CN104341268B - Continuous dehydration method for fuel ethanol - Google Patents

Continuous dehydration method for fuel ethanol Download PDF

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Publication number
CN104341268B
CN104341268B CN201310345199.7A CN201310345199A CN104341268B CN 104341268 B CN104341268 B CN 104341268B CN 201310345199 A CN201310345199 A CN 201310345199A CN 104341268 B CN104341268 B CN 104341268B
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ethanol
separation device
vacuum pump
tower
membrane separation
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CN104341268A (en
Inventor
惠继星
刘海军
徐友海
岳军
胡世洋
王龙辉
金刚
高玉玲
王继艳
吕继萍
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Petrochina Co Ltd
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Petrochina Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07CACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/74Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/76Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
    • C07C29/80Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/10Process efficiency

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention relates to a continuous dehydration method of fuel ethanol; the membrane separation device adopts a polyvinyl alcohol composite membrane, ethanol water solution with the mass fraction of 35-55% is continuously fed into an ethanol rectification tower, the liquid level of a tower kettle is 60%, a tower top condensing system is opened, the temperature of the tower kettle is raised, when reflux occurs, the total reflux lasts for 30min, and after the system is stabilized, a vacuum pump is started, so that the absolute pressure of the permeation side of the membrane separation device is controlled to be less than or equal to 10 KPa; the gaseous material at the top of the ethanol rectification tower enters a gas-liquid separation tank, and enters from an inlet at the retentate side of a membrane separation device after gas-liquid separation, and absolute ethanol is obtained at an outlet at the retentate side; gas at the permeation side enters an ethanol rectifying tower after passing through a vacuum pump; materials at the bottom of the ethanol rectification tower enter from a jacket inlet of the membrane separation device and are discharged from an outlet; the method can obtain the absolute ethyl alcohol with the ethyl alcohol content of 99.5-99.9% (V), and has the advantages of short flow, convenient operation, low energy consumption and no pollution.

Description

A kind of alcohol fuel continuous dehydration method
Technical field:
The present invention relates to fuel alcohol dewatering technology, couple even with water vapour penetration particularly to a kind of rectification Continuous separating alcohol and the technique of water.
Background technology
In recent years, in global range, face serious energy crisis, find novel fungible energy source Become the key of various countries' future source of energy strategy.Among these, alcohol fuel have renewable, efficient, The features such as low cost, safety, can be directly used as liquid fuel or be used in mixed way with gasoline, reduce Dependence to non-renewable energy resources oil, thus ensure the safety of domestically produced energy.By to paddy Thing, potato class and the fermentation of saccharine material, distillation can produce ethanol continuously.But steamed by simple Evaporate the concentration of alcohol of generation less than 96%(V/V), and as gasoline, the combustion of the effective additive of diesel oil Ethanol content in material ethanol must be not less than 99.5%(W/W), the method for ethanol dehydration substantially has following 4 kinds:
(1) quick lime method: by quick lime and the alcoholic solution heat altogether of 95%, reflux for a long time, so Rear distillation.Quick lime and calcium chloride have strong water absorption, generate calcium hydroxide and band knot after water suction Calcium chloride (the CaCl of brilliant water2·H2O).Moisture in absorbent lime ethanol solution, calcium chloride is inhaled Receive the moisture in vapour phase, thus reach to remove the effect of moisture in ethanol.Can prepare containing second by this method Alcohol is up to the ethanol of 99.5%~99.8%.But the yield of dehydrated alcohol is only the 75% of theoretical value, Labor intensity is big simultaneously, and poor product quality is the most superseded.
(2) molecular sieve dehydration: after being passed through by the ethanol of 96% with 3A type molecular sieve, molecular sieve can be Water adsorption in ethanol, so that the purity of ethanol is improved.Molecular sieve has extremely strong suction Attached ability and the adsorptive selectivity of height, good mechanical performance simultaneously, Heat stability is good, but pass The molecular sieve dehydration technique of system also exists that price is high, regeneration temperature high, energy consumption is relatively big and energy regenerating The problem that utilization rate is relatively low.
(3) azeotropic distillation: azeotropic distillation is one of conventional chemical separating method, is usually used in perseverance Boiling thing or the separation of nearly azeotrope.In the case of dehydrated alcohol cannot being produced at ambient pressure, use to It adds entrainer and carries out rectification, and conventional entrainer has benzene, hexamethylene, pentane, ether etc.. Now entrainer and the ethanol in alcoholic solution, water form new ternary azeotrope, and at this moment ternary is permanent Boiling-point difference between boiling thing and pure component ethanol or water is relatively big, thus is obtained by rectification relatively easily The ethanol that purity is the highest.Azeotropic distillation has mechanization degree height, production is stablized, yield is big, Technology maturation, product purity advantages of higher, be the main method of Industrial Production of Anhydrous Alcohol, but It is that energy consumption is relatively big, and entrainer can cause environmental pollution the most at that time in production operation.
(4) extracting rectifying: conventional extractant has glycerol, ethylene glycol etc..Second in extractive distillation column Alcohol vapour ramps up, and solvent is taken away the moisture in ethanol vapor to the counter-current extraction declined, solvent, Dehydrated alcohol exits at tower top, and discharge at the bottom of tower is the solvent with moisture, can answer after solvent reclamation With.But solvent reclamation energy consumption is more.
Patent CN201020286456.6 discloses a kind of vapor permeable membrane for producing dehydrated alcohol Device and ethanol dehydration system, membrane module use poly-phthalimide filter membrane, in its application example by It is connected with vacuum pump and rectifying column respectively in fluid reservoir, owing to rectifying column is positive pressure operation, it is impossible to real , there is the shortcoming that ethanol recovery is low in the normal charging to rectifying column of the existing liquid storage pot liquid simultaneously.
Summary of the invention
It is an object of the invention to provide a kind of low energy consumption, free of contamination alcohol fuel continuous dehydration method. This method uses membrane separation device, has that flow process is short, energy consumption is low, low equipment investment, alcohol production Low cost and other advantages.
A kind of alcohol fuel continuous dehydration method of the present invention, it is characterised in that membrane separation device Use composite membrane of polyvinyl alcohol, specifically comprise the following steps that
(1) by mass fraction be 35~55% ethanol water be continuously introduced in Ethanol rectification column, make Tower reactor liquid level, 60%, opens overhead condenser, heats up tower reactor, when there being backflow, and infinite reflux 30min, after system stability, opens vacuum pump, makes membrane separation device per-meate side absolute pressure control ≤10KPa;
(2) Ethanol rectification column top Gaseous materials enters knockout drum, after gas-liquid separation, by film Segregation apparatus retentate side entrance enters, and obtains dehydrated alcohol in retentate side outlet;Per-meate side gas warp After vacuum pump, enter Ethanol rectification column;
(3) Ethanol rectification column bottoms material is entered by the JI of membrane separation device, outlet arrange Go out;
Described Ethanol rectification column theoretical cam curve is 35~45, tower top operation pressure be 110~ 125KPa。
Described vacuum pump uses oil-free dry vacuum pump, this pumping outlet pressure≤10KPa, aerofluxus Mouth pressure >=125KPa.
Described membrane separation device per-meate side and retentate side are equipped with water-bath chuck.
Beneficial effects of the present invention:
The present invention provides a kind of and utilizes rectification and water vapour penetration coupling continuously separating ethanol and the work of water Skill, through rectification and membrane separation device, available ethanol content is 99.5%~99.9%(V) nothing Water-ethanol, Appropriate application system thermal of the present invention, reduce the production cost of alcohol fuel, permissible Realize steady in a long-term operation, have that flow process is short, easy to operate, energy consumption is low, free of contamination advantage.
Accompanying drawing illustrates:
Fig. 1 is the process chart of the present invention.
1. inlet valve;2. Ethanol rectification column;3 condensers;4. knockout drum;5. overhead extraction valve; 6. membrane separation device;7. vacuum meter;8. heat exchanger;9. ethanol collecting tank;10. product extraction valve; 11. thermometeies;12. reflux inlets;13. vacuum pump outlet valves;14 vacuum pumps;15 vacuum pump imports Valve;Extraction valve at the bottom of 16. towers;17. tower top pressure tables;18 reboilers;
Detailed description of the invention
Embodiment 1
Open inlet valve 1, the ethanol water that mass fraction is 35% sent in Ethanol rectification column 2, When tower reactor liquid level reaches 60%, close inlet valve 1, stop charging;Open Ethanol rectification column 2 tower Top condenser 3, reflux inlet 12, open tower reactor and add thermocurrent, make tower reactor steadily heat up, work as tower top When producing backflow, infinite reflux 30min, after tower top, bottom temperature, back-flow velocity are stablized, tower top In backflow, ethanol content is 90.4%, now bottom temperature and pressure be respectively 103.2 DEG C and 125KPa, the temperature of tower top and pressure are respectively 78.5 DEG C and 120KPa;Open vacuum pump outlet valve 13 and vacuum pump inlet valve 15, start vacuum pump 14, start evacuation, stable after, membrance separation fills Putting 6 per-meate side pressure is 8KPa, and per-meate side gas is entered Ethanol rectification column by top after vacuum pump. Opening overhead extraction valve 5 and inlet valve 1, inlet amount is 2kg/h, by regulation tower top condensation flow Amount makes tower top pressure stable at 110Kpa, Ethanol rectification column substrate material after membrane separation device chuck by Outlet is discharged, and extraction valve 16 at the bottom of adjusting tower makes tower reactor Liquid level 60%, and stable rear membrance separation fills Putting jacket temperature is 85.2 DEG C, Ethanol rectification column tower top temperature and pressure be respectively 80.1 DEG C and 110KPa, bottom temperature and pressure are respectively 102.5 DEG C and 112Kpa, Ethanol rectification column top gas state Material enters knockout drum 4, after gas-liquid separation, membrane separation device retentate side entrance enters, Dehydrated alcohol is obtained in retentate side outlet.Dehydrated alcohol enters ethanol by heat exchanger 8 shell side and collects Tank 9, dehydrated alcohol is plucked out of by being arranged on the product extraction valve 10 at ethanol collecting tank 9 end.Second Alcohol rectifying tower top is provided with tower top pressure table 17, is provided with reboiler 18 at the bottom of tower, the chuck of membrane separation device Being provided with thermometer 11, between vacuum pump inlet valve and membrane separation device per-meate side, pipeline is provided with very Empty table 7, tower reactor extraction flow is 1.3kg/h, and in tower bottoms, ethanol content is 2.6%, product extraction Flow is 0.65kg/h, and product is 99.5%(V containing ethanol), ethanol recovery is 94.5%.
Embodiment 2
Open inlet valve 1, the ethanol water that mass fraction is 55% sent in Ethanol rectification column 2, When tower reactor liquid level reaches 60%, close inlet valve 1, stop charging;Open Ethanol rectification column tower top Condenser system, opens tower reactor and adds thermocurrent, makes tower reactor steadily heat up, when tower top produces backflow, Infinite reflux 30min, after tower top, bottom temperature, back-flow velocity are stablized, ethanol in overhead reflux liquid Content is 92.8%, and now temperature and the pressure of tower reactor is respectively 102.6 DEG C and 124KPa, tower top Temperature and pressure are respectively 78.9 DEG C and 122KPa;Open valve 13 and 15 before and after vacuum pump, start Vacuum pump 14 starts evacuation, and after stablizing, membrane separation device per-meate side pressure is 8KPa, per-meate side Gas is entered Ethanol rectification column by top after vacuum pump.Open overhead extraction valve 5 and charging simultaneously Valve 1, inlet amount is 2kg/h, and regulation tower top condensate flow makes tower top pressure stable at 112Kpa Left and right, Ethanol rectification column substrate material is discharged by outlet after membrane separation device chuck, adopts at the bottom of adjusting tower Going out valve 16 makes tower reactor liquid level about 60%, and stable rear membrane separation device jacket temperature is 87.2 DEG C, Ethanol rectification column tower top temperature and pressure are respectively 80.3 DEG C and 112Kpa, bottom temperature and pressure divide Not being 102.8 DEG C and 115KPa, tower reactor extraction flow is 0.92kg/h, and in tower bottoms, ethanol content is 2.8%, product extraction flow is 0.98kg/h, and product is 99.8%(V containing ethanol), ethanol reclaims Rate is 96.2%.

Claims (5)

1. an alcohol fuel continuous dehydration method, it is characterised in that: membrane separation device uses poly-second Enol composite membrane, specifically comprises the following steps that
(1) by mass fraction be 35~55% ethanol water be continuously introduced in Ethanol rectification column, make Tower reactor liquid level, 60%, opens overhead condenser, heats up tower reactor simultaneously, when there being backflow, entirely returns Stream 30min;After system stability, open vacuum pump, make membrane separation device per-meate side absolute pressure control At≤10KPa;
(2) Ethanol rectification column top Gaseous materials enters knockout drum, after gas-liquid separation, by film Segregation apparatus retentate side entrance enters, and obtains dehydrated alcohol in retentate side outlet;Per-meate side gas warp After vacuum pump, enter Ethanol rectification column;
(3) Ethanol rectification column bottoms material is entered by the JI of membrane separation device, outlet arrange Go out.
A kind of alcohol fuel continuous dehydration method the most according to claim 1, it is characterised in that The theoretical cam curve of Ethanol rectification column is 35~45, and tower top operation pressure is 110~125KPa.
A kind of alcohol fuel continuous dehydration method the most according to claim 1, it is characterised in that Vacuum pump uses oil-free dry vacuum pump.
A kind of alcohol fuel continuous dehydration method the most according to claim 1, it is characterised in that Membrane separation device per-meate side and retentate side are equipped with water-bath chuck.
A kind of alcohol fuel continuous dehydration method the most according to claim 1, it is characterised in that Vacuum pump bleeding point pressure≤10KPa, exhaust port pressure >=125KPa.
CN201310345199.7A 2013-08-09 2013-08-09 Continuous dehydration method for fuel ethanol Active CN104341268B (en)

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Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108083979B (en) * 2017-12-19 2024-04-16 江苏九天高科技股份有限公司 Ethanol production method and device
CN110483248B (en) * 2019-08-06 2022-08-23 中海油天津化工研究设计院有限公司 Method for refining fuel ethanol by coupling and strengthening three towers and two membranes
CN110511115B (en) * 2019-08-06 2022-08-23 中海油天津化工研究设计院有限公司 Method for coupling and strengthening separation of fuel ethanol by rectifying tower and membrane

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4405409A (en) * 1980-10-06 1983-09-20 Gunter Tusel Method and apparatus for dehydrating mixtures of organic liquids and water
CN101820964A (en) * 2007-10-12 2010-09-01 Epcon能源处理控制股份公司 Method for dewatering mixture of mostly ethanol and water
CN201744279U (en) * 2010-08-05 2011-02-16 安徽丰原生物化学股份有限公司 Vapour osmotic membrane device and ethanol dehydration system used for producing anhydrous ethyl alcohol
CN102180768A (en) * 2011-03-21 2011-09-14 安徽丰原生物化学股份有限公司 Method for preparing anhydrous alcohol
CN102260140A (en) * 2011-04-30 2011-11-30 白银阳明银光化工有限公司 New process for producing absolute ethanol by rectification and pervaporation method
CN103071307A (en) * 2013-01-23 2013-05-01 江苏九天高科技股份有限公司 Rectification-steam penetration-coupled organic solvent dewatering method and device

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20090117631A1 (en) * 2007-11-02 2009-05-07 Pierre Lucien Cote Alcohol extraction process for biofuel production

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4405409A (en) * 1980-10-06 1983-09-20 Gunter Tusel Method and apparatus for dehydrating mixtures of organic liquids and water
CN101820964A (en) * 2007-10-12 2010-09-01 Epcon能源处理控制股份公司 Method for dewatering mixture of mostly ethanol and water
CN201744279U (en) * 2010-08-05 2011-02-16 安徽丰原生物化学股份有限公司 Vapour osmotic membrane device and ethanol dehydration system used for producing anhydrous ethyl alcohol
CN102180768A (en) * 2011-03-21 2011-09-14 安徽丰原生物化学股份有限公司 Method for preparing anhydrous alcohol
CN102260140A (en) * 2011-04-30 2011-11-30 白银阳明银光化工有限公司 New process for producing absolute ethanol by rectification and pervaporation method
CN103071307A (en) * 2013-01-23 2013-05-01 江苏九天高科技股份有限公司 Rectification-steam penetration-coupled organic solvent dewatering method and device

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