CN109534943A - 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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- CN109534943A CN109534943A CN201710858348.8A CN201710858348A CN109534943A CN 109534943 A CN109534943 A CN 109534943A CN 201710858348 A CN201710858348 A CN 201710858348A CN 109534943 A CN109534943 A CN 109534943A
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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
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- 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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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
- C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
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- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/367—Formation of an aromatic six-membered ring from an existing six-membered ring, e.g. dehydrogenation of ethylcyclohexane to ethylbenzene
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- C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
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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 extractive distillation 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 one kind passes through
The method and apparatus of 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.
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 extractive distillation column
Agent is taken, extracting rectifying is carried out to hexamethylene raw material, hexamethylene of the purity greater than 95% is obtained (preferably greater than by extracting rectifying tower top
97%, more preferably greater than 99%, further preferably greater than 99.5%);The purity is with the gross mass of benzene, cyclohexene and hexamethylene
Score meter;The hexamethylene raw material is made of hexamethylene, acetic acid and optional benzene and/or cyclohexene;The alcohol is selected from C6
The unitary alkanol of~C12, the unitary cyclic alkanol of C6~C12, the unitary aromatic alcohol of C6~C12, C2~C8 dihydric alcohol, sweet
The mixture of one of oil, diethylene glycol (DEG), triethylene glycol and tetraethylene glycol alcohol or several alcohol (is preferably selected from the unitary alkane of C6~C12
Alcohol, the unitary cyclic alkanol of C6~C12 and the unitary aromatic alcohol of C6~C12, the dihydric alcohol of C2~C8, glycerol, diethylene glycol (DEG), triethylene glycol
With one of tetraethylene glycol 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, ethylene glycol, propylene glycol, butanediol, hexylene glycol, glycerol, 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 extractive distillation column includes the rectifying section on top, middle part
The stripping section of extraction section and lower part, the hexamethylene raw material are entered in extractive distillation column by the lower part of the extraction section, the alcohol
Entered in extractive distillation column by the top of the extraction section (preferred scheme are as follows: the theoretical cam curve of the rectifying section is 10~
30, the theoretical cam curve of the extraction section is 15~40, and the theoretical cam curve of the stripping section is 10~30).
7. according to aforementioned any method, which is characterized in that obtain the alcohol containing acetic acid by extracting rectifying tower bottom.
8. according to method described in 7, which is characterized in that the alcohol containing acetic acid obtained by extracting rectifying tower bottom, into extraction
Agent recovery tower carries out conventional distillation separation, obtains the acetic acid (preferably > 98.5%) of purity > 95% by extractant recycling tower top,
The alcohol (preferably > 99.5%) of purity > 95% is obtained by extractant recovery tower bottom.
9. according to method described in 8, which is characterized in that the extractant recovery tower include rectifying section and stripping section (preferably
Scheme are as follows: the theoretical cam curve of the rectifying section is 10~20, and the theoretical cam curve of the stripping section is 10~30)
10. according to method described in 8 or 9, which is characterized in that institute is made in the alcohol reuse that extractant recovery tower bottom obtains
State the extractant of extractive distillation column.
11. according to aforementioned any method, which is characterized in that in extracting rectifying operation, the solvent ratio (inlet amount and ring of alcohol
The mass ratio of the inlet amount of hexane raw material) be 0.2:1~20:1 (preferably 0.2:1~4.5:1, more preferably 0.2:1~1:1,
Further preferably 0.2:1~0.5:1).
12. according to aforementioned any method, which is characterized in that the operating condition of extractive distillation column are as follows: in terms of gauge pressure, operation
Pressure is -1MPa~10MPa (preferably 0.1MPa~1MPa, more preferably normal pressure);Reflux ratio be 0.3:1~30:1 (preferably
For 0.5:1~1.5:1).
13. according to aforementioned any method, which is characterized in that the operating condition of extractant recovery tower are as follows: in terms of gauge pressure, behaviour
Making pressure is -0.05MPa~1MPa (preferably -0.01MPa~0.5MPa, more preferably normal pressure);Reflux ratio be 0.5:1~
10:1 (preferably 1:1~4:1).
14. according to aforementioned any method, which is characterized in that from the hexamethylene that extracting rectifying column overhead 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).
15. a kind of device of the separating acetic acid from hexamethylene raw material, which is characterized in that including extractive distillation column and extractant
Recovery tower;The extractive distillation column includes the stripping section of the rectifying section on top, the extraction section at middle part and lower part, and the extractant returns
Receiving tower includes the rectifying section on top and the stripping section of lower part;The upper and lower side of the extraction section of the extractive distillation column have raw material into
Mouthful;The tower top of the extractive distillation column connects the entrance of the first overhead condenser, and the outlet of the first overhead condenser connects hexamethylene
The tower top of alkane storage tank and extractive distillation column, the tower reactor of the extractive distillation column connect the feed(raw material)inlet of the extractant recovery tower
The tower top of (feed(raw material)inlet is preferably the position between stripping section and rectifying section), the extractant recovery tower connects the second tower top
The entrance of condenser, the tower top of outlet connection the acetic acid storage tank and extractant recovery tower of the second overhead condenser, the extractant
The tower reactor of recovery tower is exported equipped with extractant.
16. a kind of device of cyclohexane dehydrogenation manufacture benzene, which is characterized in that (be used for from hexamethylene including extractive distillation column
Acetic acid is isolated in raw material).
17. 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 extractive distillation column (for former from hexamethylene
Acetic acid is isolated in material).
18. 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 1~17.
19. according to method described in 18, 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).
20. according to method described in 18 or 19, 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 the hexamethylene of high-purity, especially acetic acid can also be directly obtained in lower reflux ratio
Content can be controlled in 50ppm hereinafter, such hexamethylene is used directly for dehydrogenation manufacture benzene;Third, invention can also pass through
Conventional distillation obtains the acetic acid of high-purity, so as to which the acetic acid to be directly back to the esterification with cyclohexene.
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 in extractive distillation column
In, using alcohol as extractant, extracting rectifying is carried out to hexamethylene raw material, the hexamethylene that purity is greater than 95% is obtained by extracting rectifying tower top
Alkane obtains the alcohol containing acetic acid by extracting rectifying tower bottom;The purity is in terms of the total mass fraction of benzene, cyclohexene and hexamethylene;Institute
The hexamethylene raw material stated is made of hexamethylene, acetic acid and optional benzene and/or cyclohexene;The alcohol is selected from the one of C6~C12
First alkanol, the unitary cyclic alkanol of C6~C12, the unitary aromatic alcohol of C6~C12, ethylene glycol, propylene glycol, glycerol, diethylene glycol (DEG), three
The mixture of one of glycol and tetraethylene glycol alcohol or several alcohol.
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
One kind of first cyclic alkanol, the unitary aromatic alcohol of C6~C12, the dihydric alcohol of C2~C8, glycerol, diethylene glycol (DEG), triethylene glycol and tetraethylene glycol
The mixture of alcohol or several alcohol;It is preferably selected from the unitary alkanol of C6~C12, the unitary cyclic alkanol of C6~C12, C6~C12
One of unitary aromatic alcohol, the dihydric alcohol of C2~C8, glycerol, diethylene glycol (DEG), triethylene glycol and tetraethylene glycol alcohol;Be more preferably selected from C6~
It is the unitary alkanol of C8, the unitary cyclic alkanol of C6~C8, the unitary aromatic alcohol of C6~C8, the dihydric alcohol of C2~C6, glycerol, two sweet
One of alcohol, triethylene glycol and tetraethylene glycol alcohol;Further preferably selected from n-hexyl alcohol, isohexyl alcohol, n-heptanol, iso-heptanol, n-octyl alcohol,
Isooctanol, n-nonyl alcohol, isononyl alcohol, Decanol, isodecanol, lauryl alcohol, cyclohexanol, methylcyclopentanol, methyl cyclohexanol, benzene first
One of alcohol, ethylene glycol, propylene glycol, butanediol, hexylene glycol, glycerol, diethylene glycol (DEG), triethylene glycol and tetraethylene glycol.
Extraction rectifying method according to the present invention obtains the hexamethylene that purity is greater than 95% by extracting rectifying tower top, preferably
Purity is greater than 97%, and more preferable purity is greater than 99%, and further preferred purity is greater than 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 present invention is not particularly limited the form of extractive distillation column, can select various conventional extractive distillation columns.
Each section in extractive distillation column, 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 extractive distillation 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 that the extractive distillation column includes the extraction of the rectifying section on top, middle part
Take the stripping section (tower body is made of the stripping section of the rectifying section on top, the extraction section at middle part and lower part) of section and lower part, the ring
Hexane raw material is entered in extractive distillation column by the lower part (preferably lower end) of the extraction section, and the alcohol is upper by the extraction section
Portion (preferably upper end) enters in extractive distillation column.
Separation for hexamethylene and acetic acid, each section of extractive distillation 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 extraction by test
The suitable number of theoretical plate of rectifying column is 30~100, wherein the theoretical cam curve of the rectifying section is 10~30, the extraction section
Theoretical cam curve is 10~40 (preferably 15~40), and the theoretical cam curve of the stripping section is 10~30.
The dosage of extractant and the reflux ratio of extractive distillation column are two important parameters for influencing separation of extractive distillation effect.
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, generally it can reach ideal point in 0.2:1~1:1
From effect.
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, reflux ratio is generally 0.3:1~30:1, preferably 0.5:1~1.5:1.In satisfaction
Under the conditions of stating, by separation of extractive distillation acetic acid and hexamethylene, the acetic acid content in tower top hexamethylene can be lower than 50ppm (μ g/
g)。
The operation temperature and pressure of extractive distillation column are corresponding.Extraction rectifying method according to the present invention, with gauge pressure
Meter, the operating pressure of extractive distillation column are -0.05MPa~1MPa, preferably -0.01MPa~0.5MPa, further preferably often
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 extractive distillation 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 obtains the alcohol containing acetic acid by extracting rectifying tower bottom, which enters extractant
Recovery tower carries out conventional distillation separation, obtains the acetic acid (preferably > 98.5%) of purity > 95% by extractant recycling tower top, by
Extractant recovery tower bottom obtains the alcohol (preferably > 99.5%) of purity > 95%.In the embodiment, the alcohol is selected from
The unitary alkanol of C6~C12, the unitary cyclic alkanol of C6~C12, C6~C12 unitary aromatic alcohol, diethylene glycol (DEG), triethylene glycol and four
A kind of alcohol of glycol or the mixture of several alcohol, be preferably selected from the unitary alkanol of C6~C12, the unitary cyclic alkanol of C6~C12,
One of unitary aromatic alcohol, diethylene glycol (DEG), triethylene glycol and the tetraethylene glycol of C6~C12 alcohol;It is more preferably selected from the unitary chain of C6~C8
Alkanol, the unitary cyclic alkanol of C6~C8, C6~C8 one of unitary aromatic alcohol, diethylene glycol (DEG), triethylene glycol and tetraethylene glycol alcohol;Into
One step is preferably selected from n-hexyl alcohol, isohexyl alcohol, n-heptanol, iso-heptanol, n-octyl alcohol, isooctanol, n-nonyl alcohol, isononyl alcohol, Decanol, different
In decyl alcohol, lauryl alcohol, cyclohexanol, methylcyclopentanol, methyl cyclohexanol, benzyl alcohol, glycerol, diethylene glycol (DEG), triethylene glycol and tetraethylene glycol
One kind.
Extraction rectifying method according to the present invention, the extractant recovery tower include the rectifying section on top and the stripping of lower part
Section (tower body is made of the rectifying section on top and the stripping section of lower part), total theoretical cam curve are 20~50.Extractive distillation column
The alcohol containing acetic acid that bottom obtains is by entering the extractant recovery tower between the rectifying section and stripping section of the extractant recovery tower
Interior progress conventional distillation separation;Wherein, the theoretical cam curve of the rectifying section is 10~20, the theoretical cam curve of the stripping section
It is 10~30.The operating reflux ratio of the extractant recovery tower is generally 0.5:1~10:1, preferably 1:1~4:1.Meeting
Under above-mentioned condition, the acetic acid purity obtained by extractant recycling column overhead is higher than 99.5%, and the extractant-alcohol recycled
Purity also greater than 99.5%, meet the requirement of recycling.
The operation temperature and pressure of extractant recovery tower are corresponding.Extraction rectifying method according to the present invention, with table
Pressure meter, the operating pressure of extractant recovery tower are -0.05MPa~1MPa, 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 extractant recovery tower.For example, raw material to be separated usually exists in conventional distillation
It is fed under bubble point, unclassified stores is usually to feed under the tower temperature of its feed entrance point.
The alcohol reuse that extractant recovery tower bottom obtains is made the extraction 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 real in two towers of extractive distillation column and extractant recovery tower
Apply, so that it may acetic acid is isolated from hexamethylene raw material, while obtain the hexamethylene of high-purity, high-purity acetic acid and can follow
Ring is used as the alcohol of the high-purity of extractant.
The present invention also provides a kind of devices of separating acetic acid from hexamethylene raw material, which is characterized in that including extraction essence
Evaporate tower and extractant recovery tower;The extractive distillation column includes the stripping section of the rectifying section on top, the extraction section at middle part and lower part,
The extractant recovery tower includes the rectifying section on top and the stripping section of lower part;The upper and lower side of the extraction section of the extractive distillation column
There is material inlet;The tower top of the extractive distillation column connects the entrance of the first overhead condenser, and the first overhead condenser goes out
The tower top of mouth connection hexamethylene storage tank and extractive distillation column, the tower reactor of the extractive distillation column connect the extractant recovery tower
Feed(raw material)inlet (feed(raw material)inlet is preferably the position between stripping section and rectifying section), the tower top connection of the extractant recovery tower
The entrance of second overhead condenser, the tower top of outlet connection the acetic acid storage tank and extractant recovery tower of the second overhead condenser, institute
The tower reactor for stating extractant recovery tower is exported equipped with extractant.
Extracting rectifying device according to the present invention, the tower reactor extractant outlet connection extractant storage of the extractant recovery tower
Tank.
The present invention also provides a kind of devices of cyclohexane dehydrogenation manufacture benzene, which is characterized in that including extractive distillation column.
The raw material of described device be the present invention above defined in hexamethylene raw material, the extractive distillation column for use before
The method stated isolates acetic acid from the hexamethylene raw material.
Preferably, the extractive distillation column be the present invention above defined in extractive distillation 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 extractive distillation 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 extractive distillation column is used to separate from these hexamethylene raw materials using method above-mentioned
The acetic acid of high-purity out, 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, undertaking the equipment of separation task in the present invention only by extractive distillation column 5 and solvent recovery tower 11 two
Tower composition.Wherein, the tower body of extractive distillation column 5 is made of rectifying section, extraction section and stripping section, the tower body of solvent recovery tower 11 by
Rectifying section and stripping section composition, two rectifying columns are each equipped with tower reactor reboiler, tower bottom discharging pump, overhead condensation cooler, return
Flow tank and reflux pump etc..
Hexamethylene raw material (with hexamethylene+acetic acid mark in figure) to be separated is from storage tank 3 by feed pump 4 by under extraction section
Extractive distillation column 5 is sent at end, and extractant-alcohol is sent into extractive distillation column 5 through feed pump 2 by extraction section upper end by storage tank 1.?
It in extractive distillation column, is exchanged by multi-stage countercurrent gas-liquid and extraction, makes hexamethylene and separated from acetic acid, hexamethylene steam is by tower
Body enters tower top, subsequently into overhead condensation cooler, is cooled to liquid herein, and into return tank 7, the liquid in return tank is logical
Pump 8 is crossed, a part returns reflux of the extraction tower as tower, another part carrying device.
Acetic acid and extractant-alcohol mixture enter extractive distillation column tower reactor by extractive distillation column tower body, use extracting rectifying
The feed pump 10 of tower tower bottom is sent into tower 11, extractant from the position between 11 rectifying section of extractant recovery tower and stripping section
Recovery tower 11 is common rectifying tower, the acetic acid of high-purity is obtained by the tower top of extractant recovery tower, by extractant recovery tower
Tower bottom obtain the alcohol of high-purity, which can send to storage tank 1, be recycled as extractant of the invention, can also make it
He handles or arranges.
The present invention is further illustrated by the following examples.
Embodiment 1
The present embodiment is used to illustrate under bench scale, using cyclohexanol as the separating effect of extractant.
The diameter of extractive distillation column is φ 50mm, is highly 3m, and the height of rectifying section, extraction section and stripping section is respectively 1m,
Built-in φ 3mm titanium wire network θ ring filler, the theoretical cam curve of rectifying section are 20, and the theoretical cam curve of extraction section is 20, stripping section
Theoretical cam curve is 20.Hexamethylene raw material (mass fraction of hexamethylene is 84%, the mass fraction of acetic acid be 16%) with
The inlet amount of 2000g/h enters the lower end of extractive distillation column extraction section, and the feeding temperature of hexamethylene raw material is 74 DEG C, cyclohexanol with
The inlet amount of 500g/h enters the upper end of extractive distillation column extraction section in tower, carries out extracting rectifying test, controls tower top reflux ratio
It is 1, atmospheric operation after waiting devices stable operation, from tower top and tower bottom discharging sampling, is analyzed with gas chromatograph.As a result
Display: tower top discharging group becomes hexamethylene mass fraction 99.99%, and acetic acid and hexamethylene alcohol content are below 10 μ g/g;Tower bottom goes out
Material group becomes " hexamethylene mass fraction 0.01%, quality of acetic acid score 39.02%, cyclohexanol mass fraction 60.97% ".
Comparative example 1
This comparative example is used to illustrate to be not added under bench scale the separating effect of extractant.
The device and method that this comparative example uses embodiment 1, the difference is that only: being added without extractant-cyclohexanol.
Hexamethylene raw material (mass fraction of hexamethylene is 84%, the mass fraction of acetic acid be 16%) with 2000g/h into
Doses enters the lower end of extractive distillation column extraction section, and the feeding temperature of hexamethylene raw material is 74 DEG C, is added without cyclohexanol, is extracted
Rectification test is taken, control tower top reflux ratio is 1, atmospheric operation, after waiting devices stable operation, sampled from tower top and tower bottom discharging,
It is analyzed with gas chromatograph.As the result is shown: tower top and the composition of tower bottom discharging are identical with feed composition, are " ring
The mass fraction 84% of hexane, the mass fraction 16% " of acetic acid.Even if reflux ratio is increased to 5, identical result is also obtained.
This comparative example explanation is such as added without extractant for the azeotropic mixture that hexamethylene and acetic acid are formed, then can not use the side of conventional distillation
Method separates the two.
Embodiment 2
The present embodiment is used to illustrate under bench scale, using ethylene glycol as the separating effect of extractant.
The device and method that the present embodiment uses embodiment 1, the difference is that only: replacing ring with the ethylene glycol of homogenous quantities
Hexanol.
Hexamethylene raw material (mass fraction of hexamethylene is 84%, the mass fraction of acetic acid be 16%) with 2000g/h into
Doses enters the lower end of extractive distillation column extraction section, the feeding temperature of hexamethylene raw material is 74 DEG C, ethylene glycol with 500g/h into
Doses enters the upper end of extractive distillation column extraction section in tower, carries out extracting rectifying test, and control tower top reflux ratio is 1, normal pressure behaviour
Make, after waiting devices stable operation, from tower top and tower bottom discharging sampling, is analyzed with gas chromatograph.As the result is shown: tower top goes out
Material group becomes hexamethylene mass fraction 99.99%, and acetic acid content is 40 μ g/g, and ethylene glycol content is lower than 10 μ g/g;Tower bottom discharging
Group becomes (quality of acetic acid score 39.02%, quality of glycol score 60.98%).
Embodiment 3
The present embodiment is used to illustrate under bench scale, using diethylene glycol (DEG) as the separating effect of extractant.
The device and method that the present embodiment uses embodiment 1, the difference is that only: replacing ring with the diethylene glycol (DEG) of homogenous quantities
Hexanol.
Hexamethylene raw material (mass fraction of hexamethylene is 84%, the mass fraction of acetic acid be 16%) with 2000g/h into
Doses enters the lower end of extractive distillation column extraction section, the feeding temperature of hexamethylene raw material is 74 DEG C, diethylene glycol (DEG) with 500g/h into
Doses enters the upper end of extractive distillation column extraction section in tower, carries out extracting rectifying test, and control tower top reflux ratio is 1, normal pressure behaviour
Make, after waiting devices stable operation, from tower top and tower bottom discharging sampling, is analyzed with gas chromatograph.As the result is shown: tower top goes out
Material group becomes hexamethylene mass fraction 99.99%, and acetic acid content is 50 μ g/g, and diethylene glycol content is not detected;Tower bottom discharging composition
For (quality of acetic acid score 39.02%, quality of glycol score 60.98%).
Embodiment 4
The present embodiment is used to illustrate under bench scale, take isooctanol (2-Ethylhexyl Alcohol) as the separating effect of extractant.
The device and method that the present embodiment uses embodiment 1, the difference is that only: replacing ring with the isooctanol of homogenous quantities
Hexanol.
Hexamethylene raw material (mass fraction of hexamethylene is 84%, the mass fraction of acetic acid be 16%) with 2000g/h into
Doses enters the lower end of extractive distillation column extraction section, the feeding temperature of hexamethylene raw material is 74 DEG C, isooctanol with 500g/h into
Doses enters the upper end of extractive distillation column extraction section in tower, carries out extracting rectifying test, and control tower top reflux ratio is 1, normal pressure behaviour
Make, after waiting devices stable operation, from tower top and tower bottom discharging sampling, is analyzed with gas chromatograph.As the result is shown: tower top goes out
Material group becomes hexamethylene mass fraction 99.99%, and acetic acid content is 45 μ g/g, and isooctanol content is not detected;Tower bottom discharging composition
For (quality of acetic acid score 39.02%, quality of glycol score 60.98%).
Embodiment 5
The present embodiment is used to illustrate under bench scale, using cyclohexanol as the separating effect of extractant.
The device and method that the present embodiment uses embodiment 1, the difference is that only: the reflux ratio of extractive distillation column is
0.6。
After equal devices stable operation, analyzed from tower top and tower bottom discharging sampling with gas chromatograph.As the result is shown: tower
Ejecting material group becomes hexamethylene mass fraction 99.99%, and acetic acid content is 20 μ g/g, 15 μ g/g of hexamethylene alcohol content;Tower bottom discharging
Group becomes (hexamethylene mass fraction 0.01%, quality of acetic acid score 39.02%, quality of glycol score 60.97%).
Embodiment 6
The present embodiment is used to illustrate under bench scale, using cyclohexanol as the separating effect of extractant.
The device and method that the present embodiment uses embodiment 1, the difference is that only: the reflux ratio of extractive distillation column is 2.
After equal devices stable operation, analyzed from tower top and tower bottom discharging sampling with gas chromatograph.As the result is shown: tower
Ejecting material group becomes hexamethylene mass fraction 99.99%, and acetic acid content is 100 μ g/g, and hexamethylene alcohol content is not detected;Tower bottom discharging
Group becomes (hexamethylene mass fraction 0.01%, quality of acetic acid score 39.01%, quality of glycol score 60.98%).
Embodiment 7
The present embodiment is used to illustrate under pilot-scale, using cyclohexanol as the separating effect of extractant.
Pilot-plant is cyclohexene esterification plus the pilot plant test device of hydrogen cyclohexanol new process of the present inventor's exploitation
A part.The separation of its hexamethylene and acetic acid is to establish according to the method for the present invention, including extractive distillation column and extractant recycle
Tower, concrete specification are shown in Table 1.
1 acetic acid of table separates the main equipment specification of pilot-plant with hexamethylene
Cyclohexene esterification plus hydrogen cyclohexanol new process, use the mixture of cyclohexene and hexamethylene for raw material, with acetic acid
Be fixed bed and catalytic distillation esterification, cyclohexene is consumed totally by reaction, hexamethylene (containing a small amount of cyclohexene with
Benzene) from catalytic distillation be esterified overhead extraction.Due to hexamethylene and acetic acid azeotropic, a certain amount of acetic acid of content in hexamethylene.It will
This material (the hexamethylene raw material) is sent into extracting rectifying device above-mentioned and is separated.The operating condition of extractive distillation column
Are as follows: normal pressure, reflux ratio 0.6.The operating condition of solvent recovery tower are as follows: normal pressure, reflux ratio 1.2.The logistics of charging and discharging
Data and the operating condition of tower are shown in Table 2.
Table 2
Claims (20)
1. a kind of method of the separating acetic acid from hexamethylene raw material, which is characterized in that be extraction with alcohol in extractive distillation column
Agent carries out extracting rectifying to hexamethylene raw material, obtains hexamethylene of the purity greater than 95% (preferably greater than by extracting rectifying tower top
99.5%);The purity is in terms of the total mass fraction of benzene, cyclohexene and hexamethylene;The hexamethylene raw material is by hexamethylene, second
Sour and optional benzene and/or cyclohexene composition;The alcohol is selected from the unitary cycloalkanes of the unitary alkanol of C6~C12, C6~C12
One of alcohol, the unitary aromatic alcohol of C6~C12, the dihydric alcohol of C2~C8, glycerol, diethylene glycol (DEG), triethylene glycol and tetraethylene glycol alcohol or
The mixture of 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, ethylene glycol, propylene glycol, butanediol, hexylene glycol, glycerol, 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 extractive distillation column includes the rectifying section on top, middle part
Extraction section and lower part stripping section, the hexamethylene raw material is entered in extractive distillation column by the lower part of the extraction section, described
Alcohol enters in extractive distillation column (further preferred scheme are as follows: the theoretical tray of the rectifying section by the top of the extraction section
Number is 10~30, and the theoretical cam curve of the extraction section is 15~40, and the theoretical cam curve of the stripping section is 10~30).
7. according to the method for claim 1, which is characterized in that obtain the alcohol containing acetic acid by extracting rectifying tower bottom.
8. according to the method for claim 7, which is characterized in that the alcohol containing acetic acid obtained by extracting rectifying tower bottom enters
Extractant recovery tower carries out conventional distillation separation, obtains acetic acid (the preferably > of purity > 95% by extractant recycling tower top
98.5%) alcohol (preferably > 99.5%) of purity > 95%, is obtained by extractant recovery tower bottom.
9. according to the method for claim 8, which is characterized in that the extractant recovery tower includes rectifying section and stripping section
(further preferred scheme are as follows: the theoretical cam curve of the rectifying section is 10~20, and the theoretical cam curve of the stripping section is 10
~30).
10. according to method described in claim 8 or 9, which is characterized in that the alcohol reuse for obtaining extractant recovery tower bottom
Make the extractant of the extractive distillation column.
11. according to the method for claim 1, which is characterized in that in extracting rectifying operation, solvent ratio is 0.2:1~20:1
(preferably 0.2:1~1:1, more preferably 0.2:1~0.5:1).
12. according to the method for claim 1, which is characterized in that the operating pressure of extractive distillation column be -0.05MPa~
1MPa (preferably -0.01MPa~0.5MPa, more preferably normal pressure);Reflux ratio be 0.3:1~30:1 (preferably 0.5:1~
1.5:1)。
13. according to the method for claim 1, which is characterized in that the operating pressure of extractant recovery tower is normal pressure;Reflux ratio
For 0.5:1~10:1 (preferably 1:1~4:1).
14. according to the method for claim 1, which is characterized in that from the hexamethylene that extracting rectifying column overhead obtains, with matter
Meter, acetic acid content are less than 50ppm (preferably smaller than 20ppm, more preferably less than 10ppm).
15. a kind of device of the separating acetic acid from hexamethylene raw material, which is characterized in that recycled including extractive distillation column and extractant
Tower;The extractive distillation column includes the stripping section of the rectifying section on top, the extraction section at middle part and lower part, the extractant recovery tower
The stripping section of rectifying section and lower part including top;The upper and lower side of the extraction section of the extractive distillation column has material inlet;Institute
The tower top for stating extractive distillation column connects the entrance of the first overhead condenser, and the outlet of the first overhead condenser connects hexamethylene storage tank
With the tower top of extractive distillation column, the tower reactor of the extractive distillation column connects feed(raw material)inlet (raw material of the extractant recovery tower
Entrance is preferably the position between stripping section and rectifying section), the tower top of the extractant recovery tower connects the second overhead condenser
Entrance, the second overhead condenser outlet connection acetic acid storage tank and extractant recovery tower tower top, the extractant recovery tower
Tower reactor equipped with extractant export.
16. a kind of device of cyclohexane dehydrogenation manufacture benzene, which is characterized in that including extractive distillation column.
17. 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 extractive distillation column.
18. 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 method or apparatus any in claim 1~17.
19. according to the method for claim 18, 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).
20. according to method described in claim 18 or 19, which is characterized in that recycle the acetic acid separated described in being used for
Step (2).
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Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114890861A (en) * | 2022-06-28 | 2022-08-12 | 厦门大学 | Extractive distillation method for separating mixture of n-propyl acetate and methylcyclohexane by using polyhydric alcohol |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN102442882A (en) * | 2010-10-12 | 2012-05-09 | 中科合成油技术有限公司 | Separating and recovering method for organic oxygen-containing compounds in Fischer-Tropsch synthesis water phase |
CN103880598A (en) * | 2012-12-20 | 2014-06-25 | 中国石油化工股份有限公司 | Co-producing method and device for cyclohexanol and ethanol |
CN104193583A (en) * | 2014-08-05 | 2014-12-10 | 河北美邦工程科技有限公司 | Method for co-production of cyclohexanol and absolute ethyl alcohol |
US20150099905A1 (en) * | 2011-04-26 | 2015-04-09 | Celanese International Corporation | Process to Recover Alcohol with Reduced Water From Overhead of Acid Column |
-
2017
- 2017-09-21 CN CN201710858348.8A patent/CN109534943A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
CN102442882A (en) * | 2010-10-12 | 2012-05-09 | 中科合成油技术有限公司 | Separating and recovering method for organic oxygen-containing compounds in Fischer-Tropsch synthesis water phase |
US20150099905A1 (en) * | 2011-04-26 | 2015-04-09 | Celanese International Corporation | Process to Recover Alcohol with Reduced Water From Overhead of Acid Column |
CN103880598A (en) * | 2012-12-20 | 2014-06-25 | 中国石油化工股份有限公司 | Co-producing method and device for cyclohexanol and ethanol |
CN104193583A (en) * | 2014-08-05 | 2014-12-10 | 河北美邦工程科技有限公司 | Method for co-production of cyclohexanol and absolute ethyl alcohol |
Non-Patent Citations (1)
Title |
---|
王巧焕等: "萃取精馏过程溶剂筛选的分子设计方法研究", 《安徽化工》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN114890861A (en) * | 2022-06-28 | 2022-08-12 | 厦门大学 | Extractive distillation method for separating mixture of n-propyl acetate and methylcyclohexane by using polyhydric alcohol |
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