CN107652185A - The preparation facilities and preparation method of benzyltrimethylammonium hydroxide - Google Patents
The preparation facilities and preparation method of benzyltrimethylammonium hydroxide Download PDFInfo
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- CN107652185A CN107652185A CN201710533664.8A CN201710533664A CN107652185A CN 107652185 A CN107652185 A CN 107652185A CN 201710533664 A CN201710533664 A CN 201710533664A CN 107652185 A CN107652185 A CN 107652185A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/42—Electrodialysis; Electro-osmosis ; Electro-ultrafiltration; Membrane capacitive deionization
- B01D61/422—Electrodialysis
Abstract
The invention discloses a kind of preparation facilities of benzyltrimethylammonium hydroxide and preparation method, wherein device includes：One or more are sequentially connected in series or bipolar membrane electrodialysis stack in parallel；The component is included positioned at the pole liquid room at both ends, and the electrodialysis compartment positioned at centre；Pole liquid room positioned at both sides is respectively cathode chamber and anode chamber, and cathode chamber and anode chamber are connected respectively external power supply；Electrodialysis compartment includes 1 group or multigroup film unit being serially connected；Film unit is four cell structures, including Bipolar Membrane, cation-exchange membrane, anion-exchange membrane, cation-exchange membrane, the Bipolar Membrane being arranged in order, and forms surge chamber, acid solution room, feed liquid room and alkali lye room.Using the benzyltrimethylammonium hydroxide quality of the invention prepared is high, production cost is low and conversion rate of products is high.And the accessory substance halogen acid solution in production process, concentration reuse can be carried out by film distillation technology, realize the resource reclaim of discarded object, environmentally friendly, pollution is small.
Description
Technical field
The present invention relates to electrodialytic technique field, the preparation facilities and system of more particularly to a kind of benzyltrimethylammonium hydroxide
Preparation Method.
Background technology
Benzyltrimethylammonium hydroxide (BTMAH) is a kind of organic base, can be used as phase transfer catalyst, Zeolite synthesis
Alkali source, template, it is mainly used in the fields such as the agent of petroleum industry removing impurities, catalyst.
The existing method for preparing benzyltrimethylammonium hydroxide mainly has following two：
(1) silver oxide method, preparation is reacted in a solvent by raw material and silver oxide of benzyl trimethyl halo ammonium.Due to oxidation
Silver is somewhat expensive, manufacturing cost in this way it is too high；Moreover, containing a certain amount of in the silver halide precipitation thing that reaction obtains
Product, conversion rate of products are relatively low；In addition, after recovery section solvent, it is necessary to add water to make the benzyltrimethylammonium hydroxide aqueous solution,
Waste of solvent is not only caused, increases cost, and substantial amounts of solvent-laden waste water can be produced, is unfavorable for environmental protection.
(2) ion-exchange-resin process, using benzyl trimethyl halo ammonium be raw material by with basic resin carry out ion exchange
Prepare.Because resin regeneration is very frequent, regeneration every time can produce a large amount of waste water containing halogen ion, it is difficult to handle, be unfavorable for environmental protection；
In addition, basic resin must be regenerated with sodium hydroxide, the alkali metal ion of part certainly will be brought into, influence the quality of product.
Therefore, it is low, right to be primarily present cost height, conversion rate of products for the existing method for preparing benzyltrimethylammonium hydroxide
Environment is unfriendly and the defects of the product quality produced is not high.
The content of the invention
Based on problem above, the present invention proposes the preparation facilities and preparation method of a kind of benzyltrimethylammonium hydroxide,
Realize benzyltrimethylammonium hydroxide high-quality, low cost, the preparation of high conversion, low stain.
The preparation facilities of benzyltrimethylammonium hydroxide provided by the invention, including one or more are sequentially connected in series or parallel connection
Bipolar membrane electrodialysis stack；
The bipolar membrane electrodialysis stack is included positioned at the pole liquid room at both ends, and the electric osmose among the pole liquid room
Analyse compartment；
The pole liquid room positioned at both sides is respectively cathode chamber and anode chamber, and the cathode chamber and anode chamber correspond to respectively to be connected
Connect external power supply；
The electrodialysis compartment includes 1 group or multigroup film unit being serially connected；
The film unit is four cell structures, including be arranged in order Bipolar Membrane, cation-exchange membrane, anion exchange
Film, cation-exchange membrane, Bipolar Membrane, form surge chamber, acid solution room, feed liquid room and alkali lye room.
As a kind of embodiment, the quantity of the bipolar membrane electrodialysis stack is 1 to 50, the single electrodialysis
Compartment includes the film unit that 1 to 500 group is serially connected.
As a kind of embodiment, all homogeneous membranes of the Bipolar Membrane, cation-exchange membrane, anion-exchange membrane.
As a kind of embodiment, the preparation facilities of benzyltrimethylammonium hydroxide provided by the invention, in addition to use
The halogen acid solution formed in the acid solution room carries out the membrane component of concentration.
As a kind of embodiment, the structure of the membrane component is plate type membrane assembly or hollow fiber form film group
Part.
As a kind of embodiment, the material of the membrane component is hydrophobic microporous membrane, polyvinylidene fluoride dewatering
Property film, polypropylene hydrophobic film or the hydrophobic film after hydrophobic modified.
Correspondingly, the present invention also provides a kind of preparation method of benzyltrimethylammonium hydroxide, utilizes above-mentioned benzyl front three
The preparation facilities of base ammonium hydroxide prepares benzyltrimethylammonium hydroxide, and this method comprises the following steps：
S100, the aqueous solution of benzyltrimethylammon.um halogeno salt is passed through the feed liquid room, to the acid solution room and alkali lye room
Deionized water is each led into, sulfuric acid solution is each led into the pole liquid room and surge chamber；
S200, apply DC electric field on the cathode chamber and anode chamber, and control the temperature in the electrodialytic membranes component
Degree is maintained at preset temperature range, carries out bipolar membrane electrodialysis technique；
S300, after bipolar membrane electrodialysis technique terminates, halogen acids is reclaimed from the acid solution room, from the alkali lye room
Reclaim benzyltrimethylammonium hydroxide.
As a kind of embodiment, in the bipolar membrane electrodialysis technical process, the electricity of the DC electric field applied
Current density is 150A/m2To 600A/m2, the temperature in the electrodialytic membranes component is maintained at 20 DEG C to 35 DEG C, the surge chamber,
Flow rate of liquid in acid solution room, feed liquid room and alkali lye room is 200L/h to 2000L/h.
As a kind of embodiment, the mass fraction of the sulfuric acid solution each led into the pole liquid room with surge chamber is
1% to 3%.
As a kind of embodiment, the quality for the benzyltrimethylammonium hydroxide solution being recovered to from the alkali lye room
Fraction is 10% to 20%, and for the rate of recovery more than 95%, the impurity halogen ion concentration in solution is less than 70ppm.
It is further comprising the steps of after step S300 as a kind of embodiment：
Membrane distillation processing is carried out to the halogen acid solution being recovered to from the acid solution room, is up to being concentrated into mass fraction
When 15% to 20%, concentrate is collected, is back to benzyltrimethylammonium hydroxide production.
As a kind of embodiment, the halogen acid solution to being recovered to from the acid solution room is carried out at membrane distillation
Reason, comprises the following steps：
The halogen acid solution being recovered to is heated to 30 DEG C to 80 DEG C；
After temperature stabilization, the halogen acid solution after heating is inputted to the feed side of the membrane component of hydrophobic property, entered
Row concentration, feed liquid is set to be concentrated into mass fraction through constantly circulation as 15% to 20%.
As a kind of embodiment, membrane distillation processing using direct contact membrane distillation, vacuum type membrane distillation or
Gap field orientation；
The process of the direct contact membrane distillation is：Halogen acid solution is heated to 40 DEG C to 80 DEG C；Treat solution temperature
After stable, the feed side that the halogen acid solution after heating is passed through to direct contact membrane distillation component carries out membrane distillation, directly connects
The cold side of touch membrane component is coolant, and the temperature of coolant is maintained in the range of 0 DEG C to 30 DEG C；Followed through concentrating repeatedly
Ring, when it is 15% to 20% that feed liquid, which is concentrated into mass fraction, that is, complete membrane distillation process；
The process of the vacuum type membrane distillation is：Halogen acid solution is heated to 30 DEG C to 80 DEG C；Treat that solution temperature is stable
Afterwards, the feed side for the halogen acid solution after heating being passed through to membrane component carries out membrane distillation, while to the cold of membrane component
But side vacuumizes, and is 0.1kPa to 3kPa to vacuum；Through concentration cycles repeatedly, until feed liquid is concentrated into mass fraction as 15%
During to 20%, that is, complete membrane distillation process；
The process of the gap field orientation is：Halogen acid solution is heated to 40 DEG C to 80 DEG C；Treat that solution temperature is stable
Afterwards, the feed side for the halogen acid solution after heating being passed through to membrane component carries out membrane distillation, meanwhile, control membrane component
Coolant is cooled to -5 DEG C to 5 DEG C through the condenser in component；Through concentration cycles repeatedly, until feed liquid is concentrated into mass fraction and is
When 15% to 20%, that is, complete membrane distillation process；Wherein, the coolant is the second two that volumn concentration is 30% to 70%
Alcohol solution.
Based on same inventive concept, the present invention also provides a kind of preparation method of benzyltrimethylammonium hydroxide, including with
Lower step：
Using bipolar membrane electrodialysis process electrolyte benzyltrimethylammon.um halogeno salt, halide ion and benzyltrimethylammon.um are obtained
Cation；Using Bipolar Membrane water decomposition, hydrogen ion and hydroxide ion are generated；
In the presence of extra electric field, utilize amberplex, so as to get benzyltrimethylammoncation cation and hydroxyl
Ions binding generates benzyltrimethylammonium hydroxide solution, and halide ion is combined generation halogen acid solution with hydrogen ion；
The benzyltrimethylammonium hydroxide solution and halogen acid solution are reclaimed respectively.
The present invention is compared to the beneficial effect of prior art：
The preparation facilities and preparation method of benzyltrimethylammonium hydroxide provided by the invention, utilize the double of four cell structures
EDBM component in pole is electrolysed benzyltrimethylammon.um halogeno salt, obtains halide ion and benzyltrimethylammoncation cation；Profit simultaneously
With Bipolar Membrane water decomposition, hydrogen ion and hydroxide ion are generated；In the presence of extra electric field, amberplex is utilized so that
The benzyltrimethylammoncation cation arrived is combined generation benzyltrimethylammonium hydroxide solution, halide ion and hydrogen with hydroxide ion
Ions binding generates halogen acid solution.Using the benzyltrimethylammonium hydroxide quality for preparing of the present invention is high, production cost is low
And conversion rate of products is high.And the accessory substance halogen acid solution in production process, it can be concentrated back by film distillation technology
With, the resource reclaim of discarded object is realized, it is environmentally friendly, pollute small.
Brief description of the drawings
Fig. 1 is the schematic flow sheet of the preparation method for the benzyltrimethylammonium hydroxide that the embodiment of the present invention one provides；
Fig. 2 is the schematic flow sheet of the preparation method for the benzyltrimethylammonium hydroxide that the embodiment of the present invention three provides.
Embodiment
Below in conjunction with accompanying drawing, the technical characteristic above-mentioned and other to the present invention and advantage are clearly and completely described,
Obviously, described embodiment is only the section Example of the present invention, rather than whole embodiments.
Referring to Fig. 1, the embodiment of the present invention one provide firstly a kind of preparation method of benzyltrimethylammonium hydroxide, including
Following steps：
S010, using bipolar membrane electrodialysis process electrolyte benzyltrimethylammon.um halogeno salt, obtain halide ion and benzyl three
Methyl ammonium cation；Using Bipolar Membrane water decomposition, hydrogen ion and hydroxide ion are generated；
S020, in the presence of extra electric field, utilize amberplex, so as to get benzyltrimethylammoncation cation and hydrogen
Oxygen radical ion combines generation benzyltrimethylammonium hydroxide solution, and halide ion is combined generation halogen acid solution with hydrogen ion；
S030, benzyltrimethylammonium hydroxide solution and halogen acid solution are reclaimed respectively.
It should be noted that Bipolar Membrane is a kind of new ion-exchange composite membranes, it is generally by cation exchange layer (N
Type film), interface hydrophilic layer (Catalytic Layer) and anion exchange layer (p-type film) are combined, be reaction film truly.
Under DC electric field effect, hydrolytic dissociation can be respectively obtained hydrogen ion and hydroxide ion by Bipolar Membrane in film both sides.
Membrane distillation is the membrane separating process that membrane technology is combined with still-process, using dewatering microporous film as medium, in film two
In the presence of the vapour pressure of side, the volatile component in feed liquid passes through fenestra in vapour form, so as to realize separation purpose.With it is other
Conventional separation process is compared, and membrane distillation has that separative efficiency is high, operating condition is gentle, to film and feed liquid interphase interaction and film
The advantages that mechanical property requirements are not high.Generally, membrane distillation is applied to concentration process in the nonvolatile matter aqueous solution.Cross
The motive force of journey is the partial pressure difference of vapor, under the conditions of certain temperature difference, though membrane distillation process has phase transformation, in non-boiling shape
Carried out under the lower temperature of state, therefore the energy of the low heat values such as industrial exhaust heat can be utilized, and easy to operate, good separating effect.
The present invention, using bipolar membrane electrodialysis process electrolyte benzyltrimethylammon.um halogeno salt, obtains halogen according to principles above
Plain ion and benzyltrimethylammoncation cation；Meanwhile using Bipolar Membrane water decomposition, generate hydrogen ion and hydroxide ion；Connect down
Come, in the presence of extra electric field, utilize amberplex, so as to get benzyltrimethylammoncation cation and hydroxide ion knot
Into benzyltrimethylammonium hydroxide solution, halide ion is combined generation halogen acid solution with hydrogen ion for symphysis；Finally, to benzyl three
Ammonium hydroxide solution and halogen acid solution are reclaimed respectively.Benzyltrimethylammonium hydroxide quality prepared by this method
Height, cost are low, high conversion rate.And the accessory substance halogen acid solution in this method production process, carried out by film distillation technology
Concentrate reuse, it is possible to achieve the resource reclaim of discarded object, environmentally friendly, pollution is small.And membrane distillation process is compared to traditional
Still-process has the advantages that energy consumption is low, efficiency high.
Next, the embodiment of the present invention two provides a kind of preparation facilities of benzyltrimethylammonium hydroxide, embodiment one
The preparation method of the benzyltrimethylammonium hydroxide of offer can utilize the device to realize, specific as follows：
The preparation facilities for the benzyltrimethylammonium hydroxide that the embodiment of the present invention two provides, including 1 to 50 be sequentially connected in series
Or bipolar membrane electrodialysis stack in parallel.Bipolar membrane electrodialysis stack is included positioned at the pole liquid room at both ends, and positioned at pole liquid room
Middle electrodialysis compartment.Pole liquid room positioned at both sides is respectively cathode chamber and anode chamber, and cathode chamber and anode chamber correspond to respectively
Connect external power supply.Electrodialysis compartment includes the film unit that 1 to 500 group is serially connected, and film unit is four cell structures, including according to
One Bipolar Membrane BM of secondary arrangement1, a cation-exchange membrane CM1, an anion-exchange membrane AM1, a cation-exchange membrane
CM2, a Bipolar Membrane BM2, form surge chamber, acid solution room, feed liquid room and alkali lye room.Wherein, Bipolar Membrane, cation-exchange membrane,
The all homogeneous membranes of anion-exchange membrane, cation-exchange membrane, Bipolar Membrane.
The preparation facilities of the benzyltrimethylammonium hydroxide provided using embodiment two prepares benzyltrimethylammonium hydroxide
Process it is as follows：
First, the aqueous solution of benzyltrimethylammon.um halogeno salt is passed through feed liquid room, each led into acid solution room and alkali lye room
Deionized water, sulfuric acid solution is each led into cathode chamber, anode chamber and surge chamber；
Next, applying DC electric field in cathode chamber, anode chamber, Bipolar Membrane can dissociate aquatic products under DC electric field effect
Raw hydrogen ion and hydroxide ion, it is specific to reflect that process is as follows：
Bipolar Membrane BM1Caused hydrogen ion enters surge chamber under electric field action, and then passes through cation-exchange membrane CM1Enter
Enter acid solution room, with passing through anion-exchange membrane AM from feed liquid room against direction of an electric field1The halide ion for moving to acid solution room combines
Generate halogen acids；Bipolar Membrane BM2Caused hydroxide ion enters alkali lye room under electric field action, with from feed liquid room through sun from
Proton exchange CM2Benzyltrimethylammoncation cation into alkali lye room combines generation benzyltrimethylammonium hydroxide.
Accessory substance halogen acid solution in the preparation facilities production process of above-mentioned benzyltrimethylammonium hydroxide, can pass through
Film distillation technology carries out concentration reuse, realizes the resource reclaim of discarded object, and membrane distillation process compares traditional distillation
Journey has the advantages that energy consumption is low, efficiency high.
The present apparatus on the basis of three compartment electrodialysis membrane stacks, Bipolar Membrane and the anion-exchange membrane close to anode-side it
Between a cation-exchange membrane is set, this cation-exchange membrane can effectively stop the Br in acid solution room-Through Bipolar Membrane
Into alkali lye room, so as to reach the effect for obtaining high-purity methyl triethylammonium hydroxide.It is simple in construction, inexpensive, Er Qiezhuan
Rate is high, and pollution of the preparation process to environment is small.
Further, the preparation facilities for the benzyltrimethylammonium hydroxide that the embodiment of the present invention two provides, can also include
Membrane component, membrane component are mainly used in carrying out concentration to the halogen acid solution formed in acid solution room, and recovery is sharp again
With.The structure of membrane component can be plate type membrane assembly or hollow fiber form membrane module.The material of membrane component can be with
For hydrophobic microporous membrane, polyvinylidene fluoride dewatering film, polypropylene hydrophobic film or the hydrophobic film after hydrophobic modified.
Based on same inventive concept, referring to Fig. 2, the embodiment of the present invention three additionally provides a kind of benzyltrimethylammonium hydroxide
Preparation method, the preparation facilities for the benzyltrimethylammonium hydroxide that this method is provided using above-described embodiment two prepares benzyl three
Ammonium hydroxide, this method comprise the following steps：
S100, the aqueous solution of benzyltrimethylammon.um halogeno salt is passed through feed liquid room, each led into acid solution room and alkali lye room
Deionized water, sulfuric acid solution is each led into pole liquid room and surge chamber；
S200, apply DC electric field on cathode chamber and anode chamber, and control the temperature in electrodialytic membranes component to be maintained at
Preset temperature range, carry out bipolar membrane electrodialysis technique；
S300, after bipolar membrane electrodialysis technique terminates, reclaim halogen acids from acid solution room, benzyl reclaimed from alkali lye room
Trimethylammonium hydroxide.
In the above method, in bipolar membrane electrodialysis technical process, the current density of the DC electric field applied is 150A/
m2To 600A/m2, the temperature in electrodialytic membranes component is maintained at 20 DEG C to 35 DEG C, surge chamber, acid solution room, feed liquid room and alkali lye
Flow rate of liquid in room is 200L/h to 2000L/h.The mass fraction of the sulfuric acid solution each led into pole liquid room and surge chamber
For 1% to 3%.The mass fraction for the benzyltrimethylammonium hydroxide solution being recovered to from alkali lye room is 10% to 20%, is returned
For yield more than 95%, the impurity halogen ion concentration in solution is less than 70ppm.
Further, the preparation method for the benzyltrimethylammonium hydroxide that embodiment three provides, after step S300, also
It may comprise steps of：
S400, membrane distillation processing is carried out to the halogen acid solution being recovered to from acid solution room, until being concentrated into mass fraction
For 15% to 20% when, collect concentrate, be back to benzyltrimethylammonium hydroxide production.
Specifically, the process of the halogen acid solution progress concentration to being recovered to from acid solution room is：By what is be recovered to
Halogen acid solution is heated to 30 DEG C to 80 DEG C；After temperature stabilization, the halogen acid solution after heating is inputted to the film of hydrophobic property
The feed side of component is distilled, carries out concentration, feed liquid is concentrated into mass fraction through constantly circulation as 15% to 20%.
As a kind of embodiment, above-mentioned membrane distillation processing can use direct contact membrane distillation, vacuum type film to steam
Evaporate or gap field orientation.
Embodiment one：Using direct contact membrane distillation；
Halogen acid solution is heated to 40 DEG C to 80 DEG C；After solution temperature is stable, the halogen acid solution after heating is led to
The feed side for entering direct contact membrane distillation component carries out membrane distillation, and the cold side of direct contact membrane distillation component is cooling
Liquid, the temperature of coolant are maintained in the range of 0 DEG C to 30 DEG C；Through concentration cycles repeatedly, until feed liquid is concentrated into mass fraction and is
When 15% to 20%, that is, complete membrane distillation process；
Embodiment two：Using vacuum type membrane distillation；
Halogen acid solution is heated to 30 DEG C to 80 DEG C；After solution temperature is stable, the halogen acid solution after heating is led to
The feed side for entering membrane component carries out membrane distillation, while the cold side of membrane component is vacuumized, and is to vacuum
0.1kPa to 3kPa；Through concentration cycles repeatedly, when it is 15% to 20% that feed liquid, which is concentrated into mass fraction, that is, membrane distillation is completed
Process；
Embodiment three：Using gap field orientation；
Halogen acid solution is heated to 40 DEG C to 80 DEG C；After solution temperature is stable, the halogen acid solution after heating is led to
The feed side for entering membrane component carries out membrane distillation, meanwhile, control the coolant of membrane component cold through the condenser in component
But -5 DEG C to 5 DEG C are arrived；Through concentration cycles repeatedly, when it is 15% to 20% that feed liquid, which is concentrated into mass fraction, that is, completes film and steam
Evaporate process；Wherein, coolant is the glycol water that volumn concentration is 30% to 70%.
The preparation facilities for the benzyltrimethylammonium hydroxide that the embodiment of the present invention four provides, it includes 1 Bipolar Membrane electric osmose
Component is analysed, the bipolar membrane electrodialysis stack is made up of the pole liquid room of both sides with the electrodialysis compartment being clipped among two side pole liquid rooms,
Pole liquid room is respectively cathode chamber and anode chamber, and electrodialysis compartment is made up of 10 groups of film unit arranged in series.The film unit is four
Cell structure, by a Bipolar Membrane BM1, a cation-exchange membrane CM1, an anion-exchange membrane AM1, a cation hand over
Change film CM2, a Bipolar Membrane BM2It is spaced and forms surge chamber, acid solution room, feed liquid room, alkali lye room.The Bipolar Membrane that wherein uses,
Cation-exchange membrane, anion-exchange membrane are business homogeneous membrane, and negative electrode, anode etc. use Ti-Ru electrode.In addition, this
The membrane component that example uses is steamed for the doughnut hydrophobic film component after hydrophobic modified using direct contact type film
Evaporate mode.
Preparation process is as follows：
First, the aqueous solution 2L for the benzyltrimethylammonium bromide that mass fraction is 17.6% is passed through feed liquid room, by 2L matter
Charging of the sulfuric acid solution that amount fraction is 3% as anode chamber and cathode chamber, is passed through anode chamber and cathode chamber；To acid solution room and alkali
Liquid room each leads into 2L deionized waters, and 2L, 3% sulfuric acid solution are passed through to surge chamber.
Next, applying DC electric field in anode chamber and cathode chamber, it is 200A/m to keep DC electric field current density2,
The running temperature of device is 25 DEG C, and each compartment flow rate of liquid control is 200L/h.Bipolar Membrane dissociates water under DC electric field effect
Produce hydrogen ion and hydroxide ion：Bipolar Membrane BM1Caused hydrogen ion enters surge chamber under electric field action, and then passes through sun
Amberplex CM1Into acid solution room, with passing through anion-exchange membrane AM from feed liquid room against direction of an electric field1Move to acid solution room
Bromide ion combine, the hydrobromic acid that generation 1.8L mass fractions are 4.3%；Bipolar Membrane BM2Caused hydroxide ion is in electric field
Effect is lower to enter alkali lye room, with passing through cation-exchange membrane CM from feed liquid room2Into the benzyltrimethylammoncation cation of alkali lye room
With reference to generation benzyltrimethylammonium hydroxide.Through bipolar membrane electrodialysis circular treatment, it is 16.3% to obtain 1.8L mass fractions
Benzyltrimethylammonium hydroxide solution, wherein foreign ion bromide ion concentration are 50ppm.
Meanwhile the hydrobromic acid generated during bipolar membrane electrodialysis is heated to 50 DEG C, after solution temperature is stable, by hydrogen
The feed side that bromic acid solution is passed through membrane component carries out membrane distillation, is cooling in the cold side of direct contact membrane distillation component
Liquid, and temperature is maintained at 5 DEG C.Wherein, coolant is water.Through concentration cycles repeatedly, feed liquid is concentrated into mass fraction as 16.31%
When, that is, complete membrane distillation process.
Finally, concentrate is collected, is back to the production of benzyltrimethylammonium bromide.
The preparation facilities for the benzyltrimethylammonium hydroxide that the embodiment of the present invention five provides, it includes 1 Bipolar Membrane electric osmose
Component is analysed, the component is made up of the pole liquid room of both sides with the electrodialysis compartment being clipped among two side pole liquid rooms, and pole liquid room is respectively
Cathode chamber and anode chamber, electrodialysis compartment are made up of 20 groups of film unit arranged in series, and the film unit is four cell structures, by one
Open Bipolar Membrane BM1, a cation-exchange membrane CM1, an anion-exchange membrane AM1, a cation-exchange membrane CM2, one it is double
Pole film BM2It is spaced and forms surge chamber, acid solution room, feed liquid room, alkali lye room.The Bipolar Membrane that wherein uses, cation-exchange membrane,
Anion-exchange membrane is business homogeneous membrane, and negative electrode, anode etc. use Ti-Ru electrode.In addition, the film that this example uses
Component is distilled for the doughnut hydrophobic film component after hydrophobic modified, using vacuum type membrane distillation mode.
Preparation process is as follows：
First, the aqueous solution for the benzyltrimethylammonium bromide that 10L mass fractions are 14.3% is passed through feed liquid room, by 10L
Mass fraction is charging of 3% sulfuric acid solution as anode chamber and cathode chamber, is passed through anode chamber and cathode chamber.To acid solution room and alkali
Liquid room each leads into deionized water 10L, and 10L, 3% sulfuric acid solution are passed through to surge chamber.
Next, applying DC electric field on positive plate and minus plate, it is 600A/m to keep DC electric field current density2,
The running temperature of device is 25 DEG C, and each compartment flow rate of liquid control is 400L/h.Bipolar Membrane can dissociate under DC electric field effect
Water produces hydrogen ion and hydroxide ion：Bipolar Membrane BM1Caused hydrogen ion enters surge chamber under electric field action, and then passes through
Cation-exchange membrane CM1Into acid solution room, with passing through anion-exchange membrane AM from feed liquid room against direction of an electric field1Move to liquid
The bromide ion of room combines, and generation 9.7L mass fractions are 5.1% hydrobromic acid；Bipolar Membrane BM2Caused hydroxide ion is in electric field
Effect is lower to enter alkali lye room, with passing through cation-exchange membrane CM from feed liquid room2Into the benzyltrimethylammoncation cation of alkali lye room
With reference to generation benzyltrimethylammonium hydroxide.Through bipolar membrane electrodialysis circular treatment, it is 13.7% to obtain 9.6L mass fractions
Benzyltrimethylammonium hydroxide solution, wherein foreign ion bromide ion concentration are 43ppm.
Meanwhile the hydrobromic acid generated during bipolar membrane electrodialysis is heated to 40 DEG C, after solution temperature is stable, by hydrogen
The feed side that bromic acid solution is passed through membrane component carries out membrane distillation.Vacuum is evacuated in the cold side of film distillation film component
For 0.21kPa.Through concentration cycles repeatedly, when it is 17.3% that feed liquid, which is concentrated into mass fraction, that is, membrane distillation process is completed.
Finally, concentrate is collected, is back to the production of benzyltrimethylammonium bromide.
The preparation facilities for the benzyltrimethylammonium hydroxide that the embodiment of the present invention six provides, including 1 bipolar membrane electrodialysis
Component, the component are made up of the pole liquid room of both sides with the electrodialysis compartment being clipped among two side pole liquid rooms, and pole liquid room is respectively the moon
Pole room and anode chamber, electrodialysis compartment are made up of 40 groups of film unit arranged in series, and the film unit is one by four cell structures
Bipolar Membrane BM1, a cation-exchange membrane CM1, an anion-exchange membrane AM1, a cation-exchange membrane CM2, one it is bipolar
Film BM2It is spaced and forms surge chamber, acid solution room, feed liquid room, alkali lye room.The Bipolar Membrane that wherein uses, cation-exchange membrane, the moon
Amberplex is business homogeneous membrane, and negative electrode, anode etc. use Ti-Ru electrode.In addition, the film that this example uses steams
Component is evaporated for the doughnut hydrophobic film component after hydrophobic modified, using gap field orientation mode.
Preparation process is as follows：
First, the aqueous solution for the benzyltrimethylammonium bromide that 5L mass fractions are 16.6% is passed through feed liquid room, by 5L matter
The sulfuric acid solution that amount fraction is 3% is passed through anode chamber and cathode chamber, and deionized water 5L is each led into acid solution room and alkali lye room, to
Surge chamber is passed through 3% sulfuric acid solution 5L.
Next, applying DC electric field in anode chamber and cathode chamber, it is 300A/m to keep DC electric field current density2,
The running temperature of bipolar membrane electrodialysis device is 25 DEG C, and each compartment flow rate of liquid control is 100L/h.Bipolar Membrane is in DC electric field
The lower dissociation water of effect produces hydrogen ion and hydroxide ion：Bipolar Membrane BM1Caused hydrogen ion enters buffering under electric field action
Room, and then pass through cation-exchange membrane CM1Into acid solution room, with passing through anion-exchange membrane AM from feed liquid room against direction of an electric field1
The bromide ion for moving to acid solution room combines, and generation 4.7L mass fractions are 3.4% hydrobromic acid；Bipolar Membrane BM2Caused hydroxyl
Ion enters alkali lye room under electric field action, with passing through cation-exchange membrane CM from feed liquid room2Into the benzyl front three of alkali lye room
Base ammonium cation combines, and generates benzyltrimethylammonium hydroxide.Through bipolar membrane electrodialysis circular treatment, 4.6L mass fractions are obtained
For 15.7% benzyltrimethylammonium hydroxide solution, wherein foreign ion bromide ion concentration is 40ppm.
Meanwhile the hydrobromic acid generated during bipolar membrane electrodialysis is heated to 40 DEG C, after solution temperature is stable, by hydrogen
The feed side that bromic acid solution is passed through membrane component carries out membrane distillation, while the coolant of membrane component is through the condensation in component
Device is cooled to 0 DEG C, wherein, coolant is that volumn concentration is 30% glycol water.Through concentration cycles repeatedly, work as feed liquid
Be concentrated into mass fraction for 17.2% when, that is, complete membrane distillation process.
Finally, concentrate is collected, is back to the production of benzyltrimethylammonium bromide.
Particular embodiments described above, the purpose of the present invention, technical scheme and beneficial effect are carried out further
Describe in detail, it will be appreciated that the foregoing is only the specific embodiment of the present invention, the protection being not intended to limit the present invention
Scope.Particularly point out, to those skilled in the art, within the spirit and principles of the invention, that is done any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (14)
1. a kind of preparation facilities of benzyltrimethylammonium hydroxide, it is characterised in that be sequentially connected in series including one or more or in parallel
Bipolar membrane electrodialysis stack；
The bipolar membrane electrodialysis stack is included positioned at the pole liquid room at both ends, and electrodialysis among the pole liquid room every
Room；
The pole liquid room positioned at both sides is respectively cathode chamber and anode chamber, and the cathode chamber and anode chamber are connected respectively outer
Connect power supply；
The electrodialysis compartment includes 1 group or multigroup film unit being serially connected；
The film unit is four cell structures, including be arranged in order Bipolar Membrane, cation-exchange membrane, anion-exchange membrane, sun
Amberplex, Bipolar Membrane, form surge chamber, acid solution room, feed liquid room and alkali lye room.
2. the preparation facilities of benzyltrimethylammonium hydroxide according to claim 1, it is characterised in that the Bipolar Membrane electricity
The quantity of electrodialysis stack is 1 to 50, and the single electrodialysis compartment includes the film unit that 1 to 500 group is serially connected.
3. the preparation facilities of benzyltrimethylammonium hydroxide according to claim 1, it is characterised in that the Bipolar Membrane,
The all homogeneous membranes of cation-exchange membrane, anion-exchange membrane.
4. the preparation facilities of the benzyltrimethylammonium hydroxide according to any one of claims 1 to 3, it is characterised in that also
Including the membrane component for carrying out concentration to the halogen acid solution formed in the acid solution room.
5. the preparation facilities of the benzyltrimethylammonium hydroxide according to any one of claims 1 to 3, it is characterised in that institute
The structure for stating membrane component is plate type membrane assembly or hollow fiber form membrane module.
6. the preparation facilities of the benzyltrimethylammonium hydroxide according to any one of claims 1 to 3, it is characterised in that institute
The material of membrane component is stated as hydrophobic microporous membrane, polyvinylidene fluoride dewatering film, polypropylene hydrophobic film or through hydrophobicity
Modified hydrophobic film.
7. a kind of preparation method of benzyltrimethylammonium hydroxide, it is characterised in that utilize any one of the claims 1 to 6
The preparation facilities of described benzyltrimethylammonium hydroxide prepares benzyltrimethylammonium hydroxide, and this method comprises the following steps：
S100, the aqueous solution of benzyltrimethylammon.um halogeno salt is passed through the feed liquid room, distinguished to the acid solution room and alkali lye room
Deionized water is passed through, sulfuric acid solution is each led into the pole liquid room and surge chamber；
S200, apply DC electric field on the cathode chamber and anode chamber, and control the temperature in the electrodialytic membranes component to protect
Hold in preset temperature range, carry out bipolar membrane electrodialysis technique；
S300, after bipolar membrane electrodialysis technique terminates, reclaim halogen acids from the acid solution room, reclaimed from the alkali lye room
Benzyltrimethylammonium hydroxide.
8. the preparation method of benzyltrimethylammonium hydroxide according to claim 7, it is characterised in that in the Bipolar Membrane
During electrodialysis process, the current density of the DC electric field applied is 150A/m2To 600A/m2, the electrodialytic membranes component
In temperature be maintained at 20 DEG C to 35 DEG C, the flow rate of liquid in the surge chamber, acid solution room, feed liquid room and alkali lye room is
200L/h to 2000L/h.
9. the preparation method of benzyltrimethylammonium hydroxide according to claim 7, it is characterised in that to the pole liquid room
The mass fraction of the sulfuric acid solution each led into surge chamber is 1% to 3%.
10. the preparation method of benzyltrimethylammonium hydroxide according to claim 7, it is characterised in that from the alkali lye
The mass fraction for the benzyltrimethylammonium hydroxide solution being recovered in room is 10% to 20%, and the rate of recovery is more than 95%, solution
In impurity halogen ion concentration be less than 70ppm.
11. the preparation method of the benzyltrimethylammonium hydroxide according to any one of claim 7 to 10, it is characterised in that
It is further comprising the steps of after step S300：
Membrane distillation processing is carried out to the halogen acid solution being recovered to from the acid solution room, until being concentrated into mass fraction as 15%
During to 20%, concentrate is collected, is back to benzyltrimethylammonium hydroxide production.
12. the preparation method of benzyltrimethylammonium hydroxide according to claim 11, it is characterised in that described to from institute
State the halogen acid solution being recovered in acid solution room and carry out membrane distillation processing, comprise the following steps：
The halogen acid solution being recovered to is heated to 30 DEG C to 80 DEG C；
After temperature stabilization, the halogen acid solution after heating is inputted to the feed side of the membrane component of hydrophobic property, carried out dense
Contracting is handled, and feed liquid is concentrated into mass fraction through constantly circulation as 15% to 20%.
13. the preparation method of benzyltrimethylammonium hydroxide according to claim 11, it is characterised in that the membrane distillation
Processing uses direct contact membrane distillation, vacuum type membrane distillation or gap field orientation；
The process of the direct contact membrane distillation is：Halogen acid solution is heated to 40 DEG C to 80 DEG C；Treat that solution temperature is stable
Afterwards, the feed side for the halogen acid solution after heating being passed through to direct contact membrane distillation component carries out membrane distillation, direct contact type
The cold side of membrane component is coolant, and the temperature of coolant is maintained in the range of 0 DEG C to 30 DEG C；Through concentration cycles repeatedly,
When it is 15% to 20% that feed liquid, which is concentrated into mass fraction, that is, complete membrane distillation process；
The process of the vacuum type membrane distillation is：Halogen acid solution is heated to 30 DEG C to 80 DEG C；, will after solution temperature is stable
The feed side that halogen acid solution after heating is passed through membrane component carries out membrane distillation, while the cold side of membrane component is taken out
Vacuum, it is 0.1kPa to 3kPa to vacuum；Through concentration cycles repeatedly, until feed liquid is concentrated into mass fraction as 15% to 20%
When, that is, complete membrane distillation process；
The process of the gap field orientation is：Halogen acid solution is heated to 40 DEG C to 80 DEG C；, will after solution temperature is stable
The feed side that halogen acid solution after heating is passed through membrane component carries out membrane distillation, meanwhile, control the cooling of membrane component
Liquid is cooled to -5 DEG C to 5 DEG C through the condenser in component；Through concentration cycles repeatedly, until feed liquid is concentrated into mass fraction as 15%
During to 20%, that is, complete membrane distillation process；Wherein, the coolant is the ethylene glycol water that volumn concentration is 30% to 70%
Solution.
14. a kind of preparation method of benzyltrimethylammonium hydroxide, it is characterised in that comprise the following steps：
Using bipolar membrane electrodialysis process electrolyte benzyltrimethylammon.um halogeno salt, obtain halide ion and benzyltrimethylammon.um sun from
Son；Using Bipolar Membrane water decomposition, hydrogen ion and hydroxide ion are generated；
In the presence of extra electric field, utilize amberplex, so as to get benzyltrimethylammoncation cation and hydroxide ion
With reference to generation benzyltrimethylammonium hydroxide solution, halide ion is combined generation halogen acid solution with hydrogen ion；
The benzyltrimethylammonium hydroxide solution and halogen acid solution are reclaimed respectively.
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| CN109331663A (en) * | 2018-11-13 | 2019-02-15 | 北京廷润膜技术开发股份有限公司 | Bipolar membrane displacement electrodialysis plant and the method that lithium hydroxide is prepared using bipolar membrane displacement electrodialysis plant |
| CN110772997A (en) * | 2019-10-30 | 2020-02-11 | 雅邦绿色过程与新材料研究院南京有限公司 | Organic phase electromagnetic field dialysis process for upgrading purity of semiconductor chemicals |
| CN111138390A (en) * | 2019-12-30 | 2020-05-12 | 杭州蓝然环境技术股份有限公司 | Improved cleaning process for preparing vitamin C by membrane method |
| CN114591387A (en) * | 2022-03-21 | 2022-06-07 | 通用生物(滁州)有限公司 | Amine washing process after synthesis of medicinal nucleic acid |
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