CN103388155A - Device and method for continuously preparing tetramethylammonium hydroxide - Google Patents
Device and method for continuously preparing tetramethylammonium hydroxide Download PDFInfo
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Abstract
The invention discloses a device and method for continuously preparing tetramethylammonium hydroxide, aiming to solve the problems of high production cost and high impurity content of the existing tetramethylammonium hydroxide production methods. The device comprises an ion exchange column, an electrolytic cell, an anode material tank, a cathode material tank, a cathode gas storage tank, an anode gas storage tank, a boiler, a heating trough, a first liquid pump, a second liquid pump, a third liquid pump, a first pipeline, a second pipeline, a third pipeline and a fourth pipeline. In the method, a tetramethyl ammonium bicarbonate aqueous solution is taken as anode liquor, a tetramethyl ammonium hydroxide dilute solution is taken as cathode liquor, through the mutual cooperation of the production device and a process, the process flow can be effectively shortened, and the production cost can be significantly reduced. The device and method disclosed by the invention are short in process flow, simple in operation and low in production cost, and prepared products are high in purity and high in yield, so that the energy efficiency is effectively reduced, and the defects of high power consumption and low current efficiency existing in the prior art are overcome, therefore, the device and method disclosed by the invention can adapt to the needs of industrial production.
Description
Technical field
The present invention relates to chemical field, especially electrochemical field, be specially a kind of apparatus and method of continuous production Tetramethylammonium hydroxide, and the method can effectively reduce the temperature of reaction in preparation process, effectively improve yield and the purity of Tetramethylammonium hydroxide, reduce its production cost.
Background technology
Tetramethylammonium hydroxide, be called for short TMAH, is a kind of important organic bases.It is the highly basic with the caustic alkali equality strength, can residual any material after thermal degradation, especially can residual conductive ionic species, thereby be widely used in electronics industry.Cleaning, etching, polishing reagent that it is often used as the unicircuit version, also can be used as the synthetic catalyst of the organosilicon products such as silicon rubber, silicone resin and silicone oil.Along with the development of large-scale integrated circuit, increasing for the demand of Tetramethylammonium hydroxide.
At present, the production method of Tetramethylammonium hydroxide mainly contains the precipitator method, ion-exchange-resin process, additive process, ionic membrane method and ion-exchange membrane electrolysis etc.Wherein, adopt precipitator method production Tetramethylammonium hydroxide, have the shortcomings such as production cost is high, product purity is not high; Adopt ion-exchange-resin process production Tetramethylammonium hydroxide, in pre-treatment and regenerative process, can consume a large amount of high pure acid alkalis, produce simultaneously a large amount of spent acid salkali waste, thereby environment is caused severe contamination, simultaneously, resin demand is large, and production cost is high; Adopt additive process production Tetramethylammonium hydroxide, need to carry out in high-pressure sealed environment, intermediate product is very unstable, and by product is more, and product purity is low, later stage purification processes difficulty; Ionic membrane method production Tetramethylammonium hydroxide, exist ion-exchange speed slow, the problem that in product, impurity ion content is high, purity is low.Due to the problem that aforesaid method ubiquity production cost is high, foreign matter content is high, therefore, in the urgent need to a kind of Tetramethylammonium hydroxide preparation method that can effectively reduce foreign matter content and production cost in product.
Summary of the invention
Goal of the invention of the present invention is:, for the problem that production method ubiquity production cost is high, foreign matter content is high of existing Tetramethylammonium hydroxide, provide a kind of apparatus and method of continuous production Tetramethylammonium hydroxide.The method is take the tetramethyl ammonium hydrogen carbonate aqueous solution as anolyte, and the Tetramethylammonium hydroxide dilute solution is catholyte, and by cooperatively interacting of production equipment and technique, effectively shortened process, significantly reduce production costs.Technical process of the present invention is short, simple to operate, production cost is low, simultaneously prepared product purity is high, yield is high, the by product that produces also is fully used, effectively reduce Energy efficiency, overcome the shortcoming that power consumption is high, current efficiency is low that prior art exists, can adapt to the needs of suitability for industrialized production.
To achieve these goals, the present invention adopts following technical scheme:
a kind of device of continuous production Tetramethylammonium hydroxide, comprise ion exchange column, electrolyzer, the anode material tank, the cathode materials tank, the negative electrode gas-holder, the anode gas-holder, boiler, heating tank, the first liquid pump, the second liquid pump, the 3rd liquor pump, the first pipeline, second pipe, the 3rd pipeline, the 4th pipeline, described electrolyzer is by anolyte compartment, anode electrode, cathode compartment, cathode electrode, perfluorinated ion-exchange membrane, the anode liquid-inlet pipe, the anode drain pipe, the anode escape pipe, the negative electrode liquid-inlet pipe, the negative electrode drain pipe, the negative electrode escape pipe forms, and described anode material tank is connected with the anode liquid-inlet pipe by the first pipeline, described ion exchange column, the first liquid pump is separately positioned on the first pipeline, described cathode materials tank is connected with the negative electrode liquid-inlet pipe by second pipe, described second liquid pump is arranged on second pipe, be provided with water and several thickeners in described heating tank, described thickener is connected with the negative electrode drain pipe by the 3rd pipeline, and described the 3rd liquor pump is arranged on the 3rd pipeline, and described anode escape pipe is connected with the anode gas-holder, described negative electrode escape pipe is connected with the negative electrode gas-holder, described anode gas-holder, the negative electrode gas-holder is connected with boiler respectively, and described boiler is connected with heating tank by the 4th pipeline.
Described ion exchange column is H type cationic exchange coloum.
Also be provided with heating unit in described heating tank.
Adopt the method for the device of aforementioned continuous production Tetramethylammonium hydroxide, comprise the steps:
(a) initialize: the raw material anolyte in the anode material tank adds in anolyte compartment after ion exchange column, simultaneously the raw material catholyte in the cathode materials tank is added in cathode compartment, then anode electrode, cathode electrode are connected with direct current respectively, carry out constant-current electrolysis, the current density of constant-current electrolysis is 0.3-0.4KA/m
2, electrolysis 1.5-2h, complete initialization procedure, and wherein, the anodic gas that anolyte compartment produces enters in the anode gas-holder by the anode escape pipe, and the hydrogen that negative electrode produces enters in the negative electrode gas-holder by the negative electrode escape pipe;
(b) stably manufactured: after initialization procedure finishes, hydrogen in anodic gas in the anode gas-holder, negative electrode gas-holder is passed in boiler and carries out combustion reactions, the reactant gases that combustion reactions produces enters in the water of heating tank by the 4th pipeline, thickener is heated, simultaneously with the electrolysis Auto-regulating System of Density of Heavy Medium of constant-current electrolysis to 0.45-0.6KA/m
2And by the second liquid pump, the raw material catholyte in the cathode materials tank is pumped in cathode compartment, the feed rate of second liquid pump is 0.05-0.075L/h, by the 3rd liquor pump, the catholyte in cathode compartment is pumped in thickener, the feed rate of the 3rd liquor pump is identical with the feed rate of second liquid pump; After catholyte heating 4-6h in thickener, take out the product Tetramethylammonium hydroxide in thickener;
(c) produce continuously: when the anolyte mass concentration in anolyte compartment is reduced to 10-15%, by the first liquid pump, the raw material anolyte is pumped in anolyte compartment, controlling electrolysis density is 0.45-0.6KA/m
2, the feed rate of second liquid pump, the 3rd liquor pump is 0.05-0.075L/h, keeps the carrying out of boiler internal combustion reaction, repeating step (c), can realize the continuous production of Tetramethylammonium hydroxide.
In described step (a), the raw material anolyte is the tetramethyl ammonium hydrogen carbonate solution of mass concentration 28-35%, and the raw material catholyte is the tetramethyl ammonium hydroxide solution of mass concentration 5-15%.
In described step (a), raw material anolyte in the anode material tank adds in anolyte compartment after ion exchange column, simultaneously the raw material catholyte in the cathode materials tank is added in cathode compartment, then anode electrode, cathode electrode are connected with direct current respectively, carry out constant-current electrolysis, the current density of constant-current electrolysis is 0.35KA/m
2, electrolysis 2h, complete initialization procedure.
In described step (b), after initialization procedure finishes, hydrogen in anodic gas in the anode gas-holder, negative electrode gas-holder is passed in boiler and carries out combustion reactions, the reactant gases that combustion reactions produces enters in the water of heating tank by the 4th pipeline, thickener is heated, simultaneously with the electrolysis Auto-regulating System of Density of Heavy Medium of constant-current electrolysis to 0.5KA/m
2, and by the second liquid pump, the raw material catholyte in the cathode materials tank is pumped in cathode compartment, by the 3rd liquor pump, the catholyte in cathode compartment being pumped in thickener, the feed rate of second liquid pump, the 3rd liquor pump is 0.06L/h; After catholyte heating 5h in thickener, take out the product Tetramethylammonium hydroxide in thickener.
In described step (b), after initialization procedure finishes, hydrogen in anodic gas in the anode gas-holder, negative electrode gas-holder is passed in boiler and carries out combustion reactions, the reactant gases that combustion reactions produces enters in the water of heating tank by the 4th pipeline, thickener is heated, simultaneously with the electrolysis Auto-regulating System of Density of Heavy Medium of constant-current electrolysis to 0.45KA/m
2And by the second liquid pump, the raw material catholyte in the cathode materials tank is pumped in cathode compartment, by the 3rd liquor pump, the catholyte in cathode compartment is pumped in thickener, the feed rate of second liquid pump, the 3rd liquor pump is 0.075L/h, after catholyte heating 4.5h in thickener, take out the product Tetramethylammonium hydroxide in thickener.
In described step (c), when the anolyte mass concentration in anolyte compartment is reduced to 15%, by the first liquid pump, the raw material anolyte is pumped in anolyte compartment, controlling electrolysis density is 0.45KA/m
2, the feed rate of second liquid pump, the 3rd liquor pump is 0.075L/h, keeps the carrying out of boiler internal combustion reaction, repeating step (c), can realize the continuous production of Tetramethylammonium hydroxide.
The mode that the present invention adopts ion-exchange and ion-exchange membrane electrolysis to combine prepares Tetramethylammonium hydroxide, and the method technique is simple, and finished product purity is high, and production cost is low, and environmentally safe can be prepared the Tetramethylammonium hydroxide of high purity electronic-grade.In the clear 62-190890 of patent JP., the clear 61-180588 of JP., the clear 63-24080 of JP., US4776929 and WO9001076, all adopt electrolysis mode to prepare the high purity Tetramethylammonium hydroxide, catholyte all adopts pure water, in electrolytic process, concentration of electrolyte changes greatly, and is large for the membrane properties impact, simultaneously, the following problem of these method ubiquities: 1) contain the impurity negatively charged ion of trace in electrolysate, as chlorion, bromide anion etc.; 2) catholyte, anode solution concentration are poor large, cause the two poles of the earth change in concentration large, have affected the work-ing life of barrier film, and production cost is increased.CN200910099696.7, CN 201110109673.7 and CN 201110380374.7 all adopt ion-exchange membrane electrolysis to prepare Tetramethylammonium hydroxide, the raw material that adopts is tetramethyl ammonium hydrogen carbonate, and there is the problem that production cost is high, product purity is low, current efficiency is low in these methods.And the present invention adopts the tetramethyl ammonium hydrogen carbonate solution of mass concentration 28-35% as anolyte, use the tetramethyl ammonium hydroxide solution of mass concentration 5-15% as catholyte, by the improvement to Preparation equipment, and preparation technology's optimization, thereby can prepare highly purified Tetramethylammonium hydroxide.Adopt the present invention, can realize the serialization production of Tetramethylammonium hydroxide, foreign matter content is low, the perfluorinated ion-exchange membrane long service life, production cost is low, and by the reasonable utilization to Exhaust Gas, effectively reduce the disposal costs of Exhaust Gas, improved utilization efficiency of heat energy.
Method of the present invention comprises the steps: (1) initialize, (2) stably manufactured, and (3) produce continuously.In step (1) initialize, at first raw material anolyte in the anode material tank enters in anolyte compartment after ion exchange column, the raw material catholyte is added in cathode compartment, then anode electrode, cathode electrode are connected with direct current respectively, carry out constant-current electrolysis, the current density of constant-current electrolysis is 0.3-0.4KA/m
2, electrolysis 1.5-2h, complete initialization procedure.The raw material anolyte is the tetramethyl ammonium hydrogen carbonate solution (example: the tetramethyl ammonium hydrogen carbonate of getting 28-35g of mass concentration 28-35%, add water and be mixed with the tetramethyl ammonium hydrogen carbonate solution that total mass is 100g), the raw material catholyte is the tetramethyl ammonium hydroxide solution of mass concentration 5-15%.Adopt this step, can guarantee to have certain concentration difference between the cathode compartment of electrolyzer and anolyte compartment, be conducive to the conversion of tetramethyl ammonium hydrogen carbonate, simultaneously, by initialization step, can make relative the stablizing of the inner maintenance of electrolyzer, be conducive to extend the work-ing life of perfluorinated ion-exchange membrane.The ion exchange column that adopts is H type cationic exchange coloum, and can be the divinylbenzene massfraction is the high glue connection degree polystyrolsulfon acid amberlite of 10 %.
Initialization procedure enters stably manufactured after finishing.Hydrogen in anodic gas in the anode gas-holder, negative electrode gas-holder is passed in boiler and carries out combustion reactions, and the reactant gases that combustion reactions produces enters in the water of heating tank by the 4th pipeline, and thickener is heated.Simultaneously with the electrolysis Auto-regulating System of Density of Heavy Medium of constant-current electrolysis to 0.45-0.6KA/m
2, and by the second liquid pump, the raw material catholyte in the cathode materials tank is pumped in cathode compartment, by the 3rd liquor pump, the catholyte in cathode compartment being pumped in thickener, the feed rate of second liquid pump, the 3rd liquor pump is 0.05-0.075L/h.After initialization procedure, the catholyte mass concentration in cathode compartment is promoted to 15-25%, can meet concentrated requirement of purifying.Simultaneously, the fusing point of Tetramethylammonium hydroxide is 63 ℃, and boiling point is 120 ℃, very easily decomposes, and in electrolytic process, the heat that electrolysis produces can make Tetramethylammonium hydroxide decompose.Because electrolyzer is sealed state, can't dispel the heat by modes such as stirrings, thereby Tetramethylammonium hydroxide is decomposed, reduce electrolytic efficiency, the Tetramethylammonium hydroxide yield is reduced.Simultaneously, stir and also may make in electrolyzer and contain impurity, affect the purity of product.The present patent application people, by studying for a long period of time, exploring,, by controlling the flow of second liquid pump, the 3rd liquor pump, can effectively address this problem.By the second liquid pump, the raw material catholyte is pumped in cathode compartment, the temperature of raw material catholyte is lower than the temperature in electrolyzer, and it can make the liquid of electrolyzer inside occur to flow simultaneously, and the temperature in electrolyzer is effectively reduced; On the other hand, by cooperatively interacting of second, third electrolysis pump, the catholyte of high density is transported in thickener, and the concentration in cathode compartment is reduced, thereby keep the concentration difference in electrolyzer, be conducive to the carrying out that reacts.Simultaneously, electrolysis density and feed rate must cooperatively interact, and could effectively guarantee the stability of operation in electrolyzer; Feed rate is too fast, can make the cathode liquid concentration in cathode compartment too low, and the later stage concentrated cost is raise; Feed rate is too low, can make the excess Temperature in electrolyzer, and final productive rate and electrolytic efficiency are reduced.
Wherein, the anodic gas (being oxygen and carbonic acid gas) that anolyte compartment produces enters into the anode gas-holder by the anode escape pipe, and the hydrogen that negative electrode produces enters in the negative electrode gas-holder by the negative electrode escape pipe.Hydrogen in anodic gas in the anode gas-holder, negative electrode gas-holder passes in boiler and carries out combustion reactions, and the material that produces is directly utilized, and effectively reduces energy consumption, reduces production costs and storage cost.Because boiler is connected with heating tank by the 4th pipeline, the reactant gases that combustion reactions produces can enter into heating tank, thereby thickener is heated.In stably manufactured and continuous production stage, the heat that the boiler internal combustion produces can meet the demand for heat of thickener, thereby realizes the laser heating to thickener, and catholyte is concentrated in thickener, finally obtain highly purified product Tetramethylammonium hydroxide.In the present invention, be provided with several thickeners, the 3rd liquor pump can be delivered to catholyte in different thickeners, thereby realizes serialization production., in the lower area of some temperature, can also be provided with heating unit in heating tank.
When the anolyte mass concentration in anolyte compartment is reduced to 10-15%, by the first liquid pump, the raw material anolyte is pumped in anolyte compartment again, simultaneously, by the second liquid pump, the raw material catholyte in the cathode materials tank is pumped in cathode compartment, by the 3rd liquor pump, the catholyte in cathode compartment is pumped in thickener, the feed rate of second liquid pump, the 3rd liquor pump is 0.05-0.075L/h, and controlling electrolysis density is 0.45-0.6KA/m
2, keeping normally carrying out of boiler internal combustion reaction, repeating step (c), can realize uninterrupted, the production continuously of Tetramethylammonium hydroxide.
In existing technique, usually need to carry out evaporation concentration, natural cooling crystallization to the Tetramethylammonium hydroxide dilute solution that obtains, just can obtain highly purified Tetramethylammonium hydroxide, and the present invention can guarantee low-temperature heat owing to adopting the boiler heat production to heat the Tetramethylammonium hydroxide dilute solution, effective save energy, reduce energy loss, simultaneously, avoided the handling problems of hydrogen, reduce energy consumption, also avoided the infringement to environment.
Wherein, the perfluorinated ion-exchange membrane that adopts in the present invention can be perfluorocarboxylic acid-perfluorinated sulfonic acid composite membrane, and cathode electrode can be Ni-based mesh electrode, and anode electrode is titanium base net shape electrode.
Electrolyzer is led to direct current carry out constant-current electrolysis, under electric field action, tetramethyl-ammonium radical ion in the tetramethyl ammonium hydrogen carbonate solution of anolyte compartment moves to cathode direction, and through perfluorinated ion-exchange membrane, enter in cathode compartment, and carbonic acid hydrogen ion can't and be enriched in anolyte compartment through perfluorinated ion-exchange membrane, and the migration of anode direction, discharge generates oxygen and carbonic acid gas on anode; In cathode compartment, water molecules is decomposed into hydrogen and hydroxide ion on negative electrode, and hydroxide ion is combined with the tetramethyl-ammonium radical ion of migration, thereby generates Tetramethylammonium hydroxide.
The invention provides a kind of apparatus and method of continuous production Tetramethylammonium hydroxide, by this device, adopt ion-exchange membrane electrolysis to prepare Tetramethylammonium hydroxide, its technical process is short, and is simple to operate, production cost is low, simultaneously prepared product purity is high, yield is high, and the by product that produces also is fully used, and effectively reduces Energy efficiency, overcome the shortcoming that power consumption is high, current efficiency is low that prior art exists, can adapt to the needs of suitability for industrialized production.
During electrolysis, hydrogen and the oxygen of generation are utilized effectively, and have not only reduced energy consumption, and have greatly improved the utilising efficiency of hydrogen.The present invention is environmentally friendly, has characteristics pollution-free, toxicological harmless, and current efficiency reaches more than 95%, and product yield is higher than 92%, and is existing for prior art, has significant progress.
Description of drawings
Examples of the present invention will be described by way of reference to the accompanying drawings, wherein:
Fig. 1 is structural representation of the present invention.
mark in figure: 1 is the anode material tank, 2 is the cathode materials tank, 3 is the negative electrode gas-holder, 4 is heating tank, 5 is the first liquid pump, 6 is the second liquid pump, 7 is the 3rd liquor pump, 8 is anolyte compartment, 9 is anode electrode, 10 is cathode compartment, 11 is cathode electrode, 12 is perfluorinated ion-exchange membrane, 13 is the anode liquid-inlet pipe, 14 is the anode drain pipe, 15 is the anode escape pipe, 16 is the negative electrode liquid-inlet pipe, 17 is the negative electrode drain pipe, 18 is the negative electrode escape pipe, 19 is the first pipeline, 20 is second pipe, 21 is thickener, 22 is the 3rd pipeline, 23 is boiler, 24 is the anode gas-holder, 25 is the 4th pipeline.
Embodiment
Disclosed all features in this specification sheets, or the step in disclosed all methods or process, except mutually exclusive feature and/or step, all can make up by any way.
Disclosed arbitrary feature in this specification sheets, unless special narration all can be replaced by other equivalences or the alternative features with similar purpose.That is, unless special narration, each feature is an example in a series of equivalences or similar characteristics.
As shown in Figure 1, this device comprises ion exchange column, electrolyzer, anode material tank, cathode materials tank, negative electrode gas-holder, anode gas-holder, boiler, heating tank, first liquid pump, second liquid pump, the 3rd liquor pump, the first pipeline, second pipe, the 3rd pipeline, the 4th pipeline to a kind of device for preparing Tetramethylammonium hydroxide provided by the invention.Electrolyzer is comprised of anolyte compartment, anode electrode, cathode compartment, cathode electrode, perfluorinated ion-exchange membrane, anode liquid-inlet pipe, anode drain pipe, anode escape pipe, negative electrode liquid-inlet pipe, negative electrode drain pipe, negative electrode escape pipe.The anode material tank is connected with the anode liquid-inlet pipe by the first pipeline, and ion exchange column, first liquid pump are separately positioned on the first pipeline.The cathode materials tank is connected with the negative electrode liquid-inlet pipe by second pipe, and the second liquid pump is arranged on second pipe.Be provided with water and several thickeners in heating tank, thickener floating with the water surface on, thickener is connected with the negative electrode drain pipe by the 3rd pipeline, the 3rd liquor pump is arranged on the 3rd pipeline.The anode escape pipe is connected with the anode gas-holder, and the negative electrode escape pipe is connected with the negative electrode gas-holder, and anode gas-holder, negative electrode gas-holder are connected with boiler respectively, and boiler is connected with heating tank by the 4th pipeline.Hydrogen in anodic gas in the anode gas-holder, negative electrode gas-holder passes in boiler and carries out combustion reactions, and the reactant gases that combustion reactions produces directly enters in heating tank, and thickener is heated., as preferably, also be provided with heating unit in heating tank.Wherein, perfluorinated ion-exchange membrane is perfluorocarboxylic acid-perfluorinated sulfonic acid composite membrane, and model is the N966 type, buys from E.I.Du Pont Company useful area 50cm
2Cathode electrode is Ni-based mesh electrode, and anode electrode is titanium base net shape electrode, buys from chemical industry equipment company limited of Zibo Golden Bridge.Following embodiment all adopts this device.
Embodiment 1
The raw materials anolyte: take the 28kg tetramethyl ammonium hydrogen carbonate, add wherein 72kg water, be configured to the tetramethyl ammonium hydrogen carbonate solution of 100kg, the mass concentration of this tetramethyl ammonium hydrogen carbonate solution is 28%.
The raw materials catholyte: take the 7kg Tetramethylammonium hydroxide, add wherein 93kg water, be configured to the tetramethyl ammonium hydroxide solution of 100kg, the mass concentration of this tetramethyl ammonium hydroxide solution is 7%.
Production process is as follows.
(1) initialize: the raw material anolyte is added in anolyte compartment after the dialysis of H type cationic exchange coloum, simultaneously the raw material catholyte is added in cathode compartment, then anode electrode, cathode electrode are connected with direct current respectively, carry out constant-current electrolysis, the current density of constant-current electrolysis is 0.3KA/m
2, electrolysis 1.5h, complete initialization procedure, and wherein, oxygen and carbonic acid gas (being anodic gas) that anolyte compartment produces enter into the anode gas-holder by the anode escape pipe, and the hydrogen that negative electrode produces enters in the negative electrode gas-holder by the negative electrode escape pipe.
(2) stably manufactured: after initialization procedure finishes, hydrogen in anodic gas in the anode gas-holder, negative electrode gas-holder is passed in boiler and carries out combustion reactions, the reactant gases that combustion reactions produces enters in the water of heating tank by the 4th pipeline, and thickener is heated.Simultaneously with the electrolysis Auto-regulating System of Density of Heavy Medium of constant-current electrolysis to 0.45KA/m
2And by the second liquid pump, the raw material catholyte in the cathode materials tank is pumped in cathode compartment, the feed rate of second liquid pump is 0.05L/h, simultaneously, by the 3rd liquor pump, the catholyte in cathode compartment is pumped in thickener, the feed rate of the 3rd liquor pump is identical with the feed rate of second liquid pump.The heat that in boiler, reaction produces enters into heating tank, thereby the catholyte in thickener is heated and concentrates, and after the catholyte heating 6h in thickener, takes out, and obtains product.Again after 6h, but secondary takes out product again.Namely, every 6h, get first product.
(3) produce continuously: when the anolyte mass concentration in anolyte compartment is reduced to 10%, by the first liquid pump, the raw material anolyte is pumped in anolyte compartment again, simultaneously, by the second liquid pump, the raw material catholyte in the cathode materials tank is pumped in cathode compartment, by the 3rd liquor pump, the catholyte in cathode compartment is pumped in thickener, the feed rate of second liquid pump, the 3rd liquor pump is 0.05-0.075L/h, the carrying out that keeps the reaction of boiler internal combustion, repeating step (3), can realize the continuous production of Tetramethylammonium hydroxide.
The prepared Tetramethylammonium hydroxide purity of the present embodiment is high, and its product yield is 93.2%, and current efficiency is 97.2%.
Take the tetramethyl ammonium hydrogen carbonate solution of mass concentration 30% as the raw material anolyte, take the tetramethyl ammonium hydroxide solution of mass concentration 10% as the raw material catholyte.
Production process is as follows.
(1) initialize: the raw material anolyte is added in anolyte compartment after the ion exchange column dialysis, simultaneously the raw material catholyte is added in cathode compartment, then anode electrode, cathode electrode are connected with direct current respectively, carry out constant-current electrolysis, the current density of constant-current electrolysis is 0.35KA/m
2, electrolysis 2h, complete initialization procedure, and wherein, oxygen and carbonic acid gas (being anodic gas) that anolyte compartment produces enter into the anode gas-holder by the anode escape pipe, and the hydrogen that negative electrode produces enters in the negative electrode gas-holder by the negative electrode escape pipe.
(2) stably manufactured: after initialization procedure finishes, hydrogen in anodic gas in the anode gas-holder, negative electrode gas-holder is passed in boiler and carries out combustion reactions, the reactant gases that combustion reactions produces enters in the water of heating tank by the 4th pipeline, and thickener is heated.Simultaneously with the electrolysis Auto-regulating System of Density of Heavy Medium of constant-current electrolysis to 0.5KA/m
2, and by the second liquid pump, the raw material catholyte in the cathode materials tank is pumped in cathode compartment, simultaneously, by the 3rd liquor pump, the catholyte in cathode compartment being pumped in thickener, the feed rate of second liquid pump, the 3rd liquor pump is 0.06L/h.The heat that in boiler, reaction produces enters into heating tank, thereby the catholyte in thickener is heated and concentrates, and after the catholyte heating 5.5h in thickener, takes out, and obtains product., every 5.5h, get first product.
(3) produce continuously: when the anolyte mass concentration in anolyte compartment is reduced to 10%, by the first liquid pump, the raw material anolyte is pumped in anolyte compartment again, simultaneously, by the second liquid pump, the raw material catholyte in the cathode materials tank is pumped in cathode compartment, by the 3rd liquor pump, the catholyte in cathode compartment is pumped in thickener, the feed rate of second liquid pump, the 3rd liquor pump is 0.06L/h, the carrying out that keeps the reaction of boiler internal combustion, repeating step (3), can realize the continuous production of Tetramethylammonium hydroxide.
The yield of the Tetramethylammonium hydroxide that the present embodiment is prepared is 93.6%, and current efficiency is 98.35%.
Embodiment 3
Take the tetramethyl ammonium hydrogen carbonate solution of mass concentration 32% as the raw material anolyte, take the tetramethyl ammonium hydroxide solution of mass concentration 12% as the raw material catholyte.
Production process is as follows.
(1) initialize: the raw material anolyte is added in anolyte compartment after the dialysis of H type cationic exchange coloum, simultaneously the raw material catholyte is added in cathode compartment, then anode electrode, cathode electrode are connected with direct current respectively, carry out constant-current electrolysis, the current density of constant-current electrolysis is 0.38KA/m
2, electrolysis 1.8h, complete initialization procedure, and wherein, oxygen and carbonic acid gas (being anodic gas) that anolyte compartment produces enter into the anode gas-holder by the anode escape pipe, and the hydrogen that negative electrode produces enters in the negative electrode gas-holder by the negative electrode escape pipe.
(2) stably manufactured: after initialization procedure finishes, hydrogen in anodic gas in the anode gas-holder, negative electrode gas-holder is passed in boiler and carries out combustion reactions, the reactant gases that combustion reactions produces enters in the water of heating tank by the 4th pipeline, and thickener is heated.Simultaneously with the electrolysis Auto-regulating System of Density of Heavy Medium of constant-current electrolysis to 0.55KA/m
2, and by the second liquid pump, the raw material catholyte in the cathode materials tank is pumped in cathode compartment, simultaneously, by the 3rd liquor pump, the catholyte in cathode compartment being pumped in thickener, the feed rate of second liquid pump, the 3rd liquor pump is 0.065L/h.The heat that in boiler, reaction produces enters into heating tank, thereby the catholyte in thickener is heated and concentrates, and after the catholyte heating 5h in thickener, takes out, and obtains product., every 5h, get first product.
(3) produce continuously: when the anolyte mass concentration in anolyte compartment is reduced to 12%, by the first liquid pump, the raw material anolyte is pumped in anolyte compartment again, simultaneously, by the second liquid pump, the raw material catholyte in the cathode materials tank is pumped in cathode compartment, by the 3rd liquor pump, the catholyte in cathode compartment is pumped in thickener, the feed rate of second liquid pump, the 3rd liquor pump is 0.065L/h, the carrying out that keeps the reaction of boiler internal combustion, repeating step (3), can realize the continuous production of Tetramethylammonium hydroxide.
The yield of the Tetramethylammonium hydroxide that the present embodiment is prepared is 93.32%, and current efficiency is 97.33%.
Embodiment 4
Take the tetramethyl ammonium hydrogen carbonate solution of mass concentration 32% as the raw material anolyte, take the tetramethyl ammonium hydroxide solution of mass concentration 10% as the raw material catholyte.
Production process is as follows.
(1) initialize: the raw material anolyte is added in anolyte compartment after the dialysis of H type cationic exchange coloum, simultaneously the raw material catholyte is added in cathode compartment, then anode electrode, cathode electrode are connected with direct current respectively, carry out constant-current electrolysis, the current density of constant-current electrolysis is 0.35KA/m
2, electrolysis 2h, complete initialization procedure, and wherein, oxygen and carbonic acid gas (being anodic gas) that anolyte compartment produces enter into the anode gas-holder by the anode escape pipe, and the hydrogen that negative electrode produces enters in the negative electrode gas-holder by the negative electrode escape pipe.
(2) stably manufactured: after initialization procedure finishes, hydrogen in anodic gas in the anode gas-holder, negative electrode gas-holder is passed in boiler and carries out combustion reactions, the reactant gases that combustion reactions produces enters in the water of heating tank by the 4th pipeline, and thickener is heated.Simultaneously with the electrolysis Auto-regulating System of Density of Heavy Medium of constant-current electrolysis to 0.55KA/m
2, and by the second liquid pump, the raw material catholyte in the cathode materials tank is pumped in cathode compartment, simultaneously, by the 3rd liquor pump, the catholyte in cathode compartment being pumped in thickener, the feed rate of second liquid pump, the 3rd liquor pump is 0.065L/h.The heat that in boiler, reaction produces enters into heating tank, thereby the catholyte in thickener is heated and concentrates, and after the catholyte heating 5h in thickener, takes out, and obtains product., every 5h, get first product.
When the anolyte mass concentration in anolyte compartment is reduced to 10%, by the first liquid pump, the raw material anolyte is pumped in anolyte compartment again, simultaneously, by the second liquid pump, the raw material catholyte in the cathode materials tank is pumped in cathode compartment, by the 3rd liquor pump, the catholyte in cathode compartment is pumped in thickener, the feed rate of second liquid pump, the 3rd liquor pump is 0.065L/h, keeps the carrying out of boiler internal combustion reaction, repeating step (3), can realize the continuous production of Tetramethylammonium hydroxide.
The yield of the Tetramethylammonium hydroxide that the present embodiment is prepared is 93.45%, and current efficiency is 97.07%.
Embodiment 5
Take the tetramethyl ammonium hydrogen carbonate solution of mass concentration 35% as the raw material anolyte, take the tetramethyl ammonium hydroxide solution of mass concentration 15% as the raw material catholyte.
Production process is as follows.
(1) initialize: the raw material anolyte is added in anolyte compartment after the dialysis of H type cationic exchange coloum, simultaneously the raw material catholyte is added in cathode compartment, then anode electrode, cathode electrode are connected with direct current respectively, carry out constant-current electrolysis, the current density of constant-current electrolysis is 0.4KA/m
2, electrolysis 1.6h, complete initialization procedure, and wherein, oxygen and carbonic acid gas (being anodic gas) that anolyte compartment produces enter into the anode gas-holder by the anode escape pipe, and the hydrogen that negative electrode produces enters in the negative electrode gas-holder by the negative electrode escape pipe.
(2) stably manufactured: after initialization procedure finishes, hydrogen in anodic gas in the anode gas-holder, negative electrode gas-holder is passed in boiler and carries out combustion reactions, the reactant gases that combustion reactions produces enters in the water of heating tank by the 4th pipeline, and thickener is heated.Simultaneously with the electrolysis Auto-regulating System of Density of Heavy Medium of constant-current electrolysis to 0.6KA/m
2, and by the second liquid pump, the raw material catholyte in the cathode materials tank is pumped in cathode compartment, simultaneously, by the 3rd liquor pump, the catholyte in cathode compartment being pumped in thickener, the feed rate of second liquid pump, the 3rd liquor pump is 0.075L/h.The heat that in boiler, reaction produces enters into heating tank, thereby the catholyte in thickener is heated and concentrates, and after the catholyte heating 4.5h in thickener, takes out, and obtains product., every 4.5h, get first product.
(3) produce continuously: when the anolyte mass concentration in anolyte compartment is reduced to 15%, by the first liquid pump, the raw material anolyte is pumped in anolyte compartment again, simultaneously, by the second liquid pump, the raw material catholyte in the cathode materials tank is pumped in cathode compartment, by the 3rd liquor pump, the catholyte in cathode compartment is pumped in thickener, the feed rate of second liquid pump, the 3rd liquor pump is 0.075L/h, the carrying out that keeps the reaction of boiler internal combustion, repeating step (3), can realize the continuous production of Tetramethylammonium hydroxide.
The yield of the Tetramethylammonium hydroxide that the present embodiment is prepared is 93.02%, and current efficiency is 96.88%.
The present invention is not limited to aforesaid embodiment.The present invention expands to any new feature or any new combination that discloses in this manual, and the arbitrary new method that discloses or step or any new combination of process.
Claims (9)
1. the device of a continuous production Tetramethylammonium hydroxide, is characterized in that, comprises ion exchange column, electrolyzer, anode material tank (1), cathode materials tank (2), negative electrode gas-holder (3), anode gas-holder (24), boiler (23), heating tank (4), first liquid pump (5), second liquid pump (6), the 3rd liquor pump (7), the first pipeline (19), second pipe (20), the 3rd pipeline (22), the 4th pipeline (25), described electrolyzer is by anolyte compartment (8), anode electrode (9), cathode compartment (10), cathode electrode (11), perfluorinated ion-exchange membrane (12), anode liquid-inlet pipe (13), anode drain pipe (14), anode escape pipe (15), negative electrode liquid-inlet pipe (16), negative electrode drain pipe (17), negative electrode escape pipe (18) forms, and described anode material tank (1) is connected with anode liquid-inlet pipe (13) by the first pipeline (19), described ion exchange column, first liquid pump (5) is separately positioned on the first pipeline (19), described cathode materials tank (2) is connected with negative electrode liquid-inlet pipe (16) by second pipe (20), described second liquid pump (6) is arranged on second pipe (20), be provided with water and several thickeners (21) in described heating tank (4), described thickener (21) is connected with negative electrode drain pipe (17) by the 3rd pipeline (22), described the 3rd liquor pump (7) is arranged on the 3rd pipeline (22), described anode escape pipe (15) is connected with anode gas-holder (24), described negative electrode escape pipe (18) is connected with negative electrode gas-holder (3), described anode gas-holder (24), negative electrode gas-holder (3) is connected with boiler (23) respectively, and described boiler (23) is connected with heating tank (4) by the 4th pipeline (25).
2. the device of continuous production Tetramethylammonium hydroxide according to claim 1, is characterized in that, described ion exchange column is H type cationic exchange coloum.
3. the device of according to claim 1-2 described continuous production Tetramethylammonium hydroxide of any one, is characterized in that, described heating tank also is provided with heating unit in (4).
4. the method for according to claim 1-3 described device continuous production of any one Tetramethylammonium hydroxide, is characterized in that, comprises the steps:
(a) initialize: the raw material anolyte in anode material tank (1) adds in anolyte compartment (8) after ion exchange column, simultaneously the raw material catholyte in cathode materials tank (2) is added in cathode compartment (10), then anode electrode (9), cathode electrode (11) are connected with direct current respectively, carry out constant-current electrolysis, the current density of constant-current electrolysis is 0.3-0.4KA/m
2, electrolysis 1.5-2h, complete initialization procedure, and wherein, the anodic gas that anolyte compartment (8) produce enters in anode gas-holder (24) by anode escape pipe (15), and the hydrogen that negative electrode produces enters in negative electrode gas-holder (3) by negative electrode escape pipe (18);
(b) stably manufactured: after initialization procedure finishes, hydrogen in anodic gas in anode gas-holder (24), negative electrode gas-holder (3) is passed in boiler (23) and carries out combustion reactions, the reactant gases that combustion reactions produces enters in the water of heating tank (4) by the 4th pipeline (25), thickener (21) is heated, simultaneously with the electrolysis Auto-regulating System of Density of Heavy Medium of constant-current electrolysis to 0.45-0.6KA/m
2And by second liquid pump (6), the raw material catholyte in cathode materials tank (2) is pumped in cathode compartment (10), the feed rate of second liquid pump (6) is 0.05-0.075L/h, by the 3rd liquor pump (7), the catholyte in cathode compartment (10) is pumped in thickener (21), the feed rate of the 3rd liquor pump (7) is identical with the feed rate of second liquid pump (6); After catholyte heating 4-6h in thickener (21), take out the product Tetramethylammonium hydroxide in thickener (21);
(c) produce continuously: when the anolyte mass concentration in anolyte compartment (8) is reduced to 10-15%, by first liquid pump (5), the raw material anolyte is pumped in anolyte compartment (8), controlling electrolysis density is 0.45-0.6KA/m
2, the feed rate of second liquid pump (6), the 3rd liquor pump (7) is 0.05-0.075L/h, keeps the carrying out of boiler (23) internal combustion reaction, repeating step (c), can realize the continuous production of Tetramethylammonium hydroxide.
5. method according to claim 4, is characterized in that, in described step (a), the raw material anolyte is the tetramethyl ammonium hydrogen carbonate solution of mass concentration 28-35%, and the raw material catholyte is the tetramethyl ammonium hydroxide solution of mass concentration 5-15%.
6. according to claim 4 or 5 described methods, it is characterized in that, in described step (a), raw material anolyte in anode material tank (1) adds in anolyte compartment (8) after ion exchange column, simultaneously the raw material catholyte in cathode materials tank (2) is added in cathode compartment (10), then anode electrode (9), cathode electrode (11) are connected with direct current respectively, carry out constant-current electrolysis, the current density of constant-current electrolysis is 0.35KA/m
2, electrolysis 2h, complete initialization procedure.
7. method according to claim 4, it is characterized in that, in described step (b), after initialization procedure finishes, hydrogen in anodic gas in anode gas-holder (24), negative electrode gas-holder (3) is passed in boiler (23) and carries out combustion reactions, the reactant gases that combustion reactions produces enters in the water of heating tank (4) by the 4th pipeline (25), thickener (21) is heated, simultaneously with the electrolysis Auto-regulating System of Density of Heavy Medium of constant-current electrolysis to 0.5KA/m
2And by second liquid pump (6), the raw material catholyte in cathode materials tank (2) is pumped in cathode compartment (10), by the 3rd liquor pump (7), the catholyte in cathode compartment (10) is pumped in thickener (21), the feed rate of second liquid pump (6), the 3rd liquor pump (7) is 0.06L/h; After catholyte heating 5h in thickener (21), take out the product Tetramethylammonium hydroxide in thickener (21).
8. 5, the 7 described methods of any one according to claim 4,, it is characterized in that, in described step (b), after initialization procedure finishes, hydrogen in anodic gas in anode gas-holder (24), negative electrode gas-holder (3) is passed in boiler (23) and carries out combustion reactions, the reactant gases that combustion reactions produces enters in the water of heating tank (4) by the 4th pipeline (25), thickener (21) is heated, simultaneously with the electrolysis Auto-regulating System of Density of Heavy Medium of constant-current electrolysis to 0.45KA/m
2And by second liquid pump (6), the raw material catholyte in cathode materials tank (2) is pumped in cathode compartment (10), by the 3rd liquor pump (7), the catholyte in cathode compartment (10) is pumped in thickener (21), the feed rate of second liquid pump (6), the 3rd liquor pump (7) is 0.075L/h, after catholyte heating 4.5h in thickener (21), take out the product Tetramethylammonium hydroxide in thickener (21).
9. method according to claim 8, it is characterized in that, in described step (c), when the anolyte mass concentration in anolyte compartment (8) is reduced to 15%, by first liquid pump (5), the raw material anolyte is pumped in anolyte compartment (8), controlling electrolysis density is 0.45KA/m
2, the feed rate of second liquid pump (6), the 3rd liquor pump (7) is 0.075L/h, keeps the carrying out of boiler (23) internal combustion reaction, repeating step (c), can realize the continuous production of Tetramethylammonium hydroxide.
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