CN109574804A - A kind of method of separating alcohol-water - Google Patents
A kind of method of separating alcohol-water Download PDFInfo
- Publication number
- CN109574804A CN109574804A CN201710907029.1A CN201710907029A CN109574804A CN 109574804 A CN109574804 A CN 109574804A CN 201710907029 A CN201710907029 A CN 201710907029A CN 109574804 A CN109574804 A CN 109574804A
- Authority
- CN
- China
- Prior art keywords
- water
- tower
- alcohol
- etbe
- ethyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
- C07C29/82—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation by azeotropic distillation
Abstract
The present invention provides a kind of methods of separating alcohol-water, comprising the following steps: step (1): hydrous ethanol raw material and the ethyl tert-butyl ether (ETBE) azeotropic at 70~81 DEG C obtain ethyl alcohol concentration liquid；Step (2): ethyl alcohol concentration liquid and the ethyl tert-butyl ether (ETBE) azeotropic at 63~68 DEG C；Isolated ethyl alcohol and H2O-ETBE azeotropic mixture.The method of the present invention recycles ethyl tert-butyl ether (ETBE) azeotropic dehydration first by the preliminary concentrate of Diluted Alcohol, obtains the ethyl alcohol that water content is several hundred ppm, the reconciliation for ethanol petrol.
Description
Technical field
The invention belongs to industrial chemicals separating-purifying fields, and in particular to a kind of method of separating alcohol-water.
Background technique
Methyl tertiary butyl ether(MTBE) (MTBE) is to be mainly used for promoting octane number, enhancing using wider oxygenated additive
The capability of antidetonance.The use of MTBE plays a positive role for the discharge of the atmosphere pollutions such as CO and hydro carbons after reduction burning, but
Due to high water solubility, difficult to degrade, easy to migrate and potential carcinogenic nature etc., major part cities and counties, the U.S. disable in 2008
The MTBE usage amount in the area such as MTBE, European Union and Japan is also being reduced year by year.And ethyl alcohol, ethyl tert-butyl ether (ETBE) (ETBE) are as high
Octane components have preferable advantage compared with MTBE.Alcohol fuel is added in the oil and is greatly improved its octane number, and
It can effectively improve the anti-knock properties of gasoline.Simultaneously as the oxygen content of ethyl alcohol is up to 34.7%, it can be compared with the less addition of MTEB
Amount is added in gasoline, helps the gasoline completely burned more than not oxygen-containing and carbon atomic ratio ethyl alcohol, makes the nuisance of motor vehicle exhaust emission
Matter such as CO, HC, NOX, PM2.5 etc. reduces.ETBE and gasoline concoction can reduce CO, VOC in vehicle exhaust at clean fuelS、NOX
And the discharge of the solid particles such as PM2.5.Compared with MTBE, ETBE has that blending octane number is high, Reid vapour pressure is low, easily and gasoline
The advantages that miscible, and toxicity is low, environmental pollution is small.Therefore, the country such as the U.S., Brazil is in the ratio for promoting the use of ethanol petrol.
Meanwhile as MTBE is disabled, the U.S., Europe and Japan and other countries use ETBE as octane number modifier.
Under normal pressure, ethyl alcohol and the water azeotropic at 78.1 DEG C, ethyl alcohol mass content 95.6% in azeotropic mixture, water quality content
4.4%.Industrial production dehydrated alcohol, generallys use azeotropic distillation, i.e., third component (folder is added in ethanol-water solution
Band agent), azeotropic mixture is formed with ethyl alcohol or water, with the method separating alcohol and water of rectifying.In azeotropic distillation production dehydrated alcohol
In technique, common azeotropic entrainer has: benzene, pentane, hexamethylene etc..Benzene is a kind of more traditional entrainer, and technique has compared
It is more mature, but since benzene is more toxic, do not meet environmentally protective and clean manufacturing idea of development.Entrainer is done with pentane, although
The shortcomings that avoiding benzene azeotropic rectifying, but the low boiling point (36.1 DEG C) of pentane are easy vaporization under room temperature, and solvent loss is larger and needs
Want pressurized operation.Patent US4256541 has studied the production technology of absolute alcohol by zeolite molecular sieve that hexamethylene makees entrainer.Hexamethylene has price
The cheap, advantageous properties such as toxicity is low, are the preferable substitutes of benzene, are used by many external producers.But these common entrainments
Agent is both needed to vehicle fuel could be used as to use after further progress separation, removing solvent.Patent CN101033170A record
Method will carry out pervaporation on many concatenated membrane modules, relatively be suitable for low water content (1 to 10% quality) ethyl alcohol into
Row dehydration, major defect are that film module capital investment is big, and relatively narrow to the water content adaptation range of feed ethanol.
The selection of entrainer all has a great impact to the quality of operating condition and product.Usually removed when selecting entrainer
Consider also to need to consider technological problems outside isolated complexity.Ethyl tert-butyl ether (ETBE) (ETBE) is used as entrainer azeotropic separation second
Alcohol-water has its unique advantage, and technology implementation result is good, and ETBE is that the gasoline that prospect of the application is best in current world wide adds
Add agent, the octane number for blended gasoline.The present invention carries out ethanol water as entrainer using ethyl tert-butyl ether (ETBE)
Dehydrating operations, obtained product are not required to further remove entrainer, can be directly used for gasoline concoction, have other entrainments such as pentane
The advantage that agent does not have.
Summary of the invention
To solve the technical problem that water separating difficulty is big, separating effect is bad in existing ethyl alcohol, the present invention provides one kind
It take ethyl tert-butyl ether (ETBE) (ETBE) as the method for entrainer separating alcohol-water；It is intended to simplify treatment process, promotes dehydrating effect.
The present invention also provides the processing systems for implementing the method.
A kind of method of separating alcohol-water, comprising the following steps:
Step (1): hydrous ethanol raw material and the ethyl tert-butyl ether (ETBE) azeotropic at 70~81 DEG C obtain ethyl alcohol concentration liquid；
Step (2): ethyl tert-butyl ether (ETBE) is added into ethyl alcohol concentration liquid, and control system temperature is 63~68 DEG C；Separation
Obtain ethyl alcohol and H2O-ETBE azeotropic mixture.
The present invention originally proposes a kind of using ethyl tert-butyl ether (ETBE) as the method for entrainer separating alcohol-water；It will be aqueous
Measuring preliminary concentrate of the slightly higher Diluted Alcohol (hydrous ethanol raw material) through step (1), (ethyl alcohol and ETBE are formed at a temperature of described
Azeotropic mixture, and most of water carry out initial gross separation), the second dehydration of recycle step (2), it is several hundred ppm that water content, which can be obtained,
Ethyl alcohol, the ethyl alcohol of the content can meet the field of certain specific requirements.
As preferred: in step (1), the volume of material ratio of hydrous ethanol raw material and ethyl tert-butyl ether (ETBE) is 50~800.Control
System facilitates the concentrate of ethyl alcohol, helps to improve subsequent ethanol-water separating effect under the preferred ratio.
Further preferably, in step (1), the volume of material ratio of hydrous ethanol raw material and ethyl tert-butyl ether (ETBE) is 100~
500。
Preferably, the azeotropic temperature of step (1) is 75~77 DEG C.
As preferred: the temperature of step (2) is 65~66 DEG C.
In step (2), the weight ratio of ethyl alcohol and ethyl tert-butyl ether (ETBE) is 1.5~4.5 in ethyl alcohol concentration liquid.
As preferred: H2O-ETBE azeotropic mixture is handled through water-oil separating, and isolated oil is mutually recycled in step (2).
The oily phase water content that water-oil separating obtains is very low, is recycled in step (2), can further reduce the cost, and reduces energy consumption.
Preferably, the weight ratio of the oily phase (ethyl tert-butyl ether (ETBE)) of ethyl alcohol and recycled is 2~4 in step (2).
In step (2) azeotropic process, fresh ETBE is also added into azeotropic system, for making up the ETBE in azeotropic process
Loss.
Preferably, the volume ratio of ethyl alcohol concentration liquid and the ethyl tert-butyl ether (ETBE) added is 50~500 in step (2).
As preferred: in step (2), the volume ratio of ethyl alcohol concentration liquid and the ethyl tert-butyl ether (ETBE) added is 150~350.
As preferred: the water phase that water-oil separating obtains is handled through distillation, and fraction is ethyl tert-butyl ether (ETBE), recycled to step
Suddenly in (1).It recycles obtained material and contains ethyl tert-butyl ether (ETBE), also contain certain ethyl alcohol, water, be recycled in step (1), have
Help reduce energy consumption, reduces cost, additionally aid Alcohol-water separation.
In the present invention, the azeotropic mixture (H of ETBE and water2O-ETBE azeotropic mixture) at normal temperatures and pressures can split-phase, wherein water phase
Middle water content is high, and ETBE is rich in oily phase, the recycling of entrainer can be realized by this mechanism.By the second
Base tertbutyl ether sufficiently recycles, and can help to reduce cost.
Method of the present invention is applicable to the ethanol raw material of any water content.
The water content of the hydrous ethanol raw material is > 0wt%.
Processing method of the present invention, the ethanol dehydration particularly suitable for water content in 4.5~99.5wt% are handled.
In addition, the method for the present invention, can be used for the efficient of the high ethanol water of water content, high quality separation.Side of the present invention
Method can be used for the dehydration that water content is greater than 90wt% ethanol water, and the water content of treated ethyl alcohol can be down to
100ppm or less；Compared with the prior art, dehydrating effect is obvious.
Ethanol raw material of the present invention is preferably industrial alcohol or bio-ethanol aqueous solution.
The method of the present invention industrial continuous can be handled, and by the ethyl tert-butyl ether (ETBE) recycled in system, can not only be mentioned
The treatment effect for rising ethyl alcohol, is also substantially reduced processing cost.
The method of currently preferred serialization separating alcohol-water, hydrous ethanol raw material and ethyl tert-butyl ether (ETBE), which enter, to be mentioned
Dense tower, the temperature in control concentration tower top material exit are 70~81 DEG C, obtain waste water in concentrate tower bottom, top obtains second
Alcohol concentration liquid；
Ethyl alcohol concentration liquid and ethyl tert-butyl ether (ETBE) are directed into azeotropy rectification column, control azeotropy rectification column top material goes out
Temperature at mouthful is 63~68 DEG C (75~82 DEG C of kettle temperature), obtains ethyl alcohol in azeotropic tower bottom；
The H of azeotropic distillation top of tower outflow2O-ETBE azeotropic mixture enters liquid separation tank, carries out water-oil separating；Oily is mutually ethyl
Tertbutyl ether, recycled to azeotropy rectification column；
After water phase passes through recovery tower rectifying, tower bottom discharge of wastewater, overhead product is back to concentration tower.
The preferred continuous treatment method through the invention, can efficiently, continuously obtain the ethyl alcohol of high quality, this
Outside, entrainer sufficiently recycles in system, and loss is small, and processing cost is low.
The present inventors have additionally discovered that the parameter to equipment regulates and controls, dehydrating effect can be further promoted.
As preferred: concentration tower theoretical cam curve is 15-25.
As preferred: the operating pressure of concentration tower is normal pressure.
As preferred: the operating reflux ratio of concentration tower is 0.5-5.0.
Preferably, concentration tower theoretical cam curve is 15-25, operating pressure is normal pressure, reflux ratio 0.5-5.0.
Preferably, when reaching balance, the mass ratio of the ethyl alcohol in azeotrope column and the oily phase of recycled in liquid separation tank is
2.0~4.0.In this ratio range, ETBE it is more excellent as entrainer dehydrating effect and remain in the content in alcohol product compared with
It is few.By the control of the concentrate parameter, it can control EOH the and ETBE mass ratio in the ethyl alcohol concentration liquid in the ratio
In range, facilitate the dehydration of subsequent ethyl alcohol.
Preferably, also adding ethyl tert-butyl ether (ETBE) into tower reactor in azeotropy rectification column azeotropic process；Wherein, ethyl alcohol mentions
The volume ratio of dope and the ethyl tert-butyl ether (ETBE) added is 50~500.
Preferably, the volume ratio of ethyl alcohol concentration liquid and the ethyl tert-butyl ether (ETBE) added is 150~350.
As preferred: azeotropy rectification column theoretical cam curve is 20-40.
As preferred: the operating pressure of azeotropy rectification column is normal pressure.
As preferred: azeotropy rectification column is total reflux operation.
As preferred: azeotropy rectification column theoretical cam curve is 20-40, and operating pressure is normal pressure, oily phase infinite reflux.
As preferred: recovery tower theoretical cam curve is 3-10.
As preferred: the operating pressure of recovery tower is normal pressure.
As preferred: the operating reflux ratio of recovery tower is 0.5-3.5.
Recovery tower column plate 3-10 block theoretical plate, atmospheric operation, reflux ratio is about 0.5-3.5.Pass through recovery tower, liquid separation tank water
ETBE in phase is almost recovered to concentration tower, and tower reactor discharging can be used as wastewater treatment.The main advantage of this technique is
ETBE consumption is few.
Preferably, isolated ethyl alcohol is added in gasoline as alcohol fuel.Treated for the method for the present invention
The quality of ethyl alcohol is high, and by the regulation of the temperature, reflux ratio (material ratio), contains in the ethyl alcohol that makes that treated suitable
ETBE is added in gasoline particularly suitable as adding ingredient, improves the performance of gasoline.
Further preferably, isolated ethyl alcohol is added in motor petrol.
The present invention also provides a kind of alcohol-water separation systems for implementing the method, including concentration tower, azeotropic distillation
Tower, liquid separation tank and recovery tower；Concentration tower is provided with the feed(raw material)inlet for receiving ethanol raw material and ethyl tert-butyl ether (ETBE), concentration tower
Tower bottom be provided with wastewater outlet, the tower top of concentration tower is provided with material outlet；
The material outlet of concentration tower and the material inlet of azeotropy rectification column connect；The tower bottom of azeotropy rectification column is provided with ethyl alcohol
Outlet；Material outlet is provided at the top of azeotropy rectification column；Azeotropy rectification column be additionally provided with ethyl tert-butyl ether (ETBE) fluid infusion and
Refluxing opening；
The material outlet of azeotropy rectification column is connect with the entrance of liquid separation tank, and the oil of liquid separation tank mutually exports and azeotropy rectification column
Refluxing opening connection, water phase outlet are connect with the material inlet of recovery tower；
The tower bottom of recovery tower is provided with wastewater outlet, and the outlet of tower top and the feed(raw material)inlet of concentration tower connect.
The present invention is used as entrainer using ethyl tert-butyl ether (ETBE) (ETBE), and the azeotropic mixture boiling point of itself and water is 65.5 under normal pressure
℃。
Beneficial effect
The present invention is that entrainer carries out separation of ethanol using gasoline additive ETBE, the ETBE contained in obtained product without
It need to further separate, can be used as fuel use, low energy consumption for the separating technology, and process is simple, and ethyl alcohol can be improved applies model
It encloses, while reducing bio-ethanol production cost.
The direct reflux technique invented has equipment simple, operates convenient advantage, under the conditions of can satisfy major part
Ethyl alcohol production operation requirement, obtained ethanol product concentration may be up to 98.0%-99.8%, water content 50ppm-
100ppm meets the purity requirement of vehicle fuel ethyl alcohol.
With gasoline ether additive ethyl tert-butyl ether (ETBE) (ETBE) for entrainer, with the alcohol product that can be used as vehicle fuel
The method and technique of azeotropic distillation separating alcohol-water are carried out, i.e. ETBE is in internal system point circulation, using azeotropic distillation as primary hand
The separation of ethanol method of section, low energy consumption for the method for the present invention, simple process, easy to operate.
Detailed description of the invention
Fig. 1 is the equipment flowsheet schematic diagram of processing system of the present invention.
1- ethyl alcohol concentration tower, 2- azeotropy rectification column, 3- liquid separation tank, 4-ETBE recovery tower, 5- concentration tower overhead condenser, 6-
Concentration tower tower reactor reboiler, 7- azeotrope column overhead condenser, 8- azeotrope column tower reactor reboiler, 9-ETBE recovery tower overhead condensation
Device, 10-ETBE recovery tower tower reactor reboiler
Specific embodiment
As shown in Figure 1, the alcohol-water separation system, including concentration tower 1, azeotropy rectification column 2, liquid separation tank 3 and recycling
Tower 4；Concentration tower 1 is provided with the feed(raw material)inlet for receiving ethanol raw material and ethyl tert-butyl ether (ETBE), and the tower bottom of concentration tower 1 is provided with
Wastewater outlet is provided with concentration tower tower reactor reboiler 6 on export pipeline.
The tower top of concentration tower 1 is provided with material outlet.The material outlet of concentration tower 1 and the material inlet of azeotropy rectification column 2
Connection；Concentration tower overhead condenser 5 is provided on connecting line.
The tower bottom of azeotropy rectification column 2 is provided with nol outlet, and azeotrope column tower reactor reboiler 8 is provided on export pipeline.Altogether
The top of boiling rectifying column 2 is provided with material outlet；Azeotropy rectification column 2 is additionally provided with the fluid infusion and reflux of ethyl tert-butyl ether (ETBE)
Mouthful；
The material outlet of azeotropy rectification column 2 is connect with the entrance of liquid separation tank 3, and it is cold that azeotropic column overhead is provided on connecting line
Condenser 7.
Mutually outlet is connect the oil of liquid separation tank 3 with the refluxing opening of azeotropy rectification column 2, and water phase is exported to be entered with the material of recovery tower 4
Mouth connection；
The tower bottom of recovery tower 4 is provided with wastewater outlet, and ETBE recovery tower tower reactor reboiler 10 is provided on export pipeline；Tower
The outlet on top is connect with the feed(raw material)inlet of concentration tower 1；ETBE recovery tower overhead condenser 10 is provided on connecting line.
Raw material and the entrainer of circulation enter concentration tower, obtain waste water in concentrate tower bottom, top obtains concentration liquid；Concentrate
Liquid and supplement entrainer enter azeotropy rectification column, obtain process of alcohol products in azeotropic tower bottom, azeotrope column top is through liquid separation tank
Afterwards, oil mutually directly returns azeotrope column, and entrainer is back to concentration tower after aqueous phase separation.Liquid separation tank water phase passes through recovery tower rectifying
Afterwards, tower bottom discharge of wastewater, overhead product are back to concentration tower feed inlet.
With reference to the accompanying drawing, the detailed process for illustrating this patent constitutes and operating method.
Unless specified or limited otherwise, treatment process of the present invention carries out under normal pressure.
Embodiment 1:
The low-concentration ethanol aqueous solution that mass percent is about 5% is added to ethyl alcohol concentration tower with the rate of 540g/min
In, while about 0.6% ethyl alcohol, the circulation of 3.7%ETBE (mass fraction, remaining part are water) are added with the rate of 3.5g/min
Liquid.The ethyl alcohol concentration tower number of plates is 16, reflux ratio 2: 1；Concentrate column overhead temperatures are 76.3 DEG C.
Obtaining flow is 72.2g/min, and purity is the ethyl alcohol concentration liquid of 77.6% (mass fraction), into azeotropy rectification column
In, control azeotropic distillation column overhead temperatures are 65.5 DEG C.The azeotropy rectification column number of plates is 22, and the flow of the ETBE added is
0.47g/min；Enter in liquid separation tank after the azeotropic mixture condensation that tower top obtains.
Liquid separation tank atmospheric operation, temperature be 50.5 DEG C, obtained light phase product infinite reflux into azeotrope column, heavy phase product into
Enter in ETBE recovery tower.Ethyl alcohol and light phase product matter therein is back to when reaching balance, in the ethyl alcohol concentration liquid in azeotrope column
Amount is than being 2.0~4.0.The ETBE recovery tower number of plates is 4, reflux ratio 6: 5, and obtained overhead product is recycled to concentration tower charging
Mouthful, tower kettle product is as wastewater treatment.By this process, it is 65.0g/min that azeotrope column tower reactor, which can produce flow, and purity is
The alcohol product of 99.3% (mass fraction).(water content 0.04% (mass fraction), ETBE content 0.66% (mass fraction))
Embodiment 2:
The low-concentration ethanol aqueous solution that mass percent is about 5% is added to ethyl alcohol concentration tower with the rate of 540g/min
In, while about 0.6% ethyl alcohol, the circulation of 3.7%ETBE (mass fraction, remaining part are water) are added with the rate of 3.5g/min
Liquid.The ethyl alcohol concentration tower number of plates is 16, reflux ratio 5: 2；Concentrate column overhead temperatures are 76.0 DEG C.
Obtaining flow is 61.9g/min, and purity is the ethyl alcohol concentration liquid of 80.3% (mass fraction), into azeotropy rectification column
In, control azeotropic distillation column overhead temperatures are 65.5 DEG C.The azeotropy rectification column number of plates is 22, and the flow of the ETBE added is
0.33g/min；Enter in liquid separation tank after the azeotropic mixture condensation that tower top obtains.
Liquid separation tank atmospheric operation, temperature be 50.5 DEG C, obtained light phase product infinite reflux into azeotrope column, heavy phase product into
Enter in ETBE recovery tower.Ethyl alcohol and light phase product matter therein is back to when reaching balance, in the ethyl alcohol concentration liquid in azeotrope column
Amount is than being 2.0~4.0.The ETBE recovery tower number of plates is 4, reflux ratio 5: 4, and obtained overhead product is recycled to concentration tower charging
Mouthful, tower kettle product is as wastewater treatment.By this process, it is 63.6g/min that azeotrope column tower reactor, which can produce flow, and purity is
The alcohol product of 99.5% (mass fraction).(water content 0.036% (mass fraction), (quality point of ETBE content 0.464%
Number))
Embodiment 3:
The low-concentration ethanol aqueous solution that mass percent is about 5% is added to ethyl alcohol concentration tower with the rate of 540g/min
In, while about 0.6% ethyl alcohol, the circulation of 3.7%ETBE (mass fraction, remaining part are water) are added with the rate of 3.5g/min
Liquid.The ethyl alcohol concentration tower number of plates is 16, reflux ratio 3: 1；Concentrate column overhead temperatures are 75.7 DEG C.
Obtaining flow is 54.2g/min, and purity is the ethyl alcohol concentration liquid of 83.6% (mass fraction), into azeotropy rectification column
In, control azeotropic distillation column overhead temperatures are 65.5 DEG C.The azeotropy rectification column number of plates is 22, and the flow of the ETBE added is
0.18g/min；Enter in liquid separation tank after the azeotropic mixture condensation that tower top obtains.
Liquid separation tank atmospheric operation, temperature be 50.5 DEG C, obtained light phase product infinite reflux into azeotrope column, heavy phase product into
Enter in ETBE recovery tower.Ethyl alcohol and light phase product matter therein is back to when reaching balance, in the ethyl alcohol concentration liquid in azeotrope column
Amount is than being 2.0~4.0.The ETBE recovery tower number of plates is 4, reflux ratio 4: 3, and obtained overhead product is recycled to concentration tower charging
Mouthful, tower kettle product is as wastewater treatment.By this process, it is 61.3g/min that azeotrope column tower reactor, which can produce flow, and purity is
The alcohol product of 99.7% (mass fraction).(water content 0.03% (mass fraction), ETBE content 0.27% (mass fraction))
Embodiment 4
The low-concentration ethanol aqueous solution that mass percent is about 5% is added to ethyl alcohol concentration tower with the rate of 180g/min
In, while about 0.6% ethyl alcohol, the circulation of 3.7%ETBE (mass fraction, remaining part are water) are added with the rate of 3.5g/min
Liquid.The ethyl alcohol concentration tower number of plates is 16, reflux ratio 2: 1；Concentrate column overhead temperatures are 72.8 DEG C.
Obtaining flow is 23.6g/min, and purity is the ethyl alcohol concentration liquid of 63.8% (mass fraction), into azeotropy rectification column
In, control azeotropic distillation column overhead temperatures are 65.5 DEG C.The azeotropy rectification column number of plates is 22, and the flow of the ETBE added is
0.46g/min；Enter in liquid separation tank after the azeotropic mixture condensation that tower top obtains.
Liquid separation tank atmospheric operation, temperature be 50.5 DEG C, obtained light phase product infinite reflux into azeotrope column, heavy phase product into
Enter in ETBE recovery tower.Ethyl alcohol and light phase product matter therein is back to when reaching balance, in the ethyl alcohol concentration liquid in azeotrope column
Amount is than being 2.0~4.0.The ETBE recovery tower number of plates is 4, reflux ratio 6: 5, and obtained overhead product is recycled to concentration tower charging
Mouthful, tower kettle product is as wastewater treatment.By this process, it is 20.9g/min that azeotrope column tower reactor, which can produce flow, and purity is
The alcohol product of 97.9% (mass fraction).(water content 0.1% (mass fraction), ETBE content 2.0% (mass fraction))
Embodiment 5
The low-concentration ethanol aqueous solution that mass percent is about 5% is added to ethyl alcohol concentrate with the rate of 1750g/min
In tower, while about 0.6% ethyl alcohol is added with the rate of 3.5g/min, 3.7%ETBE (mass fraction, remaining part are water) follows
Ring liquid.The ethyl alcohol concentration tower number of plates is 16, reflux ratio 2: 1；Concentrate column overhead temperatures are 76.2 DEG C.
Obtaining flow is 232.6g/min, and purity is the ethyl alcohol concentration liquid of 79.2% (mass fraction), into azeotropic distillation
In tower, control azeotropic distillation column overhead temperatures are 65.5 DEG C.The azeotropy rectification column number of plates is 22, and the flow of the ETBE added is
4.1g/min；Enter in liquid separation tank after the azeotropic mixture condensation that tower top obtains.
Liquid separation tank atmospheric operation, temperature be 50.5 DEG C, obtained light phase product infinite reflux into azeotrope column, heavy phase product into
Enter in ETBE recovery tower.Ethyl alcohol and light phase product matter therein is back to when reaching balance, in the ethyl alcohol concentration liquid in azeotrope column
Amount is than being 2.0~4.0.The ETBE recovery tower number of plates is 4, reflux ratio 6: 5, and obtained overhead product is recycled to concentration tower charging
Mouthful, tower kettle product is as wastewater treatment.By this process, it is 208.3g/min that azeotrope column tower reactor, which can produce flow, and purity is
The alcohol product of 98.0% (mass fraction).(water content 0.2% (mass fraction), ETBE content 1.8% (mass fraction))
Comparative example 1
It is compared with embodiment 1, difference is, critical component (ETBE) do not added, and directly ethanol water is distilled,
Since ethyl alcohol, water are in 78.1 DEG C of azeotropic, the ethyl alcohol of water content 4.4wt% is finally obtained.
Comparative example 2
The low-concentration ethanol aqueous solution that mass percent is about 5% is added to ethyl alcohol concentrate with the rate of 2800g/min
In tower, while about 0.6% ethyl alcohol is added with the rate of 3.5g/min, 3.7%ETBE (mass fraction, remaining part are water) follows
Ring liquid.The ethyl alcohol concentration tower number of plates is 16, reflux ratio 2: 1；Concentrate column overhead temperatures are 77.4 DEG C.
Obtaining flow is 358.4g/min, and purity is the ethyl alcohol concentration liquid of 81.9% (mass fraction), into azeotropic distillation
In tower, control azeotropic distillation column overhead temperatures are 65.5 DEG C.The azeotropy rectification column number of plates is 22, and the flow of the ETBE added is
4.3g/min；Enter in liquid separation tank after the azeotropic mixture condensation that tower top obtains.
Liquid separation tank atmospheric operation, temperature be 50.5 DEG C, obtained light phase product infinite reflux into azeotrope column, heavy phase product into
Enter in ETBE recovery tower.Ethyl alcohol and light phase product matter therein is back to when reaching balance, in the ethyl alcohol concentration liquid in azeotrope column
Amount is than being 2.0~4.0.The ETBE recovery tower number of plates is 4, reflux ratio 6: 5, and obtained overhead product is recycled to concentration tower charging
Mouthful, tower kettle product is as wastewater treatment.By this process, it is 325.8g/min that azeotrope column tower reactor, which can produce flow, and purity is
The alcohol product of 97.9% (mass fraction).(water content 0.9% (mass fraction), ETBE content 1.2% (mass fraction))
Comparative example 3
The low-concentration ethanol aqueous solution that mass percent is about 5% is added to ethyl alcohol concentrate with the rate of 4000g/min
In tower, while about 0.6% ethyl alcohol is added with the rate of 3.5g/min, 3.7%ETBE (mass fraction, remaining part are water) follows
Ring liquid.The ethyl alcohol concentration tower number of plates is 16, reflux ratio 2: 1；Concentrate column overhead temperatures are 77.9 DEG C.
Obtaining flow is 520.6g/min, and purity is the ethyl alcohol concentration liquid of 83.7% (mass fraction), into azeotropic distillation
In tower, control azeotropic distillation column overhead temperatures are 65.5 DEG C.The azeotropy rectification column number of plates is 22, and the flow of the ETBE added is
4.0g/min；Enter in liquid separation tank after the azeotropic mixture condensation that tower top obtains.
Liquid separation tank atmospheric operation, temperature be 50.5 DEG C, obtained light phase product infinite reflux into azeotrope column, heavy phase product into
Enter in ETBE recovery tower.Ethyl alcohol and light phase product matter therein is back to when reaching balance, in the ethyl alcohol concentration liquid in azeotrope column
Amount is than being 2.0~4.0.The ETBE recovery tower number of plates is 4, reflux ratio 6: 5, and obtained overhead product is recycled to concentration tower charging
Mouthful, tower kettle product is as wastewater treatment.By this process, it is 462.9g/min that azeotrope column tower reactor, which can produce flow, and purity is
The alcohol product of 96.6% (mass fraction).(water content 2.6% (mass fraction), ETBE content 0.8% (mass fraction))
A specific embodiment of the invention is described in conjunction with attached drawing above, but these explanations cannot be understood to limit
The scope of the present invention, protection scope of the present invention are limited by appended claims, any on the claims basis
On change be all protection scope of the present invention.
Claims (27)
1. a kind of method of separating alcohol-water, it is characterised in that: the following steps are included:
Step (1): hydrous ethanol raw material and the ethyl tert-butyl ether (ETBE) azeotropic at 70~81 DEG C obtain ethyl alcohol concentration liquid；
Step (2): ethyl alcohol concentration liquid and the ethyl tert-butyl ether (ETBE) azeotropic at 63~68 DEG C；Isolated ethyl alcohol and H2O-ETBE is total
Boil object.
2. the method for separating alcohol-water as described in claim 1, it is characterised in that: in step (1), hydrous ethanol raw material and
The volume of material ratio of ethyl tert-butyl ethereal solution is 50~800.
3. the method for separating alcohol-water as claimed in claim 2, it is characterised in that: hydrous ethanol raw material and ethyl tert-butyl
The volume of material ratio of ethereal solution is 100~500.
4. the method for separating alcohol-water as described in claim 1, it is characterised in that: the azeotropic temperature of step (1) is 75~77
℃。
5. the method for separating alcohol-water as described in claim 1, it is characterised in that: in step (2), second in ethyl alcohol concentration liquid
The weight ratio of alcohol and ethyl tert-butyl ether (ETBE) is 1.5~4.5.
6. the method for separating alcohol-water as described in claim 1, it is characterised in that: the temperature of step (2) is 65~66 DEG C.
7. the method for separating alcohol-water as described in claim 1, it is characterised in that: H2O-ETBE azeotropic mixture through water-oil separating at
Reason, isolated oil are mutually recycled in step (2).
8. the method for separating alcohol-water as claimed in claim 7, it is characterised in that: ethyl alcohol and circulating sleeve in ethyl alcohol concentration liquid
The mass ratio of oily phase is 2.0~4.0.
9. the method for separating alcohol-water as claimed in claim 7, it is characterised in that: the water phase that water-oil separating obtains is through distilling
Processing, fraction are ethyl tert-butyl ether (ETBE), in recycled to step (1).
10. the method for separating alcohol-water as described in claim 1, it is characterised in that: the hydrous ethanol raw material it is aqueous
Measure > 0wt%.
11. the method for separating alcohol-water as claimed in claim 10, it is characterised in that: the hydrous ethanol raw material contains
4.5~99.5wt% of water.
12. the method for separating alcohol-water as claimed in claim 11, it is characterised in that: the water content of hydrous ethanol raw material >=
90wt%.
13. as the described in any item separating alcohol-waters of claim 1~12 method, it is characterised in that: hydrous ethanol raw material and
Ethyl tert-butyl ether (ETBE) enters concentration tower, and the temperature in control concentration tower top material exit is 70~81 DEG C, in concentrate tower bottom
Waste water is obtained, top obtains ethyl alcohol concentration liquid；
Ethyl alcohol concentration liquid and ethyl tert-butyl ether (ETBE) are directed into azeotropy rectification column, azeotropy rectification column top material exit is controlled
Temperature be 63~68 DEG C, obtain ethyl alcohol in azeotropic tower bottom；
The H of azeotropic distillation top of tower outflow2O-ETBE azeotropic mixture enters liquid separation tank, carries out water-oil separating；Oily is mutually ethyl tert-butyl
Ether, recycled to azeotropy rectification column；
After water phase passes through recovery tower rectifying, tower bottom discharge of wastewater, overhead product is back to concentration tower.
14. the method for separating alcohol-water as claimed in claim 13, it is characterised in that: concentration tower theoretical cam curve is 15-
25。
15. the method for separating alcohol-water as claimed in claim 13, it is characterised in that: the operating pressure of concentration tower is normal pressure.
16. the method for separating alcohol-water as claimed in claim 13, it is characterised in that: the operating reflux ratio of concentration tower is
0.5-5.0。
17. the method for separating alcohol-water as claimed in claim 13, it is characterised in that: second when reaching balance, in azeotrope column
Alcohol and the mass ratio of the oily phase of recycled in liquid separation tank are 2.0~4.0.
18. the method for separating alcohol-water as claimed in claim 17, it is characterised in that: in azeotropy rectification column azeotropic process, also
Ethyl tert-butyl ether (ETBE) is added into tower reactor；Wherein, ethyl alcohol concentration liquid be 50 with the volume ratio of ethyl tert-butyl ether (ETBE) added~
500。
19. the method for separating alcohol-water as claimed in claim 18, it is characterised in that: ethyl alcohol concentration liquid and the ethyl added
The volume ratio of tertbutyl ether is 150~350.
20. the method for separating alcohol-water as claimed in claim 13, it is characterised in that: azeotropy rectification column theoretical cam curve is
20-40。
21. the method for separating alcohol-water as claimed in claim 13, it is characterised in that: the operating pressure of azeotropy rectification column is
Normal pressure.
22. the method for separating alcohol-water as claimed in claim 13, it is characterised in that: azeotropy rectification column is total reflux operation.
23. the method for separating alcohol-water as claimed in claim 13, it is characterised in that: recovery tower theoretical cam curve is 3-10.
24. the method for separating alcohol-water as claimed in claim 13, it is characterised in that: the operating pressure of recovery tower is normal pressure.
25. the method for separating alcohol-water as claimed in claim 13, it is characterised in that: the operating reflux ratio of recovery tower is
0.5-3.5。
26. such as the described in any item methods of claim 1~25, which is characterized in that fired isolated ethyl alcohol as ethyl alcohol
Material is added in gasoline.
27. a kind of alcohol-water separation system for implementing any one of claim 1~26 method, it is characterised in that: including concentrate
Tower, azeotropy rectification column, liquid separation tank and recovery tower；Concentration tower is provided with the raw material for receiving ethanol raw material and ethyl tert-butyl ether (ETBE)
Entrance, the tower bottom of concentration tower are provided with wastewater outlet, and the tower top of concentration tower is provided with material outlet；
The material outlet of concentration tower and the material inlet of azeotropy rectification column connect；The tower bottom of azeotropy rectification column is provided with ethyl alcohol and goes out
Mouthful；Material outlet is provided at the top of azeotropy rectification column；Azeotropy rectification column is additionally provided with the fluid infusion of ethyl tert-butyl ether (ETBE) and returns
Head piece；
The material outlet of azeotropy rectification column is connect with the entrance of liquid separation tank, and the oil of liquid separation tank mutually exports the reflux with azeotropy rectification column
Mouth connection, water phase outlet are connect with the material inlet of recovery tower；
The tower bottom of recovery tower is provided with wastewater outlet, and the outlet of tower top and the feed(raw material)inlet of concentration tower connect.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710907029.1A CN109574804A (en) | 2017-09-29 | 2017-09-29 | A kind of method of separating alcohol-water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710907029.1A CN109574804A (en) | 2017-09-29 | 2017-09-29 | A kind of method of separating alcohol-water |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109574804A true CN109574804A (en) | 2019-04-05 |
Family
ID=65914393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710907029.1A Pending CN109574804A (en) | 2017-09-29 | 2017-09-29 | A kind of method of separating alcohol-water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109574804A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5348624A (en) * | 1991-11-12 | 1994-09-20 | Institut Francais Du Petrole | Process for separating ethyl tert-butyl ether and ethanol |
| CN1127243A (en) * | 1994-05-05 | 1996-07-24 | 法国石油公司 | Method for purification ether containing two distilation steps |
| CN102719282A (en) * | 2012-07-03 | 2012-10-10 | 华东理工大学 | Ethanol-water separation method based on automotive fuel and with methyl tertiary butyl ether (MTBE) serving as entrainer |
| CN102875327A (en) * | 2012-10-30 | 2013-01-16 | 中国海洋大学 | Technique for preparing absolute ethanol from near-azeotropic-concentration ethanol-water mixture |
-
2017
- 2017-09-29 CN CN201710907029.1A patent/CN109574804A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5348624A (en) * | 1991-11-12 | 1994-09-20 | Institut Francais Du Petrole | Process for separating ethyl tert-butyl ether and ethanol |
| CN1127243A (en) * | 1994-05-05 | 1996-07-24 | 法国石油公司 | Method for purification ether containing two distilation steps |
| CN102719282A (en) * | 2012-07-03 | 2012-10-10 | 华东理工大学 | Ethanol-water separation method based on automotive fuel and with methyl tertiary butyl ether (MTBE) serving as entrainer |
| CN102875327A (en) * | 2012-10-30 | 2013-01-16 | 中国海洋大学 | Technique for preparing absolute ethanol from near-azeotropic-concentration ethanol-water mixture |
Non-Patent Citations (1)
| Title |
|---|
| 刘伟: "生物乙醇基醇醚燃料分离过程的优化", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4366032A (en) | Process for producing dehydrated alcohols for use as component of a motor fuel composition | |
| CN104529703B (en) | MAS piece-rate system and separation method | |
| CN102471195A (en) | Recovery of butanol from a mixture of butanol, water, and an organic extractant | |
| CN108531342B (en) | Production method and equipment for neutral edible brewed alcohol product | |
| CN105111079A (en) | Method and device for separating acetic acid sec-butyl ester and sec-butyl alcohol | |
| CN111100004B (en) | Method and integrated device for refining dimethyl carbonate | |
| CN103664446A (en) | Technology for separating n-hexane-methylcyclopentane through extractive distillation | |
| CN107556172B (en) | Process method for producing ethylene glycol mono-tert-butyl ether | |
| CN110835288A (en) | Method for separating ethanol and utilizing energy | |
| EP2934712B1 (en) | Production of ethanol products | |
| CN102719282A (en) | Ethanol-water separation method based on automotive fuel and with methyl tertiary butyl ether (MTBE) serving as entrainer | |
| CN109574804A (en) | A kind of method of separating alcohol-water | |
| CN111573761A (en) | Method and system for separating and recovering non-acidic oxygen-containing organic matters in Fischer-Tropsch synthesis water | |
| CN111377801B (en) | Method and system for refining low carbon alcohol | |
| CN106187717B (en) | The method for being thermally integrated variable-pressure rectification separation methyl tertiary butyl ether(MTBE) and methanol azeotrope | |
| CN107162875B (en) | Process and system for extracting refined methanol and absolute ethanol from crude methanol | |
| CN210765173U (en) | Aromatic extraction combination device | |
| CN111500316B (en) | Method for preparing heavy aromatic hydrocarbon by extractive distillation | |
| JP2009256294A (en) | Economical process for producing anhydrous alcohol or gasohol using ether solvent | |
| CN216855710U (en) | BDO byproduct butanol recovery system | |
| CN110628459A (en) | Aromatic hydrocarbon extraction combined device and process | |
| CN109679679A (en) | A kind of heavy aromatics industrial process | |
| CN110835286A (en) | Method for recovering ethanol | |
| CN116003233B (en) | Method for separating mixture of water, acetone and methyl acetate | |
| CN110668920A (en) | Method for preparing ethanol and co-producing cyclohexanol by using reactive distillation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190405 |