CN106631801B - A kind of method and device for using methanol as impurity in the secondary butyl ester of entrainer separating acetic acid - Google Patents
A kind of method and device for using methanol as impurity in the secondary butyl ester of entrainer separating acetic acid Download PDFInfo
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- CN106631801B CN106631801B CN201510734114.3A CN201510734114A CN106631801B CN 106631801 B CN106631801 B CN 106631801B CN 201510734114 A CN201510734114 A CN 201510734114A CN 106631801 B CN106631801 B CN 106631801B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/34—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping with one or more auxiliary substances
Abstract
A kind of method and device for using methanol as impurity in the secondary butyl ester of entrainer separating acetic acid, this method comprises: the sec-butyl acetate containing impurity is sent into the first azeotropy rectification column azeotropic distillation by (1)；(2) the first azeotropy rectification column tower bottom is contained into sec-butyl acetate, the mixed material of C8 alkene is sent into the second azeotropy rectification column, and entrainer methanol azeotropic rectifying is added, C8 alkene forms azeotropic mixture with methanol and steams from tower top, and sec-butyl acetate falls into tower bottom and produces as product.Method provided by the invention successfully solves sec-butyl acetate in the prior art and C8 separation of olefins degree is not high, sec-butyl acetate purity after separation is not high, the low technical problem of the yield of sec-butyl acetate, using the sec-butyl acetate purity after technology separation of the invention 99.9% or more, reach the level of pharmaceutical grade, the yield of sec-butyl acetate is 99% or more, simultaneously, low energy consumption for separation process, and process is simple, easy to operate.
Description
Technical field
The present invention relates to a kind of method and devices for using methanol as impurity in the secondary butyl ester of entrainer separating acetic acid.
Background technique
Sec-butyl acetate is also known as sec-Butyl Acetate, the second butyl ester of acetic acid, be butyl acetate four kinds of isomers it
One, it is inflammable to be colourless, it is similar to the performance of other isomers with fruity liquid, to a variety of synthetic resin and
Natural resin has excellent solvability.Be widely used in coating, ink, adhesive, pesticide, medicine, fragrance, fine chemistry industry with
And the industries such as oil product.The existing method for preparing sec-butyl acetate mainly uses C4 alkene for raw material, obtains second with acetic acidreaction
The secondary butyl ester of acid, this method raw material sources are wide and inexpensive, good in economic efficiency, environmental-friendly, are a more mature technique.Using
In C4 alkene and acetic acidreaction product, in addition to unreacted acetic acid, C4 alkene, the sec-butyl acetate reacted further includes pair
The heavy hydrocarbon of product C8 and C8 or more has had some researchs to the separation of this part by-product in existing literature.
Chinese patent 200710035741.3 discloses a kind of work that sec-butyl acetate is prepared in acetic acid and C4 olefine reaction
In skill, method that the impurity such as heavy hydrocarbon are separated from reaction product.Material is extracted out from heavy hydrocarbon enrichment region, by the material and water
It comes into full contact with, heavy hydrocarbon layer above is discharged, following water layer is refilled system by heavy hydrocarbon and water natural layering in material.
In this method, acetic acid, sec-butyl acetate and heavy hydrocarbon are contained from the material that heavy hydrocarbon enrichment region is extracted out.Wherein, acetic acid can be mixed with water
Molten, sec-butyl acetate is slightly soluble in water, and heavy hydrocarbon is insoluble in water, and heavy hydrocarbon and sec-butyl acetate density ratio water are small, therefore when rich from heavy hydrocarbon
After the material and water of Ji Qu extraction come into full contact with, it will natural layering, heavy hydrocarbon are in upper layer, and water is in lower layer, by weight above
Hydrocarbon layers discharge, refills system for following water layer.Using this method, effectively abjection sec-butyl acetate reaction product can be prepared
In the impurity such as heavy hydrocarbon, improve product quality, and operating condition can be improved, reduce energy and material consumption.It refers in the invention due to second
The secondary butyl ester of acid can increase material loss, therefore should reduce the sec-butyl acetate in extracted out material as far as possible with heavy hydrocarbon discharge system
Content, but the content for how to reduce sec-butyl acetate in extracted out material does not refer to.Meanwhile it being removed in the invention
Heavy hydrocarbon be C12 or more high-carbon hydrocarbon, C8 boiling olefins are close with sec-butyl acetate, and the azeotropic point of C8 alkene, water and water, second
The secondary butyl ester azeotropic point of acid is close, can not be removed by above method.
Chinese patent 200710192466.6 discloses one kind and reacts with butylene or mixing C4 in acetic acid and prepare acetic acid Zhong Ding
In the technique of ester, the method for the secondary butyl ester of separating acetic acid, acetic acid and heavy hydrocarbon, by the mixing containing sec-butyl acetate, acetic acid and heavy hydrocarbon
Object is sent into azeotropy rectification column, a kind of entrainer that azeotropic mixture can be formed with sec-butyl acetate is added, by azeotropic distillation by acetic acid
Secondary butyl ester and separated from acetic acid, sec-butyl acetate and entrainer are formed by azeotropic mixture and steam from tower top, and acetic acid and heavy hydrocarbon are then fallen into
Tower reactor；Materials at bottom of tower is extracted out from azeotropy rectification column, materials at bottom of tower and water are come into full contact with, and the heavy hydrocarbon and water in materials at bottom of tower are natural
Heavy hydrocarbon layer above is discharged for layering, and following water layer is injected azeotropy rectification column.The advantages of invention, is acetic acid Zhong Ding
While ester and acetic acid efficiently separate, the impurity such as heavy hydrocarbon are isolated into system, improve product quality, and operation item can be improved
Part reduces energy and material consumption.It is mentioned in the invention since sec-butyl acetate can increase material loss with heavy hydrocarbon discharge system, therefore
The sec-butyl acetate content in extracted out material should be reduced as far as possible.But do not refer to how reducing extracted out material in the invention
Middle sec-butyl acetate content does not more refer to how from extracted out material recycling sec-butyl acetate.Meanwhile it being removed in the invention
Heavy hydrocarbon be C12 or more high-carbon hydrocarbon, C8 alkene dissolves each other with sec-butyl acetate, and C8 boiling olefins are close with sec-butyl acetate, and
C8 alkene, the azeotropic point of water and water, sec-butyl acetate azeotropic point are close, can not be removed by above method.
Chinese patent CN101481307A is provided a kind of isolates acetic acid from the reaction product for prepare sec-butyl acetate
With the method for sec-butyl acetate, the reaction product contains sec-butyl acetate, acetic acid and C8 alkene, this method and includes, in azeotropic
Under the operating condition of rectifying, enters water and the reaction product in the first azeotrope column and carry out azeotropic distillation, obtained from tower top
Azeotropic mixture obtains acetic acid from tower bottom；Amount into the water in the first azeotrope column at least makes sec-butyl acetate and C8 alkene
It is obtained in the form of azeotropic mixture from tower top；Gained azeotropic mixture is subjected to water-oil separating after condensing, water-phase product is obtained and contains
The oil-phase product of C8 alkene and sec-butyl acetate；Under the operating condition of azeotropic distillation, make water and oil-phase product obtained above
Into azeotropic distillation is carried out in the second azeotropy rectification column, azeotropic mixture is obtained from tower top, obtains sec-butyl acetate from tower bottom, obtains
The amount of the water in two azeotropy rectification columns, which is at least, obtains C8 alkene in the form of azeotropic mixture from tower top.The patent of invention
In, the rate of recovery of sec-butyl acetate is not high, and part sec-butyl acetate azeotrope with water is steamed from tower top, to reduce this method
The yield of middle sec-butyl acetate.Simultaneously as water, C8 alkene azeotropic temperature differ smaller with water, sec-butyl acetate azeotropic temperature,
Cause reflux ratio very big in this way, separating difficulty is big, and energy consumption is higher.
Chinese patent application CN103980115A disclose it is a kind of with high yield from the reaction product for preparing sec-butyl acetate
The method of middle recycling sec-butyl acetate, (1) will prepare the reaction product of sec-butyl acetate in C4 knockout tower under the conditions of rectifying
Carry out rectifying separation, from overhead extraction C4 light component, produce tower bottom product from tower bottom, the tower bottom product contain sec-butyl acetate,
C8 alkene and unreacted acetic acid；(2) under the conditions of azeotropic distillation, make what step (1) obtained to contain sec-butyl acetate, C8 alkene
Enter with the tower bottom product and water of unreacted acetic acid and carry out azeotropic distillation in azeotropy rectification column, into the water in azeotrope column
Amount can make sec-butyl acetate and C8 alkene in the form of azeotropic mixture from overhead extraction, acetic acid is produced from tower bottom；(3) by step
(2) azeotropic mixture obtained carries out water-oil separating after condensing, and obtains water-phase product and the oil containing C8 alkene and sec-butyl acetate
Phase product；(4) under the conditions of azeotropic distillation, oil-phase product and water that step (3) obtains is entered in ester product purification tower and carried out
Azeotropic distillation, the amount into water described in ester product purification tower can make C8 alkene in the form of azeotropic mixture from overhead extraction, second
The secondary butyl ester of acid is produced from tower bottom；(5) sec-butyl acetate of the alkene containing C8 and sec-butyl alcohol impurity come from ester product purification column overhead
Material is sent directly into removing impurities matter azeotrope column, and the water contained in itself using in the material is as entrainer, under the conditions of azeotropic distillation altogether
Rectifying is boiled, water steams with C8 alkene from tower top, and the oil-phase product that the anhydrous fraction of tower bottom and step (3) obtain is converged with water, and one
Play the charging as ester product purification tower.This method process is simple, low energy consumption, separative efficiency is high, can recycle 92% in by-product
Above sec-butyl acetate.Differed with water, sec-butyl acetate azeotropic temperature in this method due to water, C8 alkene azeotropic temperature compared with
It is small, cause reflux ratio very big in this way, separating difficulty is big, and energy consumption is higher.
Chinese patent CN101486640A discloses a kind of preparation method of sec-butyl acetate, this method comprises: (1) is being urged
In the presence of agent and under the conditions of addition reaction, C4 alkene is contacted with acetic acid several times, is reacted；It (2), will under the conditions of rectifying
Reaction product obtained by step (1) carries out rectifying separation in first rectifying column, from overhead extraction C4 light component, produces tower from tower bottom
Bottom product, the tower bottom product contain sec-butyl acetate, C8 alkene and unreacted acetic acid；(3) under the conditions of azeotropic distillation, make to walk
What (2) obtained suddenly enters the first azeotropic distillation containing sec-butyl acetate, the tower bottom product of C8 alkene and unreacted acetic acid and water
Azeotropic distillation is carried out in tower, the amount into the water in the first azeotropy rectification column can make sec-butyl acetate and C8 alkene with altogether
The form of object is boiled from overhead extraction, and acetic acid is produced from tower bottom；(4) azeotropic mixture that step (3) obtains is subjected to grease after condensing
Separation, obtains water-phase product and the oil-phase product containing C8 alkene and sec-butyl acetate；(5) it under the conditions of azeotropic distillation, will walk
Suddenly the oil-phase product and water that (4) obtain, which enter in the second azeotropy rectification column, carries out azeotropic distillation, into the second azeotropy rectification column
The amount of the water can make C8 alkene in the form of azeotropic mixture from overhead extraction, sec-butyl acetate is produced from tower bottom.The invention
The method of offer can obtain higher yield of sec-butyl acetate, and sec-butyl acetate and recycling second can be obtained with higher degree
Acid.It differs smaller with water, sec-butyl acetate azeotropic temperature due to water, C8 alkene azeotropic temperature in this method, causes to flow back in this way
Bigger than very, separating difficulty is big, and energy consumption is higher.
Chinese patent 201110023485.2 discloses a kind of method by the secondary butyl ester crude product of dual reflux purified acetic acid
With the preparation method for the sec-butyl acetate for including the subtractive process, the refining methd of the sec-butyl acetate crude product includes: that (1) will
Sec-butyl acetate crude product is added in rectifying column by first charging aperture, and water is added by second charging aperture in the form of water vapour
Into rectifying column, azeotropic distillation is carried out under the operating condition of azeotropic distillation, obtains primary aqueous and the impurity from tower top
Mixture；(2) mixture is subjected to cooling and water-oil separating and obtains water phase and oily phase, by the reflux containing at least partly oily phase
Object flows back into rectifying column, is added at least partly water phase in rectifying column after forming water vapour by the return of third feed inlet；
Wherein, second charging aperture and third feed inlet are identical or different, and are all located at the lower section 1-10 block column plate or reason of first charging aperture
By the position at column plate.The sec-butyl acetate of high-purity can be prepared using method of the invention.But the secondary butyl ester yield of this method
It is not high, and the entrainer used is water, is flowed back bigger, energy consumption is higher.
The above patent all has studied the separation of C8 alkene or heavy hydrocarbon in sec-butyl acetate, is all made of water as entrainer pair
C8 alkene in sec-butyl acetate carries out azeotropic separation, but the yield of sec-butyl acetate only up to reach 92% or more, returns
The purity of sec-butyl acetate after receipts is not very high, and there is a problem of that separating energy consumption is high.
Summary of the invention
The purpose of the present invention is overcome the deficiencies of the prior art and provide a kind of to use methanol secondary as entrainer separating acetic acid
Impurity in sec-butyl acetate can be separated effectively, be obtained high-purity by the method and apparatus of impurity in butyl ester, this method
The sec-butyl acetate of degree, the purity of sec-butyl acetate 99.9% or more, meanwhile, the yield of sec-butyl acetate be up to 99% with
On, this method process is simple, and operation is easy, and low energy consumption.
To achieve the goals above, according to the first aspect of the invention, it provides and a kind of uses methanol as entrainer point
Method from impurity in sec-butyl acetate, in the case that impurity is C8 alkene in sec-butyl acetate, this method comprises: will contain
The sec-butyl acetate of impurity is sent into the second azeotropy rectification column, and entrainer methanol is added, and carries out azeotropic distillation, C8 alkene and methanol
It forms azeotropic mixture to steam from tower top, partially flow back after condensing, part produces, and sec-butyl acetate falls into tower bottom as product
Extraction；
Impurity is water, C8 alkene and in the case where sec-butyl alcohol in sec-butyl acetate, this method comprises: (1) will contain it is miscellaneous
The sec-butyl acetate of matter is sent into the first azeotropy rectification column azeotropic distillation, water, sec-butyl alcohol, part sec-butyl acetate and C8 alkene steam to
Tower top is layered after condensing, and water phase is discharged, and oil mutually flows back；(2) the first azeotropy rectification column tower bottom is contained into acetic acid
Mixed material the second azeotropy rectification column of feeding of secondary butyl ester, C8 alkene, and entrainer methanol is added, carry out azeotropic distillation, C8 alkene
Hydrocarbon forms azeotropic mixture with methanol and steams from tower top, partially flows back after condensing, and part produces, and sec-butyl acetate falls into tower bottom
It is produced as product；
In the case that impurity is C8 alkene and sec-butyl alcohol in sec-butyl acetate, this method comprises: (1) will contain impurity
Sec-butyl acetate is sent into the first azeotropy rectification column, and entrainer water is added, and carries out azeotropic distillation, and the amount of entrainer water at least makes secondary
Butanol is obtained in the form of azeotropic mixture from tower top, and water, sec-butyl alcohol, part sec-butyl acetate and C8 alkene are steamed to tower top, through condensing
After be layered, water phase is discharged, oil mutually flow back；(2) the first azeotropy rectification column tower bottom is contained into sec-butyl acetate, C8 alkene
The mixed material of hydrocarbon is sent into the second azeotropy rectification column, and entrainer methanol is added, and carries out azeotropic distillation, and C8 alkene is formed with methanol
Azeotropic mixture is steamed from tower top, is partially flowed back after condensing, and part produces, and sec-butyl acetate falls into tower bottom and adopts as product
Out；
In the case that impurity is water and C8 alkene in sec-butyl acetate, this method comprises: (1) is by the acetic acid containing impurity
Secondary butyl ester is sent into the first azeotropy rectification column azeotropic distillation, and water, part sec-butyl acetate and C8 alkene are steamed to tower top, laggard through condensing
Row layering, water phase is discharged, and oil mutually flows back；(2) the first azeotropy rectification column tower bottom is contained into sec-butyl acetate, C8 alkene
Mixed material is sent into the second azeotropy rectification column, and entrainer methanol is added, and carries out azeotropic distillation, and C8 alkene and methanol form azeotropic
Object is steamed from tower top, is partially flowed back after condensing, and part produces, and sec-butyl acetate falls into tower bottom and produces as product.
In the prior art, the impurity such as C8 alkene and sec-butyl alcohol are being passed through into ester product azeotropic essence from sec-butyl acetate product
When tower processed is separated, since using water, as entrainer, sec-butyl alcohol, water and sec-butyl acetate will form ternary azeotropic, water and
Sec-butyl alcohol, sec-butyl acetate and C8 alkene can be respectively formed azeotropic mixture, and the boiling point of these types of kind of azeotropic mixture is respectively as follows: 86 DEG C,
88.5 DEG C, 87.3 DEG C, 75.3~81.4 DEG C, boiling point is closer to, and therefore, can not accomplish to be kept completely separate, sec-butyl acetate
The rate of recovery will not be very high, and separate after sec-butyl acetate purity be also not very high.
In the present invention, when containing only C8 olefin impurity in sec-butyl acetate, it will can directly contain sec-butyl acetate, C8 alkene
The mixed material of hydrocarbon is sent into the second azeotropy rectification column, and entrainer methanol azeotropic rectifying is added, and C8 alkene and methanol form azeotropic
Object is steamed from tower top, is partially flowed back after condensing, and part produces, and sec-butyl acetate falls into tower bottom and produces as product.
In the present invention, when impurity includes water, C8 alkene, sec-butyl alcohol in sec-butyl acetate, first by the acetic acid containing impurity
Secondary butyl ester is sent into the first azeotropy rectification column azeotropic distillation, and azeotropic, water, sec-butyl alcohol, portion occurs using the water contained in mixed material
Divide sec-butyl acetate and C8 alkene to steam to tower top, is layered after condensing, since solubility is higher in water for sec-butyl alcohol, 20 DEG C
Water in solubility be 12.5%, and the content of sec-butyl alcohol is lower, and therefore, sec-butyl alcohol is substantially soluble in water, and other components
It is lower in water-soluble solubility, wherein solubility is that 0.62%, C8 alkene is substantially insoluble in sec-butyl acetate in water at 20 DEG C
Water, therefore, sec-butyl alcohol can be dissolved in water discharge system from water phase, and remaining oil is mutually all back to the first azeotropy rectification column,
The mixture extracted out from tower bottom is sent into the second azeotropy rectification column.
In the present invention, when impurity includes C8 alkene, sec-butyl alcohol in sec-butyl acetate, first by the acetic acid Zhong Ding containing impurity
Ester is sent into the first azeotropy rectification column, entrainer water azeotropic distillation is added, the amount of entrainer water, which is at least, makes sec-butyl alcohol with azeotropic mixture
Form obtained from tower top, water, sec-butyl alcohol, part sec-butyl acetate and C8 alkene steams to tower top, is layered after condensing, by
In sec-butyl alcohol, solubility is higher in water, and solubility is 12.5% in 20 DEG C of water, and the content of sec-butyl alcohol is lower, therefore, secondary
Butanol is substantially soluble in water, and other components are lower in water-soluble solubility, wherein sec-butyl acetate dissolves in water at 20 DEG C
Degree is that 0.62%, C8 alkene is substantially not soluble in water, and therefore, sec-butyl alcohol can be dissolved in water discharge system from water phase, and remaining oil
It all mutually is back to the first azeotropy rectification column, the mixture extracted out from tower bottom is sent into the second azeotropy rectification column.
In the prior art, there is certain understanding to the ternary azeotropic of sec-butyl acetate, sec-butyl alcohol and water, what Cheng Nenglin write
Sec-butyl acetate, sec-butyl alcohol and water are disclosed in solvent handbook fourth edition is capable of forming ternary azeotrope, the ratio of ternary azeotrope
Example are as follows:
| Sec-butyl alcohol | Sec-butyl acetate | Water |
| 45% | 23% | 32% |
Azeotropic temperature are as follows: 86 DEG C.
The present inventor has found that ternary azeotropic, the ratio of azeotropic mixture occur for sec-butyl acetate, sec-butyl alcohol and water after study
Are as follows:
| Sec-butyl alcohol | Sec-butyl acetate | Water |
| 28% | 53% | 19% |
Azeotropic temperature are as follows: 84.5 DEG C.
Therefore, in the present invention, the amount for the entrainer water that first azeotropy rectification column is added is calculated using the following equation:
W=W1 × (1+A)
Wherein, W is the amount of the water of the first azeotropy rectification column of the described entrance, is indicated with weight or weight flow, dimension and
W1 is identical；
A is 0-10%；
W1=F × X1 × 19/53,
F is the amount or flow of the sec-butyl acetate containing impurity into first azeotropy rectification column, with weight
Amount or weight flow indicate；
X1 is the quality for entering sec-butyl alcohol in the sec-butyl acetate containing impurity in first azeotropy rectification column
Percentage composition.
In the present invention, when impurity includes water, C8 alkene in the sec-butyl acetate containing impurity, first by the second containing impurity
The secondary butyl ester of acid is sent into the first azeotropy rectification column azeotropic distillation, and water, part sec-butyl acetate and C8 alkene are steamed to tower top, after condensing
It is layered, water phase is discharged, oil mutually flows back, and the mixture extracted out from tower bottom is sent into the second azeotropy rectification column.
In the present invention, azeotropic separation is carried out as mixture of the entrainer to sec-butyl acetate and C8 alkene using methanol,
Because the present inventor is found through experiments that, azeotropic can occur with C8 alkene for methanol without azeotropic occurs with sec-butyl acetate, and altogether
It is lower to boil temperature, between 63~64 DEG C, the mass ratio of methanol and methanol and C8 alkene in the azeotropic mixture composition of C8 alkene is
40%:60%~60%:40%, preferably from about 50%:50%, and the boiling point of sec-butyl acetate is 113.2 DEG C, between the two
Boiling-point difference is bigger compared with (75.3~81.4 DEG C) differences of boiling point of sec-butyl acetate and C8 alkene and the azeotropic mixture of water, is more easier point
From, meanwhile, the ratio heat of evaporation of methanol is 1.076 × 106J/kg, and the ratio heat of evaporation of water is 2.258 × 106J/kg is methanol vapor
2.1 times for changing heat, therefore, using methanol as entrainer, the steam for needing to consume is less, and energy consumption is lower.In the present invention, use
Methanol is as entrainer, and methanol prices are cheap and are easy to get, while toxicity is lower, is a kind of common solvent, obtained methanol with
The azeotropic mixture of C8 alkene can be used as methanol gasoline and be sold, and increase added value of product, or further separated,
Methanol is recycled.
In the present invention, the mass content of water impurity is 0.1%-5% in the sec-butyl acetate containing impurity, preferably
0.1%-4.9%, more preferably 0.1%-4.8%, more preferably 0.1%-4.5%, more preferably 0.1%-4.2%, it is more excellent
It is selected as 0.1%-4.0%, more preferably 0.1%-3.8%, more preferably 0.2%-3.8%, more preferably 0.2%-3.5%,
More preferably 0.2%-3.2%, more preferably 0.2%-3.0%, more preferably 0.3%-3.0%, more preferably 0.4%-
3.0%, more preferably 0.5%-3.0%, more preferably 0.8%-3.0%, more preferably 1.0%-3.0%, more preferably
1.05%-3.0%, more preferably 1.1%-3.0%, more preferably 1.2%-3.0%, more preferably 1.3%-3.0%, it is more excellent
It is selected as 1.4%-3.0%, further preferably 1.5%-3.0%；The mass content of impurity sec-butyl alcohol is 0.01%-1%, preferably
For 0.02%-1%, more preferably 0.03%-1%, more preferably 0.04%-1%, more preferably 0.05%-1%, more preferably
For 0.06%-1%, more preferably 0.07%-1%, more preferably 0.08%-1%, more preferably 0.09%-1%, more preferably
For 0.1%-1%, more preferably 0.15%-1%, more preferably 0.18%-1%, more preferably 0.2%-1%, more preferably
0.25%-1%, more preferably 0.3%-1%, more preferably 0.4%-1%, further preferably 0.5%-1%, impurity C8 alkene
The mass content of hydrocarbon is 0.05%-50%, preferably 0.08%-50%, more preferably 0.1%-50%, more preferably 0.2%-
50%, more preferably 0.3%-50%, more preferably 0.4%-50%, more preferably 0.5%-50%, more preferably 0.8%-
50%, more preferably 1%-50%, more preferably 1.1%-50%, more preferably 1.1%-48%, more preferably 1.1%-
45%, more preferably 1.1%-42%, more preferably 1.1%-40%, more preferably 1.1%-38%, more preferably 1.1%-
35%, more preferably 1.1%-32%, more preferably 1.1%-30%, more preferably 1.1%-28%, more preferably 1.1%-
25%, more preferably 1.1%-22%, more preferably 1.1%-20%, more preferably 1.1%-18%, more preferably 1.1%-
15%, more preferably 1.1%-12%, more preferably 1.1%-10%, more preferably 1.1%-8%, more preferably 1.1%-
7%, more preferably 1.1%-6%, more preferably 1.1%-5%, more preferably 1.2%-5%, further preferably 1.5%-
5%, the mass content of sec-butyl acetate is 40%-99%, preferably 40-98%, more preferably 42-98%, more preferably 45-
98%, more preferably 48-98%, more preferably 50-98%, more preferably 52-98%, more preferably 55-98%, more preferably
58-98%, more preferably 60-98%, more preferably 62-98%, more preferably 65-98%, more preferably 68-98%, it is more excellent
It is selected as 70-98%, more preferably 72-98%, more preferably 75-98%, more preferably 78-98%, more preferably 80-97%,
More preferably 80-96%, more preferably 80-95%, more preferably 82-95%, more preferably 85-94%, more preferably 85-
93%, more preferably 85-92%, more preferably 85-91%, further preferably 85-90%.
In the present invention, the impurity in sec-butyl acetate can also optionally contain C5, C6 alkene, wherein the content of C5 alkene
For 0.01%-0.5%, preferably 0.01%-0.4%, more preferably 0.01%-0.3%, more preferably 0.01%-0.2%,
Further preferably 0.01%-0.1%；The content of C6 alkene be 0.01%-0.5%, preferably 0.01%-0.4%, more preferably
For 0.01%-0.3%, more preferably 0.01%-0.2%, further preferably 0.01%-0.1%.In the present invention, C5, C6 alkene
Hydrocarbon is not soluble in water, and azeotropic can occur with methanol, and azeotropic temperature is lower, can be together with methanol from second by the azeotropic with methanol
It is separated in the secondary butyl ester of acid.
In the present invention, the sec-butyl acetate containing impurity is from a wealth of sources, can be ester product azeotropic treating column tower bottom or tower
The sec-butyl acetate product that bottom side line obtains, such as the second azeotropy rectification column tower bottom obtains second in Chinese patent CN101481307A
In the secondary butyl ester of acid or Chinese patent application CN103980115A in step (4) extraction of ester product purification tower tower bottom acetic acid
In secondary butyl ester or Chinese patent CN101486640A in step (5) extraction of the second azeotropy rectification column tower bottom acetic acid Zhong Ding
Ester；Or the mixture after acetic acid and butene reaction is after flash distillation removing gently then divides C4 hydrocarbon and azeotropic distillation to remove acetic acid
The first azeotropic distillation column overhead azeotropic mixture carries out after condensing in obtained mixed material, such as Chinese patent CN101481307A
Being total to of obtaining of tower top in step (3) in the oil-phase product or Chinese patent application CN103980115A that water-oil separating obtains
Boiling object is carried out in the oil-phase product that water-oil separating obtains or Chinese patent CN101486640A after condensing in step (4)
First azeotropic distillation column overhead azeotropic mixture carries out the oil-phase product or Chinese patent that water-oil separating obtains after condensing
Sec-butyl acetate crude product described in 201110023485.2；Or the azeotropic mixture warp of ester product azeotropic refined tower top
Obtained oil-phase product after condensation layering, such as being total to of obtaining of the second azeotropic distillation column overhead in Chinese patent CN101481307A
Boiling object carry out in the oily phase product obtained after condensation layering or Chinese patent application CN103980115A in step (5) from
The sec-butyl acetate material or Chinese patent of alkene containing C8 and sec-butyl alcohol impurity that ester product purification column overhead is come
The azeotropic mixture that the second azeotropic distillation column overhead obtains in step (5) in CN101486640A carries out the oily phase obtained after condensation layering
It is carried out under the operating condition of azeotropic distillation in product or Chinese patent 201110023485.2 after azeotropic distillation from tower top
Obtained mixture carries out the oily phase obtained after cooling and water-oil separating；It can also be the azeotropic of ester product azeotropic refined tower top
Object passes through the tower bottom product that further azeotropic separation obtains, such as takes off in step (5) in Chinese patent application CN103980115A
Tower bottom obtained in impurity azeotrope column is without aqueous distillate；It can also be the mixture of the above various products.
The present inventor is found through experiments that with C8 alkene azeotropic can occur for methanol, and azeotropic temperature is between 63~64 DEG C, first
The mass ratio of methanol and C8 alkene is 40%:60%~60%:40% in the azeotropic mixture of alcohol and C8 alkene composition, preferably from about
Therefore 50%:50% in the present invention, the C8 alkene in sec-butyl acetate mixture is removed completely by azeotropic, addition
The amount of methanol and C8 alkene is 1:1 or more, preferably 1-10:1, more preferably 1-9:1, more preferably 1-8:1, more preferably 1-
7:1, more preferably 1-6:1, more preferably 1-5:1, more preferably 1-4:1, more preferably 1-3:1, more preferably 1-2.8:1,
More preferably 1-2.5:1, more preferably 1.05-2.5:1, more preferably 1.1-2.5:1, more preferably 1.1-2.2:1, more preferably
For 1.1-2:1, more preferably 1.2-2:1, further preferably 1.3-2:1, more preferably 1.4-2:1, further preferably
1.5-2:1。
In the present invention, the pressure of first azeotropy rectification column is normal pressure, and tower top temperature is 70 DEG C -90 DEG C, preferably
71 DEG C -90 DEG C, more preferably 72 DEG C -90 DEG C, more preferably 72 DEG C -89 DEG C, more preferably 72 DEG C -88 DEG C, more preferably 73 DEG C -
88 DEG C, more preferably 74 DEG C -88 DEG C, further preferably 75 DEG C -88 DEG C, reflux ratio 0.1-10:1, preferably 0.2-9:1,
More preferably 0.5-8:1, more preferably 0.8-7:1, more preferably 1-6:1, more preferably 1-5:1, more preferably 1-4:1, more
Preferably 1-3:1, more preferably 1-2.8:1, more preferably 1-2.5:1, more preferably 1-2.2:1, further preferably 1-2:
1。
In the present invention, the tower top pressure of second azeotropy rectification column is normal pressure, and tower top temperature is 55 DEG C -70 DEG C, excellent
56 DEG C -70 DEG C, more preferably 57 DEG C -70 DEG C, more preferably 58 DEG C -70 DEG C, more preferably 58 DEG C -69 DEG C are selected as, more preferably
58 DEG C -68 DEG C, more preferably 59 DEG C -68 DEG C, more preferably 60 DEG C -68 DEG C, more preferably 60 DEG C -67 DEG C, more preferably 60 DEG C -
66 DEG C, further preferably 60 DEG C -65 DEG C, reflux ratio 1-10:1, preferably 1-9:1, more preferably 1-8:1, more preferably
1-7:1, more preferably 1-6:1, more preferably 1-5:1, more preferably 1-4:1, more preferably 1-3:1, more preferably 1-2.8:
1, more preferably 1-2.5:1, more preferably 1-2.2:1, further preferably 1-2:1.
In the present invention, the boiling point of methanol is 64.7 DEG C, and the boiling point of sec-butyl acetate is 112.3 DEG C, and the boiling point of C8 alkene is
101.5 DEG C~119.9 DEG C, the tower top temperature of the second azeotropy rectification column controls between 55 DEG C -70 DEG C, therefore, the methanol being passed through
Can vaporize and go to tower top, and sec-butyl acetate with C8 alkene since boiling point is higher, can fall toward tower reactor, therefore, in the present invention, by institute
The position for the methanol feed inlet stated enters the lower part of the feed inlet of the second azeotropy rectification column in sec-butyl acetate mixed material, this
Sample, methanol are inversely contacted with the sec-butyl acetate for falling past tower reactor with C8 alkene during vaporizing rising, methanol and C8
Alkene forms azeotropic mixture and steams from tower top, and sec-butyl acetate then falls into tower reactor.
In the present invention, methanol feed inlet 1-150 block below the sec-butyl acetate mixed material feed inlet is managed
At column plate, preferably at 1-140 block theoretical tray, more preferably at 1-130 block theoretical tray, more preferably 1-120 block is managed
At column plate, more preferably at 1-110 block theoretical tray, more preferably at 1-100 block theoretical tray, more preferably 1-90 block is managed
At column plate, more preferably at 1-85 block theoretical tray, more preferably at 1-80 block theoretical tray, more preferably 1-75 block is theoretical
At column plate, more preferably at 1-70 block theoretical tray, more preferably at 1-65 block theoretical tray, more preferably 1-60 block theory tower
At plate, more preferably at 1-55 block theoretical tray, more preferably at 1-50 block theoretical tray, more preferably 1-45 block theoretical tray
Place, more preferably at 1-40 block theoretical tray, more preferably at 1-35 block theoretical tray, more preferably 1-30 block theoretical tray
Place, more preferably at 1-25 block theoretical tray, more preferably at 1-20 block theoretical tray, more preferably 1-15 block theoretical tray
Place, more preferably at 1-10 block theoretical tray, more preferably at 1-9 block theoretical tray, more preferably at 1-8 block theoretical tray,
It is more excellent more preferably at 2-6 block theoretical tray more preferably at 1-6 block theoretical tray more preferably at 1-7 block theoretical tray
It is selected as at 2-5 block theoretical tray, further preferably at 3-5 block theoretical tray.
According to another aspect of the present invention, it provides and a kind of uses methanol as impurity in the secondary butyl ester of entrainer separating acetic acid
Device comprising the first azeotropy rectification column and the second azeotropy rectification column, the first azeotropy rectification column and the second azeotropy rectification column are each
The import of self-contained overhead condenser and return tank and bottom reboiler, the first azeotropy rectification column connects the acetic acid containing impurity
Secondary butyl ester feeding line, the tower bottom outlet line of the first azeotropy rectification column connect the import of the second azeotropy rectification column, the second azeotropic
Rectifying column is also connected with methanol feed line, which there is C8 alkene and methanol azeotrope to export, tower bottom tool
There is sec-butyl acetate products export.
Alternatively, described device includes single azeotropy rectification column, the import of the azeotropy rectification column connects the second containing impurity
The secondary butyl ester feeding line of acid, is in addition also connected with methanol feed line, which has C8 alkene and methanol total
Object outlet is boiled, tower bottom has sec-butyl acetate products export.
Preferably, the feed inlet of the second azeotropy rectification column is also connected with methanol feed line, and methanol feed line is connected
Feed inlet in the lower part from the first connected feed inlet of azeotropy rectification column tower bottom sec-butyl acetate mixed material feeding line.
Preferably, the feed inlet that the methanol feed line is connected is from the first azeotropy rectification column tower bottom acetic acid Zhong Ding
Below the connected feed inlet of ester admixture material feeding line at 1-150 block theoretical tray, preferably at 1-140 block theoretical tray,
More preferably at 1-130 block theoretical tray, more preferably at 1-120 block theoretical tray, more preferably 1-110 block theoretical tray
Place, more preferably at 1-100 block theoretical tray, more preferably at 1-90 block theoretical tray, more preferably 1-85 block theoretical tray
Place, more preferably at 1-80 block theoretical tray, more preferably at 1-75 block theoretical tray, more preferably 1-70 block theoretical tray
Place, more preferably at 1-65 block theoretical tray, more preferably at 1-60 block theoretical tray, more preferably 1-55 block theoretical tray
Place, more preferably at 1-50 block theoretical tray, more preferably at 1-45 block theoretical tray, more preferably 1-40 block theoretical tray
Place, more preferably at 1-35 block theoretical tray, more preferably at 1-30 block theoretical tray, more preferably 1-25 block theoretical tray
Place, more preferably at 1-20 block theoretical tray, more preferably at 1-15 block theoretical tray, more preferably 1-10 block theoretical tray
Place, more preferably at 1-9 block theoretical tray, more preferably at 1-8 block theoretical tray, more preferably at 1-7 block theoretical tray, more
Preferably at 1-6 block theoretical tray, more preferably at 2-6 block theoretical tray, more preferably at 2-5 block theoretical tray, further
Preferably at 3-5 block theoretical tray.
In the present invention, azeotropy rectification column can be plate column, or packed tower can also be column plate together with filler
Combined gasket packing tower, wherein the theoretical cam curve of azeotropy rectification column is 15-200 block, preferably 18-200 block, more preferably
For 20-200 block, more preferably 20-190 block, more preferably 20-180 block, more preferably 20-170 block, more preferably 20-160
Block, more preferably 20-150 block, more preferably 20-140 block, more preferably 20-130 block, more preferably 20-120 block, more preferably
For 20-110 block, more preferably 20-100 block, more preferably 20-95 block, more preferably 20-90 block, more preferably 20-85 block,
More preferably 20-80 block, more preferably 20-75 block, more preferably 20-70 block, more preferably 20-65 block, more preferably 20-60
Block, further preferably 25-60 block, more preferably 30-60 block, more preferably 30-55 block, further preferably 30-50 block.
Method provided by the invention successfully solves sec-butyl acetate in the prior art and C8 separation of olefins degree is not high,
Sec-butyl acetate purity after separation is not high, the low technical problem of the yield of sec-butyl acetate, is separated using technology of the invention
Sec-butyl acetate purity afterwards reaches the level of pharmaceutical grade, the yield of sec-butyl acetate is 99% or more, together 99.9% or more
When, low energy consumption for separation process, and process is simple, easy to operate.
Detailed description of the invention
Fig. 1 is a kind of implementation for using methanol as the method for impurity in the secondary butyl ester of entrainer separating acetic acid in the present invention
The flow chart of mode.
Fig. 2 is a kind of another implementation for using methanol as the method for impurity in the secondary butyl ester of entrainer separating acetic acid in the present invention
The flow chart of mode.
Wherein 1 is sec-butyl acetate mixed material, and 2 be the first azeotropy rectification column, and 3 be the first azeotropic distillation column overhead reboiling
Device, 4 be the first azeotropy rectification column overhead condenser, and 5 be the first azeotropy rectification column return tank of top of the tower, and 6 be the first azeotropy rectification column
Overhead reflux, 7 be the first azeotropy rectification column return tank of top of the tower water phase, and 8 be through the dewatered tower bottom acetic acid of the first azeotropy rectification column
Secondary butyl ester mixed material, 9 be the second azeotropy rectification column, and 10 be methanol, and 11 be the second azeotropy rectification column bottom reboiler, and 12 be
Two azeotropy rectification column tower bottom produce the sec-butyl acetate of material high-purity, and 13 be the second azeotropy rectification column overhead condenser, and 14 are
Second azeotropy rectification column return tank of top of the tower, 15 be the second azeotropy rectification column overhead reflux, and 16 be that the second azeotropic distillation column overhead is adopted
The mixture of the impurity such as methanol and C8 alkene out.
Specific embodiment
Further illustrate the present invention by the following examples.However, the present invention is not limited by the following examples, not inclined
In the range of present subject matter, the present invention can be made a variety of changes, these variations are still included in the scope of the present invention
It is interior.
Embodiment 1
As shown in Figure 1, the sec-butyl acetate 1 containing impurity is sent into 2 azeotropic of the first azeotropy rectification column with the speed of 10t/h
Rectifying, wherein the composition of the mixed material are as follows: water 0.20%, sec-butyl alcohol 0.01%, sec-butyl acetate 99.29%, C8 alkene
0.50%, water, sec-butyl alcohol, part sec-butyl acetate and C8 alkene are steamed to tower top, in return tank of top of the tower 5 after the condensation of condenser 4
It is layered, water phase 7 is discharged with the speed of 0.02t/h, oily phase 6 flows back, wherein the operation item of the first azeotropy rectification column
Part are as follows: tower top pressure is normal pressure, and tower top temperature is 87 DEG C, and it is secondary to be contained acetic acid by reflux ratio 4.5 for the first azeotropy rectification column tower bottom
Butyl ester, C8 alkene mixed material 8 second azeotropy rectification column 9 is sent into the speed of 9.98t/h, and it is total that entrainer methanol 10 is added
Rectifying is boiled, the feed inlet of methanol is arranged below sec-butyl acetate mixed material feed inlet at the 1st block of column plate, wherein addition
The mass ratio of the amount of the amount and C8 alkene of methanol is 10:1, the operating condition of the second azeotropy rectification column 9 are as follows: tower top pressure is normal
Pressure, tower top temperature are 65 DEG C, and reflux ratio 1, C8 alkene forms azeotropic mixture with methanol and steams from tower top, after the condensation of condenser 13
Part 15 is flowed back, and part 16 is produced with the speed of 0.55t/h, and sec-butyl acetate falls into tower bottom as product 12 with 9.93t/
The speed of h produces.
Extraction product sec-butyl acetate is taken to be analyzed, the mass content of sec-butyl acetate is 99.92%, sec-butyl acetate
The rate of recovery be 99.2%.
Embodiment 2
As shown in Fig. 2, the sec-butyl acetate 1 containing impurity is sent into the second azeotropy rectification column 9 with the speed of 10t/h,
In, the composition of the mixed material are as follows: sec-butyl acetate 40.20%, C8 alkene 59.80%, and 10 azeotropic of entrainer methanol is added
The feed inlet of rectifying, methanol is arranged below sec-butyl acetate mixed material feed inlet at the 10th block of column plate, wherein the first of addition
The mass ratio of the amount of the amount and C8 alkene of alcohol is 1:1, the operating condition of the second azeotropy rectification column 9 are as follows: tower top pressure is normal pressure, tower
Pushing up temperature is 63 DEG C, reflux ratio 10, and C8 alkene forms azeotropic mixture with methanol and steams from tower top, the part after the condensation of condenser 13
15 flow back, and part 16 is produced with the speed of 11.96t/h, and sec-butyl acetate falls into tower bottom as product 12 with 4.02t/h's
Speed extraction.
Extraction product sec-butyl acetate is taken to be analyzed, the mass content of sec-butyl acetate is 99.94%, sec-butyl acetate
The rate of recovery be 99.3%.
Embodiment 3
Sec-butyl acetate 1 containing impurity is sent into 2 azeotropic distillation of the first azeotropy rectification column with the speed of 10t/h, wherein
The composition of the mixed material are as follows: water 5.00%, sec-butyl acetate 44.55%, C8 alkene 50.45%, water, part sec-butyl acetate
And C8 alkene is steamed to tower top, is layered after the condensation of condenser 4 in return tank of top of the tower 5, and water phase 7 is arranged with the speed of 0.5t/h
Out, oily phase 6 flows back, wherein the operating condition of the first azeotropy rectification column 2 are as follows: tower top pressure is normal pressure, tower top temperature 76
DEG C, the first azeotropy rectification column tower bottom is contained the mixed material 8 of sec-butyl acetate, C8 alkene with 9.5t/h's by reflux ratio 5.7
Speed is sent into the second azeotropy rectification column 9, and 10 azeotropic distillation of entrainer methanol is added, and the feed inlet of methanol is arranged in acetic acid Zhong Ding
Below ester admixture material feed inlet at the 2nd block of column plate, wherein the amount of the methanol of addition and the mass ratio of the amount of C8 alkene are
1.05:1, the operating condition of the second azeotropy rectification column 9 are as follows: tower top pressure is normal pressure, and tower top temperature is 65 DEG C, reflux ratio 8, C8
Alkene forms azeotropic mixture with methanol and steams from tower top, and part 15 is flowed back after the condensation of condenser 13, and part 16 is with 10.34t/
The speed of h produces, and sec-butyl acetate is fallen into tower bottom as product 12 and produced with the speed of 4.46t/h.
Extraction product sec-butyl acetate is taken to be analyzed, the mass content of sec-butyl acetate is 99.93%, sec-butyl acetate
The rate of recovery be 99.4%.
Embodiment 4
Sec-butyl acetate 1 containing impurity is sent into 2 azeotropic distillation of the first azeotropy rectification column with the speed of 10t/h, wherein
The composition of the mixed material are as follows: sec-butyl alcohol 1.00%, sec-butyl acetate 57.75%, C8 alkene 41.25%, entrainer water with
The speed of 0.06t/h enters the first azeotropy rectification column, and water, sec-butyl alcohol, part sec-butyl acetate and C8 alkene are steamed to tower top, through cold
Condenser 4 is layered after condensing in return tank 5, water phase 7 is discharged with the speed of 0.16t/h, oily phase 6 flows back, wherein the
The operating condition of one azeotropy rectification column 2 are as follows: tower top pressure is normal pressure, and tower top temperature is 82 DEG C, and reflux ratio 0.6 is total to first
Sec-butyl acetate is contained at boiling rectifying tower bottom, the mixed material 8 of C8 alkene is sent into the second azeotropy rectification column with the speed of 9.9t/h
9, and 10 azeotropic distillation of entrainer methanol is added, the feed inlet of methanol is arranged below sec-butyl acetate mixed material feed inlet the
At 8 blocks of column plates, wherein the mass ratio of the amount of the amount and C8 alkene of the methanol of addition is 1.1:1, the behaviour of the second azeotropy rectification column 9
Make condition are as follows: tower top pressure is normal pressure, and tower top temperature is 58 DEG C, reflux ratio 6, and C8 alkene and methanol form azeotropic mixture from tower top
It steams, part 15 is flowed back after the condensation of condenser 13, and part 16 is produced with the speed of 8.66t/h, and sec-butyl acetate is fallen into
Tower bottom is produced as product 12 with the speed of 5.78t/h.
Extraction product sec-butyl acetate is taken to be analyzed, the mass content of sec-butyl acetate is 99.95%, sec-butyl acetate
The rate of recovery be 99.5%.
Embodiment 5
Sec-butyl acetate 1 containing impurity is sent into 2 azeotropic distillation of the first azeotropy rectification column with the speed of 10t/h, wherein
The composition of the mixed material are as follows: water 4.00%, sec-butyl alcohol 0.1%, sec-butyl acetate 63.34%, C8 alkene 32.56% are water, secondary
Butanol, part sec-butyl acetate and C8 alkene are steamed to tower top, are layered after the condensation of condenser 4 in return tank 5, by water phase 7
It is discharged with the speed of 0.41t/h, oily phase 6 flows back, wherein the operating condition of the first azeotropy rectification column 2 are as follows: tower top pressure is
Normal pressure, tower top temperature are 80 DEG C, reflux ratio 5.5, by the first azeotropy rectification column tower bottom contain sec-butyl acetate, C8 alkene it is mixed
Close material 8 and second azeotropy rectification column 9 be sent into the speed of 9.59t/h, and 10 azeotropic distillation of entrainer methanol is added, methanol into
Material mouth is arranged below sec-butyl acetate mixed material feed inlet at the 6th block of column plate, wherein the amount and C8 alkene of the methanol of addition
The mass ratio of amount be 2:1, the operating condition of the second azeotropy rectification column 9 are as follows: tower top pressure is normal pressure, and tower top temperature is 68 DEG C,
Reflux ratio is that 5, C8 alkene is steamed with methanol formation azeotropic mixture from tower top, and part 15 is flowed back after the condensation of condenser 13, portion
16 are divided to produce with the speed of 9.77t/h, sec-butyl acetate is fallen into tower bottom as product 12 and produced with the speed of 6.33t/h.
Extraction product sec-butyl acetate is taken to be analyzed, the mass content of sec-butyl acetate is 99.96%, sec-butyl acetate
The rate of recovery be 99.6%.
Embodiment 6
Sec-butyl acetate 1 containing impurity is sent into 2 azeotropic distillation of the first azeotropy rectification column with the speed of 10t/h, wherein
The composition of the mixed material are as follows: water 3.00%, sec-butyl alcohol 0.20%, sec-butyl acetate 74.96%, C8 alkene 21.84%, water,
Sec-butyl alcohol, part sec-butyl acetate and C8 alkene are steamed to tower top, are layered after the condensation of condenser 4 in return tank 5, by water phase
7 are discharged with the speed of 0.32t/h, and oily phase 6 flows back, wherein the operating condition of the first azeotropy rectification column 2 are as follows: tower top pressure
For normal pressure, tower top temperature is 78 DEG C, reflux ratio 5.2, and the first azeotropy rectification column tower bottom is contained sec-butyl acetate, C8 alkene
Mixed material 8 is sent into the second azeotropy rectification column 9 with the speed of 9.68t/h, and 10 azeotropic distillation of entrainer methanol is added, methanol
Feed inlet is arranged below sec-butyl acetate mixed material feed inlet at the 5th block of column plate, wherein the amount and C8 alkene of the methanol of addition
The mass ratio of the amount of hydrocarbon is 3:1, the operating condition of the second azeotropy rectification column are as follows: tower top pressure is normal pressure, and tower top temperature is 60 DEG C,
Reflux ratio is that 4, C8 alkene is steamed with methanol formation azeotropic mixture from tower top, and part 15 is flowed back after the condensation of condenser 13, portion
16 are divided to produce with the speed of 8.74t/h, sec-butyl acetate is fallen into tower bottom as product 12 and produced with the speed of 7.5t/h.
Extraction product sec-butyl acetate is taken to be analyzed, the mass content of sec-butyl acetate is 99.97%, sec-butyl acetate
The rate of recovery be 99.7%.
Embodiment 7
Sec-butyl acetate 1 containing impurity is sent into 2 azeotropic distillation of the first azeotropy rectification column with the speed of 10t/h, wherein
The composition of the mixed material are as follows: water 2.00%, sec-butyl alcohol 0.50%, sec-butyl acetate 84.83%, C8 alkene 12.67%, water,
Sec-butyl alcohol, part sec-butyl acetate and C8 alkene are steamed to tower top, are layered after the condensation of condenser 4 in return tank 5, by water phase
7 are discharged with the speed of 0.25t/h, and oily phase 6 flows back, wherein the operating condition of the first azeotropy rectification column are as follows: tower top pressure is
Normal pressure, tower top temperature are 75 DEG C, reflux ratio 4.1, by the first azeotropy rectification column tower bottom contain sec-butyl acetate, C8 alkene it is mixed
Close material 8 and second azeotropy rectification column 9 be sent into the speed of 9.75t/h, and 10 azeotropic distillation of entrainer methanol is added, methanol into
Material mouth is arranged below sec-butyl acetate mixed material feed inlet at the 3rd block of column plate, wherein the amount and C8 alkene of the methanol of addition
The mass ratio of amount be 5:1, the operating condition of the second azeotropy rectification column 9 are as follows: tower top pressure is normal pressure, and tower top temperature is 63 DEG C,
Reflux ratio is that 3, C8 alkene is steamed with methanol formation azeotropic mixture from tower top, and part 15 is flowed back after the condensation of condenser 13, portion
16 are divided to produce with the speed of 7.6t/h, sec-butyl acetate is fallen into tower bottom as product 12 and produced with the speed of 8.48t/h.
Extraction product sec-butyl acetate is taken to be analyzed, the mass content of sec-butyl acetate is 99.98%, sec-butyl acetate
The rate of recovery be 99.8%.
Embodiment 8
Sec-butyl acetate 1 containing impurity is sent into 2 azeotropic distillation of the first azeotropy rectification column with the speed of 10t/h, wherein
The composition of the mixed material are as follows: water 1.00%, sec-butyl alcohol 0.80%, sec-butyl acetate 92.55%, C8 alkene 5.65% are water, secondary
Butanol, part sec-butyl acetate and C8 alkene are steamed to tower top, are layered after the condensation of condenser 4 in return tank 5, by water phase 7
It is discharged with the speed of 0.18t/h, oily phase 6 flows back, wherein the operating condition of the first azeotropy rectification column are as follows: tower top pressure is
Normal pressure, tower top temperature are 84 DEG C, reflux ratio 2.2, by the first azeotropy rectification column tower bottom contain sec-butyl acetate, C8 alkene it is mixed
Close material 8 and second azeotropy rectification column 9 be sent into the speed of 9.82t/h, and 10 azeotropic distillation of entrainer methanol is added, methanol into
Material mouth is arranged below sec-butyl acetate mixed material feed inlet at the 4th block of column plate, wherein the amount and C8 alkene of the methanol of addition
The mass ratio of amount be 8:1, the operating condition of the second azeotropy rectification column are as follows: tower top pressure is normal pressure, and tower top temperature is 64 DEG C, is returned
Stream is steamed with methanol formation azeotropic mixture from tower top than being 2, C8 alkene, and part 15 is flowed back after the condensation of condenser 13, part
16 are produced with the speed of 5.09t/h, and sec-butyl acetate is fallen into tower bottom as product 12 and produced with the speed of 9.26t/h.
Extraction product sec-butyl acetate is taken to be analyzed, the mass content of sec-butyl acetate is 99.95%, sec-butyl acetate
The rate of recovery be 99.5%.
Claims (15)
1. a kind of method for using methanol as impurity in the secondary butyl ester of entrainer separating acetic acid, impurity is C8 alkene in sec-butyl acetate
In the case where hydrocarbon, this method comprises: the sec-butyl acetate containing impurity is sent into the second azeotropy rectification column, and entrainer first is added
Alcohol, carries out azeotropic distillation, and C8 alkene forms azeotropic mixture with methanol and steams from tower top, partially flows back after condensing, partially adopt
Out, sec-butyl acetate falls into tower bottom and produces as product；
In the case that impurity is water, C8 alkene and sec-butyl alcohol in sec-butyl acetate, this method comprises: (1) will contain impurity
Sec-butyl acetate is sent into the first azeotropy rectification column azeotropic distillation, and water, sec-butyl alcohol, part sec-butyl acetate and C8 alkene are steamed to tower
Top, is layered after condensing, water phase is discharged, and oil mutually flows back；(2) that the first azeotropy rectification column tower bottom is contained acetic acid is secondary
Mixed material the second azeotropy rectification column of feeding of butyl ester, C8 alkene, and entrainer methanol is added, carry out azeotropic distillation, C8 alkene
Azeotropic mixture is formed with methanol to steam from tower top, is partially flowed back after condensing, and part produces, and sec-butyl acetate falls into tower bottom work
For product extraction；
In the case that impurity is C8 alkene and sec-butyl alcohol in sec-butyl acetate, this method comprises: (1) is by the acetic acid containing impurity
Secondary butyl ester is sent into the first azeotropy rectification column, and entrainer water is added, and carries out azeotropic distillation, the amount of entrainer water, which is at least, makes sec-butyl alcohol
It is obtained in the form of azeotropic mixture from tower top, water, sec-butyl alcohol, part sec-butyl acetate and C8 alkene are steamed to tower top, laggard through condensing
Row layering, water phase is discharged, and oil mutually flows back；(2) the first azeotropy rectification column tower bottom is contained into sec-butyl acetate, C8 alkene
Mixed material is sent into the second azeotropy rectification column, and entrainer methanol is added, and carries out azeotropic distillation, and C8 alkene and methanol form azeotropic
Object is steamed from tower top, is partially flowed back after condensing, and part produces, and sec-butyl acetate falls into tower bottom and produces as product；
In the case that impurity is water and C8 alkene in sec-butyl acetate, this method comprises: (1) is by the acetic acid Zhong Ding containing impurity
Ester is sent into the first azeotropy rectification column azeotropic distillation, and water, part sec-butyl acetate and C8 alkene steam to tower top, divided after condensing
Layer, water phase is discharged, and oil mutually flows back；(2) the first azeotropy rectification column tower bottom is contained to the mixing of sec-butyl acetate, C8 alkene
Material is sent into the second azeotropy rectification column, and entrainer methanol is added, and carries out azeotropic distillation, C8 alkene and methanol formed azeotropic mixture from
Tower top steams, and partially flows back after condensing, and part produces, and sec-butyl acetate falls into tower bottom and produces as product.
2. according to the method described in claim 1, it is characterized by: in the sec-butyl acetate containing impurity C8 alkene matter
Amount content is 0.5%-60%, and the mass content of sec-butyl acetate is 40%-99.5%.
3. according to the method described in claim 2, it is characterized by: the quality of water contains in the sec-butyl acetate containing impurity
Amount is 0.1%-5%.
4. according to the method described in claim 2, it is characterized by: in the sec-butyl acetate containing impurity sec-butyl alcohol matter
Amount content is 0.01%-1%.
5. according to the method described in claim 1, it is characterized by: the mass ratio of the methanol and C8 alkene is 1-10:1.
6. according to the method described in claim 1, it is characterized by: the mass ratio of the methanol and C8 alkene is 1.05-3:
1。
7. method according to claim 1 to 6, it is characterised in that: what first azeotropy rectification column was added
The amount of entrainer water is calculated using the following equation:
W=W1 × (1+A)
Wherein, W is the amount of the water of first azeotropy rectification column of entrance, is indicated with weight or weight flow, dimension and W1 phase
Together；
A is 0-10%；
W1=F × X1 × 19/53,
F is the amount or flow into the sec-butyl acetate containing impurity in first azeotropy rectification column, with weight or
Weight flow indicates；
X1 is the quality percentage for entering sec-butyl alcohol in the sec-butyl acetate containing impurity in first azeotropy rectification column
Content.
8. method according to claim 1 to 6, it is characterised in that: the pressure of first azeotropy rectification column
For normal pressure, tower top temperature is 70 DEG C -90 DEG C, reflux ratio 0.1-10:1.
9. according to the method described in claim 8, it is characterized by: the tower top temperature of first azeotropy rectification column is 75
DEG C -88 DEG C, reflux ratio 1-3:1.
10. according to the method described in claim 8, it is characterized by: the tower top pressure of second azeotropy rectification column is normal
Pressure, tower top temperature are 55 DEG C -70 DEG C, reflux ratio 1-10:1.
11. according to the method described in claim 10, it is characterized by: the tower top temperature of second azeotropy rectification column is 60
DEG C -65 DEG C, reflux ratio 1-3:1.
12. method according to claim 1 to 6, it is characterised in that: the position of the methanol feed inlet exists
Sec-butyl acetate mixed material enters the lower part of the feed inlet of the second azeotropy rectification column.
13. according to the method for claim 12, it is characterised in that: the methanol feed inlet is mixed in the sec-butyl acetate
It closes at material feed inlet or less 1-10 block theoretical tray.
14. according to the method for claim 12, it is characterised in that: the methanol feed inlet is mixed in the sec-butyl acetate
It closes at material feed inlet or less 2-6 block theoretical tray.
15. according to the method for claim 12, it is characterised in that: the methanol feed inlet is mixed in the sec-butyl acetate
It closes at material feed inlet or less 2-5 block theoretical tray.
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| 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 |
| FR3090393B1 (en) * | 2018-12-20 | 2021-04-23 | Ifp Energies Now | Process for treating an alcohol feed for the production of olefins |
| CN110922347B (en) * | 2019-12-02 | 2022-12-06 | 山东京博聚芳新材料股份有限公司 | Method for separating N-methyl pyrrolidone from large-amount chloroform system |
| CN110862301B (en) * | 2019-12-05 | 2022-07-15 | 湖南中创化工股份有限公司 | Sec-butyl alcohol refining method and device |
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