CN110318066A - A kind of preparation method of tetra-alkyl ammonium hydroxide - Google Patents
A kind of preparation method of tetra-alkyl ammonium hydroxide Download PDFInfo
- Publication number
- CN110318066A CN110318066A CN201910534733.6A CN201910534733A CN110318066A CN 110318066 A CN110318066 A CN 110318066A CN 201910534733 A CN201910534733 A CN 201910534733A CN 110318066 A CN110318066 A CN 110318066A
- Authority
- CN
- China
- Prior art keywords
- room
- carbonate
- tetra
- concentration
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
-
- 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
- C25B3/01—Products
- C25B3/13—Organo-metallic compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention discloses a kind of preparation methods of tetra-alkyl ammonium hydroxide, including following two step to operate: (1) replacing electrodialysis: preparing tetraalkyl ammonium carbonate/tetraalkyl ammonium hydrogen carbonate in electrodialysis plant as raw material using quaternary alkylammonium halides and carbonate/bicarbonate；(2) it is electrolysed: being raw material with tetra-allkylammonium carbonate/bicarbonate prepared by step, it carries out being electrolysed obtained product tetra-alkyl ammonium hydroxide in electrolysis unit, preparation method disclosed in this invention has the characteristics that efficient, green, simplicity, it can obtain the quaternary ammonium alkali product of higher quality, energy consumption is lower, the new halide salt of by-product economic value with higher is obtained, there is significant environmental benefit and economic benefit.
Description
Technical field
The present invention relates to a kind of preparation methods of tetra-alkyl ammonium hydroxide.
Background technique
Tetra-alkyl ammonium hydroxide is that a kind of general formula is R1R2R3R4The compound of NOH, wherein R1、R2、R3、R4It is identical for four
Or different alkyl, tetra-alkyl ammonium hydroxide substance have specific use as a kind of organic alkali in a variety of industries
On the way.For example, tetramethylammonium hydroxide is the simplest tetra-alkyl ammonium hydroxide of structure, decomposition temperature is low, and decomposition product is all
Gaseous state, will not residual impurity；And tetramethylammonium hydroxide itself has that organic alkali, dissociative is good in water, inorganic impurity from
The low feature of sub- content, can be used as excellent electronic chemical product, for the development of photoresist and the cleaning of semiconductor substrate；Four
Directed agents of the propyl ammonium hydroxide as synthesis of molecular sieve synthesize first member ZSM-5 of molecular sieve Pentasil family
Molecular sieve can be used as catalyst and catalysis due to the good selectivity of ZSM-5 molecular sieve, high hydrothermal stability and catalytic activity
Agent carrier is widely used in petroleum industry, coal chemical industry, multifunctional material lamp industry；It is synthesized in acrylonitrile (AN) Electrolytic Dimeric method
In the technique of adiponitrile, tetrabutylammonium hydroxide can guarantee that reaction is gone on smoothly, tetrabutylammonium hydroxide in electrolytic process not
It only can be used as electrolyte to increase the electric conductivity of solution while increasing acrylonitrile in water molten as a kind of surfactant
Xie Du, it is often more important that it can form double electrical layers with electrode, and the selectivity of acrylonitrile is substantially improved, makes the production of adiponitrile
Rate and current efficiency surge to 90%.
As the tetra-alkyl ammonium hydroxide of such use, higher requirement is suffered to its quality purity, as electronization
Product, micro impurity lead to the deterioration of semiconductor substrate；In the catalyst process using Zeolite synthesis, tetraalkyl
The impurity that ammonium hydroxide introduces will cause the inactivation of catalyst, the reduction of reaction efficiency；It is miscellaneous in the electro synthesis reaction of adiponitrile
Matter halide ion can cause the corrosion of electrolytic bath electrode plate and the reduction of current efficiency.
Currently, the preparation method of tetra-alkyl ammonium hydroxide mainly includes silver oxide method, ion-exchange-resin process and ionic membrane
Electroosmose process, wherein silver oxide method using silver oxide as raw material, higher cost, at the same in final product silver ion content compared with
It is high；It is higher that ion-exchange-resin process obtains product content of halogen, is unable to satisfy industrial requirements；Ion-exchange membrane electrolysis be will be electrolysed with
Ion membrane technology combines, and it is a kind of green synthesis process that this method simple process, product purity are high.Patent
CN201120132212 discloses a kind of method of bi-membrane method preparation tetramethylammonium hydroxide, and the raw material used is tetramethyl carbonic acid
Hydrogen ammonium, anion CO3 2-Through anionic membrane to anode and H+In conjunction with generation CO2, it is environmental friendly simple, but be for anion
The tetraalkylammonium salt of halogen, such as when tetramethyl ammonium chloride, 4 bromide, Cl can be precipitated in anode2、Br2, due to yin from
Sub- film oxidation resistent susceptibility is low, and equipment needs to frequently replace anionic membrane, causes production cost excessively high, and simultaneity factor also can not be normal
Operation；Patent CN201110446506 discloses a kind of method using bipolar membrane electrodialysis preparation tetrapropylammonium hydroxide,
Increase Bipolar Membrane on the basis of electrodialytic, H can be dissociateed using Bipolar Membrane solution+And OH?Property, reach electrodialysis separation
Purpose, this method replace pole plate using emerging Bipolar Membrane, avoid the precipitation of halogen simple substance, while reducing energy consumption, but due to
Bipolar Membrane stops the ability penetrated with ion lower, and content of halogen is higher in product, is unable to get high-purity product.Patent
CN105112934B discloses a kind of method for preparing high-purity tetra-alkyl ammonium hydroxide using three films, four Room electrolytic cell, though this method
The tetra-alkyl ammonium hydroxide solution of higher degree can be obtained, but since interpolar is higher away from too big energy consumption, anion-exchange membrane is to hydrogen
Ion inhibition is smaller, and current efficiency is relatively low.
Summary of the invention
In order to solve the above technical problems, the present invention provides a kind of preparation method of tetra-alkyl ammonium hydroxide, to reach drop
Low energy consumption, electrolytic efficiency height, the costly purpose of by-product utilized.
In order to achieve the above objectives, technical scheme is as follows:
A kind of preparation method of tetra-alkyl ammonium hydroxide, including the operation of following two step:
(1) it replaces electrodialysis: being prepared in electrodialysis plant using quaternary alkylammonium halides and carbonate/bicarbonate as raw material
Tetraalkyl ammonium carbonate/tetraalkyl ammonium hydrogen carbonate；
(2) it is electrolysed: being raw material with tetra-allkylammonium carbonate/bicarbonate prepared by step, electricity is carried out in electrolysis unit
It solves and product tetra-alkyl ammonium hydroxide is made.
In above scheme, the main structure of the electrodialysis plant include cathode plate, anode plate and be located at cathode plate, sun
Membrane stack between pole plate, membrane stack two sides are third cation-exchange membrane, form pole liquid between cathode plate and anode plate respectively
Room；One group of electrodialysis cell is included at least among membrane stack, every group of electrodialysis cell includes two cation exchanges being arranged alternately
Film and two anion-exchange membranes, and by the second cation-exchange membrane, the second anion-exchange membrane, the first cation-exchange membrane,
First anion-exchange membrane, which is arranged successively, constitutes four compartments, i.e. the desalination room A, the concentration room A, the desalination room B, the concentration room B, and the room B is concentrated
The desalination room A is formed between pole fluid chamber；Pole fluid chamber, desalination the room A, concentration the room A, desalination the room B, concentration the room B be equipped with inlet and
Liquid outlet, each room are connected with corresponding storage tank by pipeline respectively, and a self-loopa is formed by power of respective circulating pump and is returned
Road；The electrolysis unit includes two Room electrolytic cell of a film and the anode can and cathode that are connected respectively with anode chamber and cathode chamber
Tank.
Preferably, a kind of preparation method of tetra-alkyl ammonium hydroxide, it is specific the preparation method is as follows:
(1) it prepares 2.5~60wt% carbonate/bicarbonate aqueous solution and 2.5~65wt% quaternary alkylammonium halides is water-soluble
Liquid；
(2) cathode plate of electrodialysis plant is connected with the cathode of DC power supply, the positive phase of anode plate and DC power supply
Even, respectively toward the desalination room A is passed through 2.5~60wt% carbonate/bicarbonate aqueous solution, the desalination room B is passed through 2.5~50wt% tetra-
Alkylammonium halogenation saline solution, the concentration room A are passed through deionized water, the concentration room B is passed through deionized water, 2 are passed through in pole fluid chamber~
65wt% sodium sulphate/potassium sulfate/aqueous sulfuric acid, keeps the fluid flow for flowing into each compartment identical, is then turned on electrodialysis plant, into
Row electrodialysis ion exchange；Tetra-allkylammonium carbonate/bicarbonate aqueous solution is obtained in the concentration room B and the concentration room A respectively afterwards
With new halide salt；
(3) cathode of electrolysis unit is connected with the cathode of DC power supply, anode is connected with the anode of DC power supply, will
(2) step obtains tetra-allkylammonium carbonate/bicarbonate aqueous solution is added the anode chamber of electrolysis unit, cathode chamber addition go from
Sub- water, is electrolysed, and tetra-alkyl ammonium hydroxide aqueous solution is obtained.
In above scheme, the quaternary alkylammonium halides be tetramethyl ammonium chloride, 4 bromide, etamon chloride,
One of tetraethylammonium bromide, 4-propyl ammonium chloride, 4-propyl bromide, tetrabutylammonium chloride, tetrabutylammonium bromide.
In above scheme, the carbonate/bicarbonate is sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, bicarbonate
One of potassium, ammonium hydrogen carbonate.
Through the above technical solutions, the preparation method of tetra-alkyl ammonium hydroxide provided by the invention has the advantage that
1, due to using two Room electrolysis method of a film, anion-exchange membrane selectivity through performance defect, electrolysis electricity are eliminated
Flow more efficient, the more products of generation in unit quantity of electricity, energy consumption reduction.
2, three film of original process, four Room electrolysis method, the hydrobromic acid aqueous solution of by-product low concentration recycle difficult.By setting
Changing electrodialysis adds two Room of a film to be electrolysed, and avoids the generation of hydrobromic acid.
3, by-product potassium bromide of the invention or sodium bromide are solid state, and the huge market demand, price is higher, realizes
The comprehensive utilization of bromo element.
4, the present invention uses electrodialysis plant and electrolytic cell equipment, and electrodialysis plant is membrane stack form, and device integration is high,
Occupied area reduces.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described.
Fig. 1 is electrodialysis plant structural schematic diagram disclosed in the embodiment of the present invention；
Fig. 2 is that schematic illustration (has only drawn one group of electrodialysis list inside electrodialysis plant disclosed in the embodiment of the present invention
Member)；
Fig. 3 is two Room electrolytic cell assembly schematic diagram of a film disclosed in the embodiment of the present invention；
Fig. 4 is two Room electrolysis principle schematic diagram of a film disclosed in the embodiment of the present invention.
In figure, M, electrodialysis plant；N, two Room electrolytic cell of a film；C1, the first cation-exchange membrane；C2, the second cation
Exchange membrane；C3, third cation-exchange membrane；C4, the 4th cation-exchange membrane；A1, the first anion-exchange membrane；A2, the second yin
Amberplex；1, the first inlet；2, the second inlet；3, third inlet；4, the 4th inlet；5, the first liquid outlet；
6, the second liquid outlet；7, third liquid outlet；8, the 4th liquid outlet；9, pole liquid import；10, pole liquid exports；11, B tank is concentrated；12,
Desalinate B tank；13, A tank is concentrated；14, desalinate A tank；15, pole flow container；16, cathode plate；17, anode plate；18, pole fluid chamber；19, desalinate
The room A；20, the room A is concentrated；21, desalinate the room B；22, the room B is concentrated；23, first circulation pumps；24, second circulation pumps；25, third recycles
Pump；26, the 4th circulating pump；27, the 5th circulating pump；28, anode chamber；29, cathode chamber；30, anode can；31, cathode can.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation description.
The present invention provides a kind of preparation method of tetra-alkyl ammonium hydroxide, specific embodiment is as follows:
Electrodialysis plant of the invention as shown in Figure 1, electrodialysis plant M be equipped with the first inlet 1, the second inlet 2,
Third inlet 3, the 4th inlet 4, the first liquid outlet 5, the second liquid outlet 6, third liquid outlet 7, the 4th liquid outlet 8, and
Pole liquid import 9 and pole liquid outlet 10, inlet and the liquid outlet tilt distribution on pole plate, making solution in the device has maximum stream
Dynamic path；First inlet 1 and the first liquid outlet 5 are connected with concentration B tank 11, the second inlet 2 and the second liquid outlet 6 with desalinate
B tank 12 is connected, and third inlet 3 and third liquid outlet 7 are connected with concentration A tank 13, the 4th inlet 4 and the 4th liquid outlet 8 and
Desalinate A tank 14 to be connected, pole liquid import 9 and pole liquid outlet 10 are connected with pole flow container 15.
As shown in Fig. 2, the main structure of electrodialysis plant M include cathode plate 16, anode plate 17 and be located at cathode plate 16,
Membrane stack between anode plate 17, membrane stack two sides are third cation-exchange membrane C3, respectively with cathode plate 16 and anode plate 17 it
Between formed pole fluid chamber 18；One group of electrodialysis cell is included at least among membrane stack, every group of electrodialysis cell includes two be arranged alternately
Cation-exchange membrane and two anion-exchange membranes, and by the second cation-exchange membrane C2, the second anion-exchange membrane A2, the
One cation-exchange membrane C1, the first anion-exchange membrane A1 be arranged successively constitute four compartments, i.e., desalination the room A 19, concentration the room A 20,
Desalinate the room B 21, the concentration room B 22, is concentrated between the room B 22 and pole fluid chamber 18 and forms the desalination room A 19；Pole fluid chamber 18, desalination the room A 19,
The concentration room A 20, the desalination room B 21, the concentration room B 22 are equipped with inlet and liquid outlet, and each room passes through pipe with corresponding storage tank respectively
Road is connected, and a self circular loop is formed by power of respective circulating pump.I.e. desalination A tank 14 by first circulation pump 23 with it is light
Change the room A 19 to be connected, concentration A tank 13 is connected by second circulation pump 24 with the concentration room A 20, and desalination B tank 12 passes through third circulating pump
25 are connected with the desalination room B 21, and concentration B tank 11 is connected by the 4th circulating pump 26 with the concentration room B 22, and pole flow container 15 is followed by the 5th
Ring pump 27 is connected with pole fluid chamber 18.
As shown in figure 3, electrolysis unit includes two Room electrolytic cell N of a film and is connected respectively with anode chamber 28 and cathode chamber 29
Anode can 30 and cathode can 31, anode can 30 and cathode can 31 pass through respective pump and 29 phase of anode chamber 28 and cathode chamber respectively
Even.It is separated between anode chamber 28 and cathode chamber 29 by the 4th cation-exchange membrane C4.
Embodiment one:
(1), the aqueous sodium carbonate 6L of concentration 25wt% is first added into desalination A tank 14, is added into desalination B tank 12 dense
Concentration 20wt% aqueous sodium persulfate solution 10L is added into pole flow container 15 by the tetramethyl ammonium chloride aqueous solution 12L for spending 25wt%, to
A tank 13 is concentrated, addition 10L deionized water in B tank 11 is concentrated.
(2), first circulation pump 23, second circulation pump 24, third circulating pump 25, the 4th circulating pump the 26, the 5th circulation are opened
Pump 27, adjusting flow velocity of each solution in electrodialysis plant is 7cm/s, makes aqueous sodium carbonate, deionized water, tetramethyl chlorine
Change aqueous ammonium, deionized water and pole liquid pass through respective circulating pump respectively and enter the desalination room A 19, the concentration room A 20, the desalination room B
21, the room B 22 and pole fluid chamber 18 is concentrated, it is 40 DEG C that each indoor temperature of chamber, which controls,；Tetramethyl ammonium chloride is dissociated into four in water
Methyl ammonium root cation and chloride ion.
(3), power supply is opened, control current density is 400A/m2, under electric field motive force and the collective effect of ionic membrane,
Tetramethyl ammonium root the first cationic membrane of cation permeable C1 enters the concentration room B 22, and chloride ion enters through the second anionic membrane A2
The room A 20 is concentrated；Metal cation Na+Or H+Ion enters the concentration room A 20 through the second cationic membrane C2, and carbonate anion is saturating
It crosses the first anion A1 film and enters the concentration room B 22.Carbonate is combined to form tetramethyl with tetramethyl ammonium root cation in the concentration room B 22
Base ammonium carbonate solution, and concentration B tank 11 is returned to by the first liquid outlet 5；Metal cation Na+With chloride ion in the concentration room A
20 combinations form new sodium-chloride water solution, and return to concentration A tank 13 by third liquid outlet 7.Finally obtain tetra-allkylammonium carbon
Acid salt solution 10L and sodium-chloride water solution 10L.
(4) two Room of film electricity will be added to by the tetramethyl-ammonium carbonate solution 10L that concentration B tank 11 obtains in step (3)
In the anode can 30 for solving device, 10L deionized water is added in cathode can 31.Power supply is opened, current density 1000A/m is controlled2, in electricity
Under field motive force and the collective effect of ionic membrane, tetramethyl-ammonium radical ion enters cathode chamber 29 through cation-exchange membrane C4, with
The hydroxyl that water is electrolysed on cathode, which combines, generates tetramethylammonium hydroxide.Water electrolysis generates on carbonate and anode
Hydrogen ion combine, in the form of carbon dioxide escape.Finally obtained product quality score is 25% aqueous solution, current efficiency
96%.
Embodiment two:
(1), the potassium bicarbonate aqueous solution 7L of concentration 25wt% is first added into desalination A tank 14, is added into desalination B tank 12
Concentration 20wt% potassium sulfate solution is added into pole flow container 15 by the tetraethylammonium bromide aqueous solution 14.3L of concentration 25wt%
10L deionized water is added into concentration A tank 13, concentration B tank 11 in 10L.
(2), each circulating pump is opened, adjusting flow velocity of each solution in electrodialysis plant is 9cm/s, each indoor temperature of chamber
Degree control is 40 DEG C.
(3), the power supply of electrodialysis plant is opened, control current density is 500A/m2, in electric field motive force and ionic membrane
Under collective effect, tetraethyl ammonium root the first cationic membrane of cation permeable C1 enter concentration the room B 22, bromide ion through second yin from
Sub- film A2 enters the concentration room A 20；Metal cation K+Or H+Ion enters the concentration room A 20, bicarbonate through the second cationic membrane C2
Root anion-permeable the first anion A1 film enters the concentration room B 22.Bicarbonate radical and tetraethyl ammonium root cation are in the concentration room B 22
Concentration B tank 11 is returned in conjunction with formation tetraethyl ammonium bicarbonate solution, and by the first liquid outlet 5；Metal cation K+With halogen
Plain anion combines in the concentration room A 20 and forms new kbr aqueous solution, and returns to concentration A tank 13 by third liquid outlet 7.Most
Tetraethyl ammonium bicarbonate solution 10L is obtained eventually, obtains kbr aqueous solution 10L.
(4) two Room of a film will be added to by the tetraethyl ammonium bicarbonate solution 10L that concentration B tank 11 obtains in step (3)
In the anode can 30 of electrolysis unit, 10L deionized water is added in cathode can 31.Power supply is opened, current density 800A/m is controlled2,
Under electric field motive force and the collective effect of ionic membrane, tetraethyl ammonium radical ion enters cathode chamber 29 through cation-exchange membrane C4,
Tetraethyl ammonium hydroxide is generated in conjunction with the hydroxyl that water is electrolysed on cathode.Water electrolysis on bicarbonate radical and anode
The hydrogen ion of generation combines, and is escaped in the form of carbon dioxide.Finally obtained product quality score is 25% aqueous solution, electric current
Efficiency 92%.
Embodiment three:
(1), the wet chemical 3.5L of concentration 25wt% is first added into desalination A tank 14, is added into desalination B tank 12
Concentration 10wt% potassium sulfate solution is added into pole flow container 15 by the 4-propyl bromide aqueous solution 13.5L of concentration 30wt%
10L deionized water is added into concentration A tank 13, concentration B tank 11 in 10L.
(2), each circulating pump is opened, adjusting flow velocity of each solution in electrodialysis plant is 10cm/s, and each chamber is indoor
It is 35 DEG C that temperature, which controls,.
(3), the power supply of electrodialysis plant is opened, control current density is 500A/m2, in electric field motive force and ionic membrane
Under collective effect, tetrapropyl ammonium root the first cationic membrane of cation permeable C1 enter concentration the room B 22, bromide ion through second yin from
Sub- film A2 enters the concentration room A 20；Metal cation K+Or H+Ion enters the concentration room A 20, carbonate through the second cationic membrane C2
Anion-permeable the first anion A1 film enters the concentration room B 22.Carbonate is combined with tetrapropyl ammonium root cation in the concentration room B 22
Tetrapropyl ammonium carbonate solution is formed, and concentration B tank 11 is returned to by the first liquid outlet 5；Metal cation K+Exist with bromide ion
The concentration room A 20, which combines, forms new kbr aqueous solution, and returns to concentration A tank 13 by third liquid outlet 7.Finally obtain 4 third
Base ammonium carbonate aqueous solution 10L, obtains kbr aqueous solution 10L.
(4) two Room of film electricity will be added to by the tetrapropyl ammonium carbonate solution 10L that concentration B tank 11 obtains in step (3)
In the anode can 30 for solving device, 10L deionized water is added in cathode can 31.Power supply is opened, 10~2500A/m of current density is controlled2,
Under electric field motive force and the collective effect of ionic membrane, tetrapropyl ammonium radical ion enters cathode chamber through cation-exchange membrane C4
29, tetrapropylammonium hydroxide is generated in conjunction with the hydroxyl that water is electrolysed on cathode.Water power on carbonate and anode
The hydrogen ion that solution generates combines, and is escaped in the form of carbon dioxide.Finally obtained product quality score is 25% aqueous solution, electricity
Flow efficiency 90%.
Example IV:
(1), the wet chemical 3L of concentration 25wt% is first added into desalination A tank 14, is added into desalination B tank 12 dense
Concentration 10wt% potassium sulfate solution 10L is added into pole flow container 15 by the tetrabutyl phosphonium bromide aqueous ammonium 10.5L for spending 30wt%,
10L deionized water is added into concentration A tank 13, concentration B tank 11.
(2), each circulating pump is opened, adjusting flow velocity of each solution in electrodialysis plant is 10cm/s, and each chamber is indoor
It is 40 DEG C that temperature, which controls,.
(3), the power supply of electrodialysis plant is opened, control current density is 500A/m2, in electric field motive force and ionic membrane
Under collective effect, tetrabutyl ammonium root the first cationic membrane of cation permeable C1 enter concentration the room B 22, bromide ion through second yin from
Sub- film A2 enters the concentration room A 20；Metal cation K+Or H+Ion enters the concentration room A 20, carbonate through the second cationic membrane C2
Anion-permeable the first anion A1 film enters the concentration room B 22.Carbonate is combined with tetrabutyl ammonium root cation in the concentration room B 22
Tetrabutylammonium carbonate solution is formed, and concentration B tank 11 is returned to by the first liquid outlet 5；Metal cation K+Exist with bromide ion
The concentration room A 20, which combines, forms new kbr aqueous solution, and returns to concentration A tank 13 by third liquid outlet 7.Finally obtain four fourths
Base ammonium carbonate aqueous solution 10L, obtains kbr aqueous solution 10L.
(4) two Room of film electricity will be added to by the tetrabutylammonium carbonate solution 10L that concentration B tank 11 obtains in step (3)
In the anode can 30 for solving device, 10L deionized water is added in cathode can 31.Power supply is opened, current density 500A/m is controlled2, in electricity
Under field motive force and the collective effect of ionic membrane, tetrabutylammonium radical ion enters cathode chamber 29 through cation-exchange membrane C4, with
The hydroxyl that water is electrolysed on cathode, which combines, generates tetrabutylammonium hydroxide.Water electrolysis generates on carbonate and anode
Hydrogen ion combine, in the form of carbon dioxide escape.Finally obtained product quality score is 25% aqueous solution, current efficiency
89%.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be readily apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest scope of cause.
Claims (5)
1. a kind of preparation method of tetra-alkyl ammonium hydroxide, which is characterized in that operated including following two step:
(1) it replaces electrodialysis: preparing four alkane in electrodialysis plant as raw material using quaternary alkylammonium halides and carbonate/bicarbonate
Base ammonium carbonate/tetraalkyl ammonium hydrogen carbonate；
(2) it is electrolysed: being raw material with tetra-allkylammonium carbonate/bicarbonate prepared by step, electrolysis system is carried out in electrolysis unit
Obtain product tetra-alkyl ammonium hydroxide.
2. a kind of preparation method of tetra-alkyl ammonium hydroxide according to claim 1, which is characterized in that electrodialysis plant
Main structure includes cathode plate, anode plate and the membrane stack between cathode plate, anode plate, membrane stack two sides be third sun from
Proton exchange forms pole fluid chamber between cathode plate and anode plate respectively；One group of electrodialysis cell is included at least among membrane stack, often
Group electrodialysis cell includes two cation-exchange membranes and two anion-exchange membranes being arranged alternately, and is handed over by the second cation
It changes film, the second anion-exchange membrane, the first cation-exchange membrane, the first anion-exchange membrane and is arranged successively four compartments of composition, i.e.,
Desalinate the room A, the concentration room A, the desalination room B, the concentration room B, is concentrated between the room B and pole fluid chamber and forms the desalination room A；Pole fluid chamber, desalination A
Room, the concentration room A, the desalination room B, the concentration room B are equipped with inlet and liquid outlet, and each room passes through pipeline phase with corresponding storage tank respectively
Even, a self circular loop is formed by power of respective circulating pump；The electrolysis unit include two Room electrolytic cell of a film and
The anode can and cathode being connected respectively with anode chamber and cathode chamber.
3. a kind of preparation method of tetra-alkyl ammonium hydroxide according to claim 2, which is characterized in that specific preparation method
It is as follows:
(1) 2.5~60wt% carbonate/bicarbonate aqueous solution and 2.5~65wt% tetra-alkyl-phosphonium halide aqueous ammonium are prepared；
(2) cathode plate of electrodialysis plant being connected with the cathode of DC power supply, anode plate is connected with the anode of DC power supply, point
Not toward the desalination room A is passed through 2.5~60wt% carbonate/bicarbonate aqueous solution, the desalination room B is passed through 2.5~65wt% tetraalkyl
Ammonium halogenation saline solution, the concentration room A are passed through deionized water, the concentration room B is passed through deionized water, are passed through 2~65wt% in pole fluid chamber
Sodium sulphate/potassium sulfate/aqueous sulfuric acid keeps the fluid flow for flowing into each compartment identical, is then turned on electrodialysis plant, carries out electric osmose
Analyse ion exchange；Tetra-allkylammonium carbonate/bicarbonate aqueous solution and new is obtained in the room A in the concentration room B and being concentrated respectively afterwards
Halide salt；
(3) cathode of electrolysis unit is connected with the cathode of DC power supply, anode is connected with the anode of DC power supply, by (2) step
Suddenly the anode chamber of electrolysis unit is added in the tetra-allkylammonium carbonate/bicarbonate aqueous solution obtained, and deionized water is added in cathode chamber,
It is electrolysed, obtains tetra-alkyl ammonium hydroxide aqueous solution.
4. a kind of preparation method of tetra-alkyl ammonium hydroxide according to claim 1, which is characterized in that the tetraalkyl halogen
Change ammonium is tetramethyl ammonium chloride, 4 bromide, etamon chloride, tetraethylammonium bromide, 4-propyl ammonium chloride, tetrapropyl
Ammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, front three adamantyl ammonium chloride, in front three adamantyl ammonium bromide
One kind.
5. a kind of preparation method of tetra-alkyl ammonium hydroxide according to claim 1, which is characterized in that the carbonate/
Bicarbonate is one of sodium carbonate, potassium carbonate, ammonium carbonate, sodium bicarbonate, saleratus, ammonium hydrogen carbonate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910534733.6A CN110318066A (en) | 2019-06-20 | 2019-06-20 | A kind of preparation method of tetra-alkyl ammonium hydroxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910534733.6A CN110318066A (en) | 2019-06-20 | 2019-06-20 | A kind of preparation method of tetra-alkyl ammonium hydroxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110318066A true CN110318066A (en) | 2019-10-11 |
Family
ID=68120982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910534733.6A Pending CN110318066A (en) | 2019-06-20 | 2019-06-20 | A kind of preparation method of tetra-alkyl ammonium hydroxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110318066A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113463118A (en) * | 2021-05-12 | 2021-10-01 | 肯特催化材料股份有限公司 | Energy-saving production process of tetrapropylammonium hydroxide and tetrapropylammonium hydroxide aqueous solution prepared by same |
Citations (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0393752A (en) * | 1989-09-04 | 1991-04-18 | Toyo Gosei Kogyo Kk | Production of high-purity quaternary ammonium hydroxide |
| JPH1053568A (en) * | 1996-08-12 | 1998-02-24 | Showa Denko Kk | Purification and recovery of tetraalkylammonium hydroxide from waste developer liquor |
| EP0860425A1 (en) * | 1996-07-23 | 1998-08-26 | Tokuyama Corporation | Process for the preparation of aqueous solutions of tetraalkylammonium hydroxides |
| CA2552744A1 (en) * | 2004-12-07 | 2006-06-15 | Invista Technologies S.A.R.L. | Use of modifiers in a dinitrile hydrogenation process at high pressures |
| CN1293231C (en) * | 2002-01-03 | 2007-01-03 | 塞克姆公司 | Purification of onium hydroxides by electrodialysis |
| CN101402497A (en) * | 2008-09-16 | 2009-04-08 | 王方 | Electric ion removing method and device for recycling inorganic ammonia nitrogen wastewater |
| CN101851016A (en) * | 2010-07-07 | 2010-10-06 | 浙江华友钴业股份有限公司 | Method for processing ammonium chloride waste water |
| CN102307816A (en) * | 2009-02-13 | 2012-01-04 | 株式会社神钢环境舒立净 | Method for processing waste water containing fluorine and silicon, method for producing calcium fluoride, and facility for processing fluorine-containing waste water |
| CN103086551A (en) * | 2013-01-22 | 2013-05-08 | 杭州蓝然环境技术有限公司 | Method for preparing acid-base from rare-earth sodium saponification waste water |
| CN103130362A (en) * | 2011-11-23 | 2013-06-05 | 通用电气公司 | Water treatment device and method |
| CN103318921A (en) * | 2013-06-28 | 2013-09-25 | 中国科学院过程工程研究所 | Method for preparing ammonium carbonate solution from ammonia-containing aqueous solution |
| CN103508521A (en) * | 2013-09-18 | 2014-01-15 | 中国海洋大学 | Recycling treatment method for salt-containing wastewater |
| CN103526224A (en) * | 2013-09-22 | 2014-01-22 | 镇江润晶高纯化工有限公司 | Method for preparing high-purity tetraethylammonium hydroxide by continuous electrolysis |
| CN104278288A (en) * | 2014-09-30 | 2015-01-14 | 赵文洲 | Method for preparing high-purity tetrabutyl ammonium hydroxide by continuous electrolysis |
| CN104445534A (en) * | 2014-12-05 | 2015-03-25 | 杭州水处理技术研究开发中心有限公司 | Homogeneous membrane electrodialysis unit with pH adjustment |
| CN104556314A (en) * | 2013-10-23 | 2015-04-29 | 苏州华清水处理技术有限公司 | Electrical deionization device for concentration during recycling of low-concentration ammonia-nitrogen wastewater |
| 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 |
| CN103276403B (en) * | 2013-06-04 | 2016-02-10 | 中国日用化学工业研究院 | A kind of method preparing long-chain alkyl ammonium hydroxide |
| CN105983251A (en) * | 2015-02-16 | 2016-10-05 | 秦才东 | Exchange and condensation method and device for ions in solution |
| WO2017064133A1 (en) * | 2015-10-15 | 2017-04-20 | Covestro Deutschland Ag | Method for producing amino-functional aromatic compounds |
| 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 |
| CN106958028A (en) * | 2017-05-22 | 2017-07-18 | 江苏三吉利化工股份有限公司 | A kind of membrane electrolysis of three Room two prepares the device of high-purity TPAOH |
| CN107055713A (en) * | 2017-05-18 | 2017-08-18 | 河北工业大学 | One kind is based on the selectively electrodialytic high rigidity brackish water method for concentration of univalent cation |
| CN107162023A (en) * | 2017-05-25 | 2017-09-15 | 合肥工业大学 | The preparation system and preparation method of a kind of potassium nitrate |
| CN108299209A (en) * | 2018-01-20 | 2018-07-20 | 盐城泛安化学有限公司 | A method of it is prepared using membrane integrating technique and concentrates tetraethyl ammonium hydroxide |
| CN207891095U (en) * | 2017-12-19 | 2018-09-21 | 天津渤化永利化工股份有限公司 | A kind of alkali device gives up the device that light liquid is recycled with ammonia-containing gas |
| CN108779008A (en) * | 2016-03-11 | 2018-11-09 | 株式会社片山化学工业研究所 | The inorganic agent of cyanide containing wastewater and the method for handling cyanide containing wastewater with it |
| CN109110886A (en) * | 2018-09-01 | 2019-01-01 | 赵宏伟 | A kind of cation-exchange membrane and preparation method for electrodialysis process ammonia nitrogen waste water |
| CN109231377A (en) * | 2018-08-28 | 2019-01-18 | 浙江工业大学 | A kind of displacement electrodialysis methods preparing potassium fluoride by potassium chloride and ammonium fluoride |
| CN109265358A (en) * | 2018-09-21 | 2019-01-25 | 南京元亨化工科技有限公司 | A method of based on electron ion exchange system for high-purity tetrapropylammonium hydroxide |
| CN111204755A (en) * | 2020-02-21 | 2020-05-29 | 河北省科学院能源研究所 | Preparation method and application of biomass porous carbon material |
-
2019
- 2019-06-20 CN CN201910534733.6A patent/CN110318066A/en active Pending
Patent Citations (31)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0393752A (en) * | 1989-09-04 | 1991-04-18 | Toyo Gosei Kogyo Kk | Production of high-purity quaternary ammonium hydroxide |
| EP0860425A1 (en) * | 1996-07-23 | 1998-08-26 | Tokuyama Corporation | Process for the preparation of aqueous solutions of tetraalkylammonium hydroxides |
| JPH1053568A (en) * | 1996-08-12 | 1998-02-24 | Showa Denko Kk | Purification and recovery of tetraalkylammonium hydroxide from waste developer liquor |
| CN1293231C (en) * | 2002-01-03 | 2007-01-03 | 塞克姆公司 | Purification of onium hydroxides by electrodialysis |
| CA2552744A1 (en) * | 2004-12-07 | 2006-06-15 | Invista Technologies S.A.R.L. | Use of modifiers in a dinitrile hydrogenation process at high pressures |
| CN101402497A (en) * | 2008-09-16 | 2009-04-08 | 王方 | Electric ion removing method and device for recycling inorganic ammonia nitrogen wastewater |
| CN102307816A (en) * | 2009-02-13 | 2012-01-04 | 株式会社神钢环境舒立净 | Method for processing waste water containing fluorine and silicon, method for producing calcium fluoride, and facility for processing fluorine-containing waste water |
| CN101851016A (en) * | 2010-07-07 | 2010-10-06 | 浙江华友钴业股份有限公司 | Method for processing ammonium chloride waste water |
| CN103130362A (en) * | 2011-11-23 | 2013-06-05 | 通用电气公司 | Water treatment device and method |
| CN103086551A (en) * | 2013-01-22 | 2013-05-08 | 杭州蓝然环境技术有限公司 | Method for preparing acid-base from rare-earth sodium saponification waste water |
| CN103276403B (en) * | 2013-06-04 | 2016-02-10 | 中国日用化学工业研究院 | A kind of method preparing long-chain alkyl ammonium hydroxide |
| CN103318921A (en) * | 2013-06-28 | 2013-09-25 | 中国科学院过程工程研究所 | Method for preparing ammonium carbonate solution from ammonia-containing aqueous solution |
| CN103508521A (en) * | 2013-09-18 | 2014-01-15 | 中国海洋大学 | Recycling treatment method for salt-containing wastewater |
| CN103526224A (en) * | 2013-09-22 | 2014-01-22 | 镇江润晶高纯化工有限公司 | Method for preparing high-purity tetraethylammonium hydroxide by continuous electrolysis |
| CN104556314A (en) * | 2013-10-23 | 2015-04-29 | 苏州华清水处理技术有限公司 | Electrical deionization device for concentration during recycling of low-concentration ammonia-nitrogen wastewater |
| CN104278288A (en) * | 2014-09-30 | 2015-01-14 | 赵文洲 | Method for preparing high-purity tetrabutyl ammonium hydroxide by continuous electrolysis |
| CN104445534A (en) * | 2014-12-05 | 2015-03-25 | 杭州水处理技术研究开发中心有限公司 | Homogeneous membrane electrodialysis unit with pH adjustment |
| CN105983251A (en) * | 2015-02-16 | 2016-10-05 | 秦才东 | Exchange and condensation method and device for ions in solution |
| 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 |
| WO2017064133A1 (en) * | 2015-10-15 | 2017-04-20 | Covestro Deutschland Ag | Method for producing amino-functional aromatic compounds |
| CN108779008A (en) * | 2016-03-11 | 2018-11-09 | 株式会社片山化学工业研究所 | The inorganic agent of cyanide containing wastewater and the method for handling cyanide containing wastewater with it |
| 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 |
| CN107055713A (en) * | 2017-05-18 | 2017-08-18 | 河北工业大学 | One kind is based on the selectively electrodialytic high rigidity brackish water method for concentration of univalent cation |
| CN106958028A (en) * | 2017-05-22 | 2017-07-18 | 江苏三吉利化工股份有限公司 | A kind of membrane electrolysis of three Room two prepares the device of high-purity TPAOH |
| CN107162023A (en) * | 2017-05-25 | 2017-09-15 | 合肥工业大学 | The preparation system and preparation method of a kind of potassium nitrate |
| CN207891095U (en) * | 2017-12-19 | 2018-09-21 | 天津渤化永利化工股份有限公司 | A kind of alkali device gives up the device that light liquid is recycled with ammonia-containing gas |
| CN108299209A (en) * | 2018-01-20 | 2018-07-20 | 盐城泛安化学有限公司 | A method of it is prepared using membrane integrating technique and concentrates tetraethyl ammonium hydroxide |
| CN109231377A (en) * | 2018-08-28 | 2019-01-18 | 浙江工业大学 | A kind of displacement electrodialysis methods preparing potassium fluoride by potassium chloride and ammonium fluoride |
| CN109110886A (en) * | 2018-09-01 | 2019-01-01 | 赵宏伟 | A kind of cation-exchange membrane and preparation method for electrodialysis process ammonia nitrogen waste water |
| CN109265358A (en) * | 2018-09-21 | 2019-01-25 | 南京元亨化工科技有限公司 | A method of based on electron ion exchange system for high-purity tetrapropylammonium hydroxide |
| CN111204755A (en) * | 2020-02-21 | 2020-05-29 | 河北省科学院能源研究所 | Preparation method and application of biomass porous carbon material |
Non-Patent Citations (2)
| Title |
|---|
| JIANG-NAN SHEN 等: ""Preparation of highly pure tetrapropyl ammonium hydroxide using continuous bipolar membrane electrodialysis"", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 侯震东 等: ""双极膜电渗析法制备高纯度四甲基氢氧化铵"", 《水处理技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113463118A (en) * | 2021-05-12 | 2021-10-01 | 肯特催化材料股份有限公司 | Energy-saving production process of tetrapropylammonium hydroxide and tetrapropylammonium hydroxide aqueous solution prepared by same |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jiang et al. | A comprehensive review on the synthesis and applications of ion exchange membranes | |
| CN105112934B (en) | A kind of preparation method of tetra-alkyl ammonium hydroxide | |
| CN106801233B (en) | A kind of electrolysis method prepares the system and method for high-purity tetrapropylammonium hydroxide | |
| CN102531927A (en) | Method for preparing tetrapropyl ammonium hydroxide by utilizing bipolar membrane electrodialysis | |
| CN107904618B (en) | Method for preparing parallel-connection hydrogen halide acid by four-chamber three-membrane electrolysis of short-chain quaternary ammonium hydroxide | |
| CN104557621B (en) | A kind of method that pyrovinic acid is prepared using bipolar membrane electrodialysis technology | |
| CN106958028B (en) | A kind of three Room, two membrane electrolysis prepares the device of high-purity tetrapropylammonium hydroxide | |
| JPH05504170A (en) | Electrochemical production method of chloric acid/alkali metal chlorate mixture | |
| CN105688676B (en) | The technique that a kind of bipolar membrane electrodialysis method prepares hypophosphorous acid | |
| WO2017118712A1 (en) | Method and system for electrochemical reduction of carbon dioxide employing a gas diffusion anode | |
| CN113913851B (en) | Bipolar membrane electrolysis method for preparing carbon monoxide by electrolyzing carbon dioxide in organic electrolyte and simultaneously by-producing chlorine and metal hydroxide | |
| CN104073839A (en) | Device and method for preparing high-purity tetrapropylammonium hydroxide and co-producing bromine through electrolysis | |
| CN108467347A (en) | A method of electrolysis tetrabutyl ammonium sulfate recycles tetrabutylammonium hydroxide | |
| CN110573659A (en) | Electrochemical, chlorination and oxychlorination systems and methods of forming propylene oxide or ethylene oxide | |
| CN110318066A (en) | A kind of preparation method of tetra-alkyl ammonium hydroxide | |
| CN114849478A (en) | Asymmetric bipolar membrane electrodialysis device and method for preparing acid and alkali | |
| CN108486604A (en) | A method of preparing tetrabutylammonium hydroxide by raw material of tetrabutyl ammonium sulfate | |
| CN106430463A (en) | Electrodialysis water treatment device with intermediate electrode plates and method | |
| CN109096230A (en) | One kind preparing ascorbic method by bipolar membrane electrodialysis | |
| JP2008036473A (en) | Electric deionizer | |
| CN1184005A (en) | Electrical ion exchange resin regenerating method and equipment | |
| CN112281180A (en) | Method for preparing chlorine by electrolyzing concentrated seawater through bipolar membrane | |
| CN110079822A (en) | A kind of system and method that three films, four Room electrolysis method prepares tetra-alkyl ammonium hydroxide | |
| CN113830740B (en) | Method for preparing acid and alkali by bipolar membrane based on electrodialysis technology | |
| JP3280382B2 (en) | Method for producing an acidified process stream |
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 |