CN109748791A - Produce the power-economizing method of dimethyl adipate - Google Patents
Produce the power-economizing method of dimethyl adipate Download PDFInfo
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Abstract
The purpose of the present invention is to provide the power-economizing methods of production dimethyl adipate, this method is using methanol and the adipic acid of melting as raw material, firsts and seconds esterification is carried out using the CSTR and esterification reaction rectification tower, esterification reaction rectification top of tower gas phase is sent directly into methanol distillation column without cooling；The light components impurity such as methanol distillation column removed overhead dimethyl ether, tower reactor removes the heavy constituents impurity such as water, side take-off Liquid Phase Methanol, phegma as esterification reaction rectification tower after a part is mixed with fresh methanol, to reduce esterification reaction rectification tower regurgitant volume, a part is recycled to level-one esterification as reaction solution；Methanol gasifying cooling in the CSTR, collet is using methanol as cooling medium, and methanol steam is fed as esterification reaction rectification tower, and esters product can not be purified, directly as product or is sent into hydrogenation unit production 1,6- hexylene glycol.This method high conversion rate, selectivity is good, and purity is high, low energy consumption.
Description
Invention field
The present invention relates to the power-economizing method of production dimethyl adipate, method production that pre-esterification and continuous esterification combine
Dimethyl adipate.
Background technique
Dimethyl adipate is high boiling colourless transparent liquid, is soluble in pure and mild ether, but not soluble in water.It is a kind of heavy
The difficult volatile solvent wanted, existing oneself is widely used in the products such as high-grade paint, synthetic resin, cleaning agent, ink.As excellent
Cold resistant plasticizer can assign product excellent low-temperature pliability energy, and have certain photo and thermal stability and water resistance.Molten
It has a wide range of applications in terms of agent, medical perfume synthesis, papermaking and the production of celluosic resin.In addition, dimethyl adipate is also
It is synthesis 1, the intermediate of 6- hexylene glycol.
Because the concentrated sulfuric acid has dehydration and oxidation, the technique of conventional synthesis dimethyl adipate is urged using the concentrated sulfuric acid
Agent, but cause side reaction more, equipment corrosion and three-waste pollution lead to equipment investment and the costly problem of three-protection design.In order to gram
The deficiency of sulphate method is taken, is esterified in recent years with sodiuim bisulfate, p-methyl benzenesulfonic acid, heteropoly acid, solid super-strong acid etc.
The research of catalyst has been reported that, and achieves preferable esterification effect；But still there are catalyst cannot recycle reuse,
Preparation difficulty is big, product is not easily purified, industrializes the disadvantages of difficulty is big.Storng-acid cation exchange resin has volume by solvent
Act on it is small, be easily achieved the advantages that continuous production, while required reaction condition is mild, is easy to from reaction system point
From and reuse, therefore have preferable prospects for commercial application.
Currently, the external demand to dimethyl adipate constantly rises, though and domestic demand is not very greatly, to there is one
Fixed ascendant trend.
Adipic acid reacts generation dimethyl adipate with methanol and water, the reaction are reversible reactions.By thermodynamical equilibrium
Limitation, after reaction reaches balance, sour conversion ratio no longer changes, its conversion ratio of adipic acid intermittent esterification reaction is far below
100%.And in large-scale industrial production, intermittently operated disengaging material is discontinuous, and technological parameter is continuous in production process
Fluctuation.In order to which the conversion ratio of acid is significantly increased, primary operational scheme has: methanol is constantly added into system, to increase acid-alcohol ratio,
Promote the conversion of acid.But this method methanol loop amount is big, loss is big, and later separation energy consumption is high, uneconomical.Another scheme
It is exactly that constantly the moisture in reaction solution is discharged, promotes reaction to carry out to the right, so that tending to be complete.Program research at present compared with
It is more, means multiplicity.Moisture is taken out of by water segregator with water entrainer (hexamethylene, toluene etc.), methanol and water entrainer are back to instead
Answer device.This method is using more in the research of general laboratory science, but the product that industrially obtain high-purity is also wanted
The separation problem of a large amount of water entrainers is faced, energy consumption is higher.Patent GB143069 discloses a kind of more original process,
Make catalyst using the concentrated sulfuric acid, is removed water using the method for tank reactor reaction distillation.With sulfuric acid or other inorganic liquids acid
Produce dimethyl adipate for catalyst, using inorganic liquid acid as catalyst, there are inorganic liquid acid to the corrosion of equipment and
The problem of environmental pollutions such as the three-protection design of reaction product.Patent W09008127 disclose will be divided into inside tubular reactor it is more
A bed, solid catalyst is loose to be mounted in bed, and alcohol steam is reached in a manner of bubbling and acid, solid catalysis in acid solution
Agent contact, is reacted under a certain pressure.Multiple beds are divided into using reactor, catalyst is loose to be mounted in bed, this
Sample is not easy to the filling of catalyst.Patent CN200410020789.3 discloses the production method of one kind 1,6- hexylene glycol, wherein
It has been related to the synthesis of dimethyl adipate.They are by adipic acid, methanol according to certain weight ratio from tower esterifier
Lower end is passed through, and the catalyst of homemade load type active carbon is loaded in reactor, reacts the dimethyl adipate of generation, water and not
Adipic acid, the carbinol mixture of fully reacting are flowed out from the upper end of esterifier；Height is can be obtained into effluent progress rectifying again
Pure dimethyl adipate.The process flow is complex, and catalyst preparation cost is also higher, is not suitable for industrial production.Patent
CN200920110006.9 discloses a kind of device of infiltration evaporation-reaction coupling production dimethyl adipate.The device is by anti-
Answer device, infiltrating and vaporizing membrane, delivery pump and cold-trap composition.Reactor head has feed(raw material)inlet and methanol inlet and reaction solution to go out
Mouthful.Reaction solution outlet connects delivery pump to infiltrating and vaporizing membrane liquor inlet, infiltrating and vaporizing membrane feed liquid side outlet and methanol inlet phase
Even.Infiltrating and vaporizing membrane is connect through side with the U-tube input terminal in cold well, and connects vacuum pump.Although the device can be improved
Conversion ratio, reduction energy consumption, but the membrane module higher cost used.CN103342642 uses three reaction kettle parallel connections and one
Rectifying column combines, and reaction while steams the methanol in reaction system with water, and steam carries out separating-purifying by rectifying column
Afterwards, moisture is discharged from tower reactor, and methanol returns in reaction kettle from tower top, and moisture is constantly carried over reaction system, and esterification is most
Tend to eventually complete.Reaction time needed for this method is long, and control is difficult, and energy consumption is high.
Summary of the invention
The purpose of the present invention is to provide the power-economizing methods of production dimethyl adipate, to overcome conversion sour in original process
Rate is low, energy consumption is high, production capacity is low and it is seriously polluted the problems such as.Technique of the invention becomes dimethyl adipate production process
More simple, high conversion rate, yield are big, pollution is small.To reach adipic acid conversion ratio close to 100%, using continuous esterification skill
The adipic acid conversion ratio that thermodynamical equilibrium limits in batch esterification technology greatly improved in art.
For the present invention by the way that level-one esterification occurs in the CSTR, level-one esterification reaction product is anti-in esterification
Answer on the column plate for being loaded with catalyst in rectifying column with methanol counter current contacting occur second level esterification, dimethyl adipate without
Purification, so that it may carry out hydrogenation reaction, obtain 1,6- hexylene glycol, the esterification reaction rectification column overhead gas phase containing dimethyl ether is direct
Into methanol distillation column, the above problem in the prior art can be solved.
In order to solve the above technical problems, technical scheme is as follows: producing the power-economizing method of dimethyl adipate, wrap
Include following steps:
(1) the CSTR is added in methanol and the adipic acid of melting, and level-one esterification occurs；The reaction temperature
Degree is 80~120 DEG C, and reaction pressure is 0.02~0.2MPaG；
(2) reaction kettle kettle liquid is fed from esterification reaction rectification tower top, and methanol is fed from lower part, and it is anti-that second level esterification occurs
It answers, the top gaseous phase containing dimethyl ether is directly entered methanol distillation column, and esterification reaction rectification tower conversion zone temperature is 80~120
℃；
(3) fixed gas of the methanol distillation column overhead extraction containing dimethyl ether, and the liquid phase containing light component, side line liquid phase produce back
Methanol is received, removing water and the methanol for removing light component impurity are divided into two parts, and a part of methanol is returned as esterification reaction rectification tower
Flow liquid, methanol after purification can reduce reflux ratio as phegma, reduce energy consumption, and a part of methanol loop to level-one, which is esterified, to be made
For reaction solution, tower reactor produces aqueous heavy constituent.
(4) methanol gasifying cooling in the CSTR, collet are situated between using reactant methanol in system as cooling
Matter, methanol steam are fed as esterification reaction rectification tower, and esterification reaction rectification top gaseous phase is returned without condensation directly as methanol
Tower charging is received, esters product can not be purified, directly as product or is sent into hydrogenation unit production 1,6- hexylene glycol.
The CSTR is 2, intermittently operated, and discharging switching is connected to esterification reaction rectification tower, can be real
Existing continuous production and sufficiently recycling reaction heat.
The molar ratio of methanol and adipic acid is 2~6:1, preferably 3~5:1 in the reaction kettle；Reaction time is 3~8
Hour, preferably 4~6 hours.
In the reaction kettle be equipped with storng-acid cation exchange resin, amount of resin be 1~8% (strong resin/oneself two
Acid), preferably 3~5%.
Speed of agitator has larger impact to mass-and heat-transfer in the reaction kettle, and revolving speed increase can accelerate reaction speed, but meeting
It is broken to increase resin, suitable revolving speed is 100~400r/min, preferably 200~300r/min.
The esterification reaction rectification tower and methanol distillation column top are all made of efficient low-resistance filler, and lower part is plate column,
In, esterification reaction rectification tower lower part is plate column, is conducive to increase column plate liquid holdup, thus increase reaction time, it is also square
Just more catalyst changeout.If lower reaction section all uses packed tower, it has not been convenient to more catalyst changeout, and more catalyst changeout fashionable dress
Setting must stop.
The esterification reaction rectification tower reacting section catalyst is suspended on plate in liquid layer, and any layer of catalyst is desirable
It replaces out, without influencing the operation of esterification reaction rectification tower.
The esterification reaction rectification tower upper rectifying section is filled using filler, it is therefore an objective to prevent lower catalytic agent particle from rising
It is mixed into gas phase occluding device and pipeline, catalyst granules, which is encapsulated in metal packing cage, is mixed into gas prevented also from catalyst rising
Phase occluding device and pipeline, while bed pressure drop can be reduced, the monoesters carried secretly in gas phase is effectively intercepted and is reacted,
Because Vapor Entrainment monoesters amount is low, catalyst long service life.
The esterification reaction rectification column overhead pressure is 0.02~0.6MPaG, preferably 0.04~0.2MPaG；Tower reactor group
Divide mainly dimethyl adipate, to prevent its high-temperature coking or decomposing, bottom temperature is 90-210 DEG C, preferably 150-
195℃。
Null-rate is 0.2~0.6h when the esterification reaction rectification tower liquid volume-1。
Esterification reaction rectification tower reactor dimethyl adipate product purity >=99.5%, dimethyl adipate product acid value
≤ 0.5mgKOH/g can also add hydrogen to produce 1,6- hexylene glycol product directly as selling outside product.
The method is suitable for diethylene adipate, diisooctyl adipate, dibutyl adipate, dimethyl succinate
Production.
Using technical solution of the present invention, the CSTR is added by methanol and the adipic acid of melting, is occurred
Level-one esterification；The reaction temperature is 80~120 DEG C, and reaction pressure is 0.02~0.2MpaG；Esterification reaction rectification tower is anti-
Answering section temperature is 80~120 DEG C；The CSTR is 2, intermittently operated；Mole of methanol and adipic acid in reaction kettle
Than for 2~6:1, preferably 3~5:1；Reaction time is 3~8 hours, preferably 4~6 hours；Equipped with strong in the reaction kettle
Acid cation exchange resin, amount of resin be 1~8% (strong resin/adipic acid), preferably 3~5%；The reaction kettle
In suitable revolving speed be 100~400r/min, preferably 200~300r/min；Esterification reaction rectification column overhead pressure is 0.02
~0.6MPaG, preferably 0.04~0.2MPaG；Tower reactor component is mainly dimethyl adipate, and bottom temperature is 90-210 DEG C,
Preferably 150-195 DEG C, achieve good technical effect.
Detailed description of the invention
Fig. 1 is process flow diagram of the invention.
In figure: R1 is the CSTR, and T1 is esterification reaction rectification tower, and T2 is methanol distillation column, and E1 is T1 tower
Kettle discharging cooler, E2 are T2 overhead condenser, and F1 is T1 tower reactor discharging filter, and D1 is T2 return tank of top of the tower.
The CSTR R1 is added in the adipic acid 1 for recycling recycle methanol 3 and melting, and level-one esterification occurs,
Reaction temperature is 80~120 DEG C, and reaction pressure is 0.02~0.2MPaG；Reaction kettle kettle liquid 7 is from the top esterification reaction rectification tower T1
Charging, the CSTR R1 methanol steam 5 and cooling methanol 6 are fed after mixing from the lower part T1, and it is anti-that second level esterification occurs
It answers, the top gaseous phase 11 containing dimethyl ether is directly entered methanol distillation column T2, and esterification reaction rectification tower T1 conversion zone temperature is 80
~150 DEG C；Methanol distillation column T2 tower top contains dimethyl ether gas phase 15 and produces as fixed gas, a small amount of light component 8 of overhead extraction,
The methanol of side line liquid phase extraction recycling methanol 17, dehydration and removing light component impurity is divided into two parts, a part of methanol 19 and new
Fresh methanol 2 is used as esterification reaction rectification tower phegma after mixing, a part of methanol 18 is recycled to level-one esterification as reaction solution, tower
The heavy constituent 12 of kettle extraction primary aqueous；Methanol gasifying cooling in the CSTR R1, collet are used as using methanol 4 and are removed
Thermal medium, methanol steam 6 as esterification reaction rectification tower feed, esterification reaction rectification top gaseous phase 11 without condensation directly as
Methanol distillation column charging, after esters product 9 enters the discharging filter filtering of T1 tower reactor after T1 tower reactor discharging cooler is cooling,
Can not be purified, 1,6- hexylene glycol is produced directly as selling or being sent into hydrogenation unit outside product 10.
The present invention will be further described below by way of examples.
Specific embodiment
[embodiment 1]
This implementation is referring to Fig.1 and Detailed description of the invention.
In the CSTR, level-one esterification occurs, reaction temperature is 90 DEG C, and reaction pressure is
0.04MPaG；The CSTR is 2, intermittently operated, and discharging switching is connected to esterification reaction rectification tower, it can be achieved that even
Continuous production and sufficiently recycling reaction heat.
The molar ratio of methanol and adipic acid is 4:1 in reaction kettle；Reaction time is 4 hours.
Storng-acid cation exchange resin is housed, amount of resin is 3% (strong resin/adipic acid) in reaction kettle.
Speed of agitator is 200r/min in reaction kettle.
Esterification reaction rectification column overhead pressure is 0.04MPaG；Tower reactor component is mainly dimethyl adipate, to prevent it
High-temperature coking is decomposed, and bottom temperature is 175 DEG C.
Null-rate is 0.3h when the esterification reaction rectification tower liquid volume-1。
Esterification reaction rectification tower reactor dimethyl adipate product purity=99.50%, dimethyl adipate acid value=
0.5mgKOH/g can also add hydrogen to produce 1,6- hexylene glycol product directly as selling outside product.
[embodiment 2]
This implementation is referring to Fig.1 and Detailed description of the invention.
In the CSTR, level-one esterification occurs, reaction temperature is 90 DEG C, and reaction pressure is
0.04MPaG；The CSTR is 2, intermittently operated, and discharging switching is connected to esterification reaction rectification tower, it can be achieved that even
Continuous production and sufficiently recycling reaction heat.
The molar ratio of methanol and adipic acid is 4:1 in reaction kettle；Reaction time is 4 hours.
Storng-acid cation exchange resin is housed, amount of resin is 3% (strong resin/adipic acid) in reaction kettle.
Speed of agitator is 200r/min in reaction kettle.
Esterification reaction rectification column overhead pressure is 0.04MPaG；Tower reactor component is mainly dimethyl adipate, to prevent it
High-temperature coking is decomposed, and bottom temperature is 175 DEG C.
Null-rate is 0.35h when the esterification reaction rectification tower liquid volume-1。
Esterification reaction rectification tower reactor dimethyl adipate product purity=99.50%, dimethyl adipate acid value=
0.5mgKOH/g can also add hydrogen to produce 1,6- hexylene glycol product directly as selling outside product.
[embodiment 3]
This implementation is referring to Fig.1 and Detailed description of the invention.
In the CSTR, level-one esterification occurs, reaction temperature is 90 DEG C, and reaction pressure is
0.04MPaG；The CSTR is 2, intermittently operated, and discharging switching is connected to esterification reaction rectification tower, it can be achieved that even
Continuous production and sufficiently recycling reaction heat.
The molar ratio of methanol and adipic acid is 4:1 in reaction kettle；Reaction time is 5 hours.
Storng-acid cation exchange resin is housed, amount of resin is 3% (strong resin/adipic acid) in reaction kettle.
Speed of agitator is 200r/min in reaction kettle.
Esterification reaction rectification column overhead pressure is 0.04MPaG；Tower reactor component is mainly dimethyl adipate, to prevent it
High-temperature coking is decomposed, and bottom temperature is 175 DEG C.
Null-rate is 0.3h when the esterification reaction rectification tower liquid volume-1。
Esterification reaction rectification tower reactor dimethyl adipate product purity=99.55%, dimethyl adipate acid value=
0.4mgKOH/g can also add hydrogen to produce 1,6- hexylene glycol product directly as selling outside product.
[embodiment 4]
This implementation is referring to Fig.1 and Detailed description of the invention.
In the CSTR, level-one esterification occurs, reaction temperature is 90 DEG C, and reaction pressure is
0.04MPaG；The CSTR is 2, intermittently operated, and discharging switching is connected to esterification reaction rectification tower, it can be achieved that even
Continuous production and sufficiently recycling reaction heat.
The molar ratio of methanol and adipic acid is 4:1 in reaction kettle；Reaction time is 4 hours.
Storng-acid cation exchange resin is housed, amount of resin is 4% (strong resin/adipic acid) in reaction kettle.
Speed of agitator is 200r/min in reaction kettle.
Esterification reaction rectification column overhead pressure is 0.04MPaG；Tower reactor component is mainly dimethyl adipate, to prevent it
High-temperature coking is decomposed, and bottom temperature is 175 DEG C.
Null-rate is 0.3h when the esterification reaction rectification tower liquid volume-1。
Esterification reaction rectification tower reactor dimethyl adipate product purity=99.50%, dimethyl adipate acid value=
0.35mgKOH/g can also add hydrogen to produce 1,6- hexylene glycol product directly as selling outside product.
[embodiment 5]
This implementation is referring to Fig.1 and Detailed description of the invention.
In the CSTR, level-one esterification occurs, reaction temperature is 100 DEG C, and reaction pressure is
0.08MPaG；The CSTR is 2, intermittently operated, and discharging switching is connected to esterification reaction rectification tower, it can be achieved that even
Continuous production and sufficiently recycling reaction heat.
The molar ratio of methanol and adipic acid is 5:1 in reaction kettle；Reaction time is 5 hours.
Storng-acid cation exchange resin is housed, amount of resin is 4% (strong resin/adipic acid) in reaction kettle.
Speed of agitator is 250r/min in reaction kettle.
Esterification reaction rectification column overhead pressure is 0.06MPaG；Tower reactor component is mainly dimethyl adipate, to prevent it
High-temperature coking is decomposed, and bottom temperature is 182 DEG C.
Null-rate is 0.4h when the esterification reaction rectification tower liquid volume-1。
Esterification reaction rectification tower reactor dimethyl adipate product purity=99.65%, dimethyl adipate acid value=
0.3mgKOH/g can also add hydrogen to produce 1,6- hexylene glycol product directly as selling outside product.
[embodiment 6]
This implementation is referring to Fig.1 and Detailed description of the invention.
In the CSTR, level-one esterification occurs, reaction temperature is 110 DEG C, and reaction pressure is
0.10MPaG；The CSTR is 2, intermittently operated, and discharging switching is connected to esterification reaction rectification tower, it can be achieved that even
Continuous production and sufficiently recycling reaction heat.
The molar ratio of methanol and adipic acid is 6:1 in reaction kettle；Reaction time is 6 hours.
Storng-acid cation exchange resin is housed, amount of resin is 5% (strong resin/adipic acid) in reaction kettle.
Speed of agitator is 300r/min in reaction kettle.
Esterification reaction rectification column overhead pressure is 0.08MPaG；Tower reactor component is mainly dimethyl adipate, to prevent it
High-temperature coking is decomposed, and bottom temperature is 188 DEG C.
Null-rate is 0.5h when the esterification reaction rectification tower liquid volume-1。
Esterification reaction rectification tower reactor dimethyl adipate product purity=99.70%, dimethyl adipate acid value=
0.25mgKOH/g can also add hydrogen to produce 1,6- hexylene glycol product directly as selling outside product.
[embodiment 7]
This implementation is referring to Fig.1 and Detailed description of the invention.
In the CSTR, level-one esterification occurs, reaction temperature is 90 DEG C, and reaction pressure is
0.04MPaG；The CSTR is 2, intermittently operated, and discharging switching is connected to esterification reaction rectification tower, it can be achieved that even
Continuous production and sufficiently recycling reaction heat.
The molar ratio of methanol and adipic acid is 4:1 in reaction kettle；Reaction time is 5 hours.
Storng-acid cation exchange resin is housed, amount of resin is 5% (strong resin/adipic acid) in reaction kettle.
Speed of agitator is 200r/min in reaction kettle.
Esterification reaction rectification column overhead pressure is 0.04MPaG；Tower reactor component is mainly dimethyl adipate, to prevent it
High-temperature coking is decomposed, and bottom temperature is 175 DEG C.
Null-rate is 0.35h when the esterification reaction rectification tower liquid volume-1。
Esterification reaction rectification tower reactor dimethyl adipate product purity=99.55%, dimethyl adipate acid value=
0.5mgKOH/g can also add hydrogen to produce 1,6- hexylene glycol product directly as selling outside product.
[embodiment 8]
This implementation is referring to Fig.1 and Detailed description of the invention.
In the CSTR, level-one esterification occurs, reaction temperature is 100 DEG C, and reaction pressure is
0.08MPaG；The CSTR is 2, intermittently operated, and discharging switching is connected to esterification reaction rectification tower, it can be achieved that even
Continuous production and sufficiently recycling reaction heat.
The molar ratio of methanol and adipic acid is 5:1 in reaction kettle；Reaction time is 5 hours.
Storng-acid cation exchange resin is housed, amount of resin is 4% (strong resin/adipic acid) in reaction kettle.
Speed of agitator is 300r/min in reaction kettle.
Esterification reaction rectification column overhead pressure is 0.08MPaG；Tower reactor component is mainly dimethyl adipate, to prevent it
High-temperature coking is decomposed, and bottom temperature is 195 DEG C.
Null-rate is 0.5h when the esterification reaction rectification tower liquid volume-1。
Esterification reaction rectification tower reactor dimethyl adipate product purity=99.75%, dimethyl adipate acid value=
0.3mgKOH/g can also add hydrogen to produce 1,6- hexylene glycol product directly as selling outside product.
[embodiment 9]
This implementation is referring to Fig.1 and Detailed description of the invention.
In the CSTR, level-one esterification occurs, reaction temperature is 100 DEG C, and reaction pressure is
0.08MPaG；The CSTR is 2, intermittently operated, and discharging switching is connected to esterification reaction rectification tower, it can be achieved that even
Continuous production and sufficiently recycling reaction heat.
The molar ratio of methanol and adipic acid is 5:1 in reaction kettle；Reaction time is 5 hours.
Storng-acid cation exchange resin is housed, amount of resin is 4% (strong resin/adipic acid) in reaction kettle.
Speed of agitator is 300r/min in reaction kettle.
Esterification reaction rectification column overhead pressure is 0.08MPaG；Tower reactor component is mainly dimethyl adipate, to prevent it
High-temperature coking is decomposed, and bottom temperature is 195 DEG C.
Null-rate is 0.6h when the esterification reaction rectification tower liquid volume-1。
Esterification reaction rectification tower reactor dimethyl adipate product purity=99.70%, dimethyl adipate acid value=
0.5mgKOH/g can also add hydrogen to produce 1,6- hexylene glycol product directly as selling outside product.
[embodiment 10]
This implementation is referring to Fig.1 and Detailed description of the invention.
In the CSTR, level-one esterification occurs, reaction temperature is 100 DEG C, and reaction pressure is
0.08MPaG；The CSTR is 2, intermittently operated, and discharging switching is connected to esterification reaction rectification tower, it can be achieved that even
Continuous production and sufficiently recycling reaction heat.
The molar ratio of methanol and adipic acid is 5:1 in reaction kettle；Reaction time is 5 hours.
Storng-acid cation exchange resin is housed, amount of resin is 4% (strong resin/adipic acid) in reaction kettle.
Speed of agitator is 300r/min in reaction kettle.
Esterification reaction rectification column overhead pressure is 0.08MPaG；Tower reactor component is mainly dimethyl adipate, to prevent it
High-temperature coking is decomposed, and bottom temperature is 195 DEG C.
Null-rate is 0.75h when the esterification reaction rectification tower liquid volume-1。
Esterification reaction rectification tower reactor dimethyl adipate product purity=99.20%, dimethyl adipate acid value=
0.5mgKOH/g can add hydrogen to produce 1,6- hexylene glycol product.
[comparative example]
Unlike embodiment 8, the above energy conservation measure is not used, returns to reaction kettle after gasification of methanol condensation, collet is adopted
With recirculated cooling water cooling, after esterification reaction rectification column overhead vapor condensation, a part goes Methanol Recovery as reflux, a part
For tower as charging, other conditions are identical.
Esterification reaction rectification tower reactor dimethyl adipate product purity=99.75%, dimethyl adipate acid value=
0.5mgKOH/g can also add hydrogen to produce 1,6- hexylene glycol product directly as selling outside product.
It is compared with embodiment 4, increases by 2 methanol condensers, cooling load increases by 32.7%, and heating load increases
25.8%.
Claims (12)
1. producing the power-economizing method of dimethyl adipate, comprising the following steps:
(1) the CSTR is added in methanol and the adipic acid of melting, and level-one esterification occurs；The reaction temperature is
80~120 DEG C, reaction pressure is 0.02~0.2MPaG；
(2) reaction kettle kettle liquid is fed from esterification reaction rectification tower top, and methanol is fed from lower part, and second level esterification occurs, contains
There is the top gaseous phase of dimethyl ether to be directly entered methanol distillation column, esterification reaction rectification tower conversion zone temperature is 80~120 DEG C；
(3) fixed gas of the methanol distillation column overhead extraction containing dimethyl ether, and the liquid phase containing light component, side line liquid phase extraction recycling first
Alcohol, the methanol for removing water and light component impurity are divided into two parts, are used as esterification after a part of methanol and fresh methanol mixing
Rectifier column reflux liquid, to reduce esterification reaction rectification tower regurgitant volume, a part is recycled to level-one esterification as reaction solution, tower reactor
Produce aqueous heavy constituent.
(4) methanol gasifying cooling in the CSTR, collet is using methanol as cooling medium, and methanol steam is as ester
Change reactive distillation column charging, esterification reaction rectification column overhead gas phase is fed without condensation directly as methanol distillation column, and esters produce
Product can not be purified, directly as product or is sent into hydrogenation unit production 1,6- hexylene glycol.
2. the power-economizing method of production dimethyl adipate according to claim 1, which is characterized in that described to continuously stir formula
Reaction kettle is 2, intermittently operated, and discharging switching is connected to esterification reaction rectification tower.
3. the power-economizing method of production dimethyl adipate according to claim 1, which is characterized in that first in the reaction kettle
The molar ratio of pure and mild adipic acid is 2~8:1, and the reaction time is 3~8 hours.
4. the power-economizing method of production dimethyl adipate according to claim 1, which is characterized in that in the reaction kettle
Equipped with storng-acid cation exchange resin, amount of resin is 1~8% (strong resin/adipic acid).
5. the power-economizing method of production dimethyl adipate according to claim 1, which is characterized in that in the reaction kettle
Speed of agitator is 100~400r/min.
6. the power-economizing method of production dimethyl adipate according to claim 1, which is characterized in that the esterification essence
It evaporates tower and methanol distillation column top is all made of efficient low-resistance filler, lower part is plate column.
7. the power-economizing method of production dimethyl adipate according to claim 1, which is characterized in that the esterification essence
It evaporates tower reacting section catalyst to be suspended on plate in liquid layer, any layer of catalyst can be taken off replacing, anti-without influencing esterification
Rectifying column is answered to run.
8. the power-economizing method of production dimethyl adipate according to claim 1, which is characterized in that the esterification essence
Tower upper rectifying section is evaporated, catalyst granules is encapsulated in metal packing cage.
9. the power-economizing method of production dimethyl adipate according to claim 1, which is characterized in that the esterification essence
Evaporating column overhead pressure is 0.02~0.6MPaG, preferably 0.04~0.2MPaG；Bottom temperature is 120-210 DEG C, preferably
165-195℃。
10. the power-economizing method of production dimethyl adipate according to claim 1, which is characterized in that the esterification
Null-rate is 0.2~0.6h when rectifying column liquid volume-1。
11. the power-economizing method of production dimethyl adipate according to claim 1, which is characterized in that the esterification
Tower bottom of rectifying tower dimethyl adipate product purity >=99.5%, dimethyl adipate acid value≤0.5mgKOH/g.
12. the power-economizing method of production dimethyl adipate according to claim 1, which is characterized in that the method is suitable
Production for diethylene adipate, diisooctyl adipate, dibutyl adipate, dimethyl succinate.
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| CN114160055A (en) * | 2021-10-27 | 2022-03-11 | 岳阳职业技术学院 | Membrane dryer, intermittent esterification reaction system and dimethyl adipate preparation method |
| CN115057771A (en) * | 2022-05-09 | 2022-09-16 | 湖北三宁碳磷基新材料产业技术研究院有限公司 | Method for preparing hexatomic carboxylic ester and novel production process method for preparing adipic diester product |
| CN116272815A (en) * | 2023-05-17 | 2023-06-23 | 江苏省瑞丰高分子材料有限公司 | Quick switching device of reaction kettle and rectifying tower |
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