CN107281994A - 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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- CN107281994A CN107281994A CN201710342535.0A CN201710342535A CN107281994A CN 107281994 A CN107281994 A CN 107281994A CN 201710342535 A CN201710342535 A CN 201710342535A CN 107281994 A CN107281994 A CN 107281994A
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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
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The device and method that shell and tube reactor series connection tubular reactor continuously prepares tetramethyl ammonium hydrogen carbonate is circulated the invention discloses a kind of；Oxide spinel dimethyl ester, trimethylamine and solvent methanol continuously enter circulating tank by feed pump, material again by circulating pump with squeezing into shell and tube reactor jointly from the material that goes out of circulation shell and tube reactor overflow after mixing, in the tube side of reactor, dimethyl carbonate and trimethylamine are reacted in solvent methanol, the reaction heat that course of reaction is released is pulled away through cooling medium in shell side, most of material is circulated, the pressure that fraction material is produced by reaction system itself, which enters tubular reactor, to be continued to react, complete reacted material and the recovery of methanol solvate and the extraction of bicarbonate tetramethylammonium product are carried out into downward film evaporator.Reaction system operating pressure of the present invention is low, and most of conversion reaction is carried out in circulation shell-and-tube reactor, and reaction heat can be for generation low-pressure steam；Complete equipment can be continuously produced, and product quality is stable.
Description
Technical field
Circulation shell and tube reactor series connection tubular reactor continuously synthesizes the side that TMAH is electrolysed raw material tetramethyl ammonium hydrogen carbonate
Method, belongs to organic synthesis field.
Background technology
Tetramethylphosphonihydroxide hydroxide amine is also known as tetramethyl oxyammonia (TMAH), and molecular formula is (CH3)4NOH, is a kind of most strong to have
Machine alkali, TMAH be mainly used in integrated circuit (IC) industry, LCD industry (FT-LCD), the developer solution of opto-electronic industry and
Etching agent, the integrated circuit chemistry mechanical polishing ultrapure cleaning agent of (CMP) process, therefore it is commonly known as electronic chemical product.It
Also there is purposes widely in general industrial circle, for example：It can be as the catalysis in the synthesis of organosilicon series of products
Agent, available for industries such as polyester Type of Collective, weaving, plastic products, leathers.
TMAH is synthesized by three steps, first step quaterisation, using trimethylamine and dimethyl carbonate as original
Material prepares methyl carbonic tetramethyl-ammonium, second step hydrolysis, methyl carbonic in solvent methanol by quaterisation
Tetramethyl-ammonium meets water generation hydrolysis and is generated as bicarbonate tetramethylammonium；3rd one-step electrochemistry reacts, former with bicarbonate tetramethylammonium
Tetramethyl ammonium hydroxide is made by electrolysis with ion-exchange film in a cell in material.
Specifically react and be：Trimethylamine generates methyl carbonic tetramethyl-ammonium with dimethyl carbonate quaterisation first,
Then it is hydrolyzed under the existence condition of water, reaction obtains bicarbonate tetramethyl-ammonium, its chemical equation is as follows：
Then TMAH is made by electrolysis with ion-exchange film in a cell using bicarbonate tetramethylammonium as raw material.Anode chamber and negative electrode
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, by original
Expect after dimethyl carbonate, trimethylamine and solvent mixing preheating, reaction is then carried out by tubular reactor tetramethyl carbonic acid is made
Hydrogen ammonium, the patent has referred only to solvent by recycle and reuse, specifically how recycling design patent without reference to.Separately through
Tubular reactor prepares TMAB, there is many shortcomings, and the pressure of such as reaction system is high, and equipment investment is high；Raw material preheating needs to disappear
Consume steam；The timely removal of reaction heat is difficult, and reaction system is unable to quiet run.
Granted patent CN10992055 B disclose a kind of continuous by the continuous tank reactor of multi-floating bodies before us
The method for preparing tetramethyl ammonium hydrogen carbonate.It is anti-that although the continuous tank reactor reactor of multi-floating bodies overcomes exclusive use tubular type
Some shortcomings of device are answered, by raw material being added to the feed way reached in certain conversion ratio reactant mixture, reduction
The concentration of trimethylamine in reactant mixture, while reduce the pressure of reaction system；Raw material is with being in certain reaction temperature
Material is directly mixed, it is not necessary to preheated, thus saves steam consumption；Raw material change in concentration adds with raw material in reaction system
The change change for entering amount is slow, and course of reaction is steady, is easy to serialization to operate.It is but it also has shortcomings, such as required
Reactor volume is larger, it is necessary to which multi-floating bodies, number of devices is more, and equipment investment cost is high, and reactor floor space is big, and reaction is most
Whole conversion ratio is low.
The content of the invention
TMAH electrolysis raw materials four are continuously synthesized the invention provides one kind circulation shell and tube reactor series connection tubular reactor
The method of methyl carbonic acid hydrogen ammonium, the method overcome many deficiencies of exclusive use tubular reactor and multi-continuous stirred tank reactor
Place.The quaterisation of trimethylamine and dimethyl carbonate is strong exothermal reaction, circulates shell and tube reactor unit volume heat-transfer surface
Product is big, reaction heat can be removed in time, reaction temperature is easily controlled, it is to avoid temperature runaway occurs for reaction system, reduces the generation of side reaction.
Reaction heat is vaporized by the saturation water of shell and tube reactor shell side and is removed, and whole reaction system does not consume steam not only, and
Part low-pressure steam can be obtained.Reaction mass is constantly circulated in shell and tube reactor, by control the flow of circulating pump come
Recycle ratio is controlled, 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 relatively low.Rear stage is using adiabatic tubular reactor, and the device structure is simple, and back-mixing does not occur for material, during reaction
Between it is short, with multi-floating bodies react compared with, product yield improve nearly 2%, products obtained therefrom steady quality.Due to fluid in reactor
The pressure that system itself is produced is leaned in flowing, therefore power consumption is substantially reduced.Whole reaction system equipment investment is few, and equipment is taken up an area
Area is small, and existing TMAH production technologies problem can be efficiently modified.
Technical scheme is as follows：
The circulation shell and tube reactor series connection tubular reactor of the present invention continuously prepares the device of tetramethyl ammonium hydrogen carbonate, follows
Discharging pipeline is set at the top of circular row tubular reactor, and bottom sets feeding line, and circulation shell and tube reactor passes through overflow line
Series connection tubular reactor；Tubular reactor outlet sets discharging pipeline to connect the first falling film evaporator, the first falling film evaporator top
Portion sets extraction steam pipe line, and bottom sets extraction liquid line；First falling film evaporator connects the second falling liquid film by pipeline and steamed
Send out and extraction steam pipe line is set at the top of device, the second falling film evaporator, bottom sets extraction product pipeline and connects products pot.
Circulate 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 into by feeding line by circulating pump；Circulate shell and tube reactor top right side and water vapour is set
Steam-water separator, saturation water enters 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 enter each device by feed pump respectively.Material between the individual devices flow through system
The pressure force-summing device potential difference itself produced is completed.
The circulation shell and tube reactor of present invention tubular reactor of connecting continuously prepares the method for tetramethyl ammonium hydrogen carbonate and is,
By oxide spinel dimethyl ester, trimethylamine and solvent methanol with mole material ratio 1:0.9:2-1:1.1:5 are continuously added to circulation
In tank, the material newly added is mixed with the material gone out from circulation shell and tube reactor overflow, is beaten mixed material by circulating pump
Enter to circulate in shell and tube reactor and reacted, the reaction heat that course of reaction is released is moved out of by the cooling medium of shell side, when
When reaching certain conversion ratio, the pressure that reactant mixture is produced by reaction system itself, which enters follow-up tubular reactor, to be continued
Reaction, completes reacted material and enters the downward film evaporator progress recovery of solvent and adopting for target product bicarbonate tetramethylammonium
Go out.
Shell and tube reactor series connection tubular reactor, material flows under system pressure itself, after fully reaction, enters
Falling film evaporation system.In the first falling film evaporator, easy volatile solvent methanol and raw material trimethylamine and carbonic acid two without conversion
Methyl esters vaporization is risen up at the top of evaporator, is reclaimed, is recycled, liquid material is flowed downward by film supplying tube after condenser is condensed
Flow out the first falling film evaporator.After outside is introduced water and mixed from the first falling film evaporator bottom extraction liquid material, enter simultaneously
Enter the second falling film evaporator.In the second falling film evaporator, reaction is carried out simultaneously with evaporation, and tetramethylammonium carbonic acid mono-methyl meets water hair
Raw hydrolysis, generation bicarbonate tetramethyl-ammonium and methanol, by-product carbinol and the vaporization of part water evaporation, from falling film evaporator
Top is produced, and being changed into methanol aqueous solution after condenser is condensed is reclaimed, 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 saturation water.The season of trimethylamine and dimethyl carbonate is carried out in shell and tube reactor tube side
Ammoniumization is reacted, and generates a large amount of reaction heat, and saturation water is heated fast vaporizing for saturated vapor, tube side on the one hand can be shifted in time
A large amount of reaction heat of interior accumulation, on the one hand 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 being followed
The residence time of circular row tubular reactor is 10-30min, and recycle ratio is 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
It is 20-40min to answer the residence time in device.Material is not required to be flowed by extra power device in tandem reactor system
It is dynamic, produce pressure in itself by system and enter in tubular reactor, under the premise of back-mixing is avoided, further carry out quaternized anti-
Should.
The falling film evaporation system uses economic benefits and social benefits downward film evaporator, and sets disc type to be distributed at tube sheet on an evaporator
Device, so that feed liquid is evenly distributed on every film supplying tube inside falling film evaporator.Separate after 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, generation target product bicarbonate tetramethyl aqueous ammonium flow to lower body with shaped liquid film under self gravitation effect along tube wall,
From bottom extraction.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 inventive method 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, takes up an area the big shortcoming in face, while it is high to overcome tubular reactor reaction pressure, reaction
Material needs the deficiencies such as 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, it is possible to achieve continuous production.
Brief description of the drawings
Fig. 1 continuously synthesizes TMAH electrolysis raw material tetramethyl ammonium hydrogen carbonates for circulation shell and tube reactor series connection tubular reactor
Process chart.
Fig. 1 represents explanation：
R1 circulation shell and tube reactors, R2 tubular reactors, the falling film evaporators of FE1 first, the falling film evaporators of FE2 second,
E1 the first falling film evaporator condensers, E2 the second falling film evaporator condensers, P1 trimethylamine feed pumps, the charging of P2 dimethyl carbonates
Pump, P3 solvent methanol circulating pumps, P4 pure water feed pumps, P5 circulating pumps, V1 circulating tanks, V2 solvent methanol circulating tanks, V3 methanol-waters
Tank, V4 bicarbonate tetramethylammonium products pots, SS water vapour steam-water separators.
Also include the following raw material pipeline in figure：1- raw material trimethylamines, 2- oxide spinel dimethyl esters, 3- supplementing solvent methanol,
4- process waters.
Product pipeline：17- the second falling film evaporator lime set methanol water pipelines, the 18- product tetramethyl ammonium hydrogen carbonate aqueous solution
Pipeline；
Intermediate material pipeline：5- solvent methanol reuse pipelines, 6- reactor cycles pump feeding lines, 7- reactor feed pipes
Line, 8- circulation shell and tube reactor overflow lines, 9- recirculation reactors overflowing liquid enters the pipeline of circulating tank, 10- circular responses
Device overflowing liquid enters tubular reactor material pipeline, and 11- tubular reactors physics enters the connecting pipeline of the first falling film evaporator,
12- the first falling film evaporator steam pipe lines, 13- the first falling film evaporator condensate liquid pipelines, 14- the first falling film evaporator liquid discharges
Expects pipe line, 15- tetramethylammonium carbonic acid mono-methyls enter the second falling film evaporator material pipeline with water mixed liquid, and the falling liquid films of 16- second steam
Send out device steam pipe line.
Embodiment
Accompanying drawing technique embodies advantages of the present invention, but the invention is not restricted to the technique of accompanying 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 within the scope of the present invention.The following detailed description of the present invention：Below by the auxiliary of the process chart of accompanying drawing 1
Help, illustrate present disclosure, characteristic, so that the present invention can be further appreciated.
Using shown in accompanying drawing 1 circulation shell and tube reactor connect tubular reactor produced bicarbonate tetramethylammonium method, its
Technological process is as follows：By raw material trimethylamine, dimethyl carbonate and solvent methanol with mol ratio 1:0.9:2-1:1.1:5 ratios point
Do not squeezed into by feed pump P1, P2 and P3 in circulating tank V1, raw material and the material overflowed from circulation shell and tube reactor R1
It is sufficiently mixed, is then squeezed into by circulating pump P5 in circulation shell and tube reactor R1, the raw material in the tube side of shell and tube reactor
Quaterisation occurs for trimethylamine and dimethyl carbonate, and reaction heat is vaporized by the saturation water between shell side and removed, by reaction system
The pressure itself produced is pressed into reaction mass in tubular reactor R2 by pipeline 10, proceeds reaction, after reaction terminates
Mixture entered by pipeline 11 in the first falling film evaporator FE1, 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 a small amount of unconverted trimethylamine and carbonic acid diformazan
Ester is vaporized, and the solvent and reactor product not vaporized flow downward along film supplying tube, further evaporated during decline, is evaporated
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 is flowed 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, the methanol that also small part is not evaporated, the
The liquid that one falling film evaporator comes out in pipeline 14 with from feed pump P4 water mix after by pipeline 15 flow into second
Falling film evaporator FE2, occurs hydrolysis, while by-product carbinol is evaporated, 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 the product bicarbonate tetramethyl-ammonium aqueous solution from the second falling film evaporator bottom, pass through
Pipeline 18 is flowed into products pot V4 and stored.
The present invention is further illustrated below according to embodiment
Embodiment 1
TMAH electrolysis oxide spinel hydrogen tetramethyl-ammoniums, raw material are synthesized by circulating shell and tube reactor series connection tubular reactor
Match as DMC：TMA：MEOH=1：0.95：2, the reaction pressure of circulation shell and tube reactor is 0.9MPa, and reaction temperature is 105
DEG C, residence time of the material in circulation shell and tube reactor is 30min, and recycle ratio is 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 of analysis product bicarbonate tetramethylammonium, it is 91.2% to obtain bicarbonate tetramethylammonium yield.
Embodiment 2
TMAH electrolysis oxide spinel hydrogen tetramethyl-ammoniums, raw material are synthesized by circulating shell and tube reactor series connection tubular reactor
Match as DMC：TMA：MEOH=1：1：4, the reaction pressure of circulation 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 that the recycle ratio of material in 10min, circulation 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 is 130 DEG C, the content of sampling analysis product bicarbonate tetramethylammonium, and it is 92.8% to obtain bicarbonate tetramethylammonium yield.
Embodiment 3
TMAH electrolysis oxide spinel hydrogen tetramethyl-ammoniums, raw material are synthesized by circulating shell and tube reactor series connection tubular reactor
Match as DMC：TMA：MEOH=1：1.05：3, the reaction pressure of circulation shell and tube reactor is 0.8MPa, and reaction temperature is 120
DEG C, residence time of the material in circulation shell and tube reactor is that the recycle ratio of material in 15min, circulation 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 is 120 DEG C, the content of sampling analysis product bicarbonate tetramethylammonium, and it is 96.5% to obtain bicarbonate tetramethylammonium yield.
Embodiment 4
TMAH electrolysis oxide spinel hydrogen tetramethyl-ammoniums, raw material are synthesized by circulating shell and tube reactor series connection tubular reactor
Match as DMC：TMA：MEOH=1：1：5, the reaction pressure of circulation 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 that the recycle ratio of material in 20min, circulation 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 is 110 DEG C, the content of sampling analysis product bicarbonate tetramethylammonium, and it is 95.7% to obtain bicarbonate tetramethylammonium yield.
In summary, 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 by above preferred embodiment, but it should be appreciated that above-mentioned
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 should be defined by the appended claims.
Claims (9)
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
Discharging pipeline is set at the top of shell and tube reactor, and bottom sets feeding line, and circulation shell and tube reactor passes through overflow line string
Join tubular reactor；Tubular reactor outlet sets discharging pipeline to connect at the top of the first falling film evaporator, the first falling film evaporator
Extraction steam pipe line is set, and bottom sets extraction liquid line；First falling film evaporator connects the second falling film evaporation by pipeline
Extraction steam pipe line is set at the top of device, the second falling film evaporator, and bottom sets extraction product pipeline and connects products pot.
2. device as claimed in claim 1, it is characterized in that circulation shell and tube reactor top left side sets circulating tank, raw material warp
Overflow line and material pipeline enter after circulating tank mixing, and reactor bottom is squeezed into by feeding line by circulating pump；Circulation row
Tubular reactor top right side sets water vapour steam-water separator, and saturation 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 continuous method for preparing tetramethyl ammonium hydrogen carbonate is carried out using the device of claim 1 or 2, it is characterized in that oxide spinel
Dimethyl ester, trimethylamine and solvent methanol by feed pump continuously enter after circulating tank, mixing material again by 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 course of reaction is released is pulled away through cooling medium in shell side, most of thing
Material is circulated, and the pressure that fraction material is produced by reaction system itself, which enters tubular reactor, to be continued to react, and completes anti-
Material after answering enters downward film evaporator and carries out the recovery 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 produces that flows through of material between the individual devices in itself is come
Complete.
5. method as claimed in claim 3, it is characterized in that mole dispensing 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 produced in course of reaction makes its fast transition be saturated vapor, so as to remove in time anti-in reaction tube side
Should 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 is 105-130 DEG C, and reaction mass is 10-30min, thing in the residence time of circulation shell and tube reactor
It is 15-30 to expect the recycle ratio in circulation shell and tube reactor；The pressure of the tubular reactor is 0.4-0.8MPa, reaction temperature
Spend for 110-125 DEG C, residence time of the material in tubular reactor is 20-40min.
8. method as claimed in claim 3, it is characterized in that the downward film evaporator is double-effect falling film evaporator, and in evaporation
Disc type distributor is set at device upper perforated plate；Volatile solvent methanol and the trimethylamine and dimethyl carbonate that convert completely are first
Vaporize and from top extraction, utilized by condenser condensation Posterior circle in falling film evaporator；Unboiled liquid material is by falling liquid film
Pipe flows downward to base of evaporator, and bottom extraction material flows into the second falling film evaporator after being mixed with water, while being reacted
And evaporation, methyl carbonic tetramethyl-ammonium meets water and occurs the raw bicarbonate tetramethyl-ammonium of hydrolysis generation and methanol, part water and
Product methyl alcohol vaporizing evaporates, and produces at the top of the second falling film evaporator, reclaims that to obtain methanol water-soluble after condenser is condensed
Liquid, target product bicarbonate tetramethyl aqueous ammonium flows through the second falling film evaporator and the bottom of from from top to bottom under self gravitation effect
Portion is produced.
9. method as claimed in claim 7, it is characterized in that the pressure of first falling film evaporator is 0.15-0.2MPa, steams
It is 105-120 DEG C to send out temperature；The pressure of second falling film evaporator is normal pressure, and evaporating temperature is 110-130 DEG C.
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| CN201710342535.0A CN107281994B (en) | 2017-05-16 | 2017-05-16 | Circulation shell and tube reactor series connection tubular reactor prepares the device and method of tetramethyl ammonium hydrogen carbonate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2017
- 2017-05-16 CN CN201710342535.0A patent/CN107281994B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114573458B (en) * | 2022-03-07 | 2024-09-17 | 沧州信联化工有限公司 | Method for synthesizing tetramethyl ammonium bicarbonate by using microchannel reactor and tandem tubular reactor |
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