CN111962096B - Synthetic method and equipment for tetramethylammonium hydroxide - Google Patents
Synthetic method and equipment for tetramethylammonium hydroxide Download PDFInfo
- Publication number
- CN111962096B CN111962096B CN202010814941.4A CN202010814941A CN111962096B CN 111962096 B CN111962096 B CN 111962096B CN 202010814941 A CN202010814941 A CN 202010814941A CN 111962096 B CN111962096 B CN 111962096B
- Authority
- CN
- China
- Prior art keywords
- concentration
- electrode
- anolyte
- tank
- graphite electrode
- 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.)
- Active
Links
Images
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
- C25B3/00—Electrolytic production of organic compounds
Abstract
The invention discloses a synthetic method and equipment for tetramethylammonium hydroxide, wherein the synthetic method comprises the steps of dissolving butadiene derivatives and supporting electrolyte in an organic solvent to prepare electrode electrolyte, electrifying a graphite electrode under the electrode electrolyte to form a yellow polymer film on the surface of the graphite electrode to obtain a modified graphite electrode, and applying the modified graphite electrode to an anode chamber of an electrolytic cell. The invention forms a layer of protective film on the surface of the graphite electrode, inhibits the oxidation of the graphite electrode, slows down the corrosion speed of the graphite electrode, improves the current efficiency of electrolysis, and can obtain good current efficiency and electrode service life even under the condition of large electrolyte circulation rate.
Description
Technical Field
The invention relates to a method and equipment for synthesizing an organic compound, in particular to a method and equipment for synthesizing tetramethyl ammonium hydroxide.
Background
Tetramethylammonium hydroxide (TMAH) is a strong base of the same strength as caustic alkali. Since it has strong basicity and leaves no substance after decomposition by heating, particularly, no conductive ionic substance, it has wide applications in the field of electronics industry. With the continuous development of large-scale integrated circuits, the demand of high-purity electronic grade TMAH is increasing day by day, but the traditional method for preparing TMAH has the defects of high cost, high impurity ion content and the like.
The current TMAH preparation methods mainly comprise: precipitation, ion exchange resin, addition, ion membrane, and ion membrane electrolysis. The precipitation method has the defects of high process cost, low product purity and the like. The ion exchange resin method has the defects that the resin consumption is large, a large amount of high-purity acid and alkali can be consumed in pretreatment and regeneration, a large amount of waste acid and waste alkali can be generated, the environment is polluted and the like. The addition reaction needs to be carried out in a high-pressure closed environment, the intermediate product is very unstable, the number of byproducts is large, and the product purity is not high. The ion membrane method has the defects of low ion exchange speed, high impurity ion content in the product, low purity and the like. The defects of the products obtained by the traditional methods seriously affect the quality and the application range of the TMAH. For example, chinese patent 200510047043.6 reports that quaternary ammonium hydroxide is prepared by quaternary ammonium salt and inorganic base, and the product purity is not high in the non-electrolytic method.
The ion membrane electrolysis method is a novel method for preparing high-purity electronic grade TMAH, has the advantages of simple process, high product purity, low cost, no pollution and the like, is a clean production technology, and is the best method for preparing the electronic grade TMAH at present. At present, the industrial preparation of TMAH is more common to prepare high-purity electronic grade TMAH by a two-chamber single-membrane electrolysis method with tetramethylammonium chloride (TMAC) as a raw material and a cation exchange membrane as an electrolysis diaphragm. In the preparation method, the electrode is not only a catalyst for an electrochemical process, but also a place for electrode reaction, so that the properties of the electrode material have great influence on the whole electrochemical synthesis reaction path and selectivity. The electrode material is used as a special functional material, not only relates to energy consumption in the reaction process, but also directly influences the yield of the reaction and the quality of the product, and even determines the success or failure of the whole reaction system. Therefore, in the organic electrosynthesis process, the development and selection of a suitable electrode material are crucial. Graphite has long been the most widely used anode material. However, graphite is porous and has poor mechanical strength, and is easily oxidized into carbon dioxide, and is continuously corroded and peeled off in the electrolytic process, so that the electrode spacing is gradually increased, and the cell voltage is increased. The metal oxide electrode formed by coating ruthenium oxide and titanium oxide on the titanium base proposed by h.bill in the 60 s is a great innovation of the anode material, however, the cost thereof is greatly increased. One of the factors affecting the service life of the anode is the circulation rate of the electrolyte, with greater circulation rates leading to longer service lives. However, the circulation rate of the electrolyte is not necessarily as large as possible, and the larger the circulation rate is, the shorter the residence time of the electrolyte in the electrolytic cell is, and the current efficiency of electrolysis may be lowered. Therefore, the selection of a proper electrolyte circulation rate is very heavy, the electrolyte circulation rate is generally controlled to be 6.5-6.75L/h, the current efficiency is about 73-675%, and even the titanium anode coated with ruthenium oxide has a service life of about 30 days.
Disclosure of Invention
Therefore, the invention provides a synthetic method and equipment for tetramethylammonium hydroxide, which can solve the technical problems of low electrolysis current efficiency and short service life of a graphite anode under a large electrolyte circulation rate.
In order to solve the technical problems, the invention adopts the following technical scheme:
a synthetic method for tetramethylammonium hydroxide comprises the following steps:
(1) dissolving butadiene derivatives and supporting electrolyte in an organic solvent to prepare electrode electrolyte, putting a graphite electrode serving as a reaction electrode, platinum serving as a counter electrode and a silver/silver chloride electrode serving as a reference electrode into the electrode electrolyte, electrifying under-0.3V (vs. Ag/Ag +) for polymerization, forming a yellow film on the surface of the graphite electrode after the reaction is finished to obtain a modified graphite electrode, taking out and drying the modified graphite electrode, and putting the modified graphite electrode into an anode chamber;
(2) the anode chamber and the cathode chamber are separated by a cation exchange membrane, and a cathode is arranged in the cathode chamber;
(3) connecting the current between the modified graphite electrode and the cathode, pumping the tetramethylammonium chloride solution serving as a raw material into the anode chamber through the anolyte feed tank and the anolyte intermediate tank, and circulating the anolyte between the anode chamber and the anolyte intermediate tank through a pipeline and a pump so as to stabilize the concentration of the anolyte in the anode chamber in the electrolysis process;
(4) along with the electrolysis, the concentration of the tetramethylammonium hydroxide in the cathode chamber continuously rises, when the concentration rises to a certain concentration, the catholyte is pumped into the nanofiltration device, the concentration of the tetramethylammonium hydroxide in the catholyte is concentrated by utilizing the interception capability of the nanofiltration membrane of the nanofiltration device on hydroxyl, the concentration ratio is controlled, and the concentrated catholyte is pumped into a product tank after the concentration reaches the product concentration.
Preferably, in step (1), the butadiene derivative has the following structural formula (1):
formula (1)
Wherein R is1、R2、R3、R4、R5、R6Are respectively and independently selected from one of-F, -Cl, -Br and I, R1、R2、R3、R4、R5、R6At least one of which is-Cl.
Preferably, in the step (1), the supporting electrolyte is one of tetramethylammonium chlorate, tetraethylammonium perchlorate, tetrabutylammonium perchlorate, tetramethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, lithium perchlorate, lithium tetrafluoroborate, tetramethylammonium hexafluoroarsenate, tetraethylammonium hexafluoroarsenate, tetrabutylammonium hexafluoroarsenate, sodium hexafluoroarsenate, sulfuric acid, tetramethylammonium hydrogen sulfate, tetrabutylammonium hydrogen tetrabutylsulfate, and sodium trifluoroacetate.
Preferably, in step (1), the organic solvent is one of tetrahydrofuran, hexamethylphosphoramide, dimethoxyethane, acetonitrile, propylene carbonate, nitrobenzene, benzonitrile, dichloromethane, dimethylformamide and dimethyl sulfoxide.
Preferably, in the step (1), the electrifying time is 1-6 hours.
Preferably, in the step (3), tetramethylammonium chloride solution is used as a raw material, and the concentration of the tetramethylammonium carbonate is 50-65 wt%.
Preferably, in the step (3), when the anolyte circulates between the anode chamber and the anolyte intermediate tank through a pipeline and a pump, the circulation rate of the anolyte is 7.5-8.0L/h.
Preferably, in step (4), the concentration is raised to a concentration of 15 to 18 wt%.
Preferably, in step (4), the product concentration is from 20 to 25% by weight.
The invention also provides a device for synthesizing tetramethylammonium hydroxide, which is matched with the method for synthesizing tetramethylammonium hydroxide.
The device includes, graphite electrode modification tank and tetramethyl ammonium hydroxide synthesis equipment, graphite electrode modification tank includes reaction electrode, counter electrode, reference electrode and electrode electrolyte, and tetramethyl ammonium hydroxide synthesis equipment includes the electrolysis trough, and the electrolysis trough is inside to separate into anode chamber and cathode chamber two parts through cation exchange membrane with the electrolysis trough, and the anode chamber part connects gradually anolyte pans, anolyte feed tank through the pipeline, installs the pump on the pipeline, the one-way pump of raw materials in the anolyte feed tank goes into the anolyte pans, and the allotment is gone into in the anolyte pans through a pipeline pump to partial anolyte in the anode chamber, and the anolyte of allotment concentration goes into the anode chamber through another pipeline pump again in the anolyte pans, controls the stability of anolyte concentration in the anode chamber in the electrolysis process.
The part of the cathode chamber is sequentially connected with a nanofiltration device and a product tank through pipelines, a pump is also arranged on the pipeline of the part, the cathode chamber is connected with the nanofiltration device through two pipelines, one pipeline pumps cathode liquid in the cathode chamber into the nanofiltration device, the concentration of tetramethylammonium hydroxide in the cathode liquid is concentrated by utilizing the interception capability of the nanofiltration membrane of the nanofiltration device on hydroxyl, the concentration ratio is controlled, and the cathode liquid is pumped into the product tank after the concentration reaches the product concentration; and the penetrating fluid generated by nanofiltration of the nanofiltration device is partially pumped into the cathode chamber through another pipeline to ensure that the concentration change of the tetramethylammonium hydroxide in the cathode solution is small.
Preferably, the external water pipe of the anolyte intermediate tank is used for supplementing water.
The inventor finds out through a large number of experiments that the butadiene derivative provided by the invention can modify the surface of a graphite electrode, and a layer of protective film is formed on the surface of the graphite electrode, so that the oxidation of the graphite electrode is inhibited, and the corrosion speed of the graphite electrode is slowed down. The film is a polymer film, forms a porous frame structure, has good elasticity, oxidation resistance and stability, and can improve the mechanical strength of the graphite electrode. Meanwhile, the modified graphite electrode improves the current efficiency of electrolysis, and can obtain good current efficiency and electrode service life even at a large electrolyte circulation rate.
Drawings
FIG. 1 is a flow chart of the synthetic method of tetramethylammonium hydroxide according to the present invention.
FIG. 2 is a schematic structural diagram of a tetramethylammonium hydroxide synthesizing apparatus according to the present invention.
Reference numerals: 1-anolyte feed tank; 2-a pump; 3-anolyte intermediate tank; 4-an electrolytic cell; 5-a product tank; 6-a nanofiltration device; 41-anode chamber; 42-cathode chamber.
Detailed Description
The present invention now will be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments of the invention are shown.
As shown in fig. 1, a synthesis method for tetramethylammonium hydroxide comprises the following steps:
(1) dissolving butadiene derivatives in an organic solvent to prepare electrode electrolyte, putting a graphite electrode serving as a reaction electrode, platinum serving as a counter electrode and a silver/silver chloride electrode serving as a reference electrode into the electrode electrolyte, electrifying under-0.3V (vs. Ag/Ag +) for polymerization, forming a yellow film on the surface of the graphite electrode after the reaction is finished to obtain a modified graphite electrode, taking out and drying the modified graphite electrode, and putting the modified graphite electrode into an anode chamber;
(2) the anode chamber and the cathode chamber are separated by a cation exchange membrane, and a cathode is arranged in the cathode chamber;
(3) connecting the current between the modified graphite electrode and the cathode, pumping the tetramethylammonium chloride solution serving as a raw material into the anode chamber through the anolyte feed tank and the anolyte intermediate tank, and circulating the anolyte between the anode chamber and the anolyte intermediate tank through a pipeline and a pump so as to stabilize the concentration of the anolyte in the anode chamber in the electrolysis process;
(4) along with the electrolysis, the concentration of the tetramethylammonium hydroxide in the cathode chamber continuously rises, when the concentration rises to a certain concentration, the catholyte is pumped into the nanofiltration device, the concentration of the tetramethylammonium hydroxide in the catholyte is concentrated by utilizing the interception capability of the nanofiltration membrane of the nanofiltration device on hydroxyl, the concentration ratio is controlled, and the concentrated catholyte is pumped into a product tank after the concentration reaches the product concentration.
The electrochemical reduction is performed by dissolving the butadiene derivative monomer together with the supporting electrolyte in an organic solvent and applying an electric field thereto, thereby obtaining a polymer in the form of a film on the surface of the cathode. The film thickness can be controlled by the amount of power supplied.
The structural formula of the butadiene derivative is shown as the following formula (1):
formula (1)
Wherein R is1、R2、R3、R4、R5、R6Are respectively and independently selected from one of-F, -Cl, -Br and I, R1、R2、R3、R4、R5、R6At least one of which is-Cl.
The supporting electrolyte is one of tetramethylammonium chlorate, tetraethylammonium perchlorate, tetrabutylammonium perchlorate, tetramethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, lithium perchlorate, lithium tetrafluoroborate, tetramethylammonium hexafluoroarsenate, tetraethylammonium hexafluoroarsenate, tetrabutylammonium hexafluoroarsenate, sodium hexafluoroarsenate, sulfuric acid, tetramethylammonium hydrogen sulfate, tetrabutylammonium hydrogen sulfate, and sodium trifluoroacetate.
The organic solvent is not particularly limited, and a polar solvent subjected to purification treatment such as dehydration and degassing is preferably used. For example: tetrahydrofuran, hexamethylphosphoramide, dimethoxyethane, acetonitrile, propylene carbonate, nitrobenzene, benzonitrile, dichloromethane, dimethylformamide, and dimethyl sulfoxide.
As a material of the cathode, a metal electrode such as gold, platinum, nickel, zinc, tin, stainless steel, or the like, or a glass electrode in which a metal oxide such as indium oxide, tin oxide, or the like is vapor-deposited on a glass surface can be used. The electropolymerization method can be carried out by either a constant current method or a constant current method, but the constant current method is preferable.
The energization time is not particularly limited, and may be determined depending on the film thickness, and is preferably 1 to 6 hours.
The tetramethylammonium chloride solution is used as a raw material, and the concentration of the tetramethylammonium carbonate is 50-65 wt%. The concentration is increased to a certain concentration of 15-18 wt%. The product concentration is 20-25 wt%.
As shown in FIG. 2, a synthesis apparatus for tetramethylammonium hydroxide, which is a matched apparatus of the synthesis method for tetramethylammonium hydroxide of the present invention. The device comprises an electrolytic cell 4, wherein the inside of the electrolytic cell 4 is divided into an anode chamber 41 and a cathode chamber 42 by a cation exchange membrane.
The anode chamber 41 is connected with an anolyte intermediate tank 3 and an anolyte raw material tank 1 in sequence through a pipeline, a pump 2 is installed on the pipeline, raw materials in the anolyte raw material tank 1 are pumped into the anolyte intermediate tank 3 in a one-way mode, part of anolyte in the anode chamber 41 is pumped into the anolyte intermediate tank 3 through one pipeline for blending, anolyte with blended concentration in the anolyte intermediate tank 3 is pumped into the anode chamber 41 through the other pipeline, and the stability of the anolyte concentration in the anode chamber 41 in the electrolytic process is controlled.
The part of the cathode chamber 42 is sequentially connected with the nanofiltration device 6 and the product tank 5 through pipelines, the pipeline of the part is also provided with the pump 2, the cathode chamber 42 is connected with the nanofiltration device 6 through two pipelines, one pipeline pumps cathode liquid in the cathode chamber 42 into the nanofiltration device 6, the concentration of tetramethylammonium hydroxide in the cathode liquid is concentrated by utilizing the interception capability of the nanofiltration membrane of the nanofiltration device 6 on hydroxyl, the concentration ratio is controlled, and the cathode liquid is pumped into the product tank 5 after the concentration reaches the product concentration; the penetrating fluid part generated by nanofiltration of the nanofiltration device 6 is pumped into the cathode chamber 42 through another pipeline to ensure that the concentration change of the tetramethylammonium hydroxide in the cathode solution is small.
Examples 1 to 3 of the present invention and comparative examples 1 to 3 will be provided below.
Example 1
Dissolving 1,1,4, 4-tetrachloro, 2, 3-difluorobutadiene and lithium tetrafluoroborate in tetrahydrofuran to prepare electrode electrolyte, putting a graphite electrode serving as a reaction electrode, platinum serving as a counter electrode and a silver/silver chloride electrode serving as a reference electrode into the electrode electrolyte, electrifying for 1 hour under-0.3V (vs. Ag/Ag +) for polymerization, forming a yellow film on the surface of the graphite electrode after the reaction is finished to obtain a modified graphite electrode, taking out and drying the modified graphite electrode, and putting the modified graphite electrode into an anode chamber.
The stainless steel plate is used as a cathode and is arranged in a cathode chamber, and the anode chamber and the cathode chamber are separated by a cation exchange membrane. And connecting the current between the modified graphite electrode and the cathode, pumping the tetramethylammonium chloride solution serving as a raw material into the anode chamber through the anolyte feed tank and the anolyte intermediate tank, and circulating the anolyte between the anode chamber and the anolyte intermediate tank through a pipeline and a pump, so that the concentration of the anolyte in the anode chamber is stable in the electrolysis process. Along with the electrolysis, the concentration of the tetramethylammonium hydroxide in the cathode chamber continuously rises, the concentration rises to 15 wt%, the catholyte is pumped into the nanofiltration device, the concentration of the tetramethylammonium hydroxide in the catholyte is concentrated by utilizing the interception capability of the nanofiltration membrane of the nanofiltration device on hydroxyl, the concentration ratio is controlled, and the product is pumped into a product tank after the concentration reaches 20 wt%.
In the synthesis process, the current efficiency of electrolysis was 94.3%, and the life of the modified graphite electrode was 82 days.
Example 2
The procedure of example 1 was repeated, except that 1,1,4, 4-tetrachloro, 2, 3-difluorobutadiene was replaced with hexachlorobutadiene.
In the synthesis process, the current efficiency of electrolysis was 93.0%, and the life of the modified graphite electrode was 91 days.
Example 3
The procedure of example 1 was repeated, except that 1,1,4, 4-tetrachloro, 2, 3-difluorobutadiene was replaced with 1,1,4, 4-tetrafluoro-2, 3-dichlorobutadiene.
In the synthesis process, the current efficiency of electrolysis was 95.8%, and the life of the modified graphite electrode was 87 days.
Comparative example 1
The same procedure as in example 1 was repeated, except that 1,1,4, 4-tetrachloro, 2, 3-difluorobutadiene was replaced with vinyl chloride.
In the synthesis process, the current efficiency of electrolysis was 76.6%, and the life of the modified graphite electrode was 7 days.
Comparative example 2
The procedure of example 1 was repeated, except that 1,1,4, 4-tetrachloro, 2, 3-difluorobutadiene was replaced with 1, 1-dichlorohexatriene.
In the synthesis process, the current efficiency of electrolysis was 73.6%, and the life of the modified graphite electrode was 9 days.
Comparative example 3
The same as example 1 was repeated, except that the graphite electrode was not modified.
In the synthesis process, the current efficiency of electrolysis was 72.4%, and the life of the modified graphite electrode was 4 days.
As can be seen from examples 1-3 and comparative examples 1-3, the method and the equipment for synthesizing tetramethylammonium hydroxide can solve the technical problems of low electrolysis current efficiency and short service life of the graphite anode under the condition of large electrolyte circulation rate
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (9)
1. A synthetic method for tetramethylammonium hydroxide comprises the following steps:
(1) dissolving butadiene derivatives and supporting electrolyte in an organic solvent to prepare electrode electrolyte, putting a graphite electrode serving as a reaction electrode, platinum serving as a counter electrode and a silver/silver chloride electrode serving as a reference electrode into the electrode electrolyte, electrifying under-0.3 Vvs. Ag/AgCl for polymerization, forming a yellow film on the surface of the graphite electrode after the reaction is finished to obtain a modified graphite electrode, taking out and drying the modified graphite electrode, and putting the modified graphite electrode into an anode chamber; wherein the structural formula of the butadiene derivative is shown as the following formula (1):
formula (1)
Wherein R is1、R2、R3、R4、R5、R6Are respectively and independently selected from one of-F, -Cl, -Br and I, R1、R2、R3、R4、R5、R6At least one of which is-Cl;
(2) the anode chamber and the cathode chamber are separated by a cation exchange membrane, and a cathode is arranged in the cathode chamber;
(3) connecting the current between the modified graphite electrode and the cathode, pumping the tetramethylammonium chloride solution serving as a raw material into the anode chamber through the anolyte feed tank and the anolyte intermediate tank, and circulating the anolyte between the anode chamber and the anolyte intermediate tank through a pipeline and a pump so as to stabilize the concentration of the anolyte in the anode chamber in the electrolysis process;
(4) along with the electrolysis, the concentration of the tetramethylammonium hydroxide in the cathode chamber continuously rises, when the concentration rises to a certain concentration, the catholyte is pumped into the nanofiltration device, the concentration of the tetramethylammonium hydroxide in the catholyte is concentrated by utilizing the interception capability of the nanofiltration membrane of the nanofiltration device on hydroxyl, the concentration ratio is controlled, and the concentrated catholyte is pumped into a product tank after the concentration reaches the product concentration.
2. The synthesis method according to claim 1, wherein in the step (1), the supporting electrolyte is one of tetramethylammonium chlorate, tetraethylammonium perchlorate, tetrabutylammonium perchlorate, tetramethylammonium tetrafluoroborate, tetrabutylammonium tetrafluoroborate, lithium perchlorate, lithium tetrafluoroborate, tetramethylammonium hexafluoroarsenate, tetraethylammonium hexafluoroarsenate, tetrabutylammonium hexafluoroarsenate, sodium hexafluoroarsenate, sulfuric acid, tetramethylammonium hydrogen sulfate, tetrabutylammonium hydrogen sulfate, and sodium trifluoroacetate.
3. The synthesis method according to any one of claims 1 to 2, wherein in the step (1), the organic solvent is one of tetrahydrofuran, hexamethylphosphoramide, dimethoxyethane, acetonitrile, propylene carbonate, nitrobenzene, benzonitrile, dichloromethane, dimethylformamide and dimethyl sulfoxide.
4. The synthesis method according to claim 1, wherein in the step (1), the energization time is 1 to 6 hours.
5. The synthesis method according to claim 1, wherein in the step (3), the tetramethylammonium chloride solution is used as a raw material, and the concentration of the tetramethylammonium chloride is 50-65 wt%.
6. The method of claim 1, wherein in step (4), the concentration is increased to a concentration of 15 to 18 wt%.
7. The synthesis process according to claim 1, wherein in step (4), the product concentration is 20-25 wt%.
8. A synthetic device for tetramethylammonium hydroxide, which is specially used for the synthetic method of any one of claims 1 to 7, wherein the synthetic device comprises a graphite electrode modification tank and a tetramethylammonium hydroxide synthetic device, the graphite electrode modification tank comprises a reaction electrode, a counter electrode, a reference electrode and an electrode electrolyte, the tetramethylammonium hydroxide synthetic device comprises an electrolytic tank, the electrolytic tank is divided into an anode chamber and a cathode chamber by a cation exchange membrane, the anode chamber part is sequentially connected with an anolyte intermediate tank and an anolyte raw material tank by a pipeline, a pump is arranged on the pipeline, raw materials in the anolyte raw material tank are unidirectionally pumped into the anolyte intermediate tank, part of the anolyte in the anode chamber is pumped into the anolyte intermediate tank by a pipeline for blending, and anolyte with a blended concentration in the anolyte intermediate tank is pumped into the anode chamber by another pipeline, controlling the stability of the concentration of the anode solution in the anode chamber in the electrolysis process;
the part of the cathode chamber is sequentially connected with a nanofiltration device and a product tank through pipelines, a pump is also arranged on the pipeline of the part, the cathode chamber is connected with the nanofiltration device through two pipelines, one pipeline pumps cathode liquid in the cathode chamber into the nanofiltration device, the concentration of tetramethylammonium hydroxide in the cathode liquid is concentrated by utilizing the interception capability of the nanofiltration membrane of the nanofiltration device on hydroxyl, the concentration ratio is controlled, and the cathode liquid is pumped into the product tank after the concentration reaches the product concentration; and the penetrating fluid generated by nanofiltration of the nanofiltration device is partially pumped into the cathode chamber through another pipeline to ensure that the concentration change of the tetramethylammonium hydroxide in the cathode solution is small.
9. The synthesizer according to claim 8 wherein the anolyte intermediate tank is externally connected to a water pipe for replenishing water.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010814941.4A CN111962096B (en) | 2020-08-13 | 2020-08-13 | Synthetic method and equipment for tetramethylammonium hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010814941.4A CN111962096B (en) | 2020-08-13 | 2020-08-13 | Synthetic method and equipment for tetramethylammonium hydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111962096A CN111962096A (en) | 2020-11-20 |
| CN111962096B true CN111962096B (en) | 2021-12-10 |
Family
ID=73364865
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010814941.4A Active CN111962096B (en) | 2020-08-13 | 2020-08-13 | Synthetic method and equipment for tetramethylammonium hydroxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111962096B (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52124038A (en) * | 1976-04-13 | 1977-10-18 | Kokoku Rubber Ind | Conductive resin compositions |
| CN1077758A (en) * | 1993-05-17 | 1993-10-27 | 核工业北京化工冶金研究院 | Graphite anode that electrolysis of aqueous chloride solution is used and manufacture method thereof |
| JPH05320968A (en) * | 1991-08-30 | 1993-12-07 | Nobuatsu Watanabe | Method for organic electrolytic fluoration |
| CN2698812Y (en) * | 2004-04-21 | 2005-05-11 | 杨凤林 | Electrochemical reactor for in situ hydrogen peroxide generation by electrocatalysis |
| CN103887531A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Ordered gas diffusion electrode and preparation and application thereof |
| CN104685104A (en) * | 2012-06-12 | 2015-06-03 | 莫拿什大学 | Gas permeable electrode and method of manufacture |
| CN108396327A (en) * | 2018-05-23 | 2018-08-14 | 梁小朝 | A kind of device and method of continuity method production tetramethylammonium hydroxide |
| CN208532944U (en) * | 2018-05-23 | 2019-02-22 | 梁小朝 | A kind of equipment of continuity method production tetramethylammonium hydroxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2803856B1 (en) * | 2000-01-13 | 2002-07-05 | Atofina | SYNTHESIS OF TETRAMETHYLAMMONIUM HYDROXIDE |
-
2020
- 2020-08-13 CN CN202010814941.4A patent/CN111962096B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52124038A (en) * | 1976-04-13 | 1977-10-18 | Kokoku Rubber Ind | Conductive resin compositions |
| JPH05320968A (en) * | 1991-08-30 | 1993-12-07 | Nobuatsu Watanabe | Method for organic electrolytic fluoration |
| CN1077758A (en) * | 1993-05-17 | 1993-10-27 | 核工业北京化工冶金研究院 | Graphite anode that electrolysis of aqueous chloride solution is used and manufacture method thereof |
| CN2698812Y (en) * | 2004-04-21 | 2005-05-11 | 杨凤林 | Electrochemical reactor for in situ hydrogen peroxide generation by electrocatalysis |
| CN104685104A (en) * | 2012-06-12 | 2015-06-03 | 莫拿什大学 | Gas permeable electrode and method of manufacture |
| CN103887531A (en) * | 2012-12-21 | 2014-06-25 | 中国科学院大连化学物理研究所 | Ordered gas diffusion electrode and preparation and application thereof |
| CN108396327A (en) * | 2018-05-23 | 2018-08-14 | 梁小朝 | A kind of device and method of continuity method production tetramethylammonium hydroxide |
| CN208532944U (en) * | 2018-05-23 | 2019-02-22 | 梁小朝 | A kind of equipment of continuity method production tetramethylammonium hydroxide |
Non-Patent Citations (2)
| Title |
|---|
| High capacitance properties of polyaniline by electrochemical deposition on a porous carbon substrate;S.K. Mondal et al;《Electrochimica Acta》;20061213;第3258-3264页 * |
| 石墨负极表面聚合物功能保护膜对锂离子电池存储寿命的提升;李宇杰 等;《高等学校化学学报》;20191231;第40卷(第12期);第2542-2548页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111962096A (en) | 2020-11-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4062753A (en) | Electrolysis method and apparatus | |
| JP2690730B2 (en) | Method for improving the purity of quaternary ammonium hydroxide | |
| TWI390083B (en) | An electrolytic electrode and a method for producing a quaternary ammonium aqueous ammonium hydroxide solution using the electrolytic electrode | |
| CN104087968B (en) | The selective electrochemical reduction method of haloperidid formic acid or its esters compound | |
| CN107904618B (en) | Method for preparing parallel-connection hydrogen halide acid by four-chamber three-membrane electrolysis of short-chain quaternary ammonium hydroxide | |
| CN105018962A (en) | Electrochemical method for hydrodechlorination of chlorinated organic pollutant | |
| CN102181880A (en) | Selective electrolysis hydrogenation and dechlorination method for chlorinated organic matter | |
| US4938854A (en) | Method for purifying quaternary ammonium hydroxides | |
| CN110468429B (en) | Activation method of silver electrode | |
| CN101522628B (en) | Improved electrochemical reduction of halogenated 4-aminopicolinic acids | |
| CN106350832A (en) | Preparation method of molecular sieve template high-purity hexamethonium hydroxide water solution | |
| CN111962096B (en) | Synthetic method and equipment for tetramethylammonium hydroxide | |
| JP2013508564A (en) | Improved silver cathode activation | |
| CN101603179A (en) | 3,5, the electrolyzing synthesizing method of 6-trichloropyridine formic acid | |
| CN101591787B (en) | Electrochemical synthesis method for aminophenylarsonic acid | |
| CN1523135A (en) | Process for preparing tetramethyl ammonium hydroxide by electrolysis-electrodialysis | |
| EP1487747B1 (en) | Use of an electrolyte composition for electrolysis of brine, method for electrolysis of brine, and for preparation of sodium hydroxide | |
| US7666293B2 (en) | Electrochemical reduction of halogenated 4-aminopicolinic acids | |
| CN106929875B (en) | A method of ferrate is prepared based on carbon plate plating iron | |
| Misono et al. | Selective electroreduction of the benzene nucleus | |
| KR910005058B1 (en) | Method of p-aminophenol | |
| CN112593255B (en) | Electrochemical preparation method of p-aminophenyl-beta-hydroxyethyl sulfone | |
| CA1040581A (en) | Electrochemical adiponitrile formation from acrylonitrile using ammonia | |
| KR940003268B1 (en) | Method of l-cysteine | |
| CN1238564C (en) | Process for electrically synthesizing glyoxylic acid by shell-and-tube fixed bed |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 061000 Lingang chemical industry park, Cangzhou City, Hebei Province Patentee after: Xinlian Electronic Materials Technology Co.,Ltd. Address before: 061000 Lingang chemical industry park, Cangzhou City, Hebei Province Patentee before: CANGZHOU SUNHEAT CHEMICALS CO.,LTD. |
|
| CP01 | Change in the name or title of a patent holder |