CN108947774A - A kind of method and device of separating isopropanol - Google Patents
A kind of method and device of separating isopropanol Download PDFInfo
- Publication number
- CN108947774A CN108947774A CN201810793708.5A CN201810793708A CN108947774A CN 108947774 A CN108947774 A CN 108947774A CN 201810793708 A CN201810793708 A CN 201810793708A CN 108947774 A CN108947774 A CN 108947774A
- Authority
- CN
- China
- Prior art keywords
- isopropanol
- tower
- thick
- low
- treating column
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention disclose it is a kind of from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method, the method is that the mixture after reacting isopropyl acetate with low-carbon alcohols is sent into thick isopropanol tower, mixture after the reaction carries out initial gross separation in the thick isopropanol tower, obtain mainly including isopropanol, isopropyl acetate, methanol/ethanol thick isopropanol, then thick isopropanol is fed into isopropanol treating column, pass through abundant refining spearation in isopropanol treating column, final separation obtains purity >=99.9wt% isopropanol.The method of the invention process flow is simple, separating energy consumption is low, product purity is high.Meanwhile the invention also discloses the separator for being suitable for the method, described device structure is simple, investment is less.
Description
Technical field
The present invention relates to a kind of method of separating isopropanol and separator, it is especially a kind of from isopropyl acetate with it is low
The method and separator of separating isopropanol in mixing after the reaction of carbon alcohol.
Background technique
Isopropanol also known as 2- propyl alcohol are a kind of important chemical products and raw material, are mainly used as solvent and synthetic intermediate,
Have been widely used in pesticide, electronics industry, medicine, coating, daily-use chemical industry and organic synthesis field tool.
The method of industrial production isopropanol is mainly two kinds of techniques of propylene hydration method and acetone hydrogenation method at present.Propylene water
The legal gas phase hydration method (Wei Bafa) including the exploitation of dimension Bagong department of Germany, the liquid phase water of day Bender mountain Cao Da company are legal (molten
Liquid catalysis method), the solution-air mixed phase hydration method (ion-exchange-resin process) of Texaco Oil etc., the one way of propylene hydration method
Conversion ratio only has 10% or so, and reaction carries out under 2.0~6.0MPa pressure condition, needs to introduce dehydration in product separation process
Agent can generate large amount of sewage, and separating technology process is complicated, and adverse effect can be brought to environment.Although acetone hydrogenation method has
The conversion ratio of acetone and the advantages that the selectivity of isopropanol is higher, byproduct of reaction is few, but react need to 150~300 DEG C,
It is carried out under 4.0~10.0MPa harsh conditions, and product will could be separated by complicated process flow, energy consumption is higher.
In recent years, the new method for preparing isopropanol by ester exchange reaction by isopropyl acetate and methanol/ethanol is extensive
Concern and research have the characteristics that mild reaction condition, reaction conversion ratio and selectivity are high, pollution-free.Mixture after reaction
Including isopropanol, methyl/ethyl acetate, unreacted isopropyl acetate and methanol/ethanol.
Chinese patent CN102718628A and CN102850185A disclose one kind using isopropyl acetate and methanol as raw material,
The method for being catalyzed reaction production isopropanol using basic catalysts such as sodium methoxide or cation exchange resins, reacts 25~60
DEG C, carry out under condition of normal pressure, reaction conversion ratio is up to 50~80%.Chinese patent CN102755759B and CN102976894B are then
It further illustrates isopropyl acetate and the catalytic rectification process of ester exchange reaction production isopropanol occurs for methanol, wherein patent
CN102755759B is catalyzed isopropyl acetate in catalytic rectifying tower and reacts with methanol using sodium methoxide as catalyst, catalytic distillation
Column overhead and kettle material pass through methyl esters rectifying column, methanol rectifying tower, evaporator, isopropanol treating column separating-purifying and obtain product
Isopropanol, while recycling unreacting material and catalyst；And patent CN102976894B is then in patent CN102755759B technique
On the basis of, homogeneous catalyst sodium methoxide is changed to heterogeneous catalysis cation exchange resin and is placed in catalytic rectifying tower, is kept away
Exempt from catalyst in the recycling and tower of alkali salt catalyst and is easy to the problems such as crystallizing precipitation, catalytic distillation column overhead and kettle material
Product isopropanol is obtained by methyl esters rectifying column, methanol rectifying tower, isopropanol treating column separating-purifying, while recycling unreacted original
Material, isopropanol product quality purity are greater than 99%.
Chinese patent CN105061148A discloses one kind and separates isopropyl as extractant based on ionic liquid mixed solvent
The extraction rectifying method of alcohol and isopropyl acetate, this method use ionic liquid 1- ethyl-3-methylimidazole tetrafluoroborate
([Emim] [BF4]), 1- butyl -3- methylimidazole hexafluorophosphate ([Emim] [PF6]) mixed solvent, passes through 2 rectifying columns
Isopropanol is separated with isopropyl acetate, but mixed solvent cost is very high.Document " isopropyl acetate-isopropanol-DMSO equipressure
Stream-liquid phase balance and extracting rectifying simulation " then use cost relative moderate dimethyl sulfoxide (DMSO) as extractant separate it is different
Propyl alcohol and isopropyl acetate, but the process energy consumption is higher." isopropyl acetate-isopropanol object system is thermally integrated transformation essence to document
Evaporate separation simulation " variable-pressure rectification technology and heat pump techniques combination, separating isopropanol and isopropyl acetate are then taken, the technique
Using heat pump techniques, can effectively energy conservation 28.5%, but the process conditions of high-pressure tower and vacuum tower are harsh, and equipment investment is larger.
In conclusion the existing technique skill separated to isopropyl acetate with low-carbon alcohols reaction product mixed system
Art, has that process flow is complicated, process conditions are harsh, equipment investment is big, product purity is not high, influences product using extractant
Wherein one or more problems such as quality and increase production cost.For the work of isopropyl acetate and low-carbon alcohol production isopropanol
Skill needs simplification of flowsheet, investment reduction cost, reduces operation energy consumption.
Summary of the invention
The shortcomings that it is an object of the invention to overcome the above-mentioned prior art and a kind of pair of isopropyl acetate and low-carbon alcohols are provided
The isopropanol separation method that the process flow that reaction product mixed system is separated is simple, separating energy consumption is low, product purity is high；
Meanwhile a kind of the present invention also provides structures simple, small investment isopropanol separator.
To achieve the above object, the technical scheme adopted by the invention is as follows:
A method of from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol, the method includes
Following steps；
(1) mixture after reacting isopropyl acetate with low-carbon alcohols is sent into thick isopropanol tower, the mixing after the reaction
Object mainly includes isopropanol, methyl/ethyl acetate, isopropyl acetate, methanol/ethanol, wherein methyl/ethyl acetate
Azeotropic mixture is formed with methanol/ethanol to steam from tower top, is condensed rear portion and is back to thick isopropanol tower, another part is as thick
Methyl/ethyl acetate extraction；Wherein thick isopropanol is produced through thick isopropanol tower reactor, and the thick isopropanol mainly includes different
Propyl alcohol, isopropyl acetate, methanol/ethanol；
(2) will in step (1) from thick isopropanol tower reactor produce thick isopropanol be fed into isopropanol treating column, and simultaneously to
Entrainer methanol/ethanol is supplemented in the isopropanol treating column, isopropyl acetate and methanol/ethanol form azeotropic mixture from isopropanol
The tower top for the treatment of column steams, and is condensed rear portion and is back to isopropanol treating column, another part be delivered to isopropyl acetate with
The charging of low-carbon alcohols reaction system produces isopropanol in the tower reactor of isopropanol treating column.
It is of the present invention from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method in, first will
Mixture after isopropyl acetate is reacted with low-carbon alcohols is sent into thick isopropanol tower progress separating treatment, in the thick isopropanol tower
In, methyl/ethyl acetate forms azeotropic mixture with methanol/ethanol and divides exactly from tower top, is back to slightly by condensing rear portion
Isopropanol tower, another part is then as the extraction of thick methyl/ethyl acetate as other uses；In the thick isopropanol tower
After separation from tower reactor extraction mainly comprising isopropanol, isopropyl acetate, methanol/ethanol thick isopropanol, then by thick isopropanol
It is fed into isopropanol treating column and carries out refining spearation；In the isopropanol treating column, fed simultaneously also with thick isopropanol
Entrainer methanol/ethanol, in isopropanol treating column, isopropyl acetate and methanol/ethanol form azeotropic mixture and refine from isopropanol
The tower top of tower steams, and is condensed rear portion and is back to isopropanol treating column, another part is delivered to isopropyl acetate and low-carbon
The charging of alcohol reaction system, and the isopropanol after refining spearation can be obtained in the tower reactor of the isopropanol treating column, are directly adopted
Out.After testing, the isopropanol purity produced from the tower reactor of isopropanol treating column can reach present inventor
99.9wt% or more.
As it is of the present invention from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method
Preferred embodiment, the method further includes following steps:
(3) acetic acid esters will be delivered to by the thick methyl/ethyl acetate of the overhead extraction of thick isopropanol tower in step (1)
Treating column is separated using high-pressure rectification, produces methyl/ethyl acetate product, acetic acid first in the tower reactor of acetic acid esters treating column
The high pressure azeotropic mixture that ester/ethyl acetate is formed with methanol/ethanol is then steamed from the tower top of acetic acid esters treating column, after condensing
A part is back to acetic acid esters treating column, and another part is delivered to the charging of isopropyl acetate Yu low-carbon alcohols reaction system.
Preferably, method of the invention further include will be from thick methyl acetate/acetic acid second of the overhead extraction of thick isopropanol tower
Ester is transported to the step of acetic acid esters treating column carries out rectifying separation, and thick methyl/ethyl acetate is passed through in acetic acid esters treating column
After crossing high-pressure rectification separation, methyl/ethyl acetate product, and acetic acid simultaneously can be produced in the tower reactor of acetic acid esters treating column
For the high pressure azeotropic mixture that methyl esters/ethyl acetate and methanol/ethanol are formed then after steaming condensation, a part is back to acetic acid
Ester treating column, another part can be transported to the system feeding that isopropyl acetate is reacted with low-carbon alcohols.It can be in separation process
Obtained various materials are made full use of.
As it is of the present invention from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method
Preferred embodiment, the method further includes following steps:
(3) acetic acid esters will be delivered to by the thick methyl/ethyl acetate of the overhead extraction of thick isopropanol tower in step (1)
Treating column is separated using high-pressure rectification, produces methyl/ethyl acetate product, acetic acid first in the tower reactor of acetic acid esters treating column
The high pressure azeotropic mixture that ester/ethyl acetate is formed with methanol/ethanol is then steamed from the tower top of acetic acid esters treating column, after condensing
A part is back to acetic acid esters treating column, and another part is delivered to low-carbon alcohols recovery tower；
(4) atmospheric operation is taken to the low-carbon alcohols recovery tower in step (3), the tower reactor of low-carbon alcohols recovery tower recycles low-carbon alcohols
Product, the tower top methyl/ethyl acetate and methanol/ethanol of low-carbon alcohols recovery tower form azeotropic mixture then after condensing,
A part is back to low-carbon alcohols recovery tower, and another portion is delivered to acetic acid esters treating column and carries out circulation rectifying.
It is highly preferred that method of the invention further includes the steps that carrying out low-carbon alcohols recycling, specifically, by thick isopropanol tower
The thick methyl/ethyl acetate of overhead extraction carries out high-pressure rectification separation in acetic acid esters treating column, and tower reactor produces acetic acid first
Ester/ethyl acetate product, while the methyl/ethyl acetate and the high pressure vapor of mixture of methanol/ethanol formation that tower top is formed
After object condensation, a part is back to acetic acid esters treating column, and another part is transported to low-carbon alcohols recovery tower and carries out recycling low-carbon alcohols；?
In low-carbon alcohols recovery tower, using atmospheric operation, the tower reactor of low-carbon alcohols recycles to obtain low-carbon alcohols product, and the tower top of low-carbon alcohols
Methyl/ethyl acetate and methanol/ethanol azeotropic mixture are formed, after condensation, a part is back to low-carbon alcohols recycling
Tower, and another part can be transported to acetic acid esters treating column and carry out circulation rectifying.Such method can be to isopropanol separation process
Obtained in various substances make full use of.
As it is of the present invention from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method
Preferred embodiment, the operating condition of thick isopropanol tower in the step (1) are as follows: 0.1~0.3MPa of pressure, reflux ratio 1.0~
5.0,55~90 DEG C of tower top temperature, 82~115 DEG C of bottom temperature.Present inventor has found by lot of experiments, described
The operating condition of thick isopropanol tower is extremely important for the separation of isopropanol in the application, only when the thick isopropanol tower uses
When operating condition as described above, the mixture after the isopropyl acetate is reacted with low-carbon alcohols could pass through in thick isopropanol tower
Cross crude separation, obtain mainly comprising isopropanol, isopropyl acetate, methanol/ethanol thick isopropanol.
As it is of the present invention from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method
Preferred embodiment, the operating condition of isopropanol treating column in the step (2) are as follows: 0.10~0.15MPa of pressure, reflux ratio
1.0~5.0,64~75 DEG C of tower top temperature, 82~94 DEG C of bottom temperature.Present inventor by lot of experiments find,
The operating condition of the isopropanol treating column for whether be capable of it is isolated needed for purity isopropanol it is most important, inventor
It is attempted by repetition test, finally found that the isopropanol treating column only uses operating condition as described above, step (1) warp
Thick isopropanol after crossing crude separation could obtain abundant refining spearation, the isopropanol being finally recovered in isopropanol treating column
Purity can be only achieved 99.9wt% or more.
As it is of the present invention from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method
Preferred embodiment, the mass ratio of isopropyl acetate and entrainer methanol/ethanol is 1:2~1:5 in the step (2).
As it is of the present invention from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method
Preferred embodiment, reaction condition when isopropyl acetate is reacted with low-carbon alcohols in the step (1) are that heterogeneous catalysis is anti-
It answers；Preferably, reaction condition when isopropyl acetate is reacted with low-carbon alcohols in the step (1) is catalyzing cation exchange resin
Agent reaction, 70~80 DEG C of reaction temperature, 150~300KPa of reaction pressure, alcohol ester molar ratio is 1.5~3.5；
In the step (1) the thick methyl/ethyl acetate product design of thick isopropanol column overhead extraction be 72~
81wt%.
As it is of the present invention from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method
Preferred embodiment, purity >=99.9wt% of the isopropanol produced in the tower reactor of isopropanol treating column in the step (2).
As it is of the present invention from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method
Preferred embodiment, acetic acid esters treating column operating condition in the step (3) are as follows: pressure is 0.9~1.3MPa, reflux ratio controls
For the control of 1.0~5.0, tower top temperature be 110~150 DEG C, bottom temperature control is 145~180 DEG C；
The product design of the methyl/ethyl acetate of acetic acid esters treating column tower reactor extraction is 99.0~
99.5wt%.
As it is of the present invention from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method
Preferred embodiment, low-carbon alcohols recovery tower operating condition in the step (4) are as follows: 0.1~0.2MPa of pressure, reflux ratio 1.0~
5.0,55~85 DEG C of tower top temperature, 64~95 DEG C of bottom temperature；
The low-carbon alcohols product design of the tower reactor recycling of the low-carbon alcohols recovery tower is 99.0~99.5wt%.
In addition, that another object of the present invention is to provide a kind of structures is simple, investment it is less from isopropyl acetate with it is low
The device of separating isopropanol in mixture after the reaction of carbon alcohol, in order to achieve this, the technical scheme adopted by the invention is as follows: it is a kind of
From isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol device, described device include thick isopropanol tower and
Isopropanol treating column；
The thick isopropanol tower includes rectifying section and stripping section, and the number of theoretical plate of the rectifying section is 30~60, described to mention
The number of theoretical plate for evaporating section is 10~30, is equipped with feed inlet in the middle part of the thick isopropanol tower, the top of the thick isopropanol tower is successively
It is connected with condenser and return tank, the outlet of the return tank is connected with reflux pump, and the outlet of the reflux pump is separately connected tower
Top product extraction pipe and return pipe, the return pipe are connect with the tower top of the thick isopropanol tower；The tower of the thick isopropanol tower
Kettle is equipped with tower reactor and produces mouth, and the tower reactor extraction mouth is separately connected tower reactor reboiler and tower reactor pump, and the tower reactor reboiler goes out
Mouth is connected to by pipeline with the tower reactor of the thick isopropanol tower, and the tower reactor pump is connected to the charging of the isopropanol treating column
Pipe；
The isopropanol treating column includes rectifying section and stripping section, and the number of theoretical plate of the rectifying section is 40~70, described
The number of theoretical plate of stripping section is 20~30, and the middle part of the isopropanol treating column is equipped with feed inlet, and the feed inlet is separately connected
The tower reactor pump and entrainer feed pipe of the thick isopropanol tower, be connected in turn at the top of the isopropanol treating column condenser and
Return tank, the outlet of the return tank are connected with reflux pump, the outlet of the reflux pump be separately connected overhead product extraction pipe and
Return pipe, the return pipe are connect with the tower top of the isopropanol treating column；The tower reactor of the isopropanol treating column is equipped with tower reactor
Mouth is produced, the tower reactor extraction mouth is separately connected tower reactor reboiler and isopropanol product extraction pipe, and the tower reactor reboiler goes out
Mouth is connected to by pipeline with the tower reactor of the isopropanol treating column.
It is of the present invention from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol device in, it is described
Device includes thick isopropanol tower and isopropanol treating column；
The thick isopropanol tower includes rectifying section and stripping section, after middle part is reacted equipped with isopropyl acetate with low-carbon alcohols
The tower top outlet of mixture feed pipe, the thick isopropanol tower connects overhead condenser, then connects thick isopropanol column overhead and returns
Tank, return tank outlet connection reflux pump are flowed, reflux pump discharge is divided into two-way, and extraction is used as thick acetic acid esters product, another way all the way
It is connect through reflux pipeline with thick isopropanol column overhead, the tower reactor extraction mouth of the thick isopropanol tower is divided into two-way, all the way through thick different
Thick isopropanol tower tower reactor is back to after propyl alcohol tower tower reactor reboiler, another way is after tower reactor pump extraction and in the middle part of isopropanol treating column
Feed pipe connection；
The isopropanol treating column includes rectifying section and stripping section, and portion is equipped with thick isopropanol feed pipe and entrainer is low
The tower top outlet of carbon alcohol feed pipe, the isopropanol treating column connects overhead condenser, then connects isopropanol refined tower top
Return tank, return tank outlet connection reflux pump, reflux pump discharge be divided into two-way, all the way extraction make after as isopropyl acetate with it is low
The reaction system of carbon alcohol is fed, and another way is connect through return pipe with isopropanol refined tower top, the tower of the isopropanol treating column
Kettle extraction is divided into two-way, is back to isopropanol treating column tower reactor after isopropanol treating column tower reactor reboiler all the way, another way is
Isopropanol product extraction pipe.
As it is of the present invention from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol device
Preferred embodiment, described device also include acetic acid esters treating column；
The feed inlet of the acetic acid esters treating column is connect with the overhead product of thick isopropanol tower extraction pipe, the acetic acid
The tower top of ester treating column is connected with condenser and return tank in turn, and the outlet of the return tank is connected with reflux pump, the reflux
The outlet of pump is separately connected overhead product extraction pipe and return pipe, the tower top company of the return pipe and the acetic acid esters treating column
It connects；The tower reactor of the acetic acid esters treating column is equipped with tower reactor and produces mouth, and the tower reactor extraction mouth is separately connected tower reactor reboiler and tower
Kettle product extraction pipe, the outlet of the tower reactor reboiler are connected to by pipeline with the tower reactor of the acetic acid esters treating column.
As it is of the present invention from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol device
More preferable embodiment, described device also include low-carbon alcohols recovery tower；
The feed inlet of the low-carbon alcohols recovery tower is connect with the overhead product of acetic acid esters treating column extraction pipe, described low
The tower top of carbon alcohol recovery tower is connected with condenser and return tank in turn, and the outlet of the return tank is connected with reflux pump, and described time
The outlet of stream pump is separately connected overhead product extraction pipe and return pipe, and the tower top of the return pipe and the low-carbon alcohols recovery tower connects
It connects；The tower reactor of the low-carbon alcohols recovery tower is equipped with tower reactor and produces mouth, and the tower reactor extraction mouth is separately connected tower reactor reboiler and tower
Kettle product extraction pipe, the outlet of the tower reactor reboiler are connected to by pipeline with the tower reactor of the low-carbon alcohols recovery tower.
It is of the present invention from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method, it is logical first
It crosses the mixture after reacting isopropyl acetate with low-carbon alcohols and is sent into thick isopropanol tower, the mixture after the reaction is described thick
Initial gross separation is carried out in isopropanol tower, obtain mainly including isopropanol, isopropyl acetate, methanol/ethanol thick isopropanol, then
Thick isopropanol is fed into isopropanol treating column, abundant refining spearation is passed through in isopropanol treating column, final separation obtains
Purity >=99.9wt% isopropanol, the method process flow is simple, separating energy consumption is low, and the isopropyl that final separation obtains
Alcohol purity is higher.It is of the present invention from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol device, knot
Structure is simple, investment is less, is conducive to wide popularization and application.
Detailed description of the invention
Fig. 1 is a kind of flow diagram of embodiment of the method for separating isopropanol of the present invention；
Fig. 2 is the flow diagram of another middle embodiment of the method for separating isopropanol of the present invention；
Fig. 3 is a kind of structural schematic diagram of embodiment of the device of separating isopropanol of the present invention.
In figure, 1 is thick isopropanol tower, 2 be isopropanol treating column, 3 be acetic acid esters treating column, 4 be low-carbon alcohols recovery tower, 5
It is thick isopropanol column overhead return tank for thick isopropanol column overhead condenser, 6,7 be thick isopropanol tower tower reactor reboiler, 8 is different
Propyl alcohol refined tower top condenser, 9 be isopropanol refined tower top return tank, 10 be isopropanol treating column tower reactor reboiler, P1
It is thick isopropanol tower tower reactor pump for thick isopropanol tower reflux pump, P2, P1 is isopropanol treating column reflux pump, 11 is reaction mixture
Feeding line, 12 be thick isopropanol column overhead return wire, 13 be that thick acetic acid esters produces line, 14 is that thick isopropanol produces line, 21 is altogether
Boiling agent feeding line, 22 be isopropanol treating column feeding line, 23 be isopropanol refined tower top return wire, 24 be isopropanol treating column
Overhead extraction line, 25 be isopropanol product extraction line, 31 be acetic acid esters product extraction line, 32 be acetic acid esters refined tower top reflux
Line, 33 be low-carbon alcohols recovery tower feeding line, 34 be acetic acid esters refined tower top extraction line, 41 be low-carbon alcohols product extraction line, 42
It is low-carbon alcohols recovery tower overhead extraction line for low-carbon alcohols recovery tower overhead reflux line, 43.
Specific embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with the drawings and specific embodiments pair
The present invention is described further.
Embodiment 1
The present invention from isopropyl acetate reacted with low-carbon alcohols after in mixture a kind of embodiment of separating isopropanol method,
The process flow diagram of the present embodiment the method is as shown in Fig. 1, and the low-carbon alcohols in the present embodiment are methanol, isopropyl acetate
Ester and methanol are acted in acid cation exchange resin catalyst completes ester exchange reaction, and 70~80 DEG C of reaction temperature, reaction pressure
150~300KPa of power, alcohol ester molar ratio are 1.5~3.5.Mixture is mainly isopropanol, isopropyl acetate, acetic acid first after reaction
Ester and methanol.
Method described in the present embodiment comprises the following steps:
(1) thick isopropanol tower will be sent by mixture after reaction, methyl acetate and methanol form azeotropic mixture and from tower top
It steams, is condensed rear portion and be back to thick isopropanol tower, another part is produced as thick methyl acetate, and thick isopropanol is through tower reactor
Extraction；
(2) the thick isopropanol produced in step (1) is delivered to isopropanol treating column, and is supplemented into isopropanol treating column
Entrainer methanol, isopropyl acetate and methanol quality ratio are 1:5 in control charging, isopropyl acetate and methanol formed azeotropic mixture from
Tower top steams, condensed rear portion and be back to isopropanol treating column, another part produce as ester exchange reaction system into
Material, in tower reactor side take-off isopropanol product.
In the method for the present embodiment, thick isopropanol tower and isopropanol treating column are respectively set not in step (1) and step (2)
Three groups of same operating conditions, every group of operating condition and isolated isopropanol product purity are as shown in table 1.
The separating resulting of 1 different operation condition of table
Embodiment 2
On the basis of embodiment 1, the thick methyl acetate obtained in embodiment 1 is further refined respectively, separation obtains
High purity acetic acid methyl esters product and methanol product.
The process flow diagram of the present embodiment the method is as shown in Fig. 2, and concrete operations are as follows in the present embodiment:
Respectively by embodiment 1 test group 1, test group 2, in test group 3 thick isopropanol column overhead extraction thick acetic acid
Methyl esters is delivered to acetic acid esters treating column and is refined, since methyl acetate subtracts with methanol azeotropic mass ratio under the conditions of operation with high pressure
It is small, therefore acetic acid esters treating column takes operation with high pressure, tower reactor produces methyl acetate product, the azeotropic that methyl acetate and methanol are formed
Mixture is then steamed from tower top, is condensed rear portion and is back to acetic acid esters treating column, another extraction as reaction system into
Expect or be delivered to low-carbon alcohols recovery tower；
Low-carbon alcohols recovery tower takes atmospheric operation, and tower reactor recycles low-carbon alcohols product, what tower top methyl acetate and methanol were formed
For azeotropic mixture then after condensing, a part is back to low-carbon alcohols recovery tower, and another portion is delivered to acetic acid esters treating column and is followed
Ring rectifying.
In the present embodiment method, three groups of different operating conditions are respectively set in acetic acid esters treating column and low-carbon alcohols recovery tower,
Every group of operating condition and isolated methyl acetate product purity, methanol product purity are as shown in table 2.
The separating resulting of 2 different operation condition of table
Embodiment 3
The present invention from isopropyl acetate reacted with low-carbon alcohols after in mixture a kind of embodiment of separating isopropanol method,
The process flow diagram of the present embodiment the method is as shown in Fig. 1, and the low-carbon alcohols in the present embodiment are ethyl alcohol, isopropyl acetate
Ester and ethyl alcohol are acted in acid cation exchange resin catalyst completes ester exchange reaction, and 70~80 DEG C of reaction temperature, reaction pressure
150~300KPa of power, alcohol ester molar ratio are 1.5~3.5.Mixture is mainly isopropanol, isopropyl acetate, acetic acid second after reaction
Ester and ethyl alcohol.
Method described in the present embodiment comprises the following steps:
(1) thick isopropanol tower will be sent by mixture after reaction, ethyl acetate and ethyl alcohol form azeotropic mixture and from tower top
It steams, is condensed rear portion and be back to thick isopropanol tower, another part is produced as thick ethyl acetate, and thick isopropanol is through tower reactor
Extraction；
(2) the thick isopropanol produced in step (1) is delivered to isopropanol treating column, and is supplemented into isopropanol treating column
Entrainer ethyl alcohol, isopropyl acetate and ethyl alcohol mass ratio are 1:4 in control charging, isopropyl acetate and ethyl alcohol formed azeotropic mixture from
Tower top steams, condensed rear portion and be back to isopropanol treating column, another part produce as ester exchange reaction system into
Material, in tower reactor side take-off isopropanol product.
In the method for the present embodiment, thick isopropanol tower and isopropanol treating column are respectively set not in step (1) and step (2)
Three groups of same operating conditions, every group of operating condition and isolated isopropanol product purity are as shown in table 3.
The separating resulting of 3 different operation condition of table
Embodiment 4
On the basis of embodiment 3, the thick ethyl acetate obtained in embodiment 3 is further refined respectively, separation obtains
High purity acetic acid ethyl ester product and alcohol product.
Concrete operations are as follows in the present embodiment:
Respectively by embodiment 3 test group 7, test group 8, in test group 9 thick isopropanol column overhead extraction thick acetic acid
Ethyl ester is delivered to acetic acid esters treating column respectively and is refined, due to ethyl acetate under the conditions of operation with high pressure and ethyl alcohol azeotropic quality
Than substantially reducing, therefore acetic acid esters treating column takes operation with high pressure, and tower reactor produces ethyl acetate product, ethyl acetate and ethyl alcohol shape
At azeotropic mixture then steamed from tower top, condensed rear portion and be back to acetic acid esters treating column, another extraction is used as second
Raw polyol is delivered to reaction system charging.
In the present embodiment method, three groups of different operating conditions, every group of operating condition is respectively set in acetic acid esters treating column
And isolated ethyl acetate product purity, alcohol product purity are as shown in table 4.
The separating resulting of 4 different operation condition of table
Embodiment 5
The present invention from isopropyl acetate reacted with low-carbon alcohols after in mixture the device of separating isopropanol a kind of embodiment,
The structural schematic diagram of device described in the present embodiment is as shown in Fig. 3, by attached drawing 3 it is found that the present embodiment described device includes thick
Isopropanol tower and isopropanol treating column；
The thick isopropanol tower includes rectifying section and stripping section, and the number of theoretical plate of the rectifying section is 30~60, described to mention
The number of theoretical plate for evaporating section is 10~30, and the mixture after isopropyl acetate is reacted with low-carbon alcohols is equipped in the middle part of the thick isopropanol tower
Feed inlet is connected with condenser and return tank in turn at the top of the thick isopropanol tower, and the outlet of the return tank is connected with back
Stream pump, the outlet of the reflux pump are separately connected overhead product extraction pipe and return pipe, the return pipe and the thick isopropanol
The tower top connection of tower, reflux pump discharge are divided into two-way, and extraction is used as thick acetic acid esters product all the way, and another way is through reflux pipeline and slightly
The connection of isopropanol column overhead；The tower reactor of the thick isopropanol tower is equipped with tower reactor and produces mouth, and the tower reactor extraction mouth is separately connected tower
Kettle reboiler and tower reactor pump, the outlet of the tower reactor reboiler is connected to by pipeline with the tower reactor of the thick isopropanol tower, described
Tower reactor pumps the feed pipe for being connected to the isopropanol treating column；The tower reactor extraction mouth of thick isopropanol tower is divided into two-way, all the way through thick
Thick isopropanol tower tower reactor is back to after isopropanol tower tower reactor reboiler, another way is after tower reactor pump extraction and in isopropanol treating column
The connection of portion's feed pipe；
The isopropanol treating column includes rectifying section and stripping section, and the number of theoretical plate of the rectifying section is 40~70, described
The number of theoretical plate of stripping section is 20~30, and the middle part of the isopropanol treating column is equipped with feed inlet, and the feed inlet is separately connected
The tower reactor pump and entrainer feed pipe of the thick isopropanol tower, be connected in turn at the top of the isopropanol treating column condenser and
Return tank, the outlet of the return tank are connected with reflux pump, the outlet of the reflux pump be separately connected overhead product extraction pipe and
Return pipe, the return pipe are connect with the tower top of the isopropanol treating column, and reflux pump discharge is divided into two-way, after extraction is made all the way
It is fed as isopropyl acetate and the reaction system of low-carbon alcohols, another way is connect through return pipe with isopropanol refined tower top；Institute
The tower reactor for stating isopropanol treating column is equipped with tower reactor and produces mouth, and the tower reactor extraction mouth is separately connected tower reactor reboiler and isopropanol produces
Product extraction pipe, the outlet of the tower reactor reboiler are connected to by pipeline with the tower reactor of the isopropanol treating column；The isopropanol
The tower reactor extraction for the treatment of column is divided into two-way, is back to isopropanol treating column tower after isopropanol treating column tower reactor reboiler all the way
Kettle, another way are isopropanol product extraction pipe.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (11)
1. it is a kind of from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method, which is characterized in that institute
The method of stating comprises the steps of；
(1) mixture after reacting isopropyl acetate with low-carbon alcohols is sent into thick isopropanol tower, the mixing owner after the reaction
It to include isopropanol, methyl/ethyl acetate, isopropyl acetate, methanol/ethanol, wherein methyl/ethyl acetate and first
Alcohol/ethyl alcohol forms azeotropic mixture and steams from tower top, is condensed rear portion and is back to thick isopropanol tower, another part is as thick acetic acid
Methyl esters/ethyl acetate extraction；Wherein thick isopropanol is produced through thick isopropanol tower reactor, and the thick isopropanol mainly includes isopropyl
Alcohol, isopropyl acetate, methanol/ethanol；
(2) it will be fed into isopropanol treating column from the thick isopropanol that thick isopropanol tower reactor produces in step (1), and simultaneously to described
Entrainer methanol/ethanol is supplemented in isopropanol treating column, isopropyl acetate and methanol/ethanol form azeotropic mixture and refine from isopropanol
The tower top of tower steams, and is condensed rear portion and is back to isopropanol treating column, another part is delivered to isopropyl acetate and low-carbon
The charging of alcohol reaction system produces isopropanol in the tower reactor of isopropanol treating column.
2. as described in claim 1 from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method,
It is characterized in that, the method further includes following steps:
(3) acetic acid esters purification will be delivered to by the thick methyl/ethyl acetate of the overhead extraction of thick isopropanol tower in step (1)
Tower is separated using high-pressure rectification, produces methyl/ethyl acetate product, methyl acetate/second in the tower reactor of acetic acid esters treating column
The high pressure azeotropic mixture that acetoacetic ester is formed with methanol/ethanol is then steamed from the tower top of acetic acid esters treating column, through condensing latter portion
Divide and be back to acetic acid esters treating column, another part is delivered to the charging of isopropyl acetate Yu low-carbon alcohols reaction system.
3. as described in claim 1 from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method,
It is characterized in that, the method further includes following steps:
(3) acetic acid esters purification will be delivered to by the thick methyl/ethyl acetate of the overhead extraction of thick isopropanol tower in step (1)
Tower is separated using high-pressure rectification, produces methyl/ethyl acetate product, methyl acetate/second in the tower reactor of acetic acid esters treating column
The high pressure azeotropic mixture that acetoacetic ester is formed with methanol/ethanol is then steamed from the tower top of acetic acid esters treating column, through condensing latter portion
Divide and be back to acetic acid esters treating column, another part is delivered to low-carbon alcohols recovery tower；
(4) atmospheric operation is taken to the low-carbon alcohols recovery tower in step (3), the tower reactor recycling low-carbon alcohols of low-carbon alcohols recovery tower produce
Product, the tower top methyl/ethyl acetate and methanol/ethanol of low-carbon alcohols recovery tower form azeotropic mixture then after condensing, and one
It is partly refluxed to low-carbon alcohols recovery tower, another portion is delivered to acetic acid esters treating column and carries out circulation rectifying.
4. as described in any one of claims 1 to 3 from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol
Method, which is characterized in that the operating condition of thick isopropanol tower in the step (1) are as follows: 0.1~0.3MPa of pressure, reflux ratio
1.0~5.0,55~90 DEG C of tower top temperature, 82~115 DEG C of bottom temperature.
5. as described in any one of claims 1 to 3 from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol
Method, which is characterized in that the operating condition of isopropanol treating column in the step (2) are as follows: 0.10~0.15MPa of pressure, return
Flow ratio 1.0~5.0,64~75 DEG C of tower top temperature, 82~94 DEG C of bottom temperature.
6. as described in any one of claims 1 to 3 from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol
Method, which is characterized in that the mass ratio of isopropyl acetate and entrainer methanol/ethanol is 1:2~1:5 in the step (2).
7. as described in any one of claims 1 to 3 from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol
Method, which is characterized in that reaction condition when isopropyl acetate is reacted with low-carbon alcohols in the step (1) is heterogeneous catalysis
Agent reaction；Preferably, reaction condition when isopropyl acetate is reacted with low-carbon alcohols in the step (1) is cation exchange resin
Catalyst reaction, 70~80 DEG C of reaction temperature, 150~300KPa of reaction pressure, alcohol ester molar ratio is 1.5~3.5；
The thick methyl/ethyl acetate product design of thick isopropanol column overhead extraction is 70~81wt% in the step (1).
8. as described in any one of claims 1 to 3 from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol
Method, which is characterized in that in the step (2) isopropanol treating column tower reactor produce isopropanol purity >=
99.9wt%.
9. as described in Claims 2 or 3 from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method,
It is characterized in that, acetic acid esters treating column operating condition in the step (3) are as follows: pressure is 0.9~1.3MPa, reflux ratio control is
1.0~5.0, tower top temperature control is 110~150 DEG C, bottom temperature control is 145~180 DEG C；
The product design of the methyl/ethyl acetate of the acetic acid esters treating column tower reactor extraction is 99.0~99.5wt%.
10. as claimed in claim 3 from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol method,
It is characterized in that, low-carbon alcohols recovery tower operating condition in the step (4) are as follows: 0.1~0.2MPa of pressure, reflux ratio 1.0~
5.0,55~85 DEG C of tower top temperature, 64~95 DEG C of bottom temperature；
The low-carbon alcohols product design of the tower reactor recycling of the low-carbon alcohols recovery tower is 99.0~99.5wt%.
11. it is a kind of from isopropyl acetate reacted with low-carbon alcohols after mixture in separating isopropanol device, which is characterized in that institute
Stating device includes thick isopropanol tower and isopropanol treating column；
The thick isopropanol tower includes rectifying section and stripping section, and the number of theoretical plate of the rectifying section is 30~60, the stripping section
Number of theoretical plate be 10~30, feed inlet is equipped in the middle part of the thick isopropanol tower, is sequentially connected at the top of the thick isopropanol tower
There are condenser and return tank, the outlet of the return tank is connected with reflux pump, and the outlet of the reflux pump is separately connected tower top production
Product extraction pipe and return pipe, the return pipe are connect with the tower top of the thick isopropanol tower；The tower reactor of the thick isopropanol tower is set
There is tower reactor to produce mouth, the tower reactor extraction mouth is separately connected tower reactor reboiler and tower reactor pump, and the outlet of the tower reactor reboiler is logical
Piping is connected to the tower reactor of the thick isopropanol tower, and the tower reactor pump is connected to the feed pipe of the isopropanol treating column；
The isopropanol treating column includes rectifying section and stripping section, and the number of theoretical plate of the rectifying section is 40~70, the stripping
The number of theoretical plate of section is 20~30, and the middle part of the isopropanol treating column is equipped with feed inlet, and the feed inlet is separately connected described
The tower reactor of thick isopropanol tower pumps and entrainer feed pipe, is connected with condenser and reflux in turn at the top of the isopropanol treating column
Tank, the outlet of the return tank are connected with reflux pump, and the outlet of the reflux pump is separately connected overhead product extraction pipe and reflux
Pipe, the return pipe are connect with the tower top of the isopropanol treating column；The tower reactor of the isopropanol treating column is produced equipped with tower reactor
Mouthful, the tower reactor extraction mouth is separately connected tower reactor reboiler and isopropanol product extraction pipe, and the outlet of the tower reactor reboiler is logical
Piping is connected to the tower reactor of the isopropanol treating column.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810793708.5A CN108947774B (en) | 2018-07-18 | 2018-07-18 | Method and device for separating isopropanol |
| PCT/CN2018/124091 WO2020015321A1 (en) | 2018-07-18 | 2018-12-26 | Method and device for separating isopropanol |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810793708.5A CN108947774B (en) | 2018-07-18 | 2018-07-18 | Method and device for separating isopropanol |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108947774A true CN108947774A (en) | 2018-12-07 |
| CN108947774B CN108947774B (en) | 2020-12-08 |
Family
ID=64481910
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810793708.5A Active CN108947774B (en) | 2018-07-18 | 2018-07-18 | Method and device for separating isopropanol |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN108947774B (en) |
| WO (1) | WO2020015321A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020015321A1 (en) * | 2018-07-18 | 2020-01-23 | 惠州宇新化工有限责任公司 | Method and device for separating isopropanol |
| CN111569791A (en) * | 2020-03-25 | 2020-08-25 | 南京延长反应技术研究院有限公司 | Enhanced reaction system and process for catalyzing propylene hydration by ionic liquid |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112624903B (en) * | 2020-12-17 | 2022-12-09 | 国家能源集团宁夏煤业有限责任公司 | Method and device for refining ethanol from Fischer-Tropsch synthesis water phase product |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102755759A (en) * | 2012-07-27 | 2012-10-31 | 福州大学 | Continuous reaction rectification process and rectification equipment for synthesizing isopropyl alcohol |
| CN102850185A (en) * | 2012-09-20 | 2013-01-02 | 福州大学 | Method for synthesizing isopropanol by using cation exchange resin as catalyst |
| CN102942475A (en) * | 2012-11-23 | 2013-02-27 | 福建师范大学福清分校 | Variable-pressure rectification method for separating ethyl acetate and ethanol azeotropes and production device for azeotropes |
| CN102976894A (en) * | 2012-09-20 | 2013-03-20 | 福州大学 | Catalysis rectification process for isopropanol synthesis through transesterification method, and production equipment thereof |
| CN106631801A (en) * | 2015-10-31 | 2017-05-10 | 湖南中创化工股份有限公司 | Method and device for separating impurities in sec-butyl acetate by using methanol as azeotropic agent |
| CN107235824A (en) * | 2017-06-05 | 2017-10-10 | 惠州宇新化工有限责任公司 | A kind of method that isopropyl acetate prepares isopropanol with low-carbon alcohols reaction |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103755559B (en) * | 2014-01-08 | 2016-04-06 | 沈阳化工大学 | A kind of method of ion liquid abstraction rectifying separation ethyl acetate-isopropanol |
| CN107501042B (en) * | 2017-08-17 | 2020-08-11 | 惠州宇新化工有限责任公司 | Method for preparing isopropanol by hydrolyzing isopropyl acetate |
| CN108947774B (en) * | 2018-07-18 | 2020-12-08 | 惠州宇新化工有限责任公司 | Method and device for separating isopropanol |
-
2018
- 2018-07-18 CN CN201810793708.5A patent/CN108947774B/en active Active
- 2018-12-26 WO PCT/CN2018/124091 patent/WO2020015321A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102755759A (en) * | 2012-07-27 | 2012-10-31 | 福州大学 | Continuous reaction rectification process and rectification equipment for synthesizing isopropyl alcohol |
| CN102850185A (en) * | 2012-09-20 | 2013-01-02 | 福州大学 | Method for synthesizing isopropanol by using cation exchange resin as catalyst |
| CN102976894A (en) * | 2012-09-20 | 2013-03-20 | 福州大学 | Catalysis rectification process for isopropanol synthesis through transesterification method, and production equipment thereof |
| CN102942475A (en) * | 2012-11-23 | 2013-02-27 | 福建师范大学福清分校 | Variable-pressure rectification method for separating ethyl acetate and ethanol azeotropes and production device for azeotropes |
| CN106631801A (en) * | 2015-10-31 | 2017-05-10 | 湖南中创化工股份有限公司 | Method and device for separating impurities in sec-butyl acetate by using methanol as azeotropic agent |
| CN107235824A (en) * | 2017-06-05 | 2017-10-10 | 惠州宇新化工有限责任公司 | A kind of method that isopropyl acetate prepares isopropanol with low-carbon alcohols reaction |
Non-Patent Citations (2)
| Title |
|---|
| 姚允斌 解涛: "《物理化学手册》", 31 December 1985 * |
| 穆光照: "《实用溶剂手册》", 31 December 1990 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020015321A1 (en) * | 2018-07-18 | 2020-01-23 | 惠州宇新化工有限责任公司 | Method and device for separating isopropanol |
| CN111569791A (en) * | 2020-03-25 | 2020-08-25 | 南京延长反应技术研究院有限公司 | Enhanced reaction system and process for catalyzing propylene hydration by ionic liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2020015321A1 (en) | 2020-01-23 |
| CN108947774B (en) | 2020-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110981727B (en) | Methyl methacrylate synthesis process | |
| CN101481307B (en) | Method for separating acetic acid and sec-butyl acetate from reaction products | |
| CN106883121B (en) | Method for preparing anhydrous formic acid by hydrolyzing methyl formate | |
| CN108947774A (en) | A kind of method and device of separating isopropanol | |
| CN107501042B (en) | Method for preparing isopropanol by hydrolyzing isopropyl acetate | |
| CN105111079A (en) | Method and device for separating acetic acid sec-butyl ester and sec-butyl alcohol | |
| CN110467595A (en) | A kind of no sulfuric acid process metaformaldehyde synthesizer and its synthesis route | |
| CN111423308A (en) | Product separation system and separation method for preparing ethanol by methyl acetate hydrogenation | |
| CN110862301A (en) | Sec-butyl alcohol refining method and device | |
| CN111377800A (en) | Separation device and separation method for coal-to-ethanol liquid-phase product | |
| CN100564335C (en) | A kind of preparation method of formic acid | |
| CN102557932A (en) | Method for producing isobutyl acetate | |
| CN103588618B (en) | Ritalin hydrogenation produces reactive distillation method and the device of ethanol | |
| CN103274913A (en) | Method and device for producing methyl isobutyl ketone | |
| CN103242158A (en) | Technological method for synthesizing ethyl acetate | |
| CN102134191A (en) | Process method for producing ethyl acetate by catalytic rectification | |
| CN203602526U (en) | Reactive distillation device for producing ethanol from methyl acetate by adding hydrogen | |
| CN106588596A (en) | Method for purifying polyoxymethylene dimethyl ether | |
| CN212335079U (en) | Production process device for synthesizing methyl methacrylate by methyl acetate and formaldehyde | |
| KR100339973B1 (en) | Method and apparatus of methyl acetate hydrolysis | |
| CN109646977B (en) | Reactive distillation coupling tower and application thereof in preparation of formic acid | |
| CN115253337A (en) | Method and device for preparing isopropanol through two-tower thermal coupling reaction-variable pressure mixed rectification and application | |
| CN212199065U (en) | Separation device for coal-to-ethanol liquid-phase product | |
| CN216725835U (en) | Partition plate type methyl propionate reaction rectifying tower with coupling hydrogenation | |
| CN111574336A (en) | Synthetic reaction process of ethylene glycol mono-tert-butyl ether |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |