CN107904618B - Method for preparing parallel-connection hydrogen halide acid by four-chamber three-membrane electrolysis of short-chain quaternary ammonium hydroxide - Google Patents
Method for preparing parallel-connection hydrogen halide acid by four-chamber three-membrane electrolysis of short-chain quaternary ammonium hydroxide Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 28
- 125000001453 quaternary ammonium group Chemical group 0.000 title claims abstract description 28
- 239000002253 acid Substances 0.000 title claims abstract description 18
- 239000000908 ammonium hydroxide Substances 0.000 title claims abstract description 18
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 15
- 239000012433 hydrogen halide Substances 0.000 title claims abstract description 6
- 229910000039 hydrogen halide Inorganic materials 0.000 title claims abstract description 6
- -1 halogen ions Chemical class 0.000 claims abstract description 51
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 29
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 150000001450 anions Chemical class 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 150000002367 halogens Chemical class 0.000 claims abstract description 16
- 230000009471 action Effects 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 6
- 238000004821 distillation Methods 0.000 claims abstract description 5
- 125000002091 cationic group Chemical group 0.000 claims abstract description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 22
- 150000001768 cations Chemical class 0.000 claims description 17
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 6
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 abstract description 14
- 230000007613 environmental effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000002808 molecular sieve Substances 0.000 description 7
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 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 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 4
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 229910052794 bromium Inorganic materials 0.000 description 3
- 238000000909 electrodialysis Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 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 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- JQDCIBMGKCMHQV-UHFFFAOYSA-M diethyl(dimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)CC JQDCIBMGKCMHQV-UHFFFAOYSA-M 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- UKHWJBVVWVYFEY-UHFFFAOYSA-M silver;hydroxide Chemical compound [OH-].[Ag+] UKHWJBVVWVYFEY-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- YMBCJWGVCUEGHA-UHFFFAOYSA-M tetraethylammonium chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC YMBCJWGVCUEGHA-UHFFFAOYSA-M 0.000 description 1
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 1
- QVOFCQBZXGLNAA-UHFFFAOYSA-M tributyl(methyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(CCCC)CCCC QVOFCQBZXGLNAA-UHFFFAOYSA-M 0.000 description 1
- JAJRRCSBKZOLPA-UHFFFAOYSA-M triethyl(methyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(CC)CC JAJRRCSBKZOLPA-UHFFFAOYSA-M 0.000 description 1
- OLNCQUXQEJCISO-UHFFFAOYSA-M trimethyl(propyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](C)(C)C OLNCQUXQEJCISO-UHFFFAOYSA-M 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- 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
- C25B3/00—Electrolytic production of organic compounds
-
- 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
- C25B1/24—Halogens or compounds thereof
-
- 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
- C25B1/24—Halogens or compounds thereof
- C25B1/26—Chlorine; Compounds thereof
-
- 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
- C25B13/00—Diaphragms; Spacing elements
- C25B13/02—Diaphragms; Spacing elements characterised by shape or form
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- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
- C25B9/17—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof
- C25B9/19—Cells comprising dimensionally-stable non-movable electrodes; Assemblies of constructional parts thereof with diaphragms
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for preparing parallel hydrogen halide acid by four-chamber three-membrane electrolysis of short-chain quaternary ammonium hydroxide, which comprises the following steps: (1) the halogenated short-chain quaternary ammonium salt enters a raw material chamber of a four-chamber three-membrane electrolytic cell, under the action of potential, halogen ions selectively move to an intermediate chamber through an anion membrane and combine with hydrogen cations transferred from an anode chamber to form halogen acid; quaternary ammonium cations in the raw material chamber selectively migrate to the cathode chamber through the cationic membrane under the action of potential, and hydroxide anions in the cathode chamber are combined with the quaternary ammonium cations migrated from the raw material chamber to obtain a product, namely short-chain quaternary ammonium hydroxide; (2) continuously taking out part of the feed liquid in the cathode chamber after the concentration of the feed liquid reaches 25 percent to obtain a high-purity short-chain quaternary ammonium alkali aqueous solution; (3) continuously replenishing halogenated short-chain quaternary ammonium salt aqueous solution in the material chamber, continuously taking out part of the material liquid in the middle chamber after the concentration of the material liquid reaches 10%, and preparing the halogen acid by distillation and concentration. The invention can meet the green and environmental protection requirements of producing high-purity short-chain quaternary ammonium hydroxide by an ion membrane electrolysis method.
Description
Technical Field
The invention relates to a method for preparing parallel hydrogen halide acid by four-chamber three-membrane electrolysis of short-chain quaternary ammonium hydroxide.
Background
From the middle of the 50 s of the 20 th century, the preparation and application of zeolite molecular sieves are rapidly developed, and the application and industrial development of the molecular sieves are greatly promoted by the comprehensive development from low-silicon aluminum to medium-silicon aluminum to high-silicon aluminum. The application of the template agent in the synthesis brings qualitative leap for the synthesis work of the molecular sieve. The template agent acts as a structural template during the molecular sieve generation process, resulting in the generation of a specific structure with a specific catalytic function. Some molecular sieves have only been found to be very limited, even if successfully synthesized under the action of a unique matching templating agent.
Short-chain quaternary ammonium hydroxide includes tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, methyl triethyl ammonium hydroxide, dimethyl diethyl ammonium hydroxide, trimethyl propyl ammonium hydroxide, methyl tributyl ammonium hydroxide and the like, and is mainly prepared by an inorganic alkali ion replacement method, a resin exchange method, an electrodialysis method and an ion membrane electrolysis method which take halogenated short-chain quaternary ammonium salt as a raw material at present.
And (3) carrying out ion replacement on the halogenated short-chain quaternary ammonium salt and inorganic alkali such as sodium hydroxide, potassium hydroxide, silver hydroxide and the like to generate quaternary ammonium hydroxide.
The short-chain quaternary ammonium salt halide is used as a raw material to generate silver halide precipitate with silver oxide in water to prepare the short-chain quaternary ammonium hydroxide. The defects are as follows: the cost of using precious metal raw materials is too high, and a small amount of silver ion remains.
The halogenated short-chain quaternary ammonium salt is taken as a raw material and is subjected to ion displacement reaction with potassium hydroxide in a solvent such as methanol or ethanol and the like to separate potassium halide precipitate so as to prepare the short-chain quaternary ammonium hydroxide. The defects are as follows: the product contains flammable and explosive organic solvent, the product yield is lower by about 85 percent, the product quality is poor, the content of halide ions and alkali metal ions in the product reaches about 2000PPM, and the product is used as a template agent to prepare the molecular sieve, so that the catalytic activity of the molecular sieve can be reduced.
The halogenated short-chain quaternary ammonium salt aqueous solution is taken as a raw material to carry out ion exchange with strong-base ion exchange resin to prepare the short-chain quaternary ammonium base. The defects are that the resin is regenerated frequently, a large amount of waste water containing sodium hydroxide and halide ions is generated, the product quality is poor, and the product contains halide ions and alkali metal ions because the ion exchange rate does not reach 100 percent and the residue of regenerated sodium hydroxide.
The method is characterized in that halogenated short-chain quaternary ammonium salt aqueous solution is used as a raw material, and short-chain quaternary ammonium hydroxide is prepared by using reverse migration of anions and cations under the action of an electric field and selective permeability of an electrodialysis ionic membrane through electrodialysis equipment. The defects are low current density, low production efficiency, low feed liquid concentration and high energy consumption in later-stage concentration.
The method is characterized in that halogenated short-chain quaternary ammonium salt aqueous solution is used as a raw material, and the short-chain quaternary ammonium hydroxide is prepared by utilizing the reverse migration of anions and cations under the action of an electric field, the selective permeability of an electrolytic ion membrane and the reduction reaction of a cathode chamber through ion membrane electrolysis equipment. The current density is high, the production efficiency is high, the concentration of the feed liquid is higher, the energy consumption of later-stage concentration is reduced, and the anion and cation impurities of the product are low.
Quaternary ammonium salt ion membrane electrolysis is used for preparing quaternary ammonium base, and a patent with the application number of CN201210359679.4 discloses a method for preparing high-purity quaternary ammonium base by electrolyzing organic ammonium salt by a perfluorinated ion exchange membrane method for chlor-alkali; patent No. CN201110380374.7 discloses a continuous method for preparing electronic grade tetramethylammonium hydroxide; the patent with the application number of CN200910099696.7 discloses a preparation method of high-efficiency tetramethyl ammonium hydroxide; patent application No. CN201310326292.3 discloses an apparatus and method for continuously preparing tetramethylammonium hydroxide; patent application No. CN201310429174.5 discloses a method for preparing high-purity tetraethylammonium hydroxide by continuous electrolysis; the patent with the application number of CN201410296295.1 discloses a device and a method for preparing high-purity tetrapropyl ammonium hydroxide and co-producing bromine by electrolysis; patent No. CN201410516813.6 discloses a method for preparing high-purity tetrabutylammonium hydroxide by continuous electrolysis.
Disclosure of Invention
The invention is realized by adopting the following scheme:
the method for preparing the parallel hydrogen halide acid by four-chamber three-membrane electrolysis of the short-chain quaternary ammonium hydroxide comprises the following specific steps: (1) the halogenated short-chain quaternary ammonium salt enters a raw material chamber of a four-chamber three-membrane electrolytic cell, under the action of potential, halogen ions selectively move to an intermediate chamber through an anion membrane and combine with hydrogen cations transferred from an anode chamber to form halogen acid; water molecules on an anode plate of the anode chamber are subjected to a de-electron reaction to generate oxygen and hydrogen cations, and the hydrogen cations pass through a cation membrane under the action of potential and migrate to the intermediate chamber; quaternary ammonium cations in the raw material chamber selectively migrate to the cathode chamber through the cationic membrane under the action of potential, water molecules on the cathode plate of the cathode chamber undergo an electronic reaction to generate hydrogen and hydroxyl anions, the hydroxyl anions are combined with the quaternary ammonium cations migrated from the raw material chamber to obtain a short-chain quaternary ammonium hydroxide product, and the continuous operation molar yield is close to 100%; (2) continuously taking out part of feed liquid in a cathode chamber after the concentration of the feed liquid in the cathode chamber reaches 25 percent to obtain a high-purity short-chain quaternary ammonium alkali aqueous solution; (3) continuously replenishing halogenated short-chain quaternary ammonium salt aqueous solution in the material chamber, continuously taking out part of the material liquid in the middle chamber after the concentration of the material liquid reaches 10%, and preparing the halogen acid by distillation and concentration.
According to the invention, by improving the ion membrane electrolysis equipment and process conditions, a four-chamber three-membrane method is improved and used on the basis of a single-membrane method and a double-membrane method to prepare short-chain quaternary ammonium hydroxide and produce halogen acid in parallel, so that the deterioration of the oxidation of halogen cations in the single-membrane method and the double-membrane method to the ion membrane is avoided, and halogen anions are recycled by co-producing the halogen acid. The method uses the four-cavity three-membrane type electrolytic cell to co-produce the halogen acid, eliminates the deterioration effect of the oxidability of the halogen simple substance generated in the electrolytic process on the anion membrane, improves the service life of the anion membrane, achieves the stable, continuous and large-scale production of the high-purity short-chain quaternary ammonium base, recycles the halogen anion to generate the hydrochloric acid, and realizes the green and environment-friendly requirements of the ion membrane electrolytic method for producing the high-purity short-chain quaternary ammonium base.
The invention has the advantages that: 1. by using a four-cavity three-membrane electrolytic cell and utilizing the selective permeability of the anion and cation membrane to anions and cations, the quaternary ammonium cations and the halogen anions are effectively separated, the bromine and the quaternary ammonium bromide are prevented from generating water-insoluble tribromide compound solids to block pipelines and liquid flow passages of the electrolytic cell, and the content of the halogen ions in the product is reduced. 2. The four-cavity three-membrane electrolytic cell is used, the cation membrane is used for preventing halogen from entering the anode chamber, the degradation effect of the oxidizing property of a halogen simple substance generated by halogen ions on the anode plate on the anion membrane is avoided, the service life of the anion membrane is prolonged from 30-60 days to more than 300 days, and the production cost is reduced. 3. The four-cavity three-membrane electrolytic cell is used for preventing the elementary bromine from being attached to the anode plate when the quaternary ammonium bromide is used as the raw material, so that the anode plate is prevented from being electrically corroded by breakdown, and the service life of the anode plate is prolonged. 4. The four-cavity three-membrane electrolytic cell is used, halogen ions in the halogenated quaternary ammonium salt are recycled, high-purity halogen acid is co-produced, the generation of low-purity byproducts is reduced, and the green environment-friendly process requirement of no waste water and waste solid is met.
Drawings
FIG. 1 is an electrolytic schematic diagram of a four-chamber three-membrane electrolytic cell.
Detailed Description
Example 1
As shown in fig. 1, a four-chamber three-membrane electrolytic cell, in which an anode plate is a titanium substrate coated with an oxygen-evolving coating, a cathode plate is nickel, a cation membrane is a dupont cation membrane, an anion membrane is an asahi nitroxide anion membrane, a 50% tetramethylammonium chloride aqueous solution is placed in a raw material circulation tank, a pump is used to circulate in a raw material chamber and the raw material circulation tank, pure water is added in a cathode circulation tank, a pump is used to circulate in a cathode chamber and a cathode circulation tank, pure water is added in a hydrochloric acid circulation tank, a pump is used to circulate in an intermediate chamber and a hydrochloric acid circulation tank, a 0.1% sulfuric acid aqueous solution is added as a conductive agent in an anode circulation tank, a pump is used to circulate in an anode chamber and an anode circulation tank, a current between the two electrodes is switched on, and tetramethylammonium. The main content of the prepared tetramethyl ammonium hydroxide is 25%, the color number of the prepared tetramethyl ammonium hydroxide is less than 20 Hazeng, the ion content of potassium, sodium, calcium, magnesium and iron is less than 10PPM, the ion content of halogen is less than 10PPM, and the residue content of organic solvent is less than 100 PPM. After the hydrochloric acid in the intermediate chamber is concentrated, the hydrochloric acid co-produced reaches the index requirement of GB/T622-. The device can stably and continuously run for 100 days, and the anion and cation membranes have no perforation and other obvious deteriorations.
The working principle of the preparation process is as follows: the tetramethylammonium chloride aqueous solution enters a four-chamber three-membrane electrolytic cell raw material chamber, under the action of potential, halogen ions selectively move to an intermediate chamber through an anion membrane, and combine with hydrogen cations transferred from an anode chamber to form halogen acid; water molecules on an anode plate of the anode chamber are subjected to a de-electron reaction to generate oxygen and hydrogen cations, and the hydrogen cations pass through a cation membrane under the action of potential and migrate to the intermediate chamber; selectively transferring quaternary ammonium cations in the raw material chamber to the cathode chamber through a cationic membrane under the action of potential, carrying out electronic reaction on water molecules on a cathode plate of the cathode chamber to generate hydrogen and hydroxyl anions, combining the hydroxyl anions with the quaternary ammonium cations transferred from the raw material chamber to obtain a product short-chain quaternary ammonium hydroxide, and continuously taking out a part of the feed liquid in the cathode chamber after the concentration of the feed liquid in the cathode chamber reaches 25% to obtain a product high-purity tetramethylammonium hydroxide aqueous solution; in the preparation process, the tetramethylammonium chloride aqueous solution is continuously supplemented into the raw material chamber, the continuous part of the feed liquid in the intermediate chamber is taken out after the concentration of the feed liquid reaches 10 percent, the hydrohalic acid is prepared by distillation and concentration, and the residual water after distillation is returned to the intermediate chamber for recycling.
Example 2
The starting material was 50% tetraethylammonium chloride in water, otherwise the same as in example 1. The main content of the prepared tetraethyl ammonium hydroxide is 25%, the tetraethyl ammonium hydroxide is colorless transparent liquid, the color number is less than 20 Hazeng, the ion content of potassium, sodium, calcium, magnesium and iron is less than 10PPM, the ion content of halogen is less than 10PPM, and the residue content of organic solvent is less than 100 PPM. After the hydrochloric acid in the intermediate chamber is concentrated, the hydrochloric acid co-produced reaches the index requirement of GB/T622-. The device can stably and continuously run for 100 days, and the anion and cation membranes have no perforation and other obvious deteriorations.
Example 3
The starting material was 50% tetrapropylammonium bromide in water, and the procedure was otherwise as in example 1. The prepared tetrapropylammonium hydroxide contains 25% of main content, is colorless transparent liquid, has the color number lower than 20 Hazeng, has the potassium, sodium, calcium, magnesium and iron ions lower than 10PPM, has the halogen ions lower than 10PPM, and has the organic solvent residue lower than 100 PPM. After the hydrochloric acid in the middle chamber is concentrated, the hydrobromic acid co-produced reaches the index requirement of GB/T621-2015 chemical reagent hydrobromic acid. The device can stably and continuously run for 150 days, and the anion and cation membranes have no perforation and other obvious deteriorations.
Example 4
The starting material was 50% aqueous tetrabutylammonium bromide, otherwise the same as in example 1. The prepared tetrabutyl ammonium hydroxide contains 25% of main components, is colorless transparent liquid, has the color number lower than 20 Hazeng, has the potassium, sodium, calcium, magnesium and iron ions lower than 10PPM, has the halogen ions lower than 10PPM, and has the organic solvent residue lower than 100 PPM. After the hydrochloric acid in the middle chamber is concentrated, the hydrobromic acid co-produced reaches the index requirement of GB/T621-2015 chemical reagent hydrobromic acid. The device can stably and continuously run for 150 days, and the anion and cation membranes have no perforation and other obvious deteriorations.
Claims (1)
1. The method for preparing the parallel hydrogen halide acid by four-chamber three-membrane electrolysis of the short-chain quaternary ammonium hydroxide comprises the following specific steps: (1) the halogenated short-chain quaternary ammonium salt enters a raw material chamber of a four-chamber three-membrane electrolytic cell, under the action of potential, halogen ions selectively move to an intermediate chamber through an anion membrane and combine with hydrogen cations transferred from an anode chamber to form halogen acid; water molecules on an anode plate of the anode chamber are subjected to a de-electron reaction to generate oxygen and hydrogen cations, and the hydrogen cations pass through a cation membrane under the action of potential and migrate to the intermediate chamber; quaternary ammonium cations in the raw material chamber selectively migrate to the cathode chamber through the cationic membrane under the action of potential, water molecules on the cathode plate of the cathode chamber undergo an electronic reaction to generate hydrogen and hydroxyl anions, the hydroxyl anions are combined with the quaternary ammonium cations migrated from the raw material chamber to obtain a short-chain quaternary ammonium hydroxide product, and the continuous operation molar yield is close to 100%; (2) continuously taking out part of feed liquid in a cathode chamber after the concentration of the feed liquid in the cathode chamber reaches 25 percent to obtain a high-purity short-chain quaternary ammonium alkali aqueous solution; (3) continuously replenishing halogenated short-chain quaternary ammonium salt aqueous solution in the material chamber, continuously taking out part of the material liquid in the middle chamber after the concentration of the material liquid reaches 10%, and preparing halogen acid by distillation and concentration;
the four-chamber three-membrane electrolytic cell is characterized in that an anode plate is a titanium substrate coated with an oxygen evolution coating, a cathode plate is nickel, a cation membrane is a DuPont cation membrane, an anion membrane is an Asahi nitroxide anion membrane, a 50% tetramethylammonium chloride aqueous solution is placed in a raw material circulating tank, a pump is used for circulating in the raw material chamber and the raw material circulating tank, pure water is added into a cathode circulating tank, a pump is used for circulating in a cathode chamber and a cathode circulating tank, pure water is added into a hydrochloric acid circulating tank, a pump is used for circulating in an intermediate chamber and the hydrochloric acid circulating tank, a 0.1% sulfuric acid aqueous solution is added into an anode circulating tank as a conductive agent, the pump is used for circulating in the anode chamber and the anode circulating tank, the current between the two electrodes is switched on, and tetramethylammonium hydroxide is prepared by continuous electrolysis under the voltage of 8V of a.
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| CN113265683A (en) * | 2021-05-12 | 2021-08-17 | 肯特催化材料股份有限公司 | High-efficiency production process of tetrapropylammonium hydroxide and tetrapropylammonium hydroxide aqueous solution prepared by high-efficiency production process |
| CN113463118B (en) * | 2021-05-12 | 2022-03-11 | 肯特催化材料股份有限公司 | Energy-saving production process of tetrapropylammonium hydroxide and tetrapropylammonium hydroxide aqueous solution prepared by same |
| CN113235117B (en) * | 2021-05-12 | 2022-02-22 | 肯特催化材料股份有限公司 | Production process of high-concentration tetrapropylammonium hydroxide and high-concentration tetrapropylammonium hydroxide prepared by same |
| CN113981476A (en) * | 2021-09-17 | 2022-01-28 | 镇江润晶高纯化工科技股份有限公司 | Preparation method of energy-saving tetraethylammonium hydroxide with high production efficiency |
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