CN1523135A - Process for preparing tetramethyl ammonium hydroxide by electrolysis-electrodialysis - Google Patents
Process for preparing tetramethyl ammonium hydroxide by electrolysis-electrodialysis Download PDFInfo
- Publication number
- CN1523135A CN1523135A CNA03106227XA CN03106227A CN1523135A CN 1523135 A CN1523135 A CN 1523135A CN A03106227X A CNA03106227X A CN A03106227XA CN 03106227 A CN03106227 A CN 03106227A CN 1523135 A CN1523135 A CN 1523135A
- Authority
- CN
- China
- Prior art keywords
- tetramethylammonium
- electrolysis
- cathode
- anode
- tetramethyl ammonium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 title claims abstract description 100
- 238000000909 electrodialysis Methods 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title description 4
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 15
- 239000010439 graphite Substances 0.000 claims abstract description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 10
- 239000010935 stainless steel Substances 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 239000012528 membrane Substances 0.000 claims description 24
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical class [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 239000010406 cathode material Substances 0.000 claims description 9
- 125000002091 cationic group Chemical group 0.000 claims description 5
- 239000012043 crude product Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 4
- ABDBNWQRPYOPDF-UHFFFAOYSA-N carbonofluoridic acid Chemical compound OC(F)=O ABDBNWQRPYOPDF-UHFFFAOYSA-N 0.000 claims description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims description 4
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910000457 iridium oxide Inorganic materials 0.000 claims description 4
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910000497 Amalgam Inorganic materials 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000010405 anode material Substances 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 3
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 3
- MRYQZMHVZZSQRT-UHFFFAOYSA-M tetramethylazanium;acetate Chemical compound CC([O-])=O.C[N+](C)(C)C MRYQZMHVZZSQRT-UHFFFAOYSA-M 0.000 claims description 3
- WWIYWFVQZQOECA-UHFFFAOYSA-M tetramethylazanium;formate Chemical compound [O-]C=O.C[N+](C)(C)C WWIYWFVQZQOECA-UHFFFAOYSA-M 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- VFHDWENBWYCAIB-UHFFFAOYSA-M hydrogen carbonate;tetramethylazanium Chemical compound OC([O-])=O.C[N+](C)(C)C VFHDWENBWYCAIB-UHFFFAOYSA-M 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 9
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 22
- -1 halogen ions Chemical class 0.000 description 9
- 239000012535 impurity Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- KIWQCVMQMWPCJB-UHFFFAOYSA-N [Ti].[Ir]=O Chemical compound [Ti].[Ir]=O KIWQCVMQMWPCJB-UHFFFAOYSA-N 0.000 description 3
- RQVJYRSUFJTNEP-UHFFFAOYSA-N [Ti].[Ru]=O Chemical compound [Ti].[Ru]=O RQVJYRSUFJTNEP-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229910001923 silver oxide Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WJZPIORVERXPPR-UHFFFAOYSA-L tetramethylazanium;carbonate Chemical compound [O-]C([O-])=O.C[N+](C)(C)C.C[N+](C)(C)C WJZPIORVERXPPR-UHFFFAOYSA-L 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 description 1
- 229910000645 Hg alloy Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 1
- 229910008062 Si-SiO2 Inorganic materials 0.000 description 1
- 229910006403 Si—SiO2 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005048 flame photometry Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000004945 silicone rubber Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The present invention relates to a method for preparing tetramethylammonium hydroxide by utilizing electrolysis-electrodialysis. Said invention adopts diaphragm electrolytic tank, its cathodic chamber has the tetramethyl-ammonium hydroxide whose concentration is 0.1-0.5 mol/l, and its anodic chamber has the salt solution of tetramethyl ammonium whose concentration is 0.5-4.0 mol/l, it uses stainless steel, nickel or graphite as cathode, and uses Ru-Ti oxide, Ti-Ir oxide or graphite electrode as anode, and adopts current density of 500-4000 A/sq.m, and the cathodic electrolyte and anodic electrolyte can be respectively circulated by pum, and it adopts intermittent electrolysis method to prepare high-purity tetramethylammonium hydroxide.
Description
Technical Field
The invention relates to a method for producing tetramethylammonium hydroxide (TMHA), in particular to an electrochemical synthesis method of TMHA, which is suitable for occasions of preparing high-purity TMHA by an electrolysis-electrodialysis method.
Background
Tetramethylammonium hydroxide (TMHA) is an important organic base and is a catalyst in the synthesis of silicone rubber, silicone resin, silicone oil and other organic silicon products; widely used in the electronic industry, as a cleaning, etching and polishing reagent of integrated circuit boards and also used in the semiconductor micromachining technologyIntraoperative Si-SiO2And (5) etching the interface anisotropically. Before the preparation of the invention, a silver oxide method is generally adopted as a TMHA preparation method, the chemical synthesis method has a complex process, the raw materials of the silver oxide method are expensive, and the obtained product contains higher impurity ions such as halogen ions, metal ions and the like, so that when the TMHA is used for the catalytic polymerization of an organic silicon monomer, the characteristics of the organic silicon product are seriously influenced, and the requirements of cleaning and corrosion in the electronic field can not be met. The invention adopts an electrolytic method to prepare high-purity TMHA.
According to the patents JP. Sho 62-190890, JP. Sho 61-180588, JP. Sho 63-24080, US4776929 and WO9001076, all of which electrolytically prepare high purity TMHA, pure water is used in the cathode region, 30-50% of tetramethylammonium salt is used in the anode region, the electrolyte concentration changes greatly during the electrolysis, the influence on the performance of the separator is large, and the main problems of these processes are: (1) the electrolysis product still contains traces of other impurity anions such as chloride, bromide, sulfate, etc. (2) The cathode area uses pure water, the anode area uses high-concentration tetramethyl ammonium salt, the concentration change of the two polar areas is large, the influence on the service life of the diaphragm is large, the cell voltage is as high as 15-25V in the electrolytic process, and the voltage fluctuation range is large.
Disclosure of Invention
The invention aims to provide a method for preparing tetramethylammonium hydroxide by electrolysis-electrodialysis with low cost and low pollution.
A process for preparing tetramethyl ammonium hydroxide by electrolysis-electrodialysis includes such steps as preparing tetramethyl ammonium salt from tetramethyl ammonium chloride, hydrogen carbonate, formate or acetate, preparing cathode from stainless steel, Ni, Cu, Hg alloy and graphite electrode, preparing anode from the ruthenium or iridium oxide electrode on graphite or Ti substrate, preparing cationic membrane as diaphragm, preparing the salt solution of tetramethyl ammonium hydroxide in 0.1-0.5 mol/L cathode and 0.5-4 mol/L anode, and preparing the electrolyte with the density of 500-4000A/m2Electrolyzing at 20-80 deg.c and 5-15V in an electrolyzer to synthesize coarse tetramethyl ammonium hydroxidePreparing a product; the process for refining the crude tetramethylammonium hydroxide into the high-purity tetramethylammonium hydroxide by electrodialysis comprises the following steps: adopting a diaphragm type electrolytic cell, taking a stainless steel or nickel or graphite electrode as a cathode material, taking a ruthenium or iridium oxide electrode of a graphite or titanium matrix as an anode material, taking pure water as a cathode area, taking a tetramethylammonium hydroxide crude product as an anode area, taking a diaphragm as a cationic membrane, and using 100-1000A/m2The high-purity tetramethyl ammonium hydroxide can be prepared by the current density electrolysis.
The cation membrane is a polystyrene sulfonic acid membrane or a perfluorosulfonic acid membrane or a perfluorocarboxylic acid membrane.
The principle of the invention is to adopt the principle of electrolysis-electrodialysis method, the cathode area is pure water or tetramethyl ammonium hydroxide, the anode area is the salt solution of tetramethyl ammonium, and the following electrochemical reaction occurs after electrolysis: and (3) anode reaction:
and (3) cathode reaction:
in the electrolysis process, chlorine, oxygen or carbon dioxide is separated out at the anode to free tetramethylammonium ions, after hydrogen is separated out at the cathode, hydroxyl ions are separated out, the tetramethylammonium ions permeate the ionic membrane under the action of an electric field, and the high-purity TMHA is obtained at the cathode chamber under the selective permeation action of the ionic membrane. Therefore, the TMHA prepared by the invention has higher purity. Evaporating the electrolyte to obtain TMHA products with different concentrations, wherein the total concentration of impurity anions is less than 100 ppm. And (3) taking the crude product as an anolyte and pure water as a catholyte, and further electrolyzing to obtain high-purity TMHA, wherein the total concentration of impurity ions is less than 10 ppm.
The electrolyzer of the invention adopts a plate-and-frame diaphragm electrolyzer. Adopting an electrolysis-electrodialysis method, and comprising the following process steps;
(1) pure water or tetramethylammonium hydroxide with the concentration of 0.1-0.5 mol/L is added into the cathode area by a pump circulation mode, and tetramethylammonium salt solution with the concentration of 0.5-4 mol/L is added into the anode area. The two polar regions are respectively circulated by a pump;
(2) in the electrolysis process, controlling the temperature of the electrolyte in the cathode chamber and the anode chamber to be 20-80 ℃;
(3) adjusting the working current density to 500-4000A/m2More preferably 1500 to 2500A/m2The voltage of the reaction tank is 5-15V;
(4) controlling the electrolysis time, and discharging when the TMHA concentration of the cathode chamber reaches 2-3 mol/L;
(5) the electrolyzed catholyte is decompressed and concentrated to obtain products with different concentrations, and the electrolyte in the anode chamber can be continuously electrolyzed;
(6) the refining method comprises the following steps: pure water is added into the cathode area, and the crude product obtained by electrolysis is added into the anode area, and the water concentration is 100-1000A/m2The current density electrolysis of (2) to remove a small amount of impurity anions such as chloride ions and obtain a high-purity TMHA solution.
The process adopts a plate-frame diaphragm electrolytic cell, an anode region and a cathode region both adopt a high-level cell self-flow mode, a polytetrafluoroethylene pump is used for circulation, and TMHA is prepared by batch intermittent electrolysis. Adding tetramethylammonium salt into the anode storage tank to reduce the tank voltage, and cooling the tank by using an external cooler to protect the diaphragm to realize stable electrolysis.
The invention designs a novel plate-frame diaphragm reactor, electrolyte can circulate through a pump, a storage tank and a cooler are arranged outside the tank, mass transfer of electrolytic reaction can be improved, and solution polarization is reduced; the electrolysis mode adopts an intermittent preparation TMHA, which is convenient for maintaining the electrolysis process. Secondly, tetramethylammonium salt can be continuously supplemented in the anode region, TMHA (tetramethylammonium hydroxide) with the concentration of 0.1-0.5 mol/L is used as an initial electrolyte in the cathode, so that the service life of the diaphragm can be prolonged, the cell voltage can be reduced, and the power consumption can be reduced; meanwhile, TMHA solution can be obtained after the product is refined, the total concentration of impurities is less than 10ppm, and the purity is extremely high. The TMHA prepared by the process has no wastewater discharge, so the process can be transformed into a pollution-free green production process.
Detailed Description
Example 1:
in a diaphragm type electrolytic cell, the anode was a titanium-ruthenium oxide electrode (DSA) having an area of 1dm2The cathode adopts a stainless steel electrode with an area of 1dm2The diaphragm is soaked in Nafion902 membrane (DuPont) with 5% TMHA for 24 hours, 0.1-0.5 mol/LTMHA solution is added in the cathode region, 3.5mol/L tetramethylammonium chloride solution is added in the anode region, the temperature is controlled to be 50-60 ℃, and the anode current density is respectively 500, 1500, 2500, 3000, 3500 and 4000A/m2The current density electrolysis is carried out, the alkali concentration in the catholyte during the electrolysis process is measured by an acid-base titration method, and the electrolysis is finished when the hydroxide ion concentration of the cathode reaches 2 mol/L. The corresponding current efficiencies were calculated to be 78.4%, 82.3%, 82.8%, 80.6%, 74.6%, and 56.9%, respectively.
Therefore, when the current density is more than 3000A/m2When the current efficiency begins to decrease, 2500A/m is used2The electrolysis with the current density of the left and the right has better efficiency.
Example 2:
adopting the electrolytic cell, the electrode and the diaphragm in the embodiment 1, adding 0.1-0.5 mol/L LTMHA solution into the cathode region, respectively adding 0.5, 1.0, 2.0, 3.0 and 4.0mol/L tetramethylammonium chloride solution into the anode region, controlling the temperature to be 50-60 ℃, and adopting 2500A/m2The current density electrolysis is finished when the hydroxide ion concentration of the cathode reaches 2mol/L, and the current efficiencies of the electrolysis adopting different raw material concentrations are respectively 64.2%, 76.5%, 81.7%, 82.3% and 82.1%.
Example 3:
adopting the electrolytic cell, the electrode and the diaphragm in the embodiment 1, adding 0.1-0.5 mol/L LTMHA solution into the cathode region, adding 3.5mol/L tetramethylammonium chloride solution into the anode region, adopting 2500A/m2The current density of the electrolytic cell is respectively electrolyzed at the temperature of 20, 40, 60, 70 and 80 ℃, when the concentration of hydroxide ions of a cathode reaches 2mol/L, the electrolysis is finished, and the current efficiency when different raw material concentrations are adopted for electrolysis is respectively 73.6 percent,78.7％、82.8％、82.1％、75.3％。
Example 4:
adopting the electrolytic cell and the diaphragm in the embodiment 1,adding 0.1-0.5 mol/L LTMHA solution in the cathode region, adding 3.5mol/L tetramethylammonium chloride solution in the anode region, controlling the temperature at 50-60 ℃, and adopting 2500A/m2The current density of (1). (1) Stainless steel, nickel, copper amalgam and graphite electrodes are respectively adopted as cathode materials, and the anode is a titanium-ruthenium oxide electrode (DSA); (2) stainless steel is adopted as a cathode material, anodes are respectively a titanium-ruthenium oxide electrode (DSA), a graphite electrode and a titanium iridium oxide electrode, the electrolysis is finished when the hydroxide ion concentration of the cathode reaches 3mol/L, the current efficiency and the metal ion concentration corresponding to the corresponding cathode material are respectively measured, and the surface state of the electrode is observed. The results are shown in Table 1.
TABLE 1 electrolytic preparation of TMHA from different cathode materials
Cathode material stainless steel nickel copper amalgam graphite
Current efficiency/% 82.882.681.586.281.4
The impurity ion concentration is less than 100ppm and less than 100ppm, the copper ion 2.1 percent contains 56.3ppm and less than 100ppm of mercury
Good corrosion and good powder falling of electrode surface
When graphite is used as an anode, the phenomenon of severe powder falling exists, and the titanium iridium oxide electrode is not suitable for chlorine evolution reaction; when the tetramethylammonium formate solution, the tetramethylammonium carbonate solution and the tetramethylammonium acetate solution are used as the anolyte, the titanium iridium oxide is used as the anode, and the effect is equal to that of a DSA anode.
Example 5:
adopting theelectrolytic cell, the electrode and the diaphragm in the embodiment 1, adding 0.1-0.5 mol/L LTMHA solution into the cathode area, and respectively adding 3.5mol/L tetramethyl chloride into the anode areaAmmonium solution, tetramethylammonium formate solution, tetramethylammonium carbonate solution and tetramethylammonium acetate solution, controlling the temperature at 50-60 deg.C, and adopting 2500A/m2The current density electrolysis is finished when the concentration of hydroxide ions at the cathode reaches 2mol/L, and the current efficiencies of the electrolysis adopting different raw materials are 82.8 percent, 81.5 percent, 85.9 percent and 80.2 percent respectively.
Example 6:
the electrolytic cell and the electrode in the embodiment 1 are adopted, 0.3mol/L LTMHA solution is added into the cathode region, 3.5mol/L tetramethyl ammonium chloride solution is added into the anode region, the temperature is controlled to be 50-60 ℃, and 2500A/m is adopted2The current density of (2) was measured by using a perfluorosulfonic acid membrane or a perfluorocarboxylic acid membrane (Nafion membrane) and a polystyrene sulfonic acid cation membrane as a separator (ordinary cation membrane). The contents of chloride ion and sodium ion and potassium ion were measured by potentiometric titration and flame photometry, and the results of Table 2 were obtained.
TABLE 2 influence of membrane type on product purity
Channel pressure C (Cl)-) C(Na+) C(K+)
Diaphragm type
E/V (mol/L) (mol/L) (mol/L)
Nafion film 8-152.6X 10-3＜10-4＜10-4
Common cation membrane 8-154.0X 10-2＜10-4＜10-4
Example 7
Concentrating the crude TMHA solution obtained by electrolysis to 3mol/L to be used as an anolyte, taking a perfluorosulfonic acid membrane or a perfluorocarboxylic acid membrane as a diaphragm, taking graphite or DSA as an anode, taking a stainless steel or nickel or graphite electrode as a cathode material, taking pure water as a cathode chamber and taking 100-1000A/m2The results of the electrolysis at the current density of (2) were shown in Table 3, and the concentrations of impurity ions in the catholyte after the electrolysis were analyzed.
TABLE 3 purification results of TMHA
| Crude TMHA concentration and impurities before electrolysis | Concentration and composition of electrolyzed refined TMHA |
| TMHA Cl- Na+ K+ 3mol/L 95.7ppm 1.5ppm 1.1ppm | TMHA Cl- Na+ K+ 1.3mol/L 1.3ppm 1.2ppm 1.0ppm |
Claims (2)
1. A method for preparing tetramethylammonium hydroxide by electrolysis-electrodialysis adopts tetramethylammonium salt comprising tetramethylammonium chloride or tetramethylammonium bicarbonate or tetramethylammonium formate or tetramethylammonium acetate as raw materials, stainless steel or nickel or copper amalgam and graphite electrode as cathode materials, ruthenium or iridium oxide electrode of graphite or titanium matrix as anode materials, a diaphragm is a cationic membrane, the cathode area is 0.1-0.5 mol/L tetramethylammonium hydroxide, the anode area is 0.5-4 mol/L tetramethylammonium salt solution, and the working current density is 500-4000A/m2Electrolyzing at 20-80 deg.c and 5-15V to synthesize coarse tetramethyl ammonium hydroxide product. The crude product is refined into high-purity tetramethylammonium hydroxide by electrodialysis, and the process comprises the following steps: diaphragm type electrolytic tank, stainless steel or nickel or graphite electrode as cathode material, stoneTaking a ruthenium or iridium oxide electrode with an ink or titanium matrix as an anode material, taking pure water as a cathode area, taking a tetramethyl ammonium hydroxide crude product as an anode area, taking a diaphragm as a cationic membrane, and taking 100-1000A/m2The high-purity tetramethyl ammonium hydroxide can be prepared by the current density electrolysis.
2. The method of claim 1, wherein the cationic membrane is a polystyrene sulfonic acid membrane or a perfluorosulfonic acid membrane or a perfluorocarboxylic acid membrane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA03106227XA CN1523135A (en) | 2003-02-18 | 2003-02-18 | Process for preparing tetramethyl ammonium hydroxide by electrolysis-electrodialysis |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA03106227XA CN1523135A (en) | 2003-02-18 | 2003-02-18 | Process for preparing tetramethyl ammonium hydroxide by electrolysis-electrodialysis |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1523135A true CN1523135A (en) | 2004-08-25 |
Family
ID=34282699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA03106227XA Pending CN1523135A (en) | 2003-02-18 | 2003-02-18 | Process for preparing tetramethyl ammonium hydroxide by electrolysis-electrodialysis |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1523135A (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102400173A (en) * | 2011-11-25 | 2012-04-04 | 赵文洲 | Method for preparing electronic grade tetramethylammonium hydroxide by continuous method |
| CN102776525A (en) * | 2012-08-20 | 2012-11-14 | 云南天恒通泰腐植酸有限公司 | Method for electrolyzing and recycling chromium containing waste liquid generated during oxidation decoloration of montan wax, deresinated montan wax, peat wax or deresinated peat wax |
| CN102854082A (en) * | 2012-08-29 | 2013-01-02 | 清华大学 | Evaluation method for condensation effect of hydrogen iodide in iodine-containing hydriodic acid by using electrolysis-electrodialysis device |
| CN103388155A (en) * | 2013-07-31 | 2013-11-13 | 自贡天龙化工有限公司 | Device and method for continuously preparing tetramethylammonium hydroxide |
| CN105112934A (en) * | 2015-09-16 | 2015-12-02 | 青岛润兴光电材料有限公司 | Preparation method for tetra-alkyl ammonium hydroxide |
| CN106350831A (en) * | 2016-08-26 | 2017-01-25 | 肯特催化材料股份有限公司 | Preparation method of molecular sieve template high-purity adamantyltrimethylammonium hydroxide water solution |
| CN106801233A (en) * | 2017-01-11 | 2017-06-06 | 浙江工业大学 | A kind of electrolysis prepares the system and method for high-purity TPAOH |
| CN106829898A (en) * | 2017-01-09 | 2017-06-13 | 杨洋 | A kind of method that utilization TMAH mother liquor prepares Arizona bacilli |
| CN108396327A (en) * | 2018-05-23 | 2018-08-14 | 梁小朝 | A kind of device and method of continuity method production tetramethylammonium hydroxide |
| CN110644014A (en) * | 2019-10-30 | 2020-01-03 | 盐城泛安化学有限公司 | Preparation method of tetraethyl ammonium hydroxide |
| CN111777134A (en) * | 2015-10-30 | 2020-10-16 | 中国石油化工股份有限公司 | Wastewater treatment method, molecular sieve preparation method and molecular sieve preparation system |
-
2003
- 2003-02-18 CN CNA03106227XA patent/CN1523135A/en active Pending
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102400173A (en) * | 2011-11-25 | 2012-04-04 | 赵文洲 | Method for preparing electronic grade tetramethylammonium hydroxide by continuous method |
| CN102776525A (en) * | 2012-08-20 | 2012-11-14 | 云南天恒通泰腐植酸有限公司 | Method for electrolyzing and recycling chromium containing waste liquid generated during oxidation decoloration of montan wax, deresinated montan wax, peat wax or deresinated peat wax |
| CN102854082A (en) * | 2012-08-29 | 2013-01-02 | 清华大学 | Evaluation method for condensation effect of hydrogen iodide in iodine-containing hydriodic acid by using electrolysis-electrodialysis device |
| CN103388155A (en) * | 2013-07-31 | 2013-11-13 | 自贡天龙化工有限公司 | Device and method for continuously preparing tetramethylammonium hydroxide |
| CN103388155B (en) * | 2013-07-31 | 2015-07-08 | 自贡天龙化工有限公司 | Device and method for continuously preparing tetramethylammonium hydroxide |
| CN105112934A (en) * | 2015-09-16 | 2015-12-02 | 青岛润兴光电材料有限公司 | Preparation method for tetra-alkyl ammonium hydroxide |
| CN111777134A (en) * | 2015-10-30 | 2020-10-16 | 中国石油化工股份有限公司 | Wastewater treatment method, molecular sieve preparation method and molecular sieve preparation system |
| CN106350831A (en) * | 2016-08-26 | 2017-01-25 | 肯特催化材料股份有限公司 | Preparation method of molecular sieve template high-purity adamantyltrimethylammonium hydroxide water solution |
| CN106829898A (en) * | 2017-01-09 | 2017-06-13 | 杨洋 | A kind of method that utilization TMAH mother liquor prepares Arizona bacilli |
| CN106801233B (en) * | 2017-01-11 | 2019-02-01 | 浙江工业大学 | A kind of electrolysis method prepares the system and method for high-purity tetrapropylammonium hydroxide |
| CN106801233A (en) * | 2017-01-11 | 2017-06-06 | 浙江工业大学 | A kind of electrolysis prepares the system and method for high-purity TPAOH |
| CN108396327A (en) * | 2018-05-23 | 2018-08-14 | 梁小朝 | A kind of device and method of continuity method production tetramethylammonium hydroxide |
| CN108396327B (en) * | 2018-05-23 | 2024-04-09 | 柏川新材料科技(宁波)有限公司 | Equipment and method for producing tetramethyl ammonium hydroxide by continuous method |
| CN110644014A (en) * | 2019-10-30 | 2020-01-03 | 盐城泛安化学有限公司 | Preparation method of tetraethyl ammonium hydroxide |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0652041B1 (en) | Method for producing high purity hydroxides and alkoxides | |
| KR101254682B1 (en) | Electrolysis electrode and method for producing aqueous quaternary ammonium hydroxide solution using such electrolysis electrode | |
| US4917781A (en) | Process for preparing quaternary ammonium hydroxides | |
| CN1523135A (en) | Process for preparing tetramethyl ammonium hydroxide by electrolysis-electrodialysis | |
| JPS5949318B2 (en) | Electrolytic production method of alkali metal hypohalite salt | |
| RU2059023C1 (en) | Quaternary ammonium hydroxides solutions purification method | |
| US6503386B2 (en) | Process for the production of alkali metal- and ammonium peroxodisulfate | |
| CN1312400A (en) | Synthesizing of tetramethylammonium | |
| CN113235117B (en) | Production process of high-concentration tetrapropylammonium hydroxide and high-concentration tetrapropylammonium hydroxide prepared by same | |
| CN1172028C (en) | Method for preparing hypophosphorous acid by using electrolytic method | |
| CN1247819C (en) | Paired electrolysis procss of preparing glyoxalic acid | |
| CN1137288C (en) | Oxalic acid electroreduction process of preparing glyoxalic acid | |
| CN1212430C (en) | Electrolytic reduction process of preparing bivalent europium | |
| EP0041365B1 (en) | Improved electrolytic process for the production of ozone | |
| JP3538271B2 (en) | Hydrochloric acid electrolyzer | |
| EP0021624A1 (en) | Process for the production of potassium hydroxide in an electrolytic membrane cell and potassium hydroxide obtained thereby | |
| CN1219610A (en) | Saline electrolysis process | |
| CN1641071A (en) | Alkyl hydroxylamine and its salt electrochemical synthesis method | |
| CN1297691C (en) | Method for preparing nickel hypophosphite by electrolytic method | |
| US4402805A (en) | Electrochemical process to prepare p-hydroxymethylbenzoic acid with a low level of 4-CBA | |
| CN109306503B (en) | Manganese electrolyte compound additive and use method thereof | |
| CN117512635A (en) | Electrodialysis device and method for preparing tetramethyl ammonium hydroxide | |
| CN1259455C (en) | Ethanedial electrolyzing and oxidizing process of synthesizing glyoxalic acid | |
| CN118324257A (en) | Method for maintaining electrolysis performance of water electrolysis device | |
| CN1303252C (en) | Process of preparing ethyl aldehydic acid by electrolyzing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |