CN1186450C - Method for preparing absolute ethanol by biological substance fermentation and inembrane permeation vaporization - Google Patents

Method for preparing absolute ethanol by biological substance fermentation and inembrane permeation vaporization Download PDF

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Publication number
CN1186450C
CN1186450C CNB031134408A CN03113440A CN1186450C CN 1186450 C CN1186450 C CN 1186450C CN B031134408 A CNB031134408 A CN B031134408A CN 03113440 A CN03113440 A CN 03113440A CN 1186450 C CN1186450 C CN 1186450C
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alcohol
membrane
liquid
vaporization
permeation
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CN1450166A (en
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徐南平
林晓
仲盛来
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Nanjing Tech University
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Nanjing Tech University
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    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

Abstract

The present invention relates to an absolute alcohol preparing method through biomass fermentation and membrane permeation and vaporization, which provides an absolute alcohol production process through the technology integration of biomass fermentation, permeation vaporization (PV) and vapor permeation (VP). Fermentation liquid containing low concentration alcohol in a fermentation tank is pumped out, and alcohol permeates through a micro-filtration membrane and an alcohol permeating membrane so that alcohol is densified to 40 to 95 wt%. According to the different concentration of the fermentation liquid which is pumped out, densified permeating liquid can be directly loaded into an inorganic water permeating membrane separator for permeation and water removal; or primary distillation and concentration are first carried out, and the liquid is then loaded into the inorganic water permeating membrane separator for permeation and residual water removal; an absolute alcohol product of which the alcohol content is greater than or equal to 99.5 wt% is finally obtained. In the present invention, alcohol fermentation, the permeation and the vaporization of inorganic membranes and the technology of vapor permeation are coupled; thereby, the present invention has the advantages of reduced inhibitory action of alcohol in a fermentation process, enhanced production capacity, energy consumption saving in production, and greatly reduced production cost of alcohol.

Description

Biomass ferment and membrane permeation vaporization prepare the method for dehydrated alcohol
(technical field)
The present invention relates to a kind of is that raw material prepares the method for dehydrated alcohol with the membrane permeation vaporization by fermenting with biomass.
(background technology)
Dehydrated alcohol is commonly called as raw spirit, is not only a kind of very important Organic Chemicals and solvent, and because of it renewable and environmentally safe, be considered to substitute the most promising liquid fuel of petroleum-type Nonrenewable energy resources.
At present, be that the feedstock production process of anhydrous ethyl alcohol adopts batch fermentation mostly with biomass such as agricultural-food or vegetable fibres, this is because the increase meeting of alcohol concn produces feedback inhibition to fermenting process in the fermentor tank, enzymic activity is weakened, fermentation capacity reduces, and therefore, throughput is low.In addition, when ethanol concn reaches 95.57% (weight), have lower azeotropic point, it is meaningless to continue distillation, must adopt other method further dewater dehydrated alcohol.All there are many shortcomings in dewaterings such as traditional lime evaporation, absorption method, azeotropic distn, extractive distillation method, cause that dehydrated alcohol throughput is low, energy consumption is high, facility investment is big, and cost is too high.
(summary of the invention)
The purpose of this invention is to provide a kind of biomass ferment and membrane permeation vaporization preparation dehydrated alcohol method, ceramic membrane infiltration evaporation process and ethanol fermentation process are coupled,, improve plant capacity, reduce cost to reduce energy consumption.
The present invention prepares the method for dehydrated alcohol by following rapid:
Biomass starting material is placed in the fermentor tank, hydrolysis reaction at a certain temperature, when the fermented liquid that generates in the fermentor tank contains ethanol at 3～20wt%, fermented liquid is extracted out by pump, feed the inorganic micro filtering membrane separation apparatus, the side that sees through at film adopts the vacuum pump suction, isolating through liquid through microfiltration membrane is the second alcohol and water, should see through and import inorganic alcohol permselective membrane separator after liquid is heated to 40～70 ℃, the side that sees through of alcohol permselective membrane keeps vacuum tightness 1～5 mmhg, and ethanol is through alcohol permselective membrane infiltration evaporation enrichment to 40～95wt%; After being heated to 100～150 ℃ of gasifications, send into inorganic water permeable membrane separator, the side that sees through of film keeps vacuum tightness 1～5 mmhg, and wherein contained water vapor permeation is removed, with do not see through collect after the gas cooling the dehydrated alcohol of concentration 〉=99.5wt%.
Among the present invention, according to the alcohol concn difference of extracting out from fermentor tank, different by the alcohol concn behind the alcohol permselective membrane infiltration enrichment, when fermentor tank extraction concentration was 10～20wt%, the alcohol concn behind the alcohol permselective membrane infiltration evaporation reached 80～95wt%; When fermentor tank extraction concentration was 3～10wt%, the alcohol concn behind the alcohol permselective membrane infiltration evaporation was 40～65wt%.The latter is before the water permeable membrane separator is sent in the heating vaporization, can send into the distillation tower predistillation earlier carries dense, extract the concentration liquid that contains ethanol 90～95wt% out from cat head, after concentration liquid being heated to 100～150 ℃ of gasifications then, send into inorganic water permeable membrane separator dewater 〉=dehydrated alcohol of 99.5wt%.Send fermentor tank in the lump back to and continue to participate in hydrolysis reaction from the effusive effusive effusive liquid that sees through of liquid, water permeable membrane separator that sees through of liquid, alcohol permselective membrane separator that sees through of above-mentioned inorganic micro filtering membrane separation apparatus.
The aperture of the inorganic micro filtering membrane that the present invention adopts is 0.1～1 μ m, and inorganic alcohol permselective membrane is a MFI type molecular screen membrane, and inorganic water permeable membrane is a NaA type molecular screen membrane.It is the Al of 0.1～1 μ m that inorganic micro filtering membrane adopts the aperture 2O 3Film.
The size of the alcohol concn of above-mentioned fermentor tank Extract is decided by the conditions such as quality of fermented bacterium.
The present invention is the coupling of biomass ferment and permeable inorganic membrane vaporization technology, and the fermented liquid that contains low-concentration ethanol that biomass ferment is generated is realized the ethanol initial gross separation through microfiltration membrane infiltration, alcohol permselective membrane infiltration evaporation.The circulation of the yeast cell that does not see through and fermented liquid turns back in the fermenter and together proceeds fermentation with initiate fresh culture, has eliminated the feedback inhibition of ethanol to fermenting process, has guaranteed that the biological fermentation reaction carries out continuously.The ethanol of 80～95wt% or obtain the dehydrated alcohol product by the water permeable membrane dehydration continuously in addition by 90～95wt% ethanol that predistillation obtains.The present invention is fed into from raw material and makes the dehydrated alcohol product, can realize operate continuously, compare with existing technology, and the conversion rate of products height, easy to operate, produce total energy consumption and reduce.
Among the present invention, alcohol permselective membrane adopts infiltration evaporation (PV) technology, and the second alcohol and water is with liquid feeding, and the method generation impellent of opposite side by vacuumizing at film makes ethanol infiltration evaporation constantly; Water permeable membrane adopts water vapour penetration (VP) technology, makes the feed liquid vaporization by intensification, and feed liquid contacts with film with vapor form, makes water vapor permeation and separates with ethanol.Above PV and VP are one of membrane separation techniques that is considered at present tool development prospect, have flash liberation degree height, and be simple to operate, pollution-free, the characteristics of less energy-consumption.
In sum, adopt membrane bioreaction technology, when preparing continuously, can improve bio-reactor throughput 15-80 doubly, and adopt the membrane permeation vaporization to produce dehydrated alcohol, can cut down the consumption of energy about 50%.This has just solved the key problem of utilizing biomass material directly to prepare dehydrated alcohol: the throughput of bio-reactor is separated the purification energy consumption problem with alcoholic acid.
(description of drawings)
Fig. 1 is the process flow sheet of the scheme one in biomass ferment of the present invention and the membrane permeation vaporization preparation dehydrated alcohol method.
Fig. 2 is the process flow sheet of the scheme two in the inventive method.
(embodiment)
Embodiment sees Fig. 1.
Open valve 11, inject fresh culture.Feed liquid is heated to about 35 ℃ by preheater 12, injects in the fermentor tank 1 and ferment, simultaneously, with liquid pump 9 ethanol of fermented-concentration 7wt% is transported to microfiltration membrane tripping device 2, vacuum pump 14 makes this device vacuum tightness remain on the 1-5 mmhg.Do not permeate the circulation of the yeast cell of microfiltration membrane and fermented liquid and return fermentor tank 1, be added to fresh culture in the fermentor tank with stream and mix and proceed to ferment; Pass through valve 3, liquid pump 10 and preheater 4 from the filtrate that microfiltration membrane sees through, be preheated to 60 ℃, send into alcohol permselective membrane PV tripping device 5 then.This alcohol permselective membrane device utilizes the tubular type mineral membrane to carry out infiltration evaporation, penetrated preferably ethanol; The feed liquid that does not see through is introduced into preheater 12 and carries out thermal exchange with fresh culture, injects fermentor tank recirculation then.Through alcohol concn in the liquid is 40-65wt%, through 6 heating of distillation tower preheater, sends in the distillation tower 7 and distills.Distillation temperature is about 70-90 ℃.Solution carries out thermal exchange through preheater 4 at the bottom of the tower, the back with install the solution that does not see through in 5 and mix and circulate.The gas that cat head distills out contains the ethanol of 90-95wt%, behind water permeable membrane tripping device preheater 16, temperature is brought up to 100-150 ℃, enters water permeable membrane VP tripping device 8.Vacuum pump 15 makes this device vacuum tightness remain on the 1-5 mmhg.That appears is mainly water vapor, mixes with solution at the bottom of the distillation Tata and circulates, and the gas that does not appear is 〉=finished product dehydrated alcohol and the distillation tower preheater 6 of 99.5wt% carry out thermal exchange, is collected into product storage tank 18 after being condensed into liquid.
Embodiment two is seen Fig. 2.
Open valve 11, inject fresh culture.Feed liquid is heated to about 35 ℃ by preheater 12, inject in the fermentor tank 1, is that the ethanol of 15wt% is transported to microfiltration membrane tripping device 2 with liquid pump 9 with fermented-concentration, reclaim yeast cell and circulating fermentation liquid in the fermented liquid, be added to fresh culture in the fermentor tank with stream and mix and proceed to ferment.The filtrate that sees through microfiltration membrane is preheated to 60 ℃ by liquid valve 3, pump 10 and preheater 4, sends into alcohol permselective membrane PV tripping device 5 then.Vacuum pump 14 makes this device vacuum tightness remain on the 1-5 mmhg.Penetrated preferably ethanol.The solution that does not see through is introduced into preheater 12 and carries out thermal exchange with fresh culture, injects the fermentor tank circulation then.Through alcohol concn in the liquid is 80-95wt%, behind preheater 6, temperature is brought up to 100-150 ℃, enters water permeable membrane VP tripping device 8.Vacuum pump 15 makes this device vacuum tightness remain on the 1-5 mmhg.That appears is mainly water vapor, loops back fermentor tank, and the gas that does not appear is that 99.5wt% above finished product dehydrated alcohol and preheater 4 carry out thermal exchange, is collected into product storage tank 18 after becoming liquid.

Claims (5)

1. the vaporization of biomass ferment and membrane permeation prepares the method for dehydrated alcohol, biomass starting material is placed in the fermentor tank, hydrolysis reaction at a certain temperature, it is characterized in that the fermented liquid that fermentor tank is included ethanol 3～20wt% extracts out by pump, feeding the aperture is the inorganic micro filtering membrane separation apparatus of 0.1～1 μ m, the liquid that sees through of microfiltration membrane is heated to 40～70 ℃, import MFI type molecular screen membrane separator then, the side that sees through of MFI type molecular screen membrane keeps vacuum tightness 1～5 mmhg, and ethanol is through MFI type molecular sieve film pervasion vaporization enrichment to 40～95wt%; The ethanolic soln of this enrichment is heated to 100～150 ℃ of vaporizations, send into NaA type molecular screen membrane separator, the side that sees through of film keeps vacuum tightness 1～5 mmhg, and contained water vapor permeation is removed, with do not see through collect after the gas cooling the dehydrated alcohol of concentration 〉=99.5wt%.
2. the method for preparing dehydrated alcohol according to the biomass ferment of claim 1 and membrane permeation vaporization, it is characterized in that said alcohol concn from fermentor tank extraction fermented liquid is 10～20wt%, the ethanol enrichment after the vaporization of MFI type molecular sieve film pervasion reaches 80～95wt%.
3. the method for preparing dehydrated alcohol according to the biomass ferment of claim 1 and membrane permeation vaporization, it is characterized in that said alcohol concn from fermentor tank extraction fermented liquid is 3～10wt%, ethanol enrichment after the vaporization of MFI type molecular sieve film pervasion reaches 40～65wt%, should see through liquid and before sending into NaA type molecular screen membrane separator, send into the distillation tower predistillation earlier, carry dense to containing ethanol 90～95wt%.
4. prepare the method for dehydrated alcohol according to the biomass ferment of claim 1 or 2 or 3 and membrane permeation vaporization, it is characterized in that inorganic micro filtering membrane employing Al 2O 3Film.
5. the method that prepare dehydrated alcohol according to the biomass ferment of claim 1 and membrane permeation vaporization is characterized in that returning fermentor tank and continuing the participation hydrolysis reaction from the effusive effusive effusive liquid that sees through of liquid and NaA type molecular screen membrane separator that sees through of liquid, MFI type molecular screen membrane separator that sees through of above-mentioned inorganic micro filtering membrane separation apparatus.
CNB031134408A 2003-05-13 2003-05-13 Method for preparing absolute ethanol by biological substance fermentation and inembrane permeation vaporization Expired - Lifetime CN1186450C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
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CN101230359B (en) * 2008-02-28 2011-01-19 中国石油化工股份有限公司 Cellulose ethanol concentration technology by employing modified dimethyl polysiloxane polymer membrane
CN102070401A (en) * 2011-01-27 2011-05-25 南京大学 Energy-saving process for preparing absolute ethanol from bioethanol aqueous solution

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CN101153290B (en) * 2007-08-31 2010-06-02 南京工业大学 Ethyl alcohol in situ separating method for improving biomass ferment strength
CN101235389B (en) * 2008-03-04 2011-07-20 南京工业大学 Fermentation and infiltration vaporization coupling technique for producing ethanol
CN102051329B (en) * 2009-10-27 2013-05-01 中国石油化工股份有限公司 Biomass ferment-separation coupling device and method for preparing ethanol
CN102070400A (en) * 2010-11-18 2011-05-25 清华大学 Membrane separation method of solid state fermentation ethanol
BR112013030076A2 (en) * 2011-05-25 2016-09-20 Bp Plc membranes
CN102757984B (en) * 2012-07-02 2014-07-02 北京化工大学 Production method of butyl alcohol by fermentation of biomass coupled with pervaporation separation
CN103601329B (en) * 2013-11-20 2015-06-03 上一环保科技（杭州）有限公司 Alcohol-water separation recycling device of fischer-tropsch synthesis water
CN106085514B (en) * 2016-05-30 2018-05-25 北京工业大学 A kind of no rectifying bi-membrane method production fuel-grade anhydrous butanol technique
CN106242946B (en) * 2016-09-08 2019-07-05 广东合即得能源科技有限公司 A kind of equipment and technique of solar hydrogen making synthesizing methanol
CN107904265A (en) * 2017-12-21 2018-04-13 北京首钢朗泽新能源科技有限公司 The utilization technique and device of product in a kind of legal system alcohol that ferments
CN109173734A (en) * 2018-10-31 2019-01-11 黄山学院 A kind of high concentration ethanol dehydration device based on molecular screen membrane
CN110468162B (en) * 2019-07-26 2021-05-14 清华大学 Production process and device for preparing fuel ethanol by one-time phase transition method
CN111424057A (en) * 2020-04-09 2020-07-17 中粮营养健康研究院有限公司 Process for producing ethanol

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101230359B (en) * 2008-02-28 2011-01-19 中国石油化工股份有限公司 Cellulose ethanol concentration technology by employing modified dimethyl polysiloxane polymer membrane
CN102070401A (en) * 2011-01-27 2011-05-25 南京大学 Energy-saving process for preparing absolute ethanol from bioethanol aqueous solution
CN102070401B (en) * 2011-01-27 2013-12-04 南京大学 Energy-saving process for preparing absolute ethanol from bioethanol aqueous solution

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