CN107281994B - Circulation shell and tube reactor series connection tubular reactor prepares the device and method of tetramethyl ammonium hydrogen carbonate - Google Patents
Circulation shell and tube reactor series connection tubular reactor prepares the device and method of tetramethyl ammonium hydrogen carbonate Download PDFInfo
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- CN107281994B CN107281994B CN201710342535.0A CN201710342535A CN107281994B CN 107281994 B CN107281994 B CN 107281994B CN 201710342535 A CN201710342535 A CN 201710342535A CN 107281994 B CN107281994 B CN 107281994B
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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
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/20—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of quaternary ammonium compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/22—Evaporating by bringing a thin layer of the liquid into contact with a heated surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/26—Multiple-effect evaporating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D1/00—Evaporating
- B01D1/30—Accessories for evaporators ; Constructional details thereof
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/2415—Tubular reactors
- B01J19/242—Tubular reactors in series
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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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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C68/00—Preparation of esters of carbonic or haloformic acids
- C07C68/06—Preparation of esters of carbonic or haloformic acids from organic carbonates
Abstract
The invention discloses the device and methods that a kind of circulation shell and tube reactor series connection tubular reactor continuously prepares tetramethyl ammonium hydrogen carbonate；Oxide spinel dimethyl ester, trimethylamine and solvent methanol continuously enter circulating tank by feed pump, material passes through circulating pump again and squeezes into shell and tube reactor jointly from the material that circulation shell and tube reactor overflow goes out after mixing, in the tube side of reactor, dimethyl carbonate and trimethylamine are reacted in solvent methanol, the reaction heat that reaction process is released is pulled away through cooling medium in shell side, most of material is recycled, fraction material by the pressure that reaction system itself generates enters tubular reactor, and the reaction was continued, material after completing reaction enters downward film evaporator and carries out the recycling of methanol solvate and the extraction of bicarbonate tetramethylammonium product.Reaction system operating pressure of the present invention is low, and most of conversion reaction carries out in circulation shell-and-tube reactor, and reaction heat can be used to generate low-pressure steam；Complete equipment can be continuously produced, stable product quality.
Description
Technical field
Circulation shell and tube reactor series connection tubular reactor continuously synthesizes the side of TMAH electrolysis raw material tetramethyl ammonium hydrogen carbonate
Method belongs to organic synthesis field.
Background technique
Tetramethylphosphonihydroxide hydroxide amine is also known as tetramethyl oxyammonia (TMAH), and molecular formula is (CH3)4NOH, which is that one kind is strongest, to be had
Machine alkali, TMAH be mainly used for integrated circuit (IC) industry, LCD industry (FT-LCD), opto-electronic industry developer solution and
Etching agent, integrated circuit chemistry mechanically polishes the ultrapure cleaning agent of (CMP) process, therefore it is commonly known as electronic chemical product.It
Also there is very extensive purposes in general industrial circle, such as: it can be used as the catalysis in the synthesis of organosilicon series of products
Agent can be used for the industries such as polyester Type of Collective, weaving, plastic products, leather.
Tetramethylammonium hydroxide is synthesized by three steps, first step quaternization reaction, is original with trimethylamine and dimethyl carbonate
Material prepares methyl carbonic tetramethyl-ammonium, second step hydrolysis, methyl carbonic by quaternization reaction in solvent methanol
Tetramethyl-ammonium meets water generation hydrolysis and is generated as bicarbonate tetramethylammonium；Third step electrochemical reaction, it is former with bicarbonate tetramethylammonium
Tetramethyl ammonium hydroxide is made by electrolysis with ion-exchange film in a cell in material.
Specific reaction are as follows: trimethylamine and dimethyl carbonate quaternization reaction generate methyl carbonic tetramethyl-ammonium first,
Then it is hydrolyzed under the existence condition of water, reaction obtains bicarbonate tetramethyl-ammonium, and chemical equation is as follows:
Then pass through electrolysis with ion-exchange film in a cell using bicarbonate tetramethylammonium as raw material and TMAH is made.Anode chamber and cathode
It is reacted as follows respectively room:
Anode chamber: OH_e → 1/4O2+1/2H2O
Cathode chamber:
H++e→1/2H2
Overall reaction equation:
Patent CN101314572A discloses a kind of method that tubular reactor continuously prepares tetramethyl ammonium hydrogen carbonate, will be former
After expecting dimethyl carbonate, trimethylamine and solvent mixing preheating, then carry out reacting obtained tetramethyl carbonic acid by tubular reactor
Hydrogen ammonium, the patent referred only to solvent by recycling, specifically how recycling design patent without reference to.Separately through
Tubular reactor prepares TMAB, and there are many disadvantages, and the pressure such as reaction system is high, and equipment investment is high；Raw material preheating needs disappear
Consume steam；The timely removal of reaction heat is difficult, and reaction system is unable to quiet run.
Granted patent CN10992055 B discloses a kind of continuous by the continuous tank reactor of multi-floating bodies before us
The method for preparing tetramethyl ammonium hydrogen carbonate.Although the continuous tank reactor reactor of multi-floating bodies overcomes exclusive use tubular type anti-
The some disadvantages for answering device are reduced by raw material being added to the feed way having reached in certain conversion ratio reaction mixture
The concentration of trimethylamine in reaction mixture, while reducing the pressure of reaction system；Raw material in certain reaction temperature
Material directly mixes, and does not need to be preheated, thus saves steam consumption；Material concentration variation adds with raw material in reaction system
The variation variation for entering amount is slow, and reaction process is steady, operates convenient for serialization.But it there is also shortcomings, such as needed for
Reactor volume is larger, needs multi-floating bodies, and number of devices is more, and equipment investment cost is high, and reactor takes up a large area, and reaction is most
Whole conversion ratio is low.
Summary of the invention
The present invention provides a kind of circulation shell and tube reactor series connection tubular reactors continuously to synthesize TMAH electrolysis raw material four
The method of methyl carbonic acid hydrogen ammonium, the method overcome many deficiencies that tubular reactor and multi-continuous stirred tank reactor is used alone
Place.The quaternization reaction of trimethylamine and dimethyl carbonate is strong exothermal reaction, recycles shell and tube reactor unit volume heat-transfer surface
Product is big, can remove reaction heat in time, and reaction temperature is easy to control, and avoids reaction system that temperature runaway occurs, reduces the generation of side reaction.
Reaction heat is removed by the saturated water vaporization of shell and tube reactor shell side, and entire reaction system does not consume steam not only, but also
Part low-pressure steam can be obtained.Reaction mass constantly recycles in shell and tube reactor, by control loop pump flow come
Control loop ratio, so as to the production capacity of flexible modulation reactor.Reacting system pressure is low, and device specific productivity is big, if
Standby cost of investment is lower.For rear stage using insulation tubular reactor, the device structure is simple, and back-mixing do not occur for material, when reaction
Between it is short, with multi-floating bodies reaction compared with, product yield improve nearly 2%, products obtained therefrom quality stablize.Due to fluid in reactor
The pressure that flowing is generated by system itself, therefore power consumption is substantially reduced.Entire reaction system equipment investment is few, equipment land occupation
Area is small, can be efficiently modified to existing TMAH production technology problem.
Technical scheme is as follows:
Circulation shell and tube reactor series connection tubular reactor of the invention continuously prepares the device of tetramethyl ammonium hydrogen carbonate, follows
Discharge nozzle line is set at the top of circular row tubular reactor, and feeding line is arranged in bottom, and circulation shell and tube reactor passes through overflow line
Series connection tubular reactor；Setting discharge nozzle line in tubular reactor outlet connects the first falling film evaporator, the first falling film evaporator top
Portion's setting extraction steam pipe line, bottom setting extraction liquid line；First falling film evaporator connects the second falling liquid film by pipeline and steams
Device is sent out, setting extraction steam pipe line at the top of the second falling film evaporator, bottom setting extraction product pipeline simultaneously connects products pot.
It recycles shell and tube reactor top left side and circulating tank is set, raw material enters circulating tank through overflow line and material pipeline
After mixing, reactor bottom is squeezed by feeding line by circulating pump；It recycles shell and tube reactor top right side and water vapour is set
Steam-water separator, saturated water enter shell side from reactor bottom, and steam enters water vapour steam-water separator from top；First drop
Condenser is set at the top of film evaporator, and methanol liquid flows into extraction pipeline and connects methanol loop tank, returns again to circulating tank；Second
Condenser is set at the top of falling film evaporator, and methanol aqueous solution flows into extraction pipeline and connects methanol aqueous solution tank.Trimethylamine, carbonic acid
Dimethyl ester, methanol and pure water pass through feed pump into each device respectively.Material between the individual devices flow through system
The pressure force-summing device potential difference itself generated is completed.
The method that circulation shell and tube reactor series connection tubular reactor of the invention continuously prepares tetramethyl ammonium hydrogen carbonate is,
Oxide spinel dimethyl ester, trimethylamine and solvent methanol are continuously added to recycle with a mole material ratio 1:0.9:2-1:1.1:5
In tank, the material being newly added is mixed with the material gone out from circulation shell and tube reactor overflow, is beaten mixed material by circulating pump
Entering to recycle in shell and tube reactor and be reacted, the reaction heat that reaction process is released is moved out of by the cooling medium of shell side, when
When reaching certain conversion ratio, reaction mixture is continued by the pressure that reaction system itself generates into subsequent tubular reactor
Reaction, the material after completing reaction enter downward film evaporator and carry out the recycling of solvent and adopting for target product bicarbonate tetramethylammonium
Out.
Shell and tube reactor series connection tubular reactor, material flows under system pressure itself, after sufficiently reacting, enters
Falling film evaporation system.In the first falling film evaporator, easy volatile solvent methanol and the raw material trimethylamine and carbonic acid two that do not convert
Methyl esters vaporization rises up at the top of evaporator, recycles, recycles after condenser condenses, liquid material is flowed downward by film supplying tube
Flow out the first falling film evaporator.Outside is introduced water and is produced after liquid material mixes with from the first falling film evaporator bottom, while into
Enter the second falling film evaporator.In the second falling film evaporator, reaction carries out simultaneously with evaporation, and tetramethylammonium carbonic acid mono-methyl meets water hair
Raw hydrolysis generates bicarbonate tetramethyl-ammonium and methanol, by-product carbinol and the vaporization of part water evaporation, from falling film evaporator
Top extraction, becomes methanol aqueous solution after condenser condenses and is recycled, and target product bicarbonate tetramethyl aqueous ammonium is certainly
The second falling film evaporator is flowed through under above to produce from bottom.
The cooling medium uses saturated water.The season of trimethylamine and dimethyl carbonate is carried out in shell and tube reactor tube side
Ammoniumization reaction, generates a large amount of reaction heat, and saturated water is heated fast vaporizing as saturated vapor, on the one hand can shift tube side in time
On the one hand a large amount of reaction heat of interior accumulation obtain part low-pressure steam.
The circulation shell and tube reactor operating pressure is 0.5-1.0MPa, and reaction temperature is 100-130 DEG C, and material is following
The residence time of circular row tubular reactor is 10-30min, recycle ratio 15-30.
Operating pressure is 0.4-0.8MPa in the tubular reactor, and reaction temperature is 110-140 DEG C, and material is anti-in tubular type
Answering the residence time in device is 20-40min.Material is not required to be flowed by extra power device in tandem reactor system
It is dynamic, pressure is generated by system itself and is entered in tubular reactor, and under the premise of avoiding back-mixing, further progress is quaternized anti-
It answers.
The falling film evaporation system uses economic benefits and social benefits downward film evaporator, and disc type is arranged at tube sheet on an evaporator and is distributed
Device, thus every film supplying tube for being evenly distributed on feed liquid inside falling film evaporator.After separating methanol solvate and unreacting material
Material flow into the second falling film evaporator by the first falling film evaporator, occur hydrolysis after mix with water, carry out for the second time
Separation generates target product bicarbonate tetramethyl aqueous ammonium and flow to lower body along tube wall with shaped liquid film under self gravitation effect,
It is produced from bottom.Wherein the first falling film evaporator operating pressure 0.1-0.15MPa, 100-120 DEG C of evaporating temperature；Second falling liquid film steams
The pressure for sending out device is normal pressure, and evaporating temperature is 105-125 DEG C.
The method of the present invention is effectively solved using circulation shell and tube reactor series connection tubular reactor carbonate synthesis hydrogen tetramethylammonium
Multi-continuous stirred tank reactor cost of equipment is high, the big disadvantage in land occupation face, while it is high to overcome tubular reactor reaction pressure, reaction
Material needs the deficiencies of steam preheating.The reaction system equipment investment expense is low, and feed stock conversion is high, in reaction system temperature and
Yield is easily controllable, and continuous production may be implemented.
Detailed description of the invention
Fig. 1 is that circulation shell and tube reactor series connection tubular reactor continuously synthesizes TMAH electrolysis raw material tetramethyl ammonium hydrogen carbonate
Process flow chart.
Fig. 1 shows explanations:
R1 circulation shell and tube reactor, R2 tubular reactor, the first falling film evaporator of FE1, the second falling film evaporator of FE2,
E1 the first falling film evaporator condenser, E2 the second falling film evaporator condenser, P1 trimethylamine feed pump, the charging of P2 dimethyl carbonate
Pump, P3 solvent methanol circulating pump, P4 pure water feed pump, P5 circulating pump, V1 circulating tank, V2 solvent methanol circulating tank, V3 methanol-water
Tank, V4 bicarbonate tetramethylammonium products pot, SS water vapour steam-water separator.
Further include the following raw material pipeline in figure: 1- raw material trimethylamine, 2- oxide spinel dimethyl ester, 3- supplementing solvent methanol,
4- process water.
Product pipeline: 17- the second falling film evaporator lime set methanol water pipeline, 18- product tetramethyl ammonium hydrogen carbonate aqueous solution
Pipeline；
Intermediate material pipeline: 5- solvent methanol reuse pipeline, 6- reactor cycles pump feeding line, 7- reactor feed pipe
Line, 8- recycle shell and tube reactor overflow line, and 9- recirculation reactor overflowing liquid enters the pipeline of circulating tank, 10- circular response
Device overflowing liquid enters tubular reactor material pipeline, and 11- tubular reactor physics enters the connecting pipeline of the first falling film evaporator,
12- the first falling film evaporator steam pipe line, 13- the first falling film evaporator condensate liquid pipeline, 14- the first falling film evaporator liquid discharge
Expects pipe line, 15- tetramethylammonium carbonic acid mono-methyl and water mixed liquid enter the second falling film evaporator material pipeline, and the second falling liquid film of 16- steams
Send out device steam pipe line.
Specific embodiment
Attached drawing technique embodies advantages of the present invention, but the present invention is not limited to the technique of attached drawing, those skilled in the art
Member can be designed that the various modifications and changes in the technical scope of theory of the present invention, it should explanation, these modification and
Variation is also fallen within the protection scope of the present invention.The following detailed description of the present invention: below by the auxiliary of 1 process flow chart of attached drawing
It helps, illustrates the contents of the present invention, characteristic, so that the present invention can be further appreciated.
It is connected tubular reactor produced bicarbonate tetramethylammonium method using attached circulation shell and tube reactor shown in FIG. 1,
Process flow is as follows: by raw material trimethylamine, dimethyl carbonate and solvent methanol with molar ratio 1:0.9:2-1:1.1:5 ratio point
It is not squeezed into circulating tank V1 by feed pump P1, P2 and P3, raw material and the material overflowed from circulation shell and tube reactor R1
It is sufficiently mixed, is then squeezed into circulation shell and tube reactor R1 by circulating pump P5, the raw material in the tube side of shell and tube reactor
Quaternization reaction occurs for trimethylamine and dimethyl carbonate, and reaction heat passes through the saturated water between shell side and vaporizes removal, leans on reaction system
The pressure itself generated is pressed into reaction mass in tubular reactor R2 by pipeline 10, continues to react, after reaction
Mixture entered in the first falling film evaporator FE1 by pipeline 11, in the first falling film evaporator, material is from reaction pressure 0.4-
0.8MPa is kept to 0.1-0.15MPa, is flashed, volatile solvent methanol and on a small quantity unconverted trimethylamine and carbonic acid diformazan
Ester vaporization, the solvent and reactor product not vaporized flow downward along film supplying tube, further evaporate during decline, evaporate
Steam the first falling film evaporator condenser E1 is entered by the first falling film evaporator steam pipe line 12, condensed solvent passes through
Pipeline 13 flows into solvent methanol recycling can V2, and recovered solvent returns to reaction system circulation together with the methanol solvate of supplement to be made
With, the first falling film evaporator liquid of outflow is mainly methyl carbonic tetramethyl-ammonium, there are also the methanol that small part is not evaporated, the
One falling film evaporator come out liquid in pipeline 14 with from feed pump P4 water mix after pass through pipeline 15 inflow second
Hydrolysis occurs for falling film evaporator FE2, while by-product carbinol is evaporated, and the mixed vapour of gasified methanol and water passes through
Second falling film evaporator steam pipe line 16 enters the condenser E2 of the second falling film evaporator, and methanol aqueous solution passes through pipeline after condensation
17 flow into methanol aqueous solution basin V3, produce product bicarbonate tetramethyl-ammonium aqueous solution from the second falling film evaporator bottom, pass through
Pipeline 18 is flowed into products pot V4 and is stored.
The present invention is further illustrated below according to embodiment
Embodiment 1
TMAH, which is synthesized, by circulation shell and tube reactor series connection tubular reactor is electrolysed oxide spinel hydrogen tetramethyl-ammonium, raw material
Proportion is DMC:TMA:MEOH=1:0.95:2, and the reaction pressure for recycling shell and tube reactor is 0.9MPa, reaction temperature 105
DEG C, residence time of the material in circulation shell and tube reactor is 30min, recycle ratio 30；The reaction pressure of tubular reactor
For 0.6MPa, reaction temperature is 110 DEG C, and residence time of the material in tubular reactor is 30min；First falling film evaporator
Pressure is 0.15MPa, and evaporating temperature is 105 DEG C, and the pressure of the second falling film evaporator is normal pressure, and evaporating temperature is 110 DEG C, sampling
The content for analyzing product bicarbonate tetramethylammonium, obtaining bicarbonate tetramethylammonium yield is 91.2%.
Embodiment 2
TMAH, which is synthesized, by circulation shell and tube reactor series connection tubular reactor is electrolysed oxide spinel hydrogen tetramethyl-ammonium, raw material
Proportion is DMC:TMA:MEOH=1:1:4, and the reaction pressure for recycling shell and tube reactor is 1.0MPa, and reaction temperature is 130 DEG C,
Residence time of the material in circulation shell and tube reactor is 10min, and the recycle ratio for recycling material in shell and tube reactor is 15；
The reaction pressure of tubular reactor is 0.8MPa, and reaction temperature is 110 DEG C, and residence time of the material in tubular reactor be
10min；The pressure of first falling film evaporator is 0.2MPa, and evaporating temperature is 125 DEG C, and the pressure of the second falling film evaporator is normal
Pressure, evaporating temperature are 130 DEG C, and the content of sampling analysis product bicarbonate tetramethylammonium, obtaining bicarbonate tetramethylammonium yield is 92.8%.
Embodiment 3
TMAH, which is synthesized, by circulation shell and tube reactor series connection tubular reactor is electrolysed oxide spinel hydrogen tetramethyl-ammonium, raw material
Proportion is DMC:TMA:MEOH=1:1.05:3, and the reaction pressure for recycling shell and tube reactor is 0.8MPa, reaction temperature 120
DEG C, residence time of the material in circulation shell and tube reactor is 15min, and the recycle ratio for recycling material in shell and tube reactor is
20；The reaction pressure of tubular reactor is 0.8MPa, and reaction temperature is 120 DEG C, residence time of the material in tubular reactor
For 30min；The pressure of first falling film evaporator is 0.2MPa, and evaporating temperature is 105 DEG C, and the pressure of the second falling film evaporator is normal
Pressure, evaporating temperature are 120 DEG C, and the content of sampling analysis product bicarbonate tetramethylammonium, obtaining bicarbonate tetramethylammonium yield is 96.5%.
Embodiment 4
TMAH, which is synthesized, by circulation shell and tube reactor series connection tubular reactor is electrolysed oxide spinel hydrogen tetramethyl-ammonium, raw material
Proportion is DMC:TMA:MEOH=1:1:5, and the reaction pressure for recycling shell and tube reactor is 0.8MPa, and reaction temperature is 110 DEG C,
Residence time of the material in circulation shell and tube reactor is 20min, and the recycle ratio for recycling material in shell and tube reactor is 25；
The reaction pressure of tubular reactor is 0.6MPa, and reaction temperature is 125 DEG C, and residence time of the material in tubular reactor be
40min；The pressure of first falling film evaporator is 0.15MPa, and evaporating temperature is 110 DEG C, and the pressure of the second falling film evaporator is normal
Pressure, evaporating temperature are 110 DEG C, and the content of sampling analysis product bicarbonate tetramethylammonium, obtaining bicarbonate tetramethylammonium yield is 95.7%.
In conclusion a kind of circulation shell and tube reactor series connection tubular reactor proposed by the present invention continuously synthesizes TMAH electricity
The method for solving raw material tetramethyl ammonium hydrogen carbonate, is specifically described, but it should be appreciated that above-mentioned by above preferred embodiment
Description is not considered as limitation of the present invention.It should be strongly noted that those skilled in the art are all for the present invention
Similar replacement and change will be apparent from.Therefore, protection scope of the present invention is answered defined by the appended claims.
Claims (8)
1. circulation shell and tube reactor series connection tubular reactor continuously prepares the device of tetramethyl ammonium hydrogen carbonate, it is characterized in that circulation
Discharge nozzle line is set at the top of shell and tube reactor, and feeding line is arranged in bottom, and circulation shell and tube reactor passes through overflow line string
Join tubular reactor；Setting discharge nozzle line in tubular reactor outlet connects the first falling film evaporator, the first falling film evaporator top
Setting extraction steam pipe line, bottom setting extraction liquid line；First falling film evaporator connects the second falling film evaporation by pipeline
Device, the second falling film evaporator top setting extraction steam pipe line, bottom setting extraction product pipeline simultaneously connect products pot；The drop
Kestner long-tube evaporator is double-effect falling film evaporator, and disc type distributor is arranged at tube sheet on an evaporator；Volatile solvent methanol
The trimethylamine and dimethyl carbonate not converted completely are vaporized in the first falling film evaporator and are produced from top, by condensation
It is recycled after device condensation；Unboiled liquid material flows downward to base of evaporator by film supplying tube, bottom produce material with
The second falling film evaporator is flowed into after water mixing, while being reacted and being evaporated, methyl carbonic tetramethyl-ammonium is met water and hydrolyzed
Reaction generates raw bicarbonate tetramethyl-ammonium and methanol, part water and the evaporation of product methyl alcohol vaporizing, from the second falling film evaporator top
Portion's extraction, recycling obtains methanol aqueous solution after condenser condenses, and target product bicarbonate tetramethyl aqueous ammonium is in itself weight
The second falling film evaporator is flowed through under power effect from top to bottom and is produced from bottom.
2. device as described in claim 1, it is characterized in that circulating tank, raw material warp is arranged in circulation shell and tube reactor top left side
After overflow line and material pipeline enter circulating tank mixing, reactor bottom is squeezed by feeding line by circulating pump；Circulation column
Water vapour steam-water separator is arranged in tubular reactor top right side, and saturated water enters shell side from reactor bottom, and steam is from top
Portion enters water vapour steam-water separator；Condenser is set at the top of the first falling film evaporator, and methanol liquid flows into extraction pipeline and company
Methanol loop tank is connect, circulating tank is returned again to；Condenser is set at the top of the second falling film evaporator, and methanol aqueous solution flows into extraction pipeline
And connect methanol aqueous solution tank.
3. the device using claims 1 or 22 carries out the method for continuously preparing tetramethyl ammonium hydrogen carbonate, it is characterized in that oxide spinel
Dimethyl ester, trimethylamine and solvent methanol continuously enter circulating tank by feed pump, after mixing material pass through again circulating pump with from following
The material that circular row tubular reactor overflow goes out squeezes into shell and tube reactor jointly, in the tube side of reactor, dimethyl carbonate and three
Methylamine is reacted in solvent methanol, and the reaction heat that reaction process is released is pulled away through cooling medium in shell side, most of object
Material is recycled, and fraction material by the pressure that reaction system itself generates enters tubular reactor, and the reaction was continued, and completion is instead
Material after answering enters downward film evaporator and carries out the recycling of methanol solvate and the extraction of bicarbonate tetramethylammonium product.
4. method as claimed in claim 3, it is characterized in that the trimethylamine, dimethyl carbonate, methanol and pure water pass through respectively
Feed pump enters each device；The pressure force-summing device potential difference that system itself generates that flows through of material between the individual devices is come
It completes.
5. method as claimed in claim 3, it is characterized in that mole ingredient of oxide spinel dimethyl ester, trimethylamine and solvent methanol
Than for 1:0.9:2-1:1.1:5.
6. method as claimed in claim 3, it is characterized in that cooling medium is using full in the circulation shell and tube reactor shell side
And water, the heat generated in reaction process make its fast transition saturated vapor, to remove in time anti-in reaction tube side
Answer heat.
7. method as claimed in claim 3, it is characterized in that the reaction pressure of the circulation shell and tube reactor is 0.5-
1.0MPa, reaction temperature are 105-130 DEG C, and reaction mass is 10-30min, object in the residence time of circulation shell and tube reactor
Expect that the recycle ratio in circulation shell and tube reactor is 15-30；The pressure of the tubular reactor is 0.4-0.8MPa, reaction temperature
Degree is 110-125 DEG C, and residence time of the material in tubular reactor is 20-40min.
8. the method for claim 7, being steamed it is characterized in that the pressure of first falling film evaporator is 0.15-0.2MPa
Sending out temperature is 105-120 DEG C；The pressure of second falling film evaporator is normal pressure, and evaporating temperature is 110-130 DEG C.
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| CN108404844A (en) * | 2018-05-09 | 2018-08-17 | 梁小朝 | A kind of device and method of continuity method production tetramethyl ammonium carbonate |
| CN109395691A (en) * | 2018-12-22 | 2019-03-01 | 山东大明精细化工有限公司 | It is a kind of for producing the pipeline reactor and its application method of surfactant |
| CN110479059A (en) * | 2019-09-06 | 2019-11-22 | 江苏南大华兴环保科技股份公司 | Trimethylamine exhaust gas recovery system and method in a kind of Parylene production process |
| CN114573458A (en) * | 2022-03-07 | 2022-06-03 | 沧州信联化工有限公司 | Method for synthesizing tetramethylammonium bicarbonate by using microchannel reactor and tubular reactor connected in series |
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| CN101314572A (en) * | 2008-07-08 | 2008-12-03 | 杭州格林达化学有限公司 | Method for preparing tetramethyl ammonium hydrogen carbonate with condensation reaction of pipe type reactor |
| PL205566B1 (en) * | 2001-07-09 | 2010-05-31 | Lonza Ag | In situ process for preparing quaternary ammonium bicarbonates and quaternary ammonium carbonates |
| CN103772164A (en) * | 2012-10-18 | 2014-05-07 | 中国科学院兰州化学物理研究所 | Reaction system for continuously preparing polyoxymethylene dialkyl ether, and process thereof |
| CN104926668A (en) * | 2015-05-21 | 2015-09-23 | 北京盖雅环境科技有限公司 | Method for preparing tri-long-chain alkyl-ammonium bicarbonate and carbonate |
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| PL205566B1 (en) * | 2001-07-09 | 2010-05-31 | Lonza Ag | In situ process for preparing quaternary ammonium bicarbonates and quaternary ammonium carbonates |
| CN101314572A (en) * | 2008-07-08 | 2008-12-03 | 杭州格林达化学有限公司 | Method for preparing tetramethyl ammonium hydrogen carbonate with condensation reaction of pipe type reactor |
| CN103772164A (en) * | 2012-10-18 | 2014-05-07 | 中国科学院兰州化学物理研究所 | Reaction system for continuously preparing polyoxymethylene dialkyl ether, and process thereof |
| CN104926668A (en) * | 2015-05-21 | 2015-09-23 | 北京盖雅环境科技有限公司 | Method for preparing tri-long-chain alkyl-ammonium bicarbonate and carbonate |
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