CN106278882A - A kind of butyl acrylate production system neutralized without alkali and production method thereof - Google Patents
A kind of butyl acrylate production system neutralized without alkali and production method thereof Download PDFInfo
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- CN106278882A CN106278882A CN201610624181.4A CN201610624181A CN106278882A CN 106278882 A CN106278882 A CN 106278882A CN 201610624181 A CN201610624181 A CN 201610624181A CN 106278882 A CN106278882 A CN 106278882A
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Abstract
The invention provides a kind of butyl acrylate production system neutralized without alkali and production method thereof, described system includes the first reactor, second reactor, extraction tower, azeotropy rectification column, lightness-removing column and dehydrating tower, wherein the first reactor, second reactor and extraction tower are sequentially connected, the tower top material outlet of extraction tower is connected with the material inlet of azeotropy rectification column, the tower top material outlet of azeotropy rectification column is connected with the material inlet of lightness-removing column, the materials at bottom of tower outlet of azeotropy rectification column exports with the materials at bottom of tower of extraction tower and is connected with the material inlet of the first reactor, the tower top material outlet of lightness-removing column is connected with the material inlet of dehydrating tower, weight-removing column outside the materials at bottom of tower outlet connection system of lightness-removing column, the materials at bottom of tower outlet of dehydrating tower is connected with the material inlet of the first reactor.Neutralizing tower in conventional propylene acid production process is transformed into azeotropy rectification column by the present invention, without neutralization operation, will not produce brine waste, more environmental protection.
Description
Technical field
The invention belongs to Organic Chemicals production field, relate to a kind of butyl acrylate production system and producer thereof
Method, particularly relates to a kind of butyl acrylate production system neutralized without alkali and production method thereof.
Background technology
Esters of acrylic acid is the industrial chemicals that a class is important.Butyl acrylate (BA) is as synthon, modified additive, extensively
General is applied to coating, adhesive, weaving, papermaking, leather, plastics and rubber materials.The production method of BA is acrylic acid (AA)
It is esterified under strong acid catalyst with n-butyl alcohol (BuOH) and obtains.
The butyl acrylate preparation technology flow process of main flow is as shown in Figure 1 in the market: raw material (acrylic acid and acid catalysis
Agent) join in the first reactor 1, butanol adds from dehydrating tower 6, three in the first reactor 1, decompression low temperature (90～
95 DEG C) carry out first paragraph reaction, in the first reactor 1, material overflows in the second reactor 2 after being full of, then at decompression low temperature
Under the conditions of carry out second segment reaction.In course of reaction, the water of generation is evaporated in dehydrating tower 6 discharge.Material is through second segment
After reaction, entering in catalyst extraction tower 3, recoil with aqueous phase, the acid catalyst in material is washed in aqueous phase.Material is
Organic facies, on extraction tower upper strata, extraction at the bottom of the aqueous phase tower containing catalyst, again squeeze in the first reactor 1.Upper materials is third
The organic facies of the composition such as olefin(e) acid butyl ester, acrylic acid and butanol, in overhead extraction to neutralizing tower 7.In neutralizing tower 7, third in material
Olefin(e) acid fully neutralizes with the NaOH solution that concentration is 18wt%, forms acrylates and is dissolved in aqueous phase, and aqueous phase becomes saliferous
Discharge at the bottom of waste water tower.Upper organic phase is the organic facies of the composition such as butyl acrylate and butanol, and overhead extraction enters to lightness-removing column 5
Row separates.Lightness-removing column 5 overhead extraction butanol, is back in dehydrating tower recycle, and the butyl acrylate at the bottom of tower enters weight-removing column,
Carry out follow-up rectification and purification.
Above-mentioned process operation is the most ripe, but still has unsurmountable shortcoming, it may be assumed that contain in above-mentioned technological process
The step for of having neutralization acrylic acid, acrylic acid reacts with the sodium hydroxide solution in neutralizing tower, forms acrylates and is dissolved in water
Discharge in mutually.Aqueous phase now is brine waste, and COD is up to 50000～75000mg/L, brings heavy burden to sewage disposal.
Too high COD value needs enterprise's substantial amounts of fund of input to set up sewage disposal system, and produces band can to enterprise security environmental protection
Carry out hidden danger.And the COD in brine waste is to be determined by the content of acrylates in aqueous phase.
CN 104529759 A discloses the production method of a kind of butyl acrylate, and described method is by reaction raw materials acrylic acid
With n-butyl alcohol, catalyst and polymerization inhibitor the most proportionally put into esterifying kettle, in esterifying kettle after steam reacting by heating shape
Becoming esterification products, esterification products enters esterification column with the form of ester water azeotropic mixture and separates, and then adopts from esterification column tower top
Go out, enter phase separator after the condensation of condensed device and be layered, obtain thick ester；The still liquid of esterifying kettle is through pump major part still liquid again
Return esterifying kettle to reflux, less be partially into cracking system, carry out cracking and reclaim；Most of still liquid of backflow boils again
Heat treated.But, said method still fails effectively to remove acrylic acid contained in thick ester product, and gained thick ester product remains a need for
It is neutralized and rectification concentration just can obtain required product, do not overcome the problem producing brine waste.
Therefore, how to improve the production method of butyl acrylate, especially N-process, is the pass of solution problem
Key.
Summary of the invention
For butyl acrylate production process in prior art all exists neutralization operation, and then produce a large amount of brine waste
Problem, the invention provides a kind of without alkali neutralize butyl acrylate production system and production method.Described system and
The acrylic acid of residual in material in production process can all be reclaimed by method, without neutralization operation, and then will not produce and contains
Salt waste water.
For reaching this purpose, the present invention by the following technical solutions:
First aspect, the invention provides a kind of butyl acrylate production system neutralized without alkali, and described system includes
First reactor, the second reactor, extraction tower, azeotropy rectification column, lightness-removing column and dehydrating tower, wherein the first reactor, second anti-
Answering still and extraction tower to be sequentially connected, the tower top material outlet of extraction tower is connected with the material inlet of azeotropy rectification column, azeotropic distillation
The tower top material outlet of tower is connected with the material inlet of lightness-removing column, at the bottom of the materials at bottom of tower outlet of azeotropy rectification column and the tower of extraction tower
Material outlet all material inlets with the first reactor are connected, the tower top material outlet of lightness-removing column and the material inlet phase of dehydrating tower
Even, the weight-removing column outside the materials at bottom of tower outlet connection system of lightness-removing column, materials at bottom of tower outlet and first reactor of dehydrating tower
Material inlet is connected, and the steam (vapor) outlet of the first reactor is connected with dehydrating tower charging aperture.
In the present invention, described extraction tower is for extracting catalyst from reaction mass, in order to recycle.
Following as currently preferred technical scheme, but the restriction of the technical scheme provided not as the present invention, pass through
Techniques below scheme, can preferably reach and realize technical purpose and the beneficial effect of the present invention.
As currently preferred technical scheme, described azeotropy rectification column peripheral hardware water replanishing device.
As currently preferred technical scheme, described azeotropy rectification column is normal pressure azeotropy rectification column.
In prior art, butyl acrylate production technology is generally: react → extraction → neutralize → take off gently → take off and weigh → split
Solving, wherein, being disposed to of neutralizing tower neutralizes unreacted acrylic acid in reactor.This technological process and acetate (vinegar
Acetoacetic ester or butyl acetate) technological process has significantly different: in acetate production process, high boiling acetic acid can stay esterification
Tower tower reactor, and the azeotropic mixture of lower boiling acetate and water from overhead extraction, thus can realize raw material and separate with product.So
And, in the production technology of butyl acrylate, the boiling point of acrylic acid and butyl acrylate is the most close, the most very difficult rectification
Acrylic acid is separated by way with butyl acrylate.Therefore a neutralizing tower can only be set on stream, will be mixed in butyl acrylate
Raw material propylene acid neutralize into salt, be dissolved in water formed brine waste (acrylates waste water) decontaminated water treating stations.But, acrylic acid
Salt waste water COD content is higher, generally 50000～75000mg/L, and the waste water of such high COD content can be given and increase waste water process
Load, and ecological environment may be threatened.
The boiling point of each material of butanol, acrylic acid, butyl acrylate, ethyl acetate and butyl acetate and azeotropic mixture thereof such as table 1
Shown in.As it can be seen from table 1 the boiling point of acrylic acid and butyl acrylate is closely, respectively 141 and 145.7 DEG C, by routine
The method of rectification is hardly possible to be isolated.But, acrylate, n-butyl alcohol and water can form binary or ternary azeotropic
Thing, its boiling range, at about 90～94 DEG C, differs greatly with acrylic acid boiling point 141 DEG C, it is possible to achieve separate.In view of extracting from catalyst
Take column overhead material out for containing butyl acrylate, butanol, acrylic acid and aqueous mixtures material, the side of azeotropic distillation can be used
Method, with water as entrainer, arranges an azeotropy rectification column, acrylic acid, butanol and acrylic acid is separated in this tower.
Table 1: the boiling point table of each material and azeotropic mixture thereof
| Composition or azeotropic mixture | Composition (wt%) | Atmospheric boiling point (DEG C) |
| Butanol | / | 117 |
| Acrylic acid | / | 141 |
| Butyl acrylate | / | 145.7 |
| Ethyl acetate | / | 77.0 |
| Butyl acetate | / | 126.0 |
| Water | / | 100.0 |
| Water/butanol | 44.5/55.5 | 93.0 |
| Water/ethyl acetate | 8/92 | 70.4 |
| Water/butyl acrylate | 38/62 | 94.3 |
| Water/butyl acetate | 27.1/72.9 | 90.7 |
| Water/butanol/butyl acrylate | 50/37.6/12.4 | 92.0 |
Second aspect, the invention provides the production method of aforesaid propylene acid butyl ester production system, described method include with
Lower step:
(1) raw material propylene acid, n-butyl alcohol and acid catalyst mixing being carried out esterification, reaction products therefrom recoils
Extraction, obtains aqueous phase and organic facies；
(2) step (1) gained aqueous phase recycles participation esterification, and gained organic facies carries out azeotropic distillation, separates
To light component binary or ternary azeotrope and heavy constituent acrylic acid；
(3) step (2) gained binary or ternary azeotrope are through de-light isolated butanol and butyl acrylate, gained butanol
Utilizing through processed Posterior circle and participate in esterification, gained butyl acrylate processes to obtain product through later separation；Step (2) institute
Obtain heavy constituent acrylic acid and recycle participation esterification.
The whole technological process of the method for the invention includes: reaction → extraction → azeotropic distillation → take off light → de-weigh → splitting
Solve.Whole technological process is without neutralization stage, thus without producing waste water.
In the present invention, esterification products be carried out recoil extraction by step (1), be the catalyst in order to remove in product；Step
Suddenly (2) gained binary or ternary azeotrope are water, butyl acrylate and the binary of butanol composition or ternary azeotrope.
As currently preferred technical scheme, in step (1) described raw material, the mol ratio of acrylic acid and n-butyl alcohol is 1:
(1～2), such as 1:1,1:1.2,1:1.4,1:1.6,1:1.8 or 1:2 etc., it is not limited to cited numerical value, listed model
In enclosing, other numerical value are the most feasible, more preferably 1:1.
Preferably, consumption is raw material gross mass the 1 of step (1) described acid catalyst～2wt%, such as 1wt%,
1.2wt%, 1.4wt%, 1.6wt%, 1.8wt% or 2wt% etc., it is not limited to cited numerical value, listed in the range of
Other numerical value are the most feasible, more preferably 1.5wt%.
In the present invention, acid catalyst used is catalyst commonly used in the art.
As currently preferred technical scheme, step (1) described esterification includes esterification and second for the first time
Secondary esterification.
Preferably, described first time esterification is carried out in the first reactor.
Preferably, the temperature of described first time esterification is 90～100 DEG C, such as 90 DEG C, 91 DEG C, 92 DEG C, 93 DEG C, 94
DEG C, 95 DEG C, 96 DEG C, 97,98 DEG C, 99 DEG C or 100 DEG C etc., it is not limited to cited numerical value, listed in the range of other numbers
It is worth the most feasible.
Preferably, the reaction pressure of described first time esterification is 40～50kPa, such as 40kPa, 42kPa, 44kPa,
46kPa, 48kPa or 50kPa etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible.
Preferably, described second time esterification is carried out in the second reactor.
Preferably, the temperature of described second time esterification is 90～100 DEG C, such as 90 DEG C, 91 DEG C, 92 DEG C, 93 DEG C, 94
DEG C, 95 DEG C, 96 DEG C, 97,98 DEG C, 99 DEG C or 100 DEG C etc., it is not limited to cited numerical value, listed in the range of other numbers
It is worth the most feasible.
Preferably, the reaction pressure of described second time esterification is 40～50kPa, such as 40kPa, 42kPa, 44kPa,
46kPa, 48kPa or 50kPa etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible.
As currently preferred technical scheme, recoil extraction described in step (1) is carried out in extraction tower.
Preferably, in step (1), in gained organic facies, the content of butyl acrylate is 65～70wt%, such as 65wt%,
66wt%, 67wt%, 68wt%, 69wt% or 70wt% etc., it is not limited to cited numerical value, listed in the range of other
Numerical value is the most feasible；The content of n-butyl alcohol is 9～15wt%, such as 9wt%, 10wt%, 11wt%, 12wt%, 13wt%,
14wt% or 15wt% etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible；Acrylic acid contain
Amount is 6～8wt%, such as 6wt%, 6.5wt%, 7wt%, 7.5wt% or 8wt% etc., it is not limited to cited number
Value, listed in the range of other numerical value the most feasible；Surplus is water.
As currently preferred technical scheme, step (2) described azeotropic distillation is carried out in azeotropy rectification column.
Preferably, the additional moisturizing of azeotropic distillation described in step (2) is as entrainer.
Preferably, in described azeotropic distillation, in starting material, the content of water is 40～52wt%, such as 40wt%,
41wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt%, 47wt%, 48wt%, 49wt%, 50wt%, 51wt%
Or 52wt% etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible；The content of butyl acrylate
It is 40～47wt%, such as 40wt%, 42wt%, 43wt%, 44wt%, 45wt%, 46wt% or 47wt% etc., but and not only
Be limited to cited numerical value, listed in the range of other numerical value the most feasible；The content of n-butyl alcohol is 4～10wt%, such as 4wt%,
5wt%, 6wt%, 7wt%, 8wt%, 9wt% or 10wt% etc., it is not limited to cited numerical value, listed in the range of its
His numerical value is the most feasible；Acrylic acid content is 3～5wt%, such as 3wt%, 3.5wt%, 4wt%, 4.5wt% or 5wt% etc.,
It is not limited to cited numerical value, listed in the range of other numerical value the most feasible.
Preferably, the column bottom temperature of described azeotropy rectification column is 105～110 DEG C, such as 105 DEG C, 106 DEG C, 107 DEG C, 108
DEG C, 109 DEG C or 110 DEG C etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible.
Preferably, the tower top temperature of described azeotropy rectification column is 94～98 DEG C, such as 94 DEG C, 95 DEG C, 96 DEG C, 97 DEG C or 98
DEG C etc., it is not limited to cited numerical value, listed in the range of other numerical value the most feasible.
Preferably, described in step (2), in heavy constituent acrylic acid, acrylic acid content is 85～95wt%, such as
85wt%, 87wt%, 90wt%, 93wt% or 95wt% etc., it is not limited to cited numerical value, listed in the range of other
Numerical value is the most feasible；The content of butyl acrylate is 2～5wt%, such as 2wt%, 3wt%, 4wt% or 5wt% etc., but and not only
Be limited to cited numerical value, listed in the range of other numerical value the most feasible；The content of butanol is 0.2～2wt%, such as 0.2wt%,
0.5wt%, 1wt%, 1.5wt% or 2wt% etc., it is not limited to cited numerical value, listed in the range of other numerical value equal
Feasible；Surplus is water.
As currently preferred technical scheme, heavy constituent acrylic acid described in step (3) returns the first reactor to be carried out
Esterification.
Preferably, return the acrylic acid flow of heavy constituent is the first reactor inlet amount the 5～7% of the first reactor,
Such as 5%, 5.5%, 6%, 6.5% or 7% etc., it is not limited to cited numerical value, listed in the range of other numerical value equal
Feasible.
Preferably, described de-gently separation of step (3) is carried out in lightness-removing column；
Preferably, step (3) described processed is carried out in dehydrating tower.
As currently preferred technical scheme, said method comprising the steps of:
(1) raw material propylene acid, n-butyl alcohol and acid catalyst mixing are sent in the first reactor and carry out the in 90～100 DEG C
Esterification, then overflow carries out second time esterification in the second reactor in 90～100 DEG C, reaction products therefrom enters
Be advanced into extraction tower carry out recoil extraction, obtain aqueous phase and organic facies, in gained organic facies the content of butyl acrylate be 65～
70wt%, the content of n-butyl alcohol is 9～15wt%, and acrylic acid content is 6～8wt%, and surplus is water；
(2) step (1) gained aqueous phase recycles return the first reactor and participates in esterification, and gained organic facies enters altogether
Boiling rectifying column carries out azeotropic distillation, and during azeotropic distillation, additional moisturizing is as entrainer, isolated light component binary or three
Unit's azeotropic mixture and heavy constituent acrylic acid；
(3) step (2) gained binary or ternary azeotrope enter in lightness-removing column through de-light isolated butanol and acrylic acid
Butyl ester, gained butanol entrance dehydrating tower returns the first reactor after processed and recycles participation esterification, gained third
Olefin(e) acid butyl ester processes to obtain product through later separation；Step (2) gained heavy constituent acrylic acid returns the first reactor and recycles ginseng
With esterification.
Compared with prior art, the method have the advantages that
(1) present invention is by being transformed into azeotropy rectification column, Wu Xuzhong by the neutralizing tower in conventional propylene acid production process
And operation so that whole technique will not produce the waste water containing acrylates, thus alleviates the burden of business processes waste water, has
It is beneficial to environmental protection；
(2) present invention can make the acrylic acid remaining in acrylate be recycled to completely instead by the method for azeotropic distillation
Answer in still, rather than generate acrylates with alkali reaction and discharge, saved raw material and cost.
Accompanying drawing explanation
Fig. 1 is the process chart of conventional propylene acid butyl ester preparation technology；
Fig. 2 is the structural representation of the butyl acrylate production system neutralized without alkali of the present invention；
Wherein, 1-the first reactor, 2-the second reactor, 3-extraction tower, 4-azeotropy rectification column, 5-lightness-removing column, 6-is dehydrated
Tower, 7-neutralizing tower.
Detailed description of the invention
For the present invention is better described, it is simple to understand technical scheme, below to the present invention the most specifically
Bright.But following embodiment is only the simple example of the present invention, do not represent or limit the scope of the present invention, this
Invention protection domain is as the criterion with claims.
Embodiment 1:
As in figure 2 it is shown, present embodiments provide a kind of butyl acrylate production system neutralized without alkali, described system bag
Include first reactor the 1, second reactor 2, extraction tower 3, azeotropy rectification column 4, lightness-removing column 5 and dehydrating tower 6, wherein the first reactor
1, the second reactor 2 and extraction tower 3 are sequentially connected, the tower top material outlet of extraction tower 3 and the material inlet phase of azeotropy rectification column 4
Even, the tower top material outlet of azeotropy rectification column 4 is connected with the material inlet of lightness-removing column 5, the materials at bottom of tower outlet of azeotropy rectification column 4
Export all material inlets with the first reactor 1 to be connected with the materials at bottom of tower of extraction tower 3, the tower top material outlet of lightness-removing column 5 and
The material inlet of dehydrating tower 6 is connected, the weight-removing column outside the materials at bottom of tower outlet connection system of lightness-removing column 5, the bottoms of dehydrating tower 6
Material outlet is connected with the material inlet of the first reactor 1, and the steam (vapor) outlet of the first reactor 1 is connected with dehydrating tower 6 charging aperture.
Wherein, described azeotropy rectification column 4 is normal pressure azeotropy rectification column, its peripheral hardware water replanishing device.
Embodiment 2:
Present embodiments provide the production method that a kind of butyl acrylate produces, said method comprising the steps of:
(1) raw material propylene acid being injected in the first reactor 1, n-butyl alcohol and acid catalyst enter the through dehydrating tower 6 streaming
In one reactor 1 in 95 DEG C at 48kPa under carry out for the first time esterification, wherein, acrylic acid and n-butyl alcohol ratio are 1:1, acid
Catalyst content is the 1.5wt% of total material；When the first reactor 1 is full of after material, material overflow to the second reactor 1 in
96 DEG C carry out second time esterification under 48kPa, and the water that the first reactor 1 produces in course of reaction enters dehydrating tower 6, warp
Dehydrating tower 6 tower top removes, to ensure that esterification is carried out towards positive reaction direction；Esterification for the second time, reaction products therefrom enters
Being advanced into extraction tower 3 and carry out recoil extraction, obtain aqueous phase and organic facies, in material, the catalyst of residual enters aqueous phase, and gained has
The content of machine middle butyl acrylate mutually is 65wt%, and the content of n-butyl alcohol is 13wt%, and acrylic acid content is 8wt%, water
Content is 14wt%；
(2) step (1) gained aqueous phase returns the first reactor 1 and participates in esterification and recycle, and gained organic facies enters
Azeotropy rectification column 4 carries out azeotropic distillation, and during azeotropic distillation, additional moisturizing is as entrainer so that starting material in azeotropic distillation
In material, the content of water is 44wt%, and the content of butyl acrylate is 42wt%, and the content of n-butyl alcohol is 9wt%, acrylic acid contains
Amount is 5wt%, and the column bottom temperature of azeotropy rectification column 4 is 105 DEG C, and tower top temperature is 94 DEG C, and pressure is normal pressure, light group of isolated
Dividing binary or ternary azeotrope and heavy constituent, wherein, in heavy constituent, acrylic acid content is 87wt%, the content of butyl acrylate
For 5wt%, the content of n-butyl alcohol is 1wt%, and the content of water is 7%；
(3) in step (2), gained binary or ternary azeotrope enter in lightness-removing column 5 through de-light isolated butanol and propylene
Acid butyl ester, gained butanol entrance dehydrating tower 6 returns the first reactor 1 after processed and recycles participation esterification, institute
Obtain butyl acrylate and process to obtain product through later separation；Step (2) gained heavy constituent returns the first reactor 1 and participates in esterification instead
Should, wherein the flow of heavy constituent accounts for the 5% of the first reactor 1 feedstock.
As can be seen here, the acrylic acid remained in acrylate can be returned completely by the present embodiment by the method for azeotropic distillation
Receive to reactor.
Embodiment 3:
(1) raw material propylene acid being injected in the first reactor 1, n-butyl alcohol and acid catalyst enter the through dehydrating tower 6 streaming
In one reactor 1 in 95 DEG C at 48kPa under carry out for the first time esterification, wherein, acrylic acid and n-butyl alcohol ratio are 1:1, acid
Catalyst content is the 1.5wt% of total material；When the first reactor 1 is full of after material, material overflow to the second reactor 1 in
96 DEG C carry out second time esterification under 48kPa, and the water that the first reactor 1 produces in course of reaction enters dehydrating tower 6, warp
Dehydrating tower 6 tower top removes, to ensure that esterification is carried out towards positive reaction direction；Esterification for the second time, reaction products therefrom enters
Being advanced into extraction tower 3 and carry out recoil extraction, obtain aqueous phase and organic facies, in material, the catalyst of residual enters aqueous phase, and gained has
The content of machine middle butyl acrylate mutually is 67wt%, and the content of n-butyl alcohol is 15wt%, and acrylic acid content is 7wt%, water
Content is 11wt%；
(2) step (1) gained aqueous phase returns the first reactor 1 and participates in esterification and recycle, and gained organic facies enters
Azeotropy rectification column 4 carries out azeotropic distillation, and during azeotropic distillation, additional moisturizing is as entrainer so that starting material in azeotropic distillation
In material, the content of water is 51wt%, and the content of butyl acrylate is 40wt%, and the content of n-butyl alcohol is 6wt%, acrylic acid contains
Amount is 3wt%, and the column bottom temperature of azeotropy rectification column 4 is 108 DEG C, and tower top temperature is 95.5 DEG C, and pressure is normal pressure, and isolated is light
Component binary or ternary azeotrope and heavy constituent, wherein, in heavy constituent, acrylic acid content is 90wt%, containing of butyl acrylate
Amount is 4wt%, and the content of n-butyl alcohol is 0.8wt%, and the content of water is 5.2%；
(3) in step (2), gained binary or ternary azeotrope enter in lightness-removing column 5 through de-light isolated butanol and propylene
Acid butyl ester, gained butanol entrance dehydrating tower 6 returns the first reactor 1 after processed and recycles participation esterification, institute
Obtain butyl acrylate and process to obtain product through later separation；Step (2) gained heavy constituent returns the first reactor 1 and participates in esterification instead
Should, wherein the flow of heavy constituent accounts for the 6% of the first reactor 1 feedstock.
As can be seen here, the acrylic acid remained in acrylate can be returned completely by the present embodiment by the method for azeotropic distillation
Receive to reactor.
Embodiment 4:
(1) raw material propylene acid being injected in the first reactor 1, n-butyl alcohol and acid catalyst enter the through dehydrating tower 6 streaming
In one reactor 1 in 95 DEG C at 48kPa under carry out for the first time esterification, wherein, acrylic acid and n-butyl alcohol ratio are 1:1.2,
Acid catalyst content is the 1.5wt% of total material；After being full of material in the first reactor 1, material overflow is to the second reactor 1
In 95 DEG C at 48kPa under carry out second time esterification, water that the first reactor 1 produces in course of reaction entrance dehydrating tower 6,
Remove through dehydrating tower 6 tower top, to ensure that esterification is carried out towards positive reaction direction；Esterification for the second time, reacts products therefrom
Carrying out entering extraction tower 3 and carry out recoil extraction, obtain aqueous phase and organic facies, in material, the catalyst of residual enters aqueous phase, gained
In organic facies, the content of butyl acrylate is 70wt%, and the content of n-butyl alcohol is 10.5wt%, and acrylic acid content is 6wt%,
The content of water is 13.5wt%；
(2) step (1) gained aqueous phase returns the first reactor 1 and participates in esterification and recycle, and gained organic facies enters
Azeotropy rectification column 4 carries out azeotropic distillation, and during azeotropic distillation, additional moisturizing is as entrainer so that starting material in azeotropic distillation
In material, the content of water is 48wt%, and the content of butyl acrylate is 43wt%, and the content of n-butyl alcohol is 5wt%, acrylic acid contains
Amount is 4wt%, and the column bottom temperature of azeotropy rectification column 4 is 110 DEG C, and tower top temperature is 98 DEG C, and pressure is normal pressure, light group of isolated
Dividing binary or ternary azeotrope and heavy constituent, wherein, in heavy constituent, acrylic acid content is 92wt%, the content of butyl acrylate
For 3wt%, the content of n-butyl alcohol is 0.2wt%, and the content of water is 4.8%；
(3) in step (2), gained binary or ternary azeotrope enter in lightness-removing column 5 through de-light isolated butanol and propylene
Acid butyl ester, gained butanol entrance dehydrating tower 6 returns the first reactor 1 after processed and recycles participation esterification, institute
Obtain butyl acrylate and process to obtain product through later separation；Step (2) gained heavy constituent returns the first reactor 1 and participates in esterification instead
Should, wherein the flow of heavy constituent accounts for the 7% of the first reactor 1 feedstock.
As can be seen here, the acrylic acid remained in acrylate can be returned completely by the present embodiment by the method for azeotropic distillation
Receive to reactor.
The result of integrated embodiment 1-3 is it can be seen that the present invention is by by the neutralizing tower in conventional propylene acid production process
It is transformed into azeotropy rectification column, without neutralization operation so that whole technique will not produce the waste water containing acrylates, thus subtracts
The light burden of business processes waste water, beneficially environmental protection；Meanwhile, the present invention can make the acrylic acid remaining in acrylate lead to
The method crossing azeotropic distillation is recycled in reactor completely, rather than with alkali reaction generate acrylates discharge, saved raw material and
Cost.
Applicant states, the present invention illustrates the method detailed of the present invention by above-described embodiment, but the present invention not office
It is limited to above-mentioned method detailed, does not i.e. mean that the present invention has to rely on above-mentioned method detailed and could implement.Art
Technical staff is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and auxiliary element
Interpolation, concrete way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (10)
1. the butyl acrylate production system neutralized without alkali, it is characterised in that described system includes the first reactor
(1), the second reactor (2), extraction tower (3), azeotropy rectification column (4), lightness-removing column (5) and dehydrating tower (6), wherein the first reactor
(1), the second reactor (2) and extraction tower (3) be sequentially connected, the tower top material outlet of extraction tower (3) and azeotropy rectification column (4)
Material inlet is connected, and the tower top material outlet of azeotropy rectification column (4) is connected with the material inlet of lightness-removing column (5), azeotropy rectification column
(4) materials at bottom of tower exports the material inlet all with the first reactor (1) of the materials at bottom of tower outlet with extraction tower (3) and is connected, de-
The light tower top material outlet of tower (5) is connected with the material inlet of dehydrating tower (6), and the materials at bottom of tower outlet of lightness-removing column (5) connects system
Weight-removing column outside system, the materials at bottom of tower outlet of dehydrating tower (6) is connected with the material inlet of the first reactor (1), the first reactor
(1) steam (vapor) outlet is connected with dehydrating tower (6) charging aperture.
Butyl acrylate production system the most according to claim 1, it is characterised in that described azeotropy rectification column (4) peripheral hardware
Water replanishing device.
Butyl acrylate production system the most according to claim 1 and 2, it is characterised in that described azeotropy rectification column (4) is
Normal pressure azeotropy rectification column.
4. according to the production method of the butyl acrylate production system described in any one of claim 1-3, it is characterised in that described
Method comprises the following steps:
(1) raw material propylene acid, n-butyl alcohol and acid catalyst mixing being carried out esterification, reaction products therefrom carries out recoil extraction
Take, obtain aqueous phase and organic facies；
(2) step (1) gained aqueous phase recycles participation esterification, and gained organic facies carries out azeotropic distillation, and isolated is light
Component binary or ternary azeotrope and heavy constituent acrylic acid；
(3) step (2) gained binary or ternary azeotrope are through de-light isolated butanol and butyl acrylate, and gained butanol is through de-
Water processes Posterior circle and utilizes participation esterification, and gained butyl acrylate processes to obtain product through later separation；Step (2) gained weight
Part acrylic recycles participation esterification.
Production method the most according to claim 4, it is characterised in that acrylic acid and n-butyl alcohol in step (1) described raw material
Mol ratio be 1:(1～2), more preferably 1:1；
Preferably, consumption is raw material gross mass the 1 of step (1) described acid catalyst～2wt%, more preferably
1.5wt%.
6. according to the production method described in claim 4 or 5, it is characterised in that step (1) described esterification includes for the first time
Esterification and second time esterification；
Preferably, described first time esterification is carried out in the first reactor (1)；
Preferably, the temperature of described first time esterification is 90～100 DEG C；
Preferably, the reaction pressure of described first time esterification is 40～50kPa；
Preferably, described second time esterification is carried out in the second reactor (2)；
Preferably, the temperature of described second time esterification is 90～100 DEG C；
Preferably, the reaction pressure of described second time esterification is 40～50kPa.
7. according to the production method described in any one of claim 4-6, it is characterised in that recoil extraction described in step (1) exists
Extraction tower is carried out in (3)；
Preferably, in step (1), in gained organic facies, the content of butyl acrylate is 65～70wt%, and the content of n-butyl alcohol is 9
～15wt%, acrylic acid content is 6～8wt%, and surplus is water.
8. according to the production method described in any one of claim 4-7, it is characterised in that step (2) described azeotropic distillation is altogether
Boiling rectifying column (4) is carried out；
Preferably, the additional moisturizing of azeotropic distillation described in step (2) is as entrainer；
Preferably, in described azeotropic distillation, in starting material, the content of water is 40～52wt%, and the content of butyl acrylate is 40
～47wt%, the content of n-butyl alcohol is 4～10wt%, and acrylic acid content is 3～5wt%；
Preferably, the column bottom temperature of described azeotropy rectification column (4) is 105～110 DEG C；
Preferably, the tower top temperature of described azeotropy rectification column (4) is 94～98 DEG C；
Preferably, described in step (2), in heavy constituent acrylic acid, acrylic acid content is 85～95wt%, containing of butyl acrylate
Amount is 2～5wt%, and the content of butanol is 0.2～2wt%, and surplus is water.
9. according to the production method described in any one of claim 4-8, it is characterised in that heavy constituent propylene described in step (3)
Acid returns the first reactor (1) and carries out esterification；
Preferably, return the first reactor (1) the acrylic acid flow of heavy constituent is the first reactor (1) inlet amount 5～
7%；
Preferably, described de-light separation of step (3) is carried out in lightness-removing column (5)；
Preferably, step (3) described processed is carried out in dehydrating tower (6).
10. according to the production method described in any one of claim 4-9, it is characterised in that said method comprising the steps of:
(1) raw material propylene acid, n-butyl alcohol and acid catalyst mixing are sent in the first reactor (1) and carry out the in 90～100 DEG C
Esterification, then overflow carries out second time esterification in the second reactor (2) in 90～100 DEG C, reaction gained produces
Thing carries out entering extraction tower (3) and carries out recoil extraction, obtains aqueous phase and organic facies, the content of butyl acrylate in gained organic facies
Being 65～70wt%, the content of n-butyl alcohol is 9～15wt%, and acrylic acid content is 6～8wt%, and surplus is water；
(2) step (1) gained aqueous phase recycles return the first reactor (1) and participates in esterification, and gained organic facies enters altogether
Boiling rectifying column (4) carry out azeotropic distillation, during azeotropic distillation, additional moisturizing is as entrainer, isolated light component binary or
Ternary azeotrope and heavy constituent acrylic acid；
(3) step (2) gained binary or ternary azeotrope enter in lightness-removing column (5) through de-light isolated butanol and acrylic acid fourth
Ester, gained butanol entrance dehydrating tower (6) returns the first reactor (1) after processed and recycles participation esterification, institute
Obtain butyl acrylate and process to obtain product through later separation；Step (2) gained heavy constituent acrylic acid returns the first reactor (1) circulation
Utilize and participate in esterification.
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| CN109879471A (en) * | 2018-12-22 | 2019-06-14 | 江门谦信化工发展有限公司 | In a kind of n-butyl acrylate and COD treatment process drops in waste water drop COD processing unit and waste water |
| CN110015958A (en) * | 2019-05-09 | 2019-07-16 | 山东恒正新材料有限公司 | A kind of dedicated butyl acrylate production system of aqueous adhesive and production method |
| CN110776417A (en) * | 2019-11-05 | 2020-02-11 | 常州仁晟生物能源科技有限公司 | Production method of isobutyl acrylate |
| CN111099998A (en) * | 2019-12-30 | 2020-05-05 | 东营海德新材料有限公司 | Esterification production process and production system of butyl acrylate |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109879471A (en) * | 2018-12-22 | 2019-06-14 | 江门谦信化工发展有限公司 | In a kind of n-butyl acrylate and COD treatment process drops in waste water drop COD processing unit and waste water |
| CN109879471B (en) * | 2018-12-22 | 2021-12-14 | 谦信化工集团有限公司 | COD (chemical oxygen demand) reduction treatment device and COD reduction treatment process for n-butyl acrylate neutralization wastewater |
| CN110015958A (en) * | 2019-05-09 | 2019-07-16 | 山东恒正新材料有限公司 | A kind of dedicated butyl acrylate production system of aqueous adhesive and production method |
| CN110015958B (en) * | 2019-05-09 | 2022-03-04 | 山东恒正新材料有限公司 | Special butyl acrylate production system and production method for water-based adhesive |
| CN110776417A (en) * | 2019-11-05 | 2020-02-11 | 常州仁晟生物能源科技有限公司 | Production method of isobutyl acrylate |
| CN111099998A (en) * | 2019-12-30 | 2020-05-05 | 东营海德新材料有限公司 | Esterification production process and production system of butyl acrylate |
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