CN110272333A - A method of recycling propylene glycol monomethyl ether - Google Patents
A method of recycling propylene glycol monomethyl ether Download PDFInfo
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- CN110272333A CN110272333A CN201910703972.XA CN201910703972A CN110272333A CN 110272333 A CN110272333 A CN 110272333A CN 201910703972 A CN201910703972 A CN 201910703972A CN 110272333 A CN110272333 A CN 110272333A
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- propylene glycol
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/34—Separation; Purification; Stabilisation; Use of additives
- C07C41/40—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation
- C07C41/42—Separation; Purification; Stabilisation; Use of additives by change of physical state, e.g. by crystallisation by distillation
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Abstract
The present invention provides a kind of method for recycling propylene glycol monomethyl ether, first alcohol ether aqueous solution logistics to be recycled is concentrated using concentration tower rectifying, again to concentrate logistics using extractant extraction and split-phase acquisition water phase logistics and oil phase thing stream, wherein aqueous-phase material, which flows back to, flows to concentration tower, then solvent recovery processing is carried out to oil phase thing stream, be finally carried out dehydrating；The extractant is organic oxygen-containing compound.Middle technical solution can preferably recycle the propylene glycol monomethyl ether in alcohol ether aqueous solution logistics through the invention, gained propylene glycol monomethyl ether is able to satisfy the quality standard of " the industrial propylene glycol monomethyl ether of HG/T 3939-2007 ", isomery propylene glycol monomethyl ether can satisfy relevant enterprise standard, and it is at low cost that low energy consumption, is suitble to industrialization continuous production.
Description
Technical field
The present invention relates to a kind of recovery methods, more particularly to a kind of method for recycling propylene glycol monomethyl ether.
Background technique
It is a kind of novel production technology, the technical staff with hydrogen peroxide Direct Epoxidation production of propylene propylene oxide (HPPO)
Skill process is simple, environmentally protective, is just gradually substituting traditional propylene oxide by chlorohydrination production technology.
Propylene glycol monomethyl ether, including propylene glycol monomethyl ether (PM, NBP:120.1 DEG C) and isomery propylene glycol monomethyl ether (IPM, NBP:
129.5 DEG C) two kinds of isomers, they can form azeotropic mixture with water, wherein propylene glycol monomethyl ether and water being total in 1atm
Boiling temperature is 96.7 DEG C, and the content of propylene glycol monomethyl ether is 51.8wt% in azeotropic mixture；Isomery propylene glycol monomethyl ether and water are in 1atm
Azeotropic temperature be 98.4 DEG C, in azeotropic mixture the content of isomery propylene glycol monomethyl ether be 40.3wt%.
During producing propane epoxide by using hydrogen peroxide epoxidation propylene, in addition to producing principal product propylene oxide, can also it generate
A small amount of propylene glycol monomethyl ether (PM), isomery propylene glycol monomethyl ether (IPM), 1,2- propylene glycol (PG), dipropylene glycol monomethyl ether (DPM) and
Other impurity, wherein propylene glycol monomethyl ether and isomery propylene glycol monomethyl ether are propylene oxide and the by-product that ring-opening reaction generates occurs for methanol
Object.Since the boiling point (or azeotropic point with water) of propylene glycol monomethyl ether is higher than methanol, so propylene glycol monomethyl ether will be concentrated to
In alcohol ether aqueous solution, content is about 1.5wt%-10wt%.
Propylene glycol monomethyl ether is a kind of versatility solvent of function admirable, is widely used in coating, printing, electron chemistry
The industries such as product, weaving, and can be used as chemical intermediate, there is very high economic value.Therefore, the economy to improve HPPO device
Property, it is necessary to recycle the propylene glycol monomethyl ether in alcohol ether aqueous solution.
Due to propylene glycol monomethyl ether azeotrope with water, so can not be by the method for direct rectifying from alcohol ether aqueous solution logistics
Recycling obtains propylene glycol monomethyl ether.Currently, the method mainly combined using azeotropic distillation or extraction and azeotropic distillation
To recycle the propylene glycol monomethyl ether in alcohol ether aqueous solution logistics.
CN103183589 discloses a kind of method of azeotropic distillation separating propylene glycol methyl ether aqueous solution, used azeotropic
Agent is cyclohexanol, and azeotropy rectification column overhead vapours is after condensation, split-phase, water phase outlet, and organic phase is recycled.
CN109251133 discloses a kind of liquid-liquid extraction-azeotropic distillation hybrid technique and comes separating propylene glycol methyl ether and water, extracts
Taking agent is the mixture of 2 ethyl hexanoic acid and chloroform, which first extracts propylene glycol monomethyl ether aqueous solution with extractant, is extracted
It takes and is mutually delivered to azeotropy rectification column and carries out azeotropic distillation, by phase-splitter from azeotropy rectification column removed overhead water, tower reactor 2- ethyl
The mixture of caproic acid and propylene glycol monomethyl ether is delivered to recovery tower, obtains propylene glycol monomethyl ether product, tower reactor extraction from recovery tower top
Agent 2 ethyl hexanoic acid is recycled.
Propylene glycol list first during producing propane epoxide by using hydrogen peroxide epoxidation propylene, in gained alcohol ether aqueous solution logistics
Ether content is about 1.5wt%-10wt%, and content is lower, if not only needed using the technical solution of CN103183589 by alcohol
Water in ether aqueous solution is all steamed from azeotropic distillation column overhead, it is also necessary to be steamed a large amount of entrainer from tower top, energy consumption is huge
Greatly, economically uneconomical.If the dosage of extractant will be very big, thus from altogether using the technical solution of CN109251133
The chloroform amount that steams of boiling the top of the distillation column is also very big, and energy consumption is also very high, in addition, in raffinate phase also can containing a small amount of chloroform and
2 ethyl hexanoic acid causes the loss of extractant.
Summary of the invention
In view of the foregoing deficiencies of prior art, the present invention provides a kind of sides of completely new recycling propylene glycol monomethyl ether
Method, through the invention in technical solution can preferably recycle the propylene glycol monomethyl ether in alcohol ether aqueous solution logistics, gained the third two
Alcohol methyl ether is able to satisfy the quality standard of " the industrial propylene glycol monomethyl ether of HG/T 3939-2007 ", and isomery propylene glycol monomethyl ether can satisfy
Relevant enterprise standard, and that low energy consumption is at low cost, is suitble to industrialization continuous production.
In order to achieve the above objects and other related objects, the present invention obtains by the following technical programs.
The present invention provides a kind of method for recycling propylene glycol monomethyl ether, first by alcohol ether aqueous solution logistics to be recycled using dense
Contracting tower rectifying concentration, then to concentrate logistics using extractant extraction and split-phase acquisition water phase logistics and oil phase thing stream, wherein
Aqueous-phase material, which flows back to, flows to concentration tower, then carries out solvent recovery processing to oil phase thing stream, is finally carried out dehydrating；The extraction
Taking solvent is organic oxygen-containing compound.
Alcohol ether aqueous solution logistics to be recycled described herein can come from any process for generating alcohol ether aqueous solution, and have
Necessity recycles propylene glycol monomethyl ether therein.The i.e. described alcohol ether aqueous solution logistics to be recycled can be to include propylene glycol monomethyl ether
Or/and the aqueous solution of isomery propylene glycol monomethyl ether, typically, during hydrogen peroxide Direct Epoxidation production of propylene propylene oxide,
One alcohol ether aqueous solution logistics can be generated in methanol rectifying tower tower reactor, wherein the content of propylene glycol monomethyl ether is about 1.5-
10wt%, form other than water and propylene glycol monomethyl ether, also containing a small amount of methanol, ethyl alcohol, normal propyl alcohol, isopropanol, acetone,
Butanone, 1,2- propylene glycol (PG), dipropylene glycol monomethyl ether (DPM) etc..Preferably, contain in the alcohol ether aqueous solution logistics to be recycled
There are the propylene glycol monomethyl ether and/or isomery propylene glycol monomethyl ether of 1.5wt%~45wt%.
According to the present invention, extractant plays extremely crucial effect, skill of the invention in the inventive solutions
Art scheme is achieved by the effect of solvent, in the present invention, selects organic oxygen-containing compound as extractant.
Because the propylene glycol monomethyl ether content in oil phase thing stream is lower, in solvent recovery tower, to save energy consumption, it is desirable that extraction
Solvent is taken to be discharged from tower reactor, this requires the boiling point of solvent necessarily to be greater than the boiling point of isomery propylene glycol monomethyl ether.Preferably, the extraction
The boiling point of solvent is higher than the boiling point of isomery propylene glycol monomethyl ether；Solvent recovery processing is in solvent recovery tower in oil phase thing stream
Extractant and propylene glycol monomethyl ether are clearly cut, wherein the extractant logistics recycled is arranged from the tower reactor of solvent recovery tower
Out.
Extractant enters alcohol ether concentration tower tower reactor in order to prevent simultaneously, causes extractant to lose, it is desirable that extractant
Minimum azeotrope must be formed with water energy, so that a small amount of extractant being dissolved in water phase logistics can be from the tower of alcohol ether concentration tower
Top steams.Preferably, the extractant and water form minimum azeotrope；The aqueous-phase material, which flows back to, flow to concentration tower.
Furthermore it is required that extractant has biggish distribution coefficient to propylene glycol monomethyl ether, and the solubility of water is wanted
It is low as far as possible.
Behind polarity, physicochemical property, cost and the source for having comprehensively considered organic oxygen-containing compound, it is preferable that You Jihan
Oxygen compound is selected from diisobutyl ketone (DIBK), isobutyl benzylacetone (IAMK), 4,6- dimethyl -2-HEPTANONE (IDIBK), 1,3- bis-
One of methyl butanol (MIBC) and diisobutyl carbinol (DIBC) (DIBC) are a variety of.
According to the present invention, extraction-phase process of propylene glycol monomethyl ether can be added clear using the stirred tank of single equilibrium stage
Clear slot technical solution can also need to be comprehensively considered using the extraction tower technical solution with multiple equilibrium stages, optimal technical solution
Treatment scale, propylene glycol monomethyl ether content etc. are because usually selecting.
According to the present invention, the propylene glycol monomethyl ether in alcohol ether aqueous solution logistics to be recycled obtains in concentration tower dense first
Contracting, comprehensively considers the rate of recovery of energy consumption and propylene glycol monomethyl ether, in the waste water streams of concentration tower tower reactor discharge, propylene glycol monomethyl ether
Mass content generally be preferably less than 2000ppm, preferably smaller than 500ppm.Experimental study shows that extraction temperature is higher, propylene glycol list
Distribution coefficient of the methyl ether in extractant is bigger, more advantageous to the extraction process of propylene glycol monomethyl ether, but temperature is higher, extraction
Take solvent bigger to the solubility of water, the water content in extract liquor, that is, oil phase thing stream is higher, causes to subsequent dehydrating operations
Adverse effect.To solve this problem, extraction process can be carried out at higher temperature such as 85 DEG C -108 DEG C, then again by extraction phase
I.e. oil phase thing stream temperature is cooled to lower than 45 DEG C such as 2-45 DEG C, and the free water logistics of precipitation are returned again to as being used in stirred tank
Extraction, oil phase thing stream after cooling enter back into dehydrating tower.Preferably, the operation temperature of extraction process is 85 DEG C~108 DEG C.It is preferred that
Ground, oil phase thing enter back into solvent recovery tower after flowing through the free water logistics that further cooling and removing is precipitated.It is highly preferred that into one
The temperature for walking oil phase thing stream after cooling is for example 2 DEG C~45 DEG C lower than 45 DEG C.Preferably, the free water logistics of precipitation are used for
Extraction such as returns to the stirred tank that there is the multistage extraction tower to balance each other or single-stage to balance each other.
It, can be determining according to this field routine operation and each logistics of selection during whole operation according to the present invention
Mass flow and relative discharge, generally, in the mass flow of cycling extraction solvent stream and alcohol ether aqueous solution logistics to be recycled
The ratio between propylene glycol monomethyl ether and isomery propylene glycol monomethyl ether total mass flow rate are (3~10): 1.
According to the present invention, solvent recovery tower can determine operating pressure and operation temperature according to this field routine operation.Example
Such as operating absolute pressure is 3KPa~140KPa, and operation temperature is 25 DEG C~204 DEG C.But it is considered that extractant needs to recycle
It uses, and ehter bond, carbonyl or hydroxyl in extractant containing less stable, to protect solvent, solvent is prevented to be recycled
It is denaturalized in the process, solvent recovery tower preferably operates under lower pressure and temperature, such as preferred operation absolute pressure is
6KPa~15KPa, preferred operation temperature are 38 DEG C~108 DEG C.
According to the present invention, the main function of dehydrating tower is the moisture removed in solvent recovery column overhead stream, in order to guarantee
Moisture content in propylene glycol monomethyl ether product is able to satisfy the quality requirement of " the industrial propylene glycol monomethyl ether of HG/T 3939-2007 ".It is de-
Water tower tower reactor obtains the logistics of removing moisture, and biodiversity content is less than 400ppmw, preferably smaller than 50ppm.
Light component in the logistics of alcohol ether aqueous solution in order to prevent, such as methanol, ethyl alcohol, normal propyl alcohol, isopropanol, acetone, fourth
Ketone etc. is accumulated in systems, and dehydration column overhead is dehydrated logistics, is needed outlet part to go removing light component, is such as removed the direct ring of hydrogen peroxide
Propylene oxide produces the methanol rectifying tower in propylene oxide unit, and propylene glycol monomethyl ether therein will be with methanol rectifying tower tower reactor
Alcohol ether aqueous solution returns to alcohol ether concentration tower, can also partially remove the lightness-removing column being separately provided, and the logistics after removing light component returns
Alcohol ether concentration tower or the stirred tank that balances each other.If there is no methanol, ethyl alcohol, normal propyl alcohol, isopropanol, third in alcohol ether aqueous solution logistics
Ketone, butanone etc. generate the light component of accumulation in systems, then dehydration column overhead dehydration logistics directly can all return to stirred tank.
If containing propylene glycol monomethyl ether (PM) and isomery propylene glycol monomethyl ether (IPM) in dewatered material simultaneously, it is preferable that
The method also includes the materials to dehydration to use rectifying column rectifying separating propylene glycol methyl ether and isomery propylene glycol monomethyl ether.It presses
According to the present invention, propylene glycol monomethyl ether rectifying column can determine operating condition according to this field routine operation, need to only guarantee propylene glycol
Propylene glycol monomethyl ether content in ether products logistics is greater than 99.5wt%, preferably greater than 99.8wt%.Particularly, if alcohol ether is water-soluble
In liquid logistics in addition to water, only propylene glycol monomethyl ether or isomery propylene glycol monomethyl ether one of which component, then can be directly from dehydrating tower
Tower reactor obtains corresponding product stream.Preferably, propylene glycol monomethyl ether product stream is obtained from propylene glycol monomethyl ether the top of the distillation column,
The content of propylene glycol monomethyl ether (PM) is greater than 99.5wt%, preferably greater than 99.8wt%, the propylene glycol monomethyl ether content in tower base stream
Less than 3wt%, preferably smaller than 0.5wt%.
According to the present invention, since the energy consumption for recycling propylene glycol monomethyl ether from alcohol ether aqueous solution logistics is larger, for drop
Low energy consumption, the rectifying column in the technical program can be thermally integrated with the rectifying column outside the technical program, such as the direct ring of hydrogen peroxide
Methanol rectifying tower in propylene oxide production propylene oxide be thermally integrated or the technical program in heat is carried out inside rectifying column
It is integrated, such as alcohol ether concentration tower, using heat pump distillation or double-effect rectification, these should not influence protection scope of the present invention.
Propylene glycol monomethyl ether phase is recycled with azeotropic distillation or extraction-azeotropic distillation hybrid technique is passed through in the prior art
Than, the present invention achieves apparent technological progress, it specifically includes following aspects:
1. the propylene glycol monomethyl ether content in alcohol ether aqueous solution to be recycled is lower, total using azeotropic distillation or extraction-
The energy consumption for boiling rectifying hybrid technique is very high, and the present invention had both been not necessarily to all steam the moisture in solution to be recycled, without general
Extractant steams, and extractant is recycled from solvent recovery tower tower bottom, has apparent power savings advantages；
2. extractant used in the present invention and water energy form minimum azeotrope, so extractant will not enter concentration
The tower reactor of tower, extractant hardly cause damages in use.
3. in short, technical solution can preferably recycle the propylene glycol list first in alcohol ether aqueous solution logistics in through the invention
Ether, gained propylene glycol monomethyl ether are able to satisfy the quality standard of " the industrial propylene glycol monomethyl ether of HG/T 3939-2007 ", isomery propylene glycol
Methyl ether can satisfy relevant enterprise standard, and that low energy consumption is at low cost, be suitble to industrialization continuous production.
Detailed description of the invention
Fig. 1 is the first process flow diagram of the invention；
Fig. 2 is second of process flow diagram of the invention；
Fig. 3 is the third process flow diagram of the invention；
Fig. 4 is the 4th kind of process flow diagram of the invention.
In the drawings, identical equipment and logistics are indicated with identical appended drawing reference, wherein representated by each appended drawing reference
Content it is specific as follows:
T101- concentration tower, T102- extraction tower, T201- solvent recovery tower, T301- dehydrating tower, T401- propylene glycol monomethyl ether essence
Evaporate tower；
E101- alcohol ether condenser, E102- oil phase thing stream cooler；
V101- balances each other stirred tank, V102- defecator, V103- coalescer.
101- alcohol ether aqueous solution to be recycled, 102- alcohol ether concentration tower overhead vapours, 103- extractant logistics, 104- mixing
Material logistics, 105- water phase logistics, 106- oil phase thing stream, 107- waste water streams, 108- oil phase thing stream after cooling, 109- coalescence
Dehydration logistics, logistics of the 201- comprising components such as propylene glycol monomethyl ether, isomery propylene glycol monomethyl ether, water, 202- recycling design logistics,
301- is dehydrated logistics, and 302- returns to the dehydration logistics for the stirred tank that balances each other, and 303- removes the dehydration logistics of removing light component, 304- packet
Logistics containing the components such as propylene glycol monomethyl ether, isomery propylene glycol monomethyl ether and removing moisture, 401- propylene glycol monomethyl ether product stream, 402-
Isomery propylene glycol monomethyl ether product stream.
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book understands further advantage and effect of the invention easily.
Before further describing the specific embodiments of the present invention, it should be appreciated that protection scope of the present invention is not limited to down
State specific specific embodiment；It is also understood that term used in the embodiment of the present invention is specific specific in order to describe
Embodiment, rather than limiting the scope of protection of the present invention.The test method of actual conditions is not specified in the following example,
Usually according to normal condition, or according to condition proposed by each manufacturer.
When embodiment provides numberical range, it should be appreciated that except non-present invention is otherwise noted, two ends of each numberical range
Any one numerical value can be selected between point and two endpoints.Unless otherwise defined, the present invention used in all technologies and
Scientific term is identical as the normally understood meaning of those skilled in the art of the present technique.Except specific method, equipment used in embodiment,
Outside material, grasp and record of the invention according to those skilled in the art to the prior art can also be used and this
Any method, equipment and the material of the similar or equivalent prior art of method described in inventive embodiments, equipment, material come real
The existing present invention.
Embodiment 1
Fig. 1 is shown in process flow, and extractant selects diisobutyl carbinol (DIBC) (DIBC), for handling certain hydrogen peroxide epoxidation third
Alkene produces the alcohol ether aqueous solution logistics 101 of propylene oxide unit discharge, which, which removes, includes water, propylene glycol monomethyl ether (PM) and isomery
Propylene glycol monomethyl ether (IPM) outside, also contains a small amount of methanol, ethyl alcohol, propyl alcohol, propylene glycol (PG) and dipropylene glycol monomethyl ether (DPM),
The logistics enters the top concentration tower T101, and overhead vapor stream 102 is after alcohol ether condenser E101 is condensed to bubble point and from dehydration
Dehydration logistics 302 that tower T301 tower top comes enters the stirred tank V101 that balances each other after mixing, and with recycling design logistics 202 and mend
It fills solvent stream 103 to be thoroughly mixed, mixed material logistics 104 enters defecator V102 split-phase, and wherein water phase logistics 105 passes through
Reflux after pump pressurization as concentration tower T101, oil phase thing stream 106 enter solvent recovery tower T201.In solvent recovery tower T201
In, recovered solvent logistics 202 is obtained from tower reactor and returns to the stirred tank V101 recycling that balances each other, and is obtained from tower top comprising third
The logistics 201 of the components such as glycol methyl ether, isomery propylene glycol monomethyl ether, water simultaneously enters dehydrating tower T301.It is taken off from dehydration column overhead
Water logistics 301, part 302 return to the stirred tank that balances each other, and remainder 303 enters the logistics of alcohol ether aqueous solution after removing light component
In, it obtains from dehydrating tower tower reactor comprising components such as propylene glycol monomethyl ether, isomery propylene glycol monomethyl ethers and removes the logistics 304 of moisture then
Into propylene glycol monomethyl ether rectifying column T401.In propylene glycol monomethyl ether rectifying column, propylene glycol monomethyl ether product stream is obtained from tower top
401, tower reactor obtains isomery propylene glycol monomethyl ether product stream 402.The material balance table of the process flow is as shown in table 1.
1 embodiment of table, 1 material balance table
Embodiment 2
Process flow is shown in that Fig. 2, extractant select diisobutyl ketone (DIBK) and 4,6- dimethyl -2-HEPTANONE (IDIBK)
Mixture, for handle certain producing propane epoxide by using hydrogen peroxide epoxidation propylene device discharge alcohol ether aqueous solution logistics 101, should
Logistics also contains a small amount of methanol, ethyl alcohol, third in addition to comprising water, propylene glycol monomethyl ether (PM) and isomery propylene glycol monomethyl ether (IPM)
Alcohol, propylene glycol (PG) and dipropylene glycol monomethyl ether (DPM), the logistics enter the top concentration tower T101, and overhead vapor stream 102 passes through
Alcohol ether condenser E101 condense to bubble point after with from the dehydration logistics 302 that dehydrating tower T301 tower top comes mix after enter balance each other
Stirred tank V101, and being thoroughly mixed with recycling design logistics 202 and supplementing solvent logistics 103, mixed material logistics 104 into
Enter defecator V102 split-phase, wherein reflux of the water phase logistics 105 after pump pressurization as alcohol ether concentration tower T101, oil phase thing stream
106 enter coalescer V103 after oil phase thing stream cooler E102 is cooled to 5 DEG C, the water phase logistics deviate from from coalescer V103
109 return to the stirred tank V101 that balances each other after pump pressurization, and oil phase thing stream 108 enters solvent recovery tower T201.In solvent recovery tower
In T201, recovered solvent logistics 202 is obtained from tower reactor and returns to the stirred tank V101 recycling that balances each other, is wrapped from tower top
Logistics 201 containing components such as propylene glycol monomethyl ether, isomery propylene glycol monomethyl ether, water simultaneously enters dehydrating tower T301.It is obtained from dehydration column overhead
To dehydration logistics 301, part 302 returns to the kettle that balances each other, and remainder 303 enters the logistics of alcohol ether aqueous solution after removing light component
In, it obtains from dehydrating tower tower reactor comprising components such as propylene glycol monomethyl ether, isomery propylene glycol monomethyl ethers and removes the logistics 304 of moisture then
Into propylene glycol monomethyl ether rectifying column T401.In propylene glycol monomethyl ether rectifying column, propylene glycol monomethyl ether product stream is obtained from tower top
401, tower reactor obtains isomery propylene glycol monomethyl ether product stream 402.The material balance table of the process flow is as shown in table 2.
2 embodiment of table, 2 material balance table
Embodiment 3
Process flow is shown in that Fig. 3, extractant select isobutyl benzylacetone (IAMK), for handling the alcohol ether water of certain device discharge
Solution stream 101, the logistics only include water and propylene glycol monomethyl ether (PM), which enters the top concentration tower T101, overhead vapours
After logistics 102 mixes after alcohol ether condenser E101 is condensed to bubble point with the dehydration logistics 302 to come from dehydrating tower T301 tower top
It is thoroughly mixed into the stirred tank V101 that balances each other, and with recycling design logistics 202 and supplementing solvent logistics 103, mixture
Material stream 104 enters defecator V102 split-phase, wherein reflux of the water phase logistics 105 after pump pressurization as concentration tower T101, oil
Phase logistics 106 enters solvent recovery tower T201.In solvent recovery tower T201, recovered solvent logistics 202 is obtained simultaneously from tower reactor
Return balances each other stirred tank V101 recycling, obtains the logistics 201 comprising propylene glycol monomethyl ether and water from tower top and enters dehydration
Tower T301.Dehydration logistics 301 is obtained from dehydration column overhead, the stirred tank that balances each other all is returned, is wrapped from dehydrating tower tower reactor
Dehydration logistics 304 containing propylene glycol monomethyl ether, can be directly used as propylene glycol monomethyl ether product.
3 embodiment of table, 3 material balance table
Embodiment 4
Fig. 4 is shown in process flow, extractant select diisobutyl ketone (DIBK), 4,6- dimethyl -2-HEPTANONE (IDIBK),
The mixture of 1,3- dimethyl butyrate alcohol (MIBC), diisobutyl carbinol (DIBC) (DIBC), the alcohol ether for handling the discharge of certain device are water-soluble
Liquid logistics 101, the logistics include that water, propylene glycol monomethyl ether (PM) and isomery propylene glycol monomethyl ether (IPM), the logistics enter concentration tower
The top T101, overhead vapor stream 102 after alcohol ether condenser E101 is condensed to bubble point with come from dehydrating tower T301 tower top
Be dehydrated after logistics 301 mixes and enter the top extraction tower T102, recycling design logistics 202 and supplementing solvent logistics 103 mix after from
The charging of the lower part extraction tower T102, reflux of the extraction tower tower reactor water phase logistics 105 after pump pressurization as concentration tower T101, overhead oil
Phase logistics 106 enters solvent recovery tower T201.In solvent recovery tower T201, recovered solvent logistics 202 is obtained simultaneously from tower reactor
It returns to extraction tower T102 to be recycled, obtains the logistics comprising components such as propylene glycol monomethyl ether, isomery propylene glycol monomethyl ether, water from tower top
201 and entrance dehydrating tower T301.In dehydrating tower T301, dehydration logistics 301 is obtained from tower top and returns to extraction tower T102, tower reactor
It obtains comprising propylene glycol monomethyl ether, isomery propylene glycol monomethyl ether and removes the logistics 304 of moisture subsequently into propylene glycol monomethyl ether rectifying column
T401.In propylene glycol monomethyl ether rectifying column, propylene glycol monomethyl ether product stream 401 is obtained from tower top, tower reactor obtains isomery propylene glycol
Ether products logistics 402.The material balance table of the process flow is as shown in table 4.
4 embodiment of table, 4 material balance table
The above-described embodiments merely illustrate the principles and effects of the present invention, and is not intended to limit the present invention.It is any ripe
The personage for knowing this technology all without departing from the spirit and scope of the present invention, carries out modifications and changes to above-described embodiment.Cause
This, institute is complete without departing from the spirit and technical ideas disclosed in the present invention by those of ordinary skill in the art such as
At all equivalent modifications or change, should be covered by the claims of the present invention.
Claims (10)
1. a kind of method for recycling propylene glycol monomethyl ether, which is characterized in that first by alcohol ether aqueous solution logistics to be recycled using concentration
Tower rectifying concentration, then to concentrate logistics using extractant extraction and split-phase acquisition water phase logistics and oil phase thing stream, it is then right
Oil phase thing stream carries out solvent recovery processing, is finally carried out dehydrating；The extractant is organic oxygen-containing compound.
2. the method according to claim 1, wherein the extractant and water form minimum azeotrope, water phase
Logistics flows back into concentration tower.
3. the method according to claim 1, wherein the boiling point of the extractant is higher than isomery propylene glycol first
Ether；Solvent recovery processing be in solvent recovery tower in oil phase thing stream extractant and propylene glycol monomethyl ether cut,
The extractant logistics of recycling is discharged from the tower reactor of solvent recovery tower.
4. described in any item methods according to claim 1~3, which is characterized in that the extractant be selected from diisobutyl ketone,
One of isobutyl benzylacetone, 4,6- dimethyl -2-HEPTANONE, the pure and mild diisobutyl carbinol (DIBC) of 1,3- dimethyl butyrate are a variety of.
5. the method according to claim 1, wherein including one of following feature or a variety of:
Dehydration is that the logistics that will be discharged from solvent recovery column overhead carries out rectifying and dewatering in dehydrating tower, the logistics comprising water
It is discharged from dehydration column overhead, the logistics comprising propylene glycol monomethyl ether is obtained from dehydrating tower tower reactor；
The method also includes using rectifying column rectifying separating propylene glycol methyl ether and isomery to the resulting tower reactor logistics of dehydration
Propylene glycol monomethyl ether；
The alcohol ether aqueous solution logistics to be recycled is the aqueous solution logistics comprising propylene glycol monomethyl ether or/and isomery propylene glycol monomethyl ether；
The total content of propylene glycol monomethyl ether or/and isomery propylene glycol monomethyl ether is 1.5wt% in the alcohol ether aqueous solution logistics to be recycled
~45wt%.
6. according to the method described in claim 3, it is characterised in that it includes one of following feature or a variety of:
The logistics being discharged from the tower reactor of solvent recovery tower is recycled as extractant；
The mass flow and alcohol ether aqueous solution logistics to be recycled for the cycling extraction solvent stream being discharged from the tower reactor of solvent recovery tower
The ratio between middle propylene glycol monomethyl ether and isomery propylene glycol monomethyl ether total mass flow rate are (3~10): 1；
The operation absolute pressure of solvent recovery tower is 4KPa~140Kpa；Preferably 6KPa~15KPa；
The operation temperature of solvent recovery tower is 29 DEG C~181 DEG C, preferably 38 DEG C~108 DEG C.
7. according to the method described in claim 5, it is characterised in that it includes one of following feature or a variety of:
The dehydration logistics that dehydration column overhead obtains is used further to extract；
Dehydration logistics a portion that dehydration column overhead obtains is used further to extract；Another part is used as after removing light component wait return
It receives alcohol ether aqueous solution or is used further to extract, the light component includes being selected from methanol, ethyl alcohol, normal propyl alcohol, isopropanol, acetone, butanone
One of or it is a variety of；
The mass content for obtaining moisture in the logistics comprising propylene glycol monomethyl ether from dehydrating tower tower reactor is less than 400ppm, preferably smaller than
50ppm。
8. the method according to claim 1, wherein including one or both of following feature:
The temperature of extraction is 85 DEG C~108 DEG C；
It is first that oil phase thing stream is cooling and remove the free water logistics of precipitation before carrying out solvent recovery processing to oil phase thing stream.
9. according to the method described in claim 8, it is characterised in that it includes one or both of following feature:
Oil phase thing stream is cooled to lower than 45 DEG C；
The free water logistics being precipitated are used further to extract.
10. the method according to claim 1, wherein balancing each other in the extraction step using with multistage
The combination of extraction tower or the stirred tank and defecator that are balanced each other using single-stage.
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