate through multiple recrystallization to obtain sodium chloride with the purity of 99.99%;
step 5, preparing the pure sodium chloride in the step 4 into a 20% aqueous solution by using ultrapure water, pumping the aqueous solution into an electrolytic tank, introducing current with the voltage of 5V, purifying and separating the electrolyzed chlorine and hydrogen by a chlorine separation device, and respectively storing the purified and separated chlorine and hydrogen in corresponding storage tanks;
and 6, synthesizing high-purity chlorine and hydrogen into hydrogen chloride gas through a tubular reactor, absorbing the hydrogen chloride gas by high-purity water to generate electronic-grade hydrochloric acid, and measuring the content and metal ions of the rest electrolyte to meet the requirement of electronic-grade sodium hydroxide.
Example two
Step 1, preparing saturated aqueous sodium chloride solution from industrial sodium chloride by using ultrapure water, and filtering to remove colloid and solid particle impurities;
step 2, collecting the filtrate in the step 1, adding an excessive barium chloride solution with the mass fraction of 26% and the addition amount of 1.1 times of sulfate ions in the filtrate, stirring, naturally settling, and removing the sulfate ions by adopting filtration;
step 3, collecting the filtrate in the step 2, adding 26% sodium carbonate solution by mass fraction, and then filtering to remove calcium and magnesium and excessive barium ions;
step 4, collecting the filtrate in the step 3, regulating the pH value to be in a pH=10.5 range by using NaOH solution, removing residual magnesium ions, and removing iron ions from the filtrate through multiple recrystallization to obtain sodium chloride with the purity of 99.99%;
step 5, preparing the pure sodium chloride obtained in the step 4 into a 23% aqueous solution by using ultrapure water, pumping into an electrolytic tank, introducing current with the voltage of 8V, purifying and separating the electrolyzed chlorine and hydrogen by a chlorine separation device, and then respectively storing the purified and separated chlorine and hydrogen into corresponding storage tanks;
and 6, synthesizing high-purity chlorine and hydrogen into hydrogen chloride gas through a tubular reactor, absorbing the hydrogen chloride gas by high-purity water to generate electronic-grade hydrochloric acid, and measuring the content and metal ions of the rest electrolyte to meet the requirement of electronic-grade sodium hydroxide.
Example III
Step 1, preparing saturated aqueous sodium chloride solution from industrial sodium chloride by using ultrapure water, and then filtering to remove impurities such as colloid, solid particles and the like;
step 2, collecting the filtrate in the step 1, adding an excessive barium chloride solution with the mass fraction of 27% and the addition amount of 1.1 times of sulfate ions in the filtrate, stirring, naturally settling, and removing the sulfate ions by adopting filtration;
step 3, collecting the filtrate in the step 2, adding 17% sodium carbonate solution by mass percent, and then filtering to remove calcium and magnesium and excessive barium ions;
step 4, collecting the filtrate in the step 3, regulating the pH value to be in a pH=11 range by using NaOH solution, removing residual magnesium ions, and removing iron ions from the filtrate through multiple recrystallization to obtain sodium chloride with the purity of 99.99%;
preparing the pure sodium chloride in the step (4) into a 26% aqueous solution by using ultrapure water, pumping the aqueous solution into an electrolytic tank, introducing current with the voltage of 10V, purifying and separating the electrolyzed chlorine and hydrogen by using a chlorine separation device, and storing the purified and separated chlorine and hydrogen in corresponding storage tanks respectively;
and 6, synthesizing high-purity chlorine and hydrogen into hydrogen chloride gas through a tubular reactor, absorbing the hydrogen chloride gas by high-purity water to generate electronic-grade hydrochloric acid, and measuring the content and metal ions of the rest electrolyte to meet the requirement of electronic-grade sodium hydroxide.
Example IV
Step 1, preparing saturated aqueous sodium chloride solution from industrial sodium chloride by using ultrapure water, and then filtering to remove impurities such as colloid, solid particles and the like;
step 2, collecting the filtrate in the step 1, adding an excessive barium chloride solution with the mass fraction of 29% and the addition amount of 1.1 times of sulfate ions in the filtrate, stirring, naturally settling, and removing the sulfate ions by adopting filtration;
step 3, collecting the filtrate in the step 2, adding a sodium carbonate solution with the mass fraction of 19%, and then filtering to remove calcium and magnesium and excessive barium ions;
step 4, collecting the filtrate in the step 3, regulating the pH value to be in a pH=11.5 range by using NaOH solution, removing residual magnesium ions, and removing iron ions from the filtrate through multiple recrystallization to obtain sodium chloride with the purity of 99.99%;
preparing the pure sodium chloride in the step (4) into 28% aqueous solution by using ultrapure water, pumping the aqueous solution into an electrolytic tank, introducing current with the voltage of 12V, purifying and separating the electrolyzed chlorine and hydrogen by using a chlorine separation device, and respectively storing the purified and separated chlorine and hydrogen in corresponding storage tanks;
and 6, synthesizing high-purity chlorine and hydrogen into hydrogen chloride gas through a tubular reactor, absorbing the hydrogen chloride gas by high-purity water to generate electronic-grade hydrochloric acid, and measuring the content and metal ions of the rest electrolyte to meet the requirement of electronic-grade sodium hydroxide.
Example five
Step 1, preparing saturated aqueous sodium chloride solution from industrial sodium chloride by using ultrapure water, and then filtering to remove impurities such as colloid, solid particles and the like;
step 2, collecting the filtrate in the step 1, adding an excessive barium chloride solution with the mass fraction of 30% and the addition amount of 1.1 times of sulfate ions in the filtrate, stirring, naturally settling, and removing the sulfate ions by adopting filtration;
step 3, collecting the filtrate in the step 2, adding a sodium carbonate solution with the mass fraction of 20%, and then filtering to remove calcium and magnesium and excessive barium ions;
step 4, collecting the filtrate in the step 3, regulating the pH value to be in a pH=12 range by using NaOH solution, removing residual magnesium ions, and removing iron ions from the filtrate through multiple recrystallization to obtain sodium chloride with the purity of 99.99%;
step 5, preparing the pure sodium chloride in the step 4 into 30% aqueous solution by using ultrapure water, pumping the aqueous solution into an electrolytic tank, introducing current with the voltage of 15V, purifying and separating the electrolyzed chlorine and hydrogen by a chlorine separation device, and respectively storing the purified and separated chlorine and hydrogen in corresponding storage tanks;
and 6, synthesizing high-purity chlorine and hydrogen into hydrogen chloride gas through a tubular reactor, absorbing the hydrogen chloride gas by high-purity water to generate electronic-grade hydrochloric acid, and measuring the content and metal ions of the rest electrolyte to meet the requirement of electronic-grade sodium hydroxide.
The foregoing description of the preferred embodiments of the invention is not intended to limit the invention to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the invention are intended to be included within the scope of the invention.
Claims (4)
1. A method for preparing electronic grade sodium hydroxide, hydrochloric acid, hydrogen and chlorine by electrolyzing sodium chloride by a one-step method, which is characterized by comprising the following steps:
step 1, preparing an aqueous solution of sodium chloride from industrial sodium chloride by using ultrapure water, and filtering to remove colloid and solid particle impurities;
step 2, collecting the filtrate in the step 1, adding excessive barium chloride solution for reaction, and filtering to remove sulfate ions after the reaction is completed;
step 3, collecting the filtrate in the step 2, adding sodium carbonate solution for reaction, and filtering to remove calcium and magnesium and excessive barium ions after the reaction is completed;
step 4, collecting the filtrate in the step 3, regulating the pH value to be in the range of 10-12 by using NaOH solution, filtering to remove residual magnesium ions, recrystallizing the obtained filtrate, and removing iron ions to obtain high-purity sodium chloride solid;
step 5, preparing the high-purity sodium chloride solid in the step 4 into an aqueous solution by using ultrapure water, electrolyzing to obtain chlorine, hydrogen and electronic-grade sodium hydroxide,
step 6, synthesizing hydrogen chloride gas by reacting high-purity chlorine and hydrogen, and then generating electronic-grade hydrochloric acid by absorbing the hydrogen chloride gas with the high-purity water;
in the step 5, preparing 20% -30% aqueous solution of purified sodium chloride solid, wherein the used electrolytic tank is a stainless steel lining polytetrafluoroethylene electrolytic tank;
in the step 2, the mass fraction of the barium chloride solution is 25% -35%, and the molar ratio of barium ions to sulfate ions is 1.1-1.5;
in the step 3, the mass fraction of the sodium carbonate solution is 15% -25% of the aqueous solution, and the addition amount is 1.1 times of the total amount of calcium and magnesium ions;
in the step 5, the electrolysis conditions are as follows: the voltage is 5V-15V.
2. The method for preparing electronic grade sodium hydroxide, hydrochloric acid, hydrogen and chlorine by electrolyzing sodium chloride according to claim 1, wherein in the step 1, the aqueous sodium chloride solution is a saturated aqueous solution.
3. The method for preparing electronic grade sodium hydroxide, hydrochloric acid, hydrogen and chlorine gas by electrolyzing sodium chloride according to claim 1, wherein in the step 4, the pH of the prepared solution is=11.
4. The method for preparing electronic grade sodium hydroxide, hydrochloric acid, hydrogen and chlorine by electrolyzing sodium chloride according to claim 1, wherein in the step 5, the voltage is controlled to be 8V-12V after the current is introduced.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210272985.8A CN114645287B (en) | 2022-03-18 | 2022-03-18 | Method for preparing electronic grade sodium hydroxide, hydrochloric acid, hydrogen and chlorine by one-step electrolysis of sodium chloride |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210272985.8A CN114645287B (en) | 2022-03-18 | 2022-03-18 | Method for preparing electronic grade sodium hydroxide, hydrochloric acid, hydrogen and chlorine by one-step electrolysis of sodium chloride |
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| CN114645287A CN114645287A (en) | 2022-06-21 |
| CN114645287B true CN114645287B (en) | 2024-02-06 |
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| CN202210272985.8A Active CN114645287B (en) | 2022-03-18 | 2022-03-18 | Method for preparing electronic grade sodium hydroxide, hydrochloric acid, hydrogen and chlorine by one-step electrolysis of sodium chloride |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4155820A (en) * | 1977-04-20 | 1979-05-22 | Asahi Kasei Kogyo Kabushiki Kaisha | Purification of aqueous sodium chloride solution |
| JP2002167218A (en) * | 2000-09-13 | 2002-06-11 | Asahi Glass Co Ltd | Refining method for alkaline metal chloride and manufacturing method for alkaline metal hydroxide |
| CN103482658A (en) * | 2013-09-27 | 2014-01-01 | 江苏久吾高科技股份有限公司 | Membrane refining process of medicinal sodium chloride |
| CN105540958A (en) * | 2016-01-26 | 2016-05-04 | 河北省电力勘测设计研究院 | Zero-discharge treatment process of power plant wastewater |
| CN109384198A (en) * | 2018-12-13 | 2019-02-26 | 中南大学 | A method of hydrochloric acid is produced with sodium chloride |
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2022
- 2022-03-18 CN CN202210272985.8A patent/CN114645287B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4155820A (en) * | 1977-04-20 | 1979-05-22 | Asahi Kasei Kogyo Kabushiki Kaisha | Purification of aqueous sodium chloride solution |
| JP2002167218A (en) * | 2000-09-13 | 2002-06-11 | Asahi Glass Co Ltd | Refining method for alkaline metal chloride and manufacturing method for alkaline metal hydroxide |
| CN103482658A (en) * | 2013-09-27 | 2014-01-01 | 江苏久吾高科技股份有限公司 | Membrane refining process of medicinal sodium chloride |
| CN105540958A (en) * | 2016-01-26 | 2016-05-04 | 河北省电力勘测设计研究院 | Zero-discharge treatment process of power plant wastewater |
| CN109384198A (en) * | 2018-12-13 | 2019-02-26 | 中南大学 | A method of hydrochloric acid is produced with sodium chloride |
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| CN114645287A (en) | 2022-06-21 |
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