CN109534986A - The method and apparatus of separating acetic acid from hexamethylene raw material - Google Patents
The method and apparatus of separating acetic acid from hexamethylene raw material Download PDFInfo
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- CN109534986A CN109534986A CN201710858416.0A CN201710858416A CN109534986A CN 109534986 A CN109534986 A CN 109534986A CN 201710858416 A CN201710858416 A CN 201710858416A CN 109534986 A CN109534986 A CN 109534986A
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- next door
- hexamethylene
- alcohol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C7/00—Purification; Separation; Use of additives
- C07C7/04—Purification; Separation; Use of additives by distillation
- C07C7/05—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds
- C07C7/08—Purification; Separation; Use of additives by distillation with the aid of auxiliary compounds by extractive distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
- B01D3/14—Fractional distillation or use of a fractionation or rectification column
- B01D3/141—Fractional distillation or use of a fractionation or rectification column where at least one distillation column contains at least one dividing wall
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
- C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
- C07C29/147—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof
- C07C29/149—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of carboxylic acids or derivatives thereof with hydrogen or hydrogen-containing gases
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
- C07C5/393—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation with cyclisation to an aromatic six-membered ring, e.g. dehydrogenation of n-hexane to benzene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
- C07C51/44—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/04—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides onto unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The present invention relates to a kind of method and apparatus of separating acetic acid from hexamethylene raw material, method therein includes:, using alcohol as extractant, to carry out extracting rectifying in next door rectifying column to hexamethylene raw material, obtain the hexamethylene of high-purity by tower top.The invention is particularly suited to handle the azeotropic mixture of hexamethylene and acetic acid, in a simpler manner, while the hexamethylene of high-purity and the acetic acid of high-purity can be obtained.
Description
Technical field
The present invention relates to a kind of method and apparatus of separating acetic acid from hexamethylene raw material, and in particular to a kind of use
The method and apparatus that next door rectifying column passes through extracting rectifying separating acetic acid from hexamethylene raw material.
Background technique
The investment of chemical separation process, energy consumption are often very big, in the chemical plant that separation is complicated, operation is more, separation costs
Up to 90% or more of totle drilling cost, even if general chemical plant, separation equipment also tends to quantitatively investing more than reactor
It is upper to be not less than reactor.Therefore, for Chemical Manufacture, separation process is very crucial, always to try hard to design, arrange out more to close
Reason, efficient separation process.
Both although hexamethylene and acetic acid are all very common basic organic compounds, in open source literature, rarely have
The report of isolation technics.The atmospheric boiling point of hexamethylene is 80.1 DEG C, and the atmospheric boiling point of acetic acid is 117 DEG C, seems and is easy with common
The method of rectifying separates, but actually the two can form minimum azeotrope, can not be separated the two by conventional distillation.
(method and apparatus for removing acetic acid from hexamethylene in adipic acid production, RPC are public by CN1270578A/US6177053B1
Department) disclose a kind of in the production process that hexamethylene is direct oxidation into adipic acid, the method for removing acetic acid from hexamethylene
And device.The removing of acetic acid in one to three-level (preferential two-stage) extraction tank using a small amount of washing water preferably by being carried out.
Though this method can remove the acetic acid in hexamethylene；But the later separation of acetic acid and water is very difficult, at present industrial separation
The conventional distillation and azeotropic distillation energy consumption used when water and acetic acid is all very high.
In the technique of the cyclohexene esterification of the present inventor's invention plus hydrogen coproduction cyclohexanol and ethyl alcohol, hexamethylene is also related to
The mixture of alkane and acetic acid, the visible CN103664529B, CN103664586B of pertinent literature, CN103664587B,
CN103880598B,CN103880599B,CN103664531B,US 9561991B2.In those references, without reference to acetic acid
With the efficient separation method of hexamethylene.
In conclusion also lacking the efficient separation method of hexamethylene and acetic acid in the prior art.
Next door tower is a kind of novel distillation knockout tower to be grown up based on the complete thermal coupling principle of Petlyuk tower, is passed through
One or more vertical wall (vertical wall can also be extended to tower top and tower reactor as needed) is set in the interlude of rectifying column, is made
One rectifying column can achieve the effect that multiple rectifying columns, and investment and energy consumption can reduce by 25% or more.Next door rectifying column one
As be used for multi-component rectifying separation process, can be used for extracting rectifying process.
Up to now, in publication and non-patent literature without using extracting rectifying and next door tower separating benzene-cyclohexane and
Any information of acetic acid.
Summary of the invention
It is an object of the invention to be isolated acetic acid with simple mode from hexamethylene raw material, obtained high-purity
Hexamethylene.It is a further object of the invention that obtaining the acetic acid of high-purity while realizing foregoing purpose.
For the present inventor in practice, it has been found that in the azeotropic mixture of hexamethylene and acetic acid, acetic acid content is much higher than existing document
The data (2w%) of record.When the present inventor carries out esterification of the cyclohexene (containing hexamethylene) with acetic acid in catalytic rectifying tower
It has been surprisingly found that, if the excess of acetic acid is more, regardless of the operating condition of catalytic rectifying tower, hexamethylene and excessive acetic acid are total
Be with constant boiling point (about 74 DEG C) and it is constant form (hexamethylene mass fraction about 84%, quality of acetic acid score about 16%) from
The tower top of rectifying column steams, i.e., the two forms minimum constant boiling azeotropic object.It is thus necessary to research and solve two practical problems, a side
Face will thoroughly remove the acetic acid in hexamethylene, so that the hexamethylene can be manufactured by later use, such as dehydrogenation reaction
Benzene；On the other hand, the separated from acetic acid in hexamethylene is come out and is recycled.Clearly as azeotropic is formed, it can not be using common
Rectifying separates acetic acid with hexamethylene.For the separation problem for solving hexamethylene and acetic acid azeotropic system, the present inventor has carried out greatly
Quantifier elimination simultaneously explores various separation methods, by diligent effort, it has unexpectedly been found that some alcohol can effectively increase acetic acid
The rectifying separation of the two is realized, this completes this to destroy the formation of the two azeotropic mixture with the relative volatility of hexamethylene
Invention.
Main contents of the invention are as follows.
1. a kind of method of the separating acetic acid from hexamethylene raw material, which is characterized in that be extraction with alcohol in next door rectifying column
Agent is taken, extracting rectifying is carried out to hexamethylene raw material, next door rectifying tower top obtains hexamethylene (the preferably > of purity > 95%
97%, more preferable > 99%, further preferred > 99.5%)；Acetic acid (the preferably > of purity > 95% is obtained in side line
98.5%)；Next door rectifying column bottom obtains the alcohol (preferably > 99.5%) of purity > 95%；The purity of the hexamethylene with
The total mass fraction meter of benzene, cyclohexene and hexamethylene；The hexamethylene raw material by hexamethylene, acetic acid and optional benzene and/or
Cyclohexene composition；The alcohol is selected from the unitary of the unitary alkanol of C6~C12, the unitary cyclic alkanol of C6~C12, C6~C12
The mixture of one of aromatic alcohol, diethylene glycol (DEG), triethylene glycol and tetraethylene glycol alcohol or several alcohol (is preferably selected from the unitary of C6~C12
One of alkanol, the unitary cyclic alkanol of C6~C12 and unitary aromatic alcohol, diethylene glycol (DEG), triethylene glycol and the tetraethylene glycol of C6~C12
Alcohol).
2. according to aforementioned any method, which is characterized in that the alcohol is selected from n-hexyl alcohol, isohexyl alcohol, n-heptanol, different heptan
Alcohol, n-octyl alcohol, isooctanol, n-nonyl alcohol, isononyl alcohol, Decanol, isodecanol, lauryl alcohol, cyclohexanol, methylcyclopentanol, methyl ring
One of hexanol, benzyl alcohol, diethylene glycol (DEG), triethylene glycol and tetraethylene glycol.
3. according to aforementioned any method, which is characterized in that in the hexamethylene raw material, the mass fraction of acetic acid is
1%~99% (it can be 1%~70%, or 5%~50%, preferably 10%~35%, more preferably 10%~
20%).
4. according to aforementioned any method, which is characterized in that the hexamethylene raw material is the azeotropic of hexamethylene and acetic acid
Object, or be hexamethylene, acetic acid and cyclohexene and/or the azeotropic mixture of benzene.
5. according to aforementioned any method, which is characterized in that in the hexamethylene raw material, the mass fraction of benzene is 0~
10%, the mass fraction of cyclohexene is 0~20% (generally, the mass fraction of benzene is 0.2%~1%, the quality point of cyclohexene
Number is 0.5%~2%).
6. according to aforementioned any method, which is characterized in that the middle part of the next door rectifying column be equipped with one piece it is vertical
Next door, the next door rectifying column is divided into five regions: the top in next door is rectification zone I；The side in next door, top are extraction essence
Area II is evaporated, lower section is extraction stripping zone III；The other side in next door is that extractant recycles rectification zone IV；The lower section in next door is public
Stripping zone V.
7. according to method described in 6, which is characterized in that the upper end closed of extractant recycling rectification zone IV.
8. according to method described in 6 or 7, which is characterized in that the theoretical cam curve of rectification zone I is 10~30, extracting rectifying
The theoretical cam curve in area II is 10~30 (preferably 15~30), and the theoretical cam curve of extraction stripping zone III is 5~20, is extracted molten
The theoretical cam curve that rectification zone IV is recycled in agent is 10~30, and the theoretical cam curve of public stripping zone V is 10~30.
9. according to the method any in 6~8, which is characterized in that the alcohol by the extracting rectifying area II top
(preferably upper end) enters the next door rectifying column；The hexamethylene raw material by the extracting rectifying area II lower part (preferably
For lower end) enter the next door rectifying column.
10. according to aforementioned any method, which is characterized in that the tower is made in the alcohol reuse that next door rectifying column bottom obtains
Extractant.
11. according to aforementioned any method, which is characterized in that in the operation of next door rectifying column, the solvent ratio (charging of alcohol
The mass ratio of amount and the inlet amount of hexamethylene raw material) it is 0.2:1~20:1 (preferably 0.2:1~4.5:1, more preferably 0.2:1
~1:1, further preferably 0.4:1~0.6:1).
12. according to aforementioned any method, which is characterized in that the operating pressure of next door rectifying column is -1MPa~10MPa
(preferably 0.1MPa~1MPa, more preferably normal pressure).
13. according to aforementioned any method, which is characterized in that the reflux ratio of next door the top of the distillation column is 0.3:1~30:1
(preferably 0.5:1~1.5:1).
14. according to aforementioned any method, which is characterized in that the reflux ratio of next door rectifying column side line is 0.5:1~10:1
(preferably 1:1~4:1).
15. according to aforementioned any method, which is characterized in that from the hexamethylene that next door the top of the distillation column obtains, with matter
Meter, acetic acid content are less than 50ppm (preferably smaller than 20ppm is further preferably no larger than 5ppm more preferably less than 10ppm).
16. a kind of device of the separating acetic acid from hexamethylene raw material, which is characterized in that including next door rectifying column, hexamethylene
Raw material storage tank and alcohol storage tank；
It is equipped with one piece of vertical next door at the middle part of the next door rectifying column, the next door rectifying column is divided into five areas
Domain: the top in next door is rectification zone I；The side in next door, top are extracting rectifying area II, and lower section is extraction stripping zone III；Next door
The other side be extractant recycle rectification zone IV；The lower section in next door is public stripping zone V；
Material inlet is arranged at the top (preferably upper end) and lower part (preferably lower end) in the extracting rectifying area II；It is described
The material inlet on II top of extracting rectifying area (preferably upper end) is connected with the alcohol storage tank；II lower part of extracting rectifying area
The material inlet of (preferably lower end) is connected with the hexamethylene raw material storage tank；
The tower bottom of the next door rectifying column is equipped with the outlet of discharge alcohol, which is connected with the alcohol storage tank.
17. a kind of device of cyclohexane dehydrogenation manufacture benzene, which is characterized in that (be used for from hexamethylene including next door rectifying column
Acetic acid is isolated in raw material).
18. a kind of device for manufacturing cyclohexyl acetate, including the mixture formed with cyclohexene, hexamethylene and optional benzene
With the catalytic rectifying tower of acetic acidreaction manufacture cyclohexyl acetate, which is characterized in that including next door rectifying column (for former from hexamethylene
Acetic acid is isolated in material).
19. a kind of method of coproduction cyclohexanol and ethyl alcohol includes the steps that (1) benzene selective hydrogenation manufactures cyclohexene, (2) ring
The step of hexene and acetic acidreaction manufacture cyclohexyl acetate, and the step of (3) ethyl cyclohexyl ester through hydrogenation manufacture cyclohexanol and ethyl alcohol,
It is characterised in that it includes method or apparatus any in aforementioned 1~18.
20. according to method described in 19, which is characterized in that the hexamethylene raw material after removing acetic acid is used for dehydrogenation reaction system
Benzene is made, and benzene circulation is used for the step (1).
21. according to method described in 19 or 20, which is characterized in that the acetic acid separated circulation is used for the step
(2)。
The present invention has following advantageous effects.First, the present invention have process it is short, it is easy to operate it is low with equipment investment,
The advantages of low energy consumption, in the azeotropic mixture of the azeotropic mixture or hexamethylene of separating benzene-cyclohexane and acetic acid, acetic acid and cyclohexene and/or benzene
When more advantage；Second, even if containing for the hexamethylene of high-purity, especially acetic acid can also be directly obtained under low reflux ratio
Amount can be controlled in 50ppm hereinafter, such hexamethylene is used directly for dehydrogenation manufacture benzene；Third, invention can also be with same
A next door rectifying column obtains the acetic acid of high-purity and the alcohol of high-purity simultaneously, so as to directly be back to the acetic acid and hexamethylene
The alcohol is recycled as the extractant of next door rectifying column by the esterification of alkene.
Detailed description of the invention
Fig. 1 is schematic flow diagram of the invention.
Other features and advantages of the present invention will be further described in specific embodiment part.
Specific embodiment
Below in conjunction with the specific embodiment detailed description present invention, but it should be noted that, protection scope of the present invention is not by these
The limitation that specific embodiment or principle are explained, but determined by claims.
In the present invention, other than the content clearly stated, any matters or item that do not mention are directly applicable in ability
Content known to domain is without carrying out any change.Moreover, any embodiment described herein can with it is described herein
One or more other embodiments freely combine, and the technical solution or technical idea being consequently formed are accordingly to be regarded as the original public affairs of the present invention
It opens or a part of original description, and is not considered as the new content for not disclosing or being expected herein, unless this field skill
Art personnel think that the combination is obvious unreasonable.
All features disclosed in this invention can in any combination, these combinations should be understood presently disclosed or note
The content of load, unless those skilled in the art think that the combination is obviously unreasonable.Numerical point disclosed in this specification, is not only wrapped
Specifically disclosed numerical point in embodiment is included, further includes the endpoint of each numberical range in specification, any group of these numerical points institute
The range of conjunction is regarded as the range that the present invention is disclosed or recorded.
Technical and scientific term in the present invention, provide definition be subject to its definition, do not provide definition then by ability
The common meaning in domain understands.
In the present invention, " optional ", which is meant that, to be contained or not contain, for example " optional A " refers to containing A or without containing A.
The present invention provides a kind of methods of separating acetic acid from hexamethylene raw material, which is characterized in that next door rectifying column
In, using alcohol as extractant, extracting rectifying is carried out to hexamethylene raw material, next door rectifying tower top obtains the hexamethylene that purity is greater than 95%
Alkane；The acetic acid of purity > 95% is obtained in side line；Next door rectifying column bottom obtains the alcohol of purity > 95%；The hexamethylene
Purity in terms of the total mass fraction of benzene, cyclohexene and hexamethylene；The hexamethylene raw material is by hexamethylene, acetic acid and optional
Benzene and/or cyclohexene composition；The alcohol is selected from unitary cyclic alkanol, the C6~C12 of the unitary alkanol of C6~C12, C6~C12
One of unitary aromatic alcohol, diethylene glycol (DEG), triethylene glycol and tetraethylene glycol alcohol or several alcohol mixture.
Extraction rectifying method according to the present invention, the hexamethylene raw material is by hexamethylene, acetic acid and optional benzene and/or ring
Hexene composition.The hexamethylene raw material may be from the coproduction cyclohexanol of the present inventor's invention and the technique of ethyl alcohol, pertinent literature
Thus it is clear that CN103664529B, CN103664586B, CN103664587B, CN103880598B, CN103880599B,
CN103664531B, US 9561991B2 etc., an object of the present invention are thoroughly to remove acetic acid from these hexamethylene raw materials,
So that the hexamethylene raw material can manufacture benzene by later use, such as by dehydrogenation reaction.
It is said from applicability angle of the invention, the acetic acid content range of the hexamethylene raw material can be very loose, such as acetic acid
Mass fraction can be 1%~99%；But for general hexamethylene raw material, the mass fraction of acetic acid usually 1%~
Between 70%.
Extraction rectifying method according to the present invention, in the hexamethylene raw material, the mass fraction of acetic acid is preferably 5%~
50%, more preferably 10%~35%, further preferably 10%~20%.
Extraction rectifying method according to the present invention, the hexamethylene raw material be preferably hexamethylene and acetic acid azeotropic mixture or
Person is the azeotropic mixture of hexamethylene, acetic acid and cyclohexene and/or benzene.
Extraction rectifying method according to the present invention, the hexamethylene raw material are generally made of hexamethylene and acetic acid, sometimes
Contain a small amount of benzene and/or cyclohexene.Generally, the mass fraction of benzene is 0~10%, the mass fraction of cyclohexene is 0~
20%；Further, the mass fraction of benzene is 0.2%~1%, and the mass fraction of cyclohexene is 0.5%~2%.
Extraction rectifying method according to the present invention, the alcohol be selected from the unitary alkanol of C6~C12, C6~C12 one
First cyclic alkanol, one of unitary aromatic alcohol, diethylene glycol (DEG), triethylene glycol and the tetraethylene glycol alcohol of C6~C12 or the mixture of several alcohol；
Be preferably selected from the unitary alkanol of C6~C12, the unitary aromatic alcohol of the unitary cyclic alkanol of C6~C12 and C6~C12, diethylene glycol (DEG),
One of triethylene glycol and tetraethylene glycol alcohol；Be more preferably selected from the unitary alkanol of C6~C8, the unitary cyclic alkanol of C6~C8, C6~
One of unitary aromatic alcohol, diethylene glycol (DEG), triethylene glycol and the tetraethylene glycol of C8 alcohol；Further preferably selected from n-hexyl alcohol, isohexyl alcohol, just
Enanthol, iso-heptanol, n-octyl alcohol, isooctanol, n-nonyl alcohol, isononyl alcohol, Decanol, isodecanol, lauryl alcohol, cyclohexanol, methyl ring penta
One of alcohol, methyl cyclohexanol, benzyl alcohol, diethylene glycol (DEG), triethylene glycol and tetraethylene glycol.
Extraction rectifying method according to the present invention obtains the hexamethylene of purity > 95% by extracting rectifying tower top, preferably pure
Spend > 97%, more preferable purity > 99%, further preferred purity > 99.5%.
Extraction rectifying method according to the present invention obtains the acetic acid of purity > 95%, preferably purity > 98.5% in side line,
More preferable purity > 99%, further preferred purity > 99.5%.
Extraction rectifying method according to the present invention, next door rectifying column bottom obtains the alcohol of purity > 95%, preferably pure
Spend > 99.5%.
Extraction rectifying method according to the present invention, in the hexamethylene obtained by extracting rectifying column overhead, in mass, acetic acid
Content is less than 50ppm (preferably smaller than 20ppm is further preferably no larger than 5ppm more preferably less than 10ppm), such hexamethylene
It can be directly used for dehydrogenation reaction manufacture benzene.
The form of counter septum rectifying column of the present invention is not particularly limited, and can select any suitable next door rectifying column.
Each section in the rectifying column of next door, in bulk or structured packing can be both loaded, various forms of column plates, such as valve tower can also be installed
Plate, sieve plate etc..The tower internals of the next door rectifying column must select the material of resistance to acetic acid corrosion, preferably in tower made of selection titanium
Part.
A kind of preferred embodiment of the invention is, the middle part of the next door rectifying column be equipped with one piece it is vertical every
Wall, the next door rectifying column (referring to tower body) is divided into five regions: the top in next door is rectification zone I；The side in next door, top are
Extracting rectifying area II, lower section are extraction stripping zone III；The other side in next door is that extractant recycles rectification zone IV；The lower section in next door
For public stripping zone V.
Preferably, the upper end closed of extractant recycling rectification zone IV.
Preferably, the alcohol enters the next door rectifying column by the upper end in the extracting rectifying area II；The hexamethylene
Raw material enters the next door rectifying column by the lower end in the extracting rectifying area II.
Separation for hexamethylene and acetic acid, each section of next door rectifying column must have suitable theoretical cam curve, Cai Nengda
To ideal separating effect.The inventors discovered that the separation for hexamethylene and acetic acid, using existing theoretical modeling calculating side
Method, the result and actual deviation of calculating are very big, it is impossible to be used in the design of commercial plant.The present inventor has determined next door by test
Each section of rectifying column of suitable number of theoretical plate: the theoretical cam curve of rectification zone I is 10~30, the theoretical cam curve in extracting rectifying area II
For 10~30 (preferably 15~30), the theoretical cam curve for extracting stripping zone III is 5~20, and extractant recycles rectification zone IV
Theoretical cam curve is 10~30, and the theoretical cam curve of public stripping zone V is 10~30.
Extractant-alcohol dosage and the reflux ratio of next door rectifying column are that two of influence separation of extractive distillation effect are important
Parameter.
Solvent quantity is conducive to the separation of hexamethylene and acetic acid more, but can dramatically increase the recovery cost of extractant.With
Toward other extracting rectifyings experience have shown that, the dosage of extractant is generally bigger, common solvent ratio (extractant and original to be separated
The mass ratio of material) it is 5~9.Extracting rectifying virtue method according to the present invention, extracting rectifying operation in, solvent ratio (inlet amount of alcohol with
The mass ratio of the inlet amount of hexamethylene raw material) it can be 0.2:1~20:1, preferably 0.2:1~4.5:1, more preferably 0.2:1
~1:1 generally can reach ideal separating effect in 0.4:1~1:1.
For distillation operation, it is considered that increase reflux ratio and be always conducive to improve separating effect, but the present inventor is in reality
Middle discovery is trampled, the separation for hexamethylene and acetic acid, reflux ratio only in a certain range just can guarantee acetic acid and hexamethylene
Separating effect, too high or too low reflux ratio is not able to satisfy the separation requirement of acetic acid and hexamethylene.Extraction according to the present invention
Take rectificating method, in extracting rectifying operation, next door rectifying column top return than being generally 0.3:1~30:1, preferably 0.5:1~
1.5:1.In the case where meeting above-mentioned condition, by separation of extractive distillation acetic acid and hexamethylene, the acetic acid content in tower top hexamethylene can
Lower than 50ppm (μ g/g).
The operation temperature and pressure of next door rectifying column are corresponding.Extraction rectifying method according to the present invention, with gauge pressure
Meter, the operating pressure of next door rectifying column are -1MPa~10MPa, preferably -0.1MPa~1MPa, further preferably normal pressure.
Introduction according to the present invention, and combine existing knowledge and experience, those skilled in the art be easy directly or by
Simple experiment determines other operating parameters of next door rectifying column.For example, raw material to be separated is usually to steep in extracting rectifying
The lower charging of point, the unclassified stores such as extractant are usually to feed under the tower temperature of its feed entrance point.
Extraction rectifying method according to the present invention, the operating reflux ratio of the next door rectifying column side line be generally 0.5:1~
10:1, preferably 1:1~4:1.In the case where meeting above-mentioned condition, the acetic acid purity obtained by the next door rectifying column side line is usually high
In 98.5%, and extractant-alcohol purity of next door rectifying tower bottom recycling meets and is recycled also greater than 99.5%
Requirement.
The alcohol reuse that next door rectifying tower bottom obtains is made the next door essence by extraction rectifying method according to the present invention
Evaporate the extractant of tower.
Extraction rectifying method according to the present invention, it is only necessary to implement in one tower of next door rectifying column, so that it may from hexamethylene
Acetic acid is isolated in alkane raw material, at the same obtain the hexamethylene of high-purity, high-purity acetic acid and extractant can be recycled as
The alcohol of high-purity.
The present invention also provides a kind of devices of separating acetic acid from hexamethylene raw material, which is characterized in that including next door essence
Evaporate tower, hexamethylene raw material storage tank and alcohol storage tank；
It is equipped with one piece of vertical next door at the middle part of the next door rectifying column, the next door rectifying column is divided into five areas
Domain: the top in next door is rectification zone I；The side in next door, top are extracting rectifying area II, and lower section is extraction stripping zone III；Next door
The other side be extractant recycle rectification zone IV；The lower section in next door is public stripping zone V；
Material inlet is arranged at the top (preferably upper end) and lower part (preferably lower end) in the extracting rectifying area II；It is described
The material inlet on II top of extracting rectifying area (preferably upper end) is connected with the alcohol storage tank；II lower part of extracting rectifying area
The material inlet of (preferably lower end) is connected with the hexamethylene raw material storage tank；
The tower bottom of the next door rectifying column is equipped with the outlet of discharge alcohol, which is connected with the alcohol storage tank.
The tower top of the next door rectifying column is connected with the first condensate cooler entrance, the outlet of the first condensate cooler and the
The entrance of one return tank is connected.The outlet of first return tank is connected with the tower top of the next door rectifying column.
The top (preferably upper end) of extractant recycling rectification zone IV is equipped with acetic acid outlet, the outlet and second cold
The entrance of solidifying cooler is connected, and the outlet of the second condensate cooler is connected with the entrance of the second return tank, and the second return tank goes out
Mouth is connected with the top of extractant recycling rectification zone IV.
The present invention also provides a kind of devices of cyclohexane dehydrogenation manufacture benzene, which is characterized in that including next door rectifying column.
The raw material of described device be the present invention above defined in hexamethylene raw material, the next door rectifying column is used for from the ring
Acetic acid is isolated in hexane raw material.
Preferably, the next door rectifying column be the present invention above defined in next door rectifying column.
The present invention also provides a kind of devices for manufacturing cyclohexyl acetate, including with cyclohexene, hexamethylene and optional benzene
The catalytic rectifying tower of mixture and acetic acidreaction the manufacture cyclohexyl acetate of composition, which is characterized in that including next door rectifying column.
About manufacture cyclohexyl acetate, it is documented in detail in CN103664586B, CN103664587B, the present invention exists
This introduces entire content of these documents in a manner of citation, as the full text of these documents is directly recorded by this specification.
Cyclohexyl acetate is manufactured using these methods, inevitably generates the hexamethylene raw material containing a certain amount of acetic acid, the hexamethylene
Raw material is generally the azeotropic mixture of acetic acid and hexamethylene or the azeotropic mixture of acetic acid and hexamethylene and optional cyclohexene and/or benzene,
Contain more acetic acid sometimes.The next door rectifying column is used to isolate the second of high-purity from these hexamethylene raw materials
Acid, so as to which the acetic acid is back to manufacture cyclohexyl acetate.
The present invention also provides the methods of a kind of coproduction cyclohexanol and ethyl alcohol, including (1) benzene selective hydrogenation to manufacture cyclohexene
The step of, (2) cyclohexene and acetic acidreaction manufacture cyclohexyl acetate the step of, and (3) ethyl cyclohexyl ester through hydrogenation manufacture cyclohexanol
And the step of ethyl alcohol, which is characterized in that including aforementioned any method or apparatus.
About step (1), (2) and (3), CN103664529B, CN103664586B, CN103664587B,
It is documented in detail in CN103880598B, CN103880599B, CN103664531B, US 9561991B2, the present invention is herein
Entire content of these documents are introduced in a manner of citation, as the full text of these documents is directly recorded by this specification.
According to the method for coproduction cyclohexanol and ethyl alcohol above-mentioned, the hexamethylene raw material after removing acetic acid is used for dehydrogenation reaction
Benzene is manufactured, and benzene obtained circulation is used for the step (1).
According to the method for coproduction cyclohexanol and ethyl alcohol above-mentioned, the acetic acid separated circulation is used for the step
(2)。
Below in conjunction with Detailed description of the invention one embodiment of the present invention.
As shown in Figure 1, the present invention provides the techniques for passing through separation of extractive distillation hexamethylene and acetic acid with next door rectifying column
Process.
The core of the process flow is next door rectifying column 5, and the next door of one piece of setting is arranged in the middle part of next door rectifying column 5,
By next door rectifying column 5 (referring to tower body) is separated into 5 regions into and out of material mouth and the next door: rectification zone I (top in next door),
Extracting rectifying area II (on the left of next door on top), extraction stripping zone III (lower section on the left of next door), extractant recycle rectification zone IV
(on the right side of next door, the closing of the upper end) and public stripping zone V (lower section in next door).
Specific operation process is as follows: hexamethylene raw material (with the mark of alkane containing ethyl cyclohexyl in figure) is from storage tank 3 by feed pump 4
From II lower end of extracting rectifying area be sent into next door rectifying column 5, extractant-alcohol (in figure with it is fresh or regeneration extractant mark) by
Storage tank 1 is sent into next door rectifying column 5 through feed pump 2 by II upper end of extracting rectifying area.In extracting rectifying area II, by multistage inverse
The extraction of gas liquid exchange and alcohol, separates hexamethylene and acetic acid, hexamethylene steam rise to behind rectification zone I with extraction
It takes solvent to separate, subsequently into liquid is cooled in the first condenser 6 for being located at tower top, finally enters the first return tank 7,
Liquid in first return tank is by pump 8, and a part returns reflux of the next door the top of the distillation column as tower, and another part is as ring
The raw material carrying device of hexane product or cyclohexane dehydrogenation benzene production equipment.
The material for leaving extraction III lower end of stripping zone is the mixture of acetic acid and alcohol, which recycles essence in extractant
It evaporates and carries out rectifying separation in the distillation system that area IV and public stripping zone V are constituted.Acetic acid is pushed up from extractant recycling rectification zone IV
Portion is produced in a manner of side line, after the second condenser 9 is cooled to liquid, into the second return tank 10, in the second return tank
Liquid by pump 11, a part is returned at the top of extractant recycling rectification zone IV as side reflux, and another part is as second
Acid product carrying device.By rectifying centrifugation, the liquid into tower reactor is alcohol, and a part of the alcohol enters reboiler 12
In, the steam after gasification as next door rectifying column after another part is by the cooling of cooler 13, is recycled back to storage tank 1 by pump 14, as
The extractant of next door rectifying column uses, and part alcohol can also be made to other processing or arranged.
The present invention is further illustrated by the following examples.
The test of each embodiment carries out on the small test device established by Fig. 1.The next door rectifying column of experimental rig
It is 50mm by 3 section diameters, is highly 1m tower section composition, the partition of one setting of installation in one Jie Tajie of centre therein, by this
Section tower is separated into two regions in left and right, and the volume ratio in two regions is 5:2 (VRegion II+region III:VRegion IV), right area (region IV) top
Portion is closed with blind plate, and partition and blind plate are dismountable.Each region is respectively arranged with φ 3mm titanium wire network θ ring filler in tower, rectification zone I
Theoretical cam curve is 20, and the theoretical cam curve in extracting rectifying area II is 10, and the theoretical cam curve of extraction stripping zone III is 10, extraction
The theoretical cam curve of solvent recovery rectification zone IV is 20, and the theoretical cam curve of public stripping zone V is 20.In addition to the rectifying column of next door,
Also adopted by Fig. 1 configured with feedstock metering system, extractant-alcohol charging metering system, tower top cooling for reflux system, side line
Vapour cooling for reflux system, tower reactor heating produce system with material out.The flow measuring and controlling of device, system temperature and pressure observing and controlling,
Liquid level controlling, cooling and the observing and controlling of heating power are controlled by DCS control system and are carried out.
Embodiment 1
The present embodiment is used to illustrate the separating effect using n-hexyl alcohol as extractant.
Hexamethylene raw material (hexamethylene mass fraction 84%, quality of acetic acid score 16%) is entered with the inlet amount of 2500g/h
The lower end in extracting rectifying area II in the rectifying column of next door；N-hexyl alcohol is with the inlet amount of 1000g/h, into the upper of extracting rectifying area II
End carries out extracting rectifying test, adjusts the operating conditions such as tower reactor heating power, reflux ratio, takes from tower top, tower bottom and lateral line discharging
Sample is analyzed with gas chromatograph.Operating condition and separating resulting when stable operation are shown in Table 1.
The operating condition and test result of 1 embodiment 1 of table
Embodiment 2
The present embodiment is used to illustrate the separating effect using cyclohexanol as extractant.
Hexamethylene raw material (hexamethylene mass fraction 84%, quality of acetic acid score 16%) is entered with the inlet amount of 2500g/h
The lower end in extracting rectifying area II in the rectifying column of next door；Cyclohexanol is with the inlet amount of 1000g/h, into the upper of extracting rectifying area II
End carries out extracting rectifying test, adjusts the operating conditions such as tower reactor heating power, reflux ratio, takes from tower top, tower bottom and lateral line discharging
Sample is analyzed with gas chromatograph.Operating condition and separating resulting when stable operation are shown in Table 2.
The operating condition and test result of 2 embodiment 2 of table
Embodiment 3
The present embodiment is used to illustrate the separating effect using n-octyl alcohol as extractant.
Hexamethylene raw material (hexamethylene mass fraction 84%, quality of acetic acid score 16%) is entered with the inlet amount of 2500g/h
The lower end in extracting rectifying area II in the rectifying column of next door；N-octyl alcohol is with the inlet amount of 1500g/h, into the upper of extracting rectifying area II
End carries out extracting rectifying test, adjusts the operating conditions such as tower reactor heating power, reflux ratio, takes from tower top, tower bottom and lateral line discharging
Sample is analyzed with gas chromatograph.Operating condition and separating resulting when stable operation are shown in Table 3.
The operating condition and test result of 3 embodiment 3 of table
Embodiment 4
The present embodiment is used to illustrate the separating effect using diethylene glycol (DEG) as extractant.
Hexamethylene raw material (hexamethylene mass fraction 84%, quality of acetic acid score 16%) is entered with the inlet amount of 2500g/h
The lower end in extracting rectifying area II in the rectifying column of next door；Diethylene glycol (DEG) is with the inlet amount of 1000g/h, into the upper of extracting rectifying area II
End carries out extracting rectifying test, adjusts the operating conditions such as tower reactor heating power, reflux ratio, takes from tower top, tower bottom and lateral line discharging
Sample is analyzed with gas chromatograph.Operating condition and separating resulting when stable operation are shown in Table 4.
The operating condition and test result of 4 embodiment 4 of table
Embodiment 5
The present embodiment is used to illustrate the separating effect using triethylene glycol as extractant.
Hexamethylene raw material (hexamethylene mass fraction 84%, quality of acetic acid score 16%) is entered with the inlet amount of 2500g/h
The lower end in extracting rectifying area II in the rectifying column of next door；Triethylene glycol is with the inlet amount of 1000g/h, into the upper of extracting rectifying area II
End carries out extracting rectifying test, adjusts the operating conditions such as tower reactor heating power, reflux ratio, takes from tower top, tower bottom and lateral line discharging
Sample is analyzed with gas chromatograph.Operating condition and separating resulting when stable operation are shown in Table 5.
The operating condition and test result of 5 embodiment 5 of table
Embodiment 6
The present embodiment is used to illustrate the separating effect using benzyl alcohol as extractant.
Hexamethylene raw material (hexamethylene mass fraction 84%, quality of acetic acid score 16%) is entered with the inlet amount of 2500g/h
The lower end in extracting rectifying area II in the rectifying column of next door；Benzyl alcohol is with the inlet amount of 1000g/h, into the upper of extracting rectifying area II
End carries out extracting rectifying test, adjusts the operating conditions such as tower reactor heating power, reflux ratio, takes from tower top, tower bottom and lateral line discharging
Sample is analyzed with gas chromatograph.Operating condition and separating resulting when stable operation are shown in Table 6.
The operating condition and test result of 6 embodiment 6 of table
Embodiment 7
The present embodiment is used to illustrate the separating effect using methyl cyclohexanol as extractant.
Hexamethylene raw material (hexamethylene mass fraction 84%, quality of acetic acid score 16%) is entered with the inlet amount of 2500g/h
The lower end in extracting rectifying area II in the rectifying column of next door；Methyl cyclohexanol is with the inlet amount of 1000g/h, into extracting rectifying area II
Upper end carries out extracting rectifying test, the operating conditions such as tower reactor heating power, reflux ratio is adjusted, from tower top, tower bottom and lateral line discharging
Sampling, is analyzed with gas chromatograph.Operating condition and separating resulting when stable operation are shown in Table 7.
The operating condition and test result of 7 embodiment 7 of table
Embodiment 8
The present embodiment is used to illustrate the separating effect using cyclohexanol as extractant.
Hexamethylene raw material (total mass fraction 84% of hexamethylene, cyclohexene and benzene, quality of acetic acid score 16%) with
The inlet amount of 2500g/h, into the lower end in extracting rectifying area II in the rectifying column of next door；Cyclohexanol with the inlet amount of 1200g/h, into
Enter the upper end in extracting rectifying area II, carry out extracting rectifying test, the operating conditions such as tower reactor heating power, reflux ratio is adjusted, from tower
Top, tower bottom and lateral line discharging sampling, are analyzed with gas chromatograph.Operating condition and separating resulting when stable operation are shown in Table
8。
The operating condition and test result of 8 embodiment 8 of table
Embodiment 9
The present embodiment is used to illustrate the separating effect with cyclohexanol and triethylene glycol (mass ratio 1:1) for extractant.
Hexamethylene raw material (total mass fraction 84% of hexamethylene, cyclohexene and benzene, quality of acetic acid score 16%) with
The inlet amount of 2500g/h, into the lower end in extracting rectifying area II in the rectifying column of next door；Cyclohexanol with the inlet amount of 1000g/h, into
Enter the upper end in extracting rectifying area II, carry out extracting rectifying test, the operating conditions such as tower reactor heating power, reflux ratio is adjusted, from tower
Top, tower bottom and lateral line discharging sampling, are analyzed with gas chromatograph.Operating condition and separating resulting when stable operation are shown in Table
9。
The operating condition and test result of 9 embodiment 9 of table
Claims (21)
1. a kind of method of the separating acetic acid from hexamethylene raw material, which is characterized in that be extraction with alcohol in next door rectifying column
Agent carries out extracting rectifying to hexamethylene raw material, and next door rectifying tower top obtains the hexamethylene of purity > 95%；It is obtained in side line pure
Spend the acetic acid of > 95%；Next door rectifying column bottom obtains the alcohol of purity > 95%；The purity of the hexamethylene is with benzene, hexamethylene
The total mass fraction meter of alkene and hexamethylene；The hexamethylene raw material is by hexamethylene, acetic acid and optional benzene and/or cyclohexene group
At；The alcohol is selected from the unitary alkanol of C6~C12, the unitary cyclic alkanol of C6~C12, the unitary aromatic alcohol of C6~C12, two
The mixture of one of glycol, triethylene glycol and tetraethylene glycol alcohol or several alcohol.
2. according to the method for claim 1, which is characterized in that the alcohol is selected from n-hexyl alcohol, isohexyl alcohol, n-heptanol, different
Enanthol, n-octyl alcohol, isooctanol, n-nonyl alcohol, isononyl alcohol, Decanol, isodecanol, lauryl alcohol, cyclohexanol, methylcyclopentanol, methyl
One of cyclohexanol, benzyl alcohol, diethylene glycol (DEG), triethylene glycol and tetraethylene glycol.
3. according to the method for claim 1, which is characterized in that in the hexamethylene raw material, the mass fraction of acetic acid is
1%~99% (preferably 10%~35%, more preferably 10%~20%).
4. according to the method for claim 1, which is characterized in that the hexamethylene raw material is the azeotropic of hexamethylene and acetic acid
Object, or be hexamethylene, acetic acid and cyclohexene and/or the azeotropic mixture of benzene.
5. according to the method for claim 1, which is characterized in that in the hexamethylene raw material, the mass fraction of benzene is
0.2%~1%, the mass fraction of cyclohexene is 0.5%~2%.
6. according to the method for claim 1, which is characterized in that the middle part of the next door rectifying column be equipped with one piece it is vertical
Next door, the next door rectifying column is divided into five regions: the top in next door is rectification zone I；The side in next door, top are extraction essence
Area II is evaporated, lower section is extraction stripping zone III；The other side in next door is that extractant recycles rectification zone IV；The lower section in next door is public
Stripping zone V.
7. according to the method for claim 6, which is characterized in that the upper end closed of extractant recycling rectification zone IV.
8. according to the method for claim 6, which is characterized in that the theoretical cam curve of rectification zone I is 10~30, extracting rectifying
The theoretical cam curve in area II is 10~30 (preferably 15~30), and the theoretical cam curve of extraction stripping zone III is 5~20, is extracted molten
The theoretical cam curve that rectification zone IV is recycled in agent is 10~30, and the theoretical cam curve of public stripping zone V is 10~30.
9. according to the method for claim 6, which is characterized in that the alcohol by the extracting rectifying area II top (preferably
For upper end) enter the next door rectifying column；The hexamethylene raw material is by the lower part in the extracting rectifying area II (under preferably
End) enter the next door rectifying column.
10. according to the method for claim 1, which is characterized in that the alcohol reuse that next door rectifying column bottom obtains to be somebody's turn to do
The extractant of tower.
11. according to the method for claim 1, which is characterized in that in the operation of next door rectifying column, solvent ratio (alcohol into
The mass ratio of the inlet amount of doses and hexamethylene raw material) be 0.2:1~20:1 (preferably 0.2:1~4.5:1, more preferably
0.2:1~1:1, further preferably 0.4:1~0.6:1).
12. according to the method for claim 1, which is characterized in that the operating pressure of next door rectifying column is -1MPa~10MPa
(preferably 0.1MPa~1MPa, more preferably normal pressure).
13. according to the method for claim 1, which is characterized in that the reflux ratio of next door the top of the distillation column is 0.3:1~30:1
(preferably 0.5:1~1.5:1).
14. according to the method for claim 1, which is characterized in that the reflux ratio of next door rectifying column side line is 0.5:1~10:1
(preferably 1:1~4:1).
15. according to the method for claim 1, which is characterized in that from the hexamethylene that next door the top of the distillation column obtains, with matter
Meter, acetic acid content are less than 50ppm (preferably smaller than 20ppm is further preferably no larger than 5ppm more preferably less than 10ppm).
16. a kind of device of the separating acetic acid from hexamethylene raw material, which is characterized in that including next door rectifying column, hexamethylene raw material
Storage tank and alcohol storage tank；
It is equipped with one piece of vertical next door at the middle part of the next door rectifying column, the next door rectifying column is divided into five regions: every
The top of wall is rectification zone I；The side in next door, top are extracting rectifying area II, and lower section is extraction stripping zone III；Next door it is another
Side is that extractant recycles rectification zone IV；The lower section in next door is public stripping zone V；
Material inlet is arranged at the top (preferably upper end) and lower part (preferably lower end) in the extracting rectifying area II；The extraction
The material inlet on II top of rectification zone (preferably upper end) is connected with the alcohol storage tank；II lower part of extracting rectifying area is (preferably
For lower end) material inlet be connected with the hexamethylene raw material storage tank；
The tower bottom of the next door rectifying column is equipped with the outlet of discharge alcohol, which is connected with the alcohol storage tank.
17. a kind of device of cyclohexane dehydrogenation manufacture benzene, which is characterized in that including next door rectifying column.
18. a kind of device for manufacturing cyclohexyl acetate, including the mixture formed with cyclohexene, hexamethylene and optional benzene and second
The catalytic rectifying tower of acid reaction manufacture cyclohexyl acetate, which is characterized in that including next door rectifying column.
19. a kind of method of coproduction cyclohexanol and ethyl alcohol includes the steps that (1) benzene selective hydrogenation manufactures cyclohexene, (2) cyclohexene
The step of manufacturing cyclohexyl acetate with acetic acidreaction, and the step of (3) ethyl cyclohexyl ester through hydrogenation manufacture cyclohexanol and ethyl alcohol, it is special
Sign is, including any method or apparatus in aforementioned 1~18.
20. according to the method for claim 19, which is characterized in that it is anti-that the hexamethylene raw material after removing acetic acid is used for dehydrogenation
Benzene should be manufactured, and benzene circulation is used for the step (1).
21. according to method described in claim 19 or 20, which is characterized in that recycle the acetic acid separated described in being used for
Step (2).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111643915A (en) * | 2019-09-10 | 2020-09-11 | 上海浦景化工技术股份有限公司 | Rectification device and rectification method for oxo-synthesis of acetic acid |
| CN112354205A (en) * | 2020-11-02 | 2021-02-12 | 雅邦绿色过程与新材料研究院南京有限公司 | Multifunctional rectification experimental system for comprehensive utilization of waste organic solvent resources |
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| CN103910603A (en) * | 2013-01-05 | 2014-07-09 | 中国石油化工股份有限公司 | Method for co-producing cyclohexanol and ethanol |
| CN104557465A (en) * | 2013-10-25 | 2015-04-29 | 中国石油化工股份有限公司 | Method for coproducing cyclohexanol and alkanol |
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| CN1270578A (en) * | 1997-09-19 | 2000-10-18 | Rpc公司 | Methods and devices for removing acetic acid from cyclohexane in the production of adipic acid |
| CN103664529A (en) * | 2012-09-18 | 2014-03-26 | 中国石油化工股份有限公司 | Method for coproducing cyclohexanol and ethanol |
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| CN111643915A (en) * | 2019-09-10 | 2020-09-11 | 上海浦景化工技术股份有限公司 | Rectification device and rectification method for oxo-synthesis of acetic acid |
| WO2021047393A1 (en) * | 2019-09-10 | 2021-03-18 | 上海浦景化工技术股份有限公司 | Rectification device and rectification method for oxo synthesis of acetic acid |
| CN111643915B (en) * | 2019-09-10 | 2021-09-10 | 上海浦景化工技术股份有限公司 | Rectification device and rectification method for oxo-synthesis of acetic acid |
| CN112354205A (en) * | 2020-11-02 | 2021-02-12 | 雅邦绿色过程与新材料研究院南京有限公司 | Multifunctional rectification experimental system for comprehensive utilization of waste organic solvent resources |
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