CN103374592A - Method for producing ethanol through gaseous-phase substrate fermentation - Google Patents
Method for producing ethanol through gaseous-phase substrate fermentation Download PDFInfo
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- CN103374592A CN103374592A CN2012101303233A CN201210130323A CN103374592A CN 103374592 A CN103374592 A CN 103374592A CN 2012101303233 A CN2012101303233 A CN 2012101303233A CN 201210130323 A CN201210130323 A CN 201210130323A CN 103374592 A CN103374592 A CN 103374592A
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- 241000894006 Bacteria Species 0.000 claims description 19
- 238000012545 processing Methods 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 9
- 241000193403 Clostridium Species 0.000 claims description 7
- 241001656810 Clostridium aceticum Species 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 241001656809 Clostridium autoethanogenum Species 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 4
- 238000009833 condensation Methods 0.000 claims description 4
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- 235000007847 Acetobacter aceti Nutrition 0.000 claims description 3
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- 241000186394 Eubacterium Species 0.000 claims description 3
- 235000013305 food Nutrition 0.000 claims description 3
- 210000003097 mucus Anatomy 0.000 claims description 3
- 239000007789 gas Substances 0.000 abstract description 130
- 238000005265 energy consumption Methods 0.000 abstract description 6
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- 229910000831 Steel Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
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- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
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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
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention belongs to the field of bioengineering and relates to a method for producing ethanol through gaseous-phase substrate fermentation. The method comprises the following steps of: (1) introducing synthesis gas to a bioreactor with microorganisms to ferment to obtain a fermentation liquid and gas, wherein the synthesis gas contains CO and/or H2, and the gas is escaped from the fermentation liquid; (2) separating ethanol and water from the gas to obtain fermentation tail gas, wherein the gas is escaped from the fermentation liquid; (3) separating CO2 in the fermentation tail gas to enrich the CO and/or H2 in the fermentation tail gas, wherein the fermentation tail gas is obtained in the step (2); and (4) mixing the treated fermentation tail gas and fresh synthesis gas, and then, introducing the mixed gas to the bioreactor for reacting, wherein the treated fermentation tail gas is obtained in the step (3). By using the method provided by the invention, the conversion rate of gaseous-phase substrates can be increased, the yield of the ethanol can be increased, and the energy consumption can be reduced.
Description
Technical field
The invention belongs to bioengineering field, relate to a kind of method of utilizing the gas phase fermenting substrate to produce ethanol.
Background technology
The energy is the basis that modern society depends on for existence and development.For the deficiency, the Optimization of Energy Structure that remedy fossil oil with preserve the ecological environment, the Devoting Major Efforts To Developing new and renewable sources of energy is the focus of world today's research and development, wherein utilizes to contain CO and/or H
2Gas is that substrate through anaerobic fermentation production ethanol is exactly very potential and technology competitive power.
Contain CO and/or H
2The waste gas that mainly produces from: factories such as carbon black, coke, ammonia processed, refining of petroleum, iron and steel of gas.Discharge above 600 ten thousand ton COs with near 400 ten thousand ton Hs by industrial mixture every year
2In many situations, these gases are discharged in the atmosphere, and environment is caused serious pollution.
Another kind of CO and/or the H of containing
2Gas source from the gasification of the carbonaceous materials such as coal, oil, biomass and organic waste, its main component is CO, H
2And CO
2, also contain a small amount of CH
4With some sulphur, nitrogen compound, it is the abundant and cheap biological processing raw material of a class.These gases can be converted into various useful fuels and chemicals by anaerobically fermenting, such as methane, acetic acid, butyric acid, ethanol and butanols etc.
Compare with the syngas chemistry conversion, bio-transformation has following advantage: the reaction conditions of (1) bio-transformation is gentle; (2) specificity of enzyme is higher than organic catalyst, thereby efficiency of pcr product is high, and by product is few; (3) bio-transformation does not need the CO and the H that fix
2Ratio; (4) zymophyte has tolerance to the sulfide in the synthetic gas, has reduced the gas sweetening cost.
With CO and/or H
2For the process of gas phase substrate by production of ethanol from microbial fermentation comprises: will contain CO and/or H
2Synthetic gas be passed in the bio-reactor that is added with microorganism and ferment, with product solution and cellular segregation, the cell of separation is back in the bio-reactor fermented liquid that obtains through cell separation apparatus, product solution obtains ethanol product through rectifying.
With CO and/or H
2The reaction equation of producing ethanol for substrate through anaerobic fermentation is as follows:
6CO+3H
2O＝C
2H
5OH+4CO
2 (1)
6H
2+2CO
2＝C
2H
5OH+3H
2O (2)
4CO+2H
2O＝CH
3COOH+2CO
2 (3)
4H
2+2CO
2＝CH
3COOH+2H
2O (4)
Synthetic gas passes in the bio-reactor continuously, and fermentation produces acetic acid, ethanol and CO
2N
2Do not participate in fermentation reaction with nonreactive gass such as methane.By unconverted CO and H
2, by product CO
2, N
2Discharge from bio-reactor with the fermentation tail gas that the nonreactive gas such as methane forms.Fermentation tail gas contains (volume %, component is relevant with composition, the substrate conversion efficiency of fresh synthesis gas) CO
250～60%, CO 16～30%, H
216～28%, N
2With methane etc. 0.1～5%.
Gas such as CO or H as the synthetic gas fermentation substrate
2Solubleness is little in water.The transmission of gaseous substrate relates to gas, solid, liquid three-phase: gaseous substrate, substratum (fermented liquid, liquid phase) and be suspended in microorganism cells (solid phase) in the substratum, be present in the substrate in the gas phase, must be diffused into first liquid-vapo(u)r interface, the microorganism cells surface is that cell is used in liquid phase again, and the gas-liquid mass transfer main resistance is on liquid-vapo(u)r interface.Therefore, in the fermenting process, the transformation efficiency of gas phase substrate is not high.
Contain CO, H
2Reducing gas substrate through anaerobic fermentation process in, by the draft speed that reduces the gas phase substrate, the transformation efficiency that the increase residence time of gas in reactor can be improved gas, but simultaneously also corresponding reduction of alcohol yied is uneconomical for the production of continuously fermenting.Generally speaking, the transformation efficiency of CO is 60-90%, H
2Transformation efficiency be 10-80%.So produce in the technique of ethanol at continuous batch, have a certain proportion of unconverted reducing gas in the fermentation tail gas.
Chinese patent ZL200510109722.1 " solvent of producing the microbiological processes of acetic acid and from fermented liquid, extracting acetic acid ", ZL99810663.1 " produces the microbiological processes of acetic acid and the solvent of extraction acetic acid from fermented liquid ", and ZL96180363.0 " prepares acetic acid with biology technique " and disclose the method for the useful chemical such as method scale operation acetic acid that ferment with this type of gas, substratum and one or more anerobes in bio-reactor from waste gas.In these patented methods the gas phase substrate through behind the bio-reactor wherein nonreactive gas and unreacted matrix gas discharge as waste gas, do not mention processing and the reuse of fermentation tail gas, cause waste and environmental pollution.
In addition, owing to the reason such as CO restraining effect and redox-potential thereof be lower, bacterium preferentially selects to absorb CO in the fermenting process.Especially take ethanol in the fermentation reaction of advantage product, H
2Transformation efficiency than the low conversion rate of CO, the two comprehensive transformation efficiency (CO and H
2The mean value of transformation efficiency) relatively low, the gas phase substrate is not fully utilized yet.
In Chinese patent application CN1444658A record " improving the method for production of ethanol from microbial fermentation ", disclose to use and contained CO and H
2Deng mixed gas through the technique of Young clostridium alcohol prepared by fermenting; Fermentation tail gas is directly emptying in the patent; If keep ethanol in the product and acetic acid (salt) ratio more than 4: 1, its CO and H
2Comprehensive transformation efficiency on average 65%.
On the other hand, in industrial actual production, fermented liquid evolving gas tolerance is very large, when these evolving gas effusion fermented liquids, can carry out the second alcohol and water that part generates; If do not take measures, can cause that moisture runs off in a large number in the bio-reactor, need to constantly keep the skin wet to continue fermenting process; And the ethanol that generates is overflowed thereupon and has also been affected the whole output of ethanol.
Summary of the invention
The purpose of this invention is to provide a kind of gas phase fermenting substrate and produce the method for ethanol, to improve the gas phase substrate conversion efficiency, increase ethanol production, reduce energy consumption.
Method provided by the invention may further comprise the steps:
(1) will contain CO and/or H
2Synthetic gas pass into to cultivate in the bio-reactor that microorganism is arranged and ferment, obtain the gas of fermented liquid and effusion fermented liquid;
(2) from the gas of effusion fermented liquid, isolate the second alcohol and water, obtain fermentation tail gas;
(3) CO in the fermentation tail gas that obtains of separating step (2)
2With the CO in the enrichment fermentation tail gas and/or H
2
(4) fermentation tail gas after the processing that step (3) is obtained reacts with passing in the bio-reactor after fresh synthesis gas mixes.
Preferably, present method further comprises step (5): the bacterium in the fermented liquid that separating step (1) obtains is back to isolated bacterium in the bio-reactor and reuses; Preferably a part of bacterium is reused, remaining discharges as fermented waste fluid.More preferably, described bacterium separation is finished by centrifugal, hollow fibre filtering, precipitation or ultrafiltration.
Preferably, present method further comprises step (6): the organic solution of isolating bacterium in the step (5) is carried out rectifying obtain product ethanol, the residue raffinate is back in the bio-reactor; Preferably, a part is remained raffinate be back in the bio-reactor, remaining discharges as fermented waste fluid.
Preferably, described method further comprises step (7): the second alcohol and water of separating in the step (2) is carried out rectifying obtain product ethanol, or the second alcohol and water of separating in the step (2) is switched in rectification process and defeated being back between the bioreactor for treatment.
Preferably, in the step (3), the fermentation tail gas that a part of step (2) is obtained carries out CO
2Separating treatment; More preferably, the fermentation tail gas that 40%～80% step (2) is obtained carries out CO
2Separating treatment; Most preferably, the fermentation tail gas that 80% step (2) is obtained carries out CO
2Separating treatment.
Preferably, the method for isolating the second alcohol and water in the step (2) from the gas of effusion fermented liquid is condensation method, membrane separation process or solvent absorption.
Preferably, CO in the middle separate fermentation tail gas of step (3)
2Method adopt physical separation method or chemical reaction method, wherein physical separation method can be rectification method, physisorphtion or membrane separation process etc.
Preferably, synthetic gas of the present invention is from the processing of coal, Sweet natural gas, oil, biomass and organic waste, the waste gas that produces in carbon black, synthetic ammonia, methyl alcohol or coke manufacturing and refining of petroleum, the steel manufacture process.Described synthetic gas comprises CO and/or H
2And CO
2, N
2, other gas such as methane.
The microorganism of preferably, using among the present invention includes but not limited to: Wu Shi bacillus aceticus, food methylbutyric bacillus, clostridium aceticum, acetone clostridium butylicum, hot clostridium aceticum, mucus Eubacterium, Young clostridium, Clostridium autoethanogenum and peptostreptococcus productus.
Preferably, the bio-reactor among the present invention includes but not limited to immobilized cell reactor or the suspension cell reactors such as continuous-stirring reactor, airlift reactor such as trickle-bed reactor.
Preferably, the pressure in the described bio-reactor keeps more than or equal to a normal atmosphere, is preferably a normal atmosphere.
CO and/or H in method enrichment of the present invention and the recycle fermentation tail gas
2, improved CO and/or H
2Transformation efficiency, improved output and the productive rate of ethanol; The gas of effusion fermented liquid is processed isolated second alcohol and water through gas-liquid separation and is directly used in the preparation high purity ethanol, avoids being back to repeated isolation in the bio-reactor, has saved the energy.In embodiment more specifically, present method has improved CO and H
2Comprehensive transformation efficiency, reduced H
2With CO transformation efficiency difference; The bacterium that separates in conjunction with reuse simultaneously and the raffinate behind the rectifying ethanol have been controlled the content of acetic acid in the bio-reactor, make that the ratio of ethanol and acetic acid (salt) is not less than 4: 1 in the fermented liquid.In addition, the by product CO of recovery
2Can be used for conventional the application, reduce pollutant emission, resource is fully utilized.
Description of drawings
Fig. 1 is the process flow diagram of synthetic gas fermentative production of ethanol of the present invention.
Embodiment
Further specify the present invention in conjunction with embodiment, but protection scope of the present invention is not limited to following content.
The invention provides a kind of gas phase fermenting substrate and produce the method for ethanol, the method is isolated first the second alcohol and water that gas carries from the gas of effusion fermented liquid, the aqueous ethanolic solution of recovery is transported in the ethanol rectifier unit and generates product ethanol or be back in the bio-reactor; The fermentation tail gas that removes the second alcohol and water is treated recovery CO again
2, enrichment CO and/or H wherein
2, mix rear recycle with fresh synthesis gas, with under original production condition and technique, improve CO and/or H
2Transformation efficiency, thereby improve output and the productive rate of ethanol; More specifically, improve CO and H
2Comprehensive transformation efficiency, reduce the two poor conversion; And reclaim the ethanol that evolving gas carries, improve ethanol production, reduce energy consumption.
Adopt the gas phase fermenting substrate to produce in the method for ethanol CO and H
2Transformation efficiency is important control index.In the present invention, detect the variation of each component content in the synthetic gas enter bio-reactor and the fermentation tail gas by on-line mass spectroscopy, utilize the value that records to calculate transformation efficiency.The method of calculation of transformation efficiency are:
Transformation efficiency=(X
Advance-X
Go out) * 100%/X
Advance
Wherein, X
AdvanceRepresentation unit enters CO (or H in the synthetic gas of bio-reactor in the time
2) mole number.X
Go outRepresentation unit does not enter CO in the time
2(or the H of CO in the fermentation tail gas of recycling program
2) mole number.
As shown in Figure 1, in one embodiment, method of the present invention may further comprise the steps:
(1) will contain CO and/or H
2Synthetic gas pass into to cultivate in the bio-reactor that microorganism is arranged and ferment, obtain the gas of fermented liquid and effusion fermented liquid.
In this step, employed microorganism and bio-reactor all are that this area is conventional general.Particularly, the microorganism of use can be Wu Shi bacillus aceticus, food methylbutyric bacillus, clostridium aceticum, third heir's clostridium butylicum, hot clostridium aceticum, mucus Eubacterium, Young clostridium, Clostridium autoethanogenum or peptostreptococcus productus.Using bio-reactor can be immobilized cell reactor or the suspension cell reactors such as continuous-stirring reactor, airlift reactor such as trickle-bed reactor.Pressure in the bio-reactor keeps more than or equal to 1 normal atmosphere.
Obtain comprising in the fermented liquid ethanol, acetic acid (salt), bacterium etc. in this step; Comprise unreacted CO and/or H in the gas of effusion fermented liquid
2, CO
2, and non-reaction gas, such as N
2, CH
4Deng.
(2) from the gas of effusion fermented liquid, isolate the second alcohol and water, obtain fermentation tail gas.
In this step, can utilize separating alcohol and the water from evolving gas such as condensation method, membrane separation process or solvent absorption.
Condensation method can adopt conventional interchanger.Cold medium lays respectively at inside and outside the interchanger in the journey to carry out heat exchange such as low temperature refrigerant etc. and evolving gas, and the second alcohol and water condenses with the form of the aqueous solution, collects from the interchanger below; Fermentation tail gas enters follow-up flow process from the interchanger top.
Membrane separation process can adopt single-stage or multi-stage gas-liquid separatory membrane chunk, and material can be polysulfones, aromatic heterocycle class, vinyl-based.When evolving gas process film, aqueous ethanolic solution separates with fermentation tail gas, thereby realizes sepn process.
Solvent absorption adopts the organic solvent can absorb aqueous ethanolic solution but not absorb fermentation tail gas to process.Such organic solvent comprises glycerine, glycol ether etc.
(3) CO in separation and the recovery fermentation tail gas
2With the CO in the enrichment fermentation tail gas and/or H
2
In this step, can adopt the physical separation method such as rectification method, physisorphtion, membrane separation process, or chemical reaction method reclaims CO
2Thereby, improve CO and/or H in the fermentation tail gas
2Concentration, to guarantee not affect after fermentation tail gas after processing passes into bio-reactor the concentration of gas phase substrate, the assurance fermenting process carries out smoothly.Simultaneously, the CO of recovery
2Can be used for conventional industrial application.
In preferred embodiment, in this step, the fermentation tail gas that the step with 40%～80% (2) obtains carries out CO
2Separating treatment; In most preferred embodiments, the fermentation tail gas that 80% step (2) is obtained carries out CO
2Separating treatment.Remaining ferment tail gas can pass in the torch and burn.
(4) fermentation tail gas after will processing reacts with passing in the bio-reactor after fresh synthesis gas mixes.
The CO and/or the H that contain high density in the fermentation tail gas after the processing
2, again pass into to bio-reactor and ferment, thereby improve CO and/or H
2Transformation efficiency, then improve the output of ethanol.
From some embodiments of the present invention as seen, when a part of fermentation tail gas through removing CO
2When processing rear reuse, can improve significantly CO and H
2Transformation efficiency.
For obtaining highly purified ethanol, method of the present invention further comprises:
(5) bacterium in the fermented liquid that obtains of separating step (1) is back to isolated bacterium in the bio-reactor and reuses.In specific embodiment, those skilled in the art can reuse a part of bacterium according to actual needs, to guarantee the concentration of bacterium alive in the bio-reactor; Remaining bacterium is discharged as fermented waste fluid.
Described bacterium separates and can finish by centrifugal, hollow fibre filtering, precipitation or the ultra-filtration technique of this area routine.
(6) organic solution of isolating bacterium that step (5) is obtained carries out rectifying and obtains product ethanol, and the residue raffinate is back in the bio-reactor.Comprising in the raffinate does not have to consume and be not heated the nutritive substance that still-process destroys in acetic acid (salt) and the fermenting process, such as trace-metal and other mineral substance.Because the molecular balance of ethanol and acetic acid, so the circulation of acetic acid (salt) has suppressed the further generation of acetic acid.In specific embodiment, those skilled in the art can remain raffinate with a part and be back in the bio-reactor according to actual needs, and remaining discharges as fermented waste fluid.
(7) the second alcohol and water of separating in the step (2) is carried out rectifying and obtain product ethanol, or the second alcohol and water of separating in the step (2) is switched in rectification process and defeated being back between the bioreactor for treatment.
In reaction process, when ethanol production was few, the liquid major part that evolving gas carries was water, and ethanol content seldom at this moment should not carry out rectifying with the second alcohol and water of separating in the step (2).Therefore, those skilled in the art can be according to actual needs and requirement, such as the energy consumption of the ethanol tolerance level of the microorganism of using, ethanol content, regulation etc., when the ethanol content in the fermented liquid is low, the second alcohol and water of separating in the step (2) is back in the bio-reactor; And when ethanol content was high in the fermented liquid, the second alcohol and water of separating in the step (2) is delivered to the ethanol rectifier unit carried out rectifying, obtained product ethanol.That is, the second alcohol and water of separating in the step (2) is switched in rectification process and defeated being back between the bioreactor for treatment, to realize better the object of the invention.
Embodiment 1
To consist of (volume content) 34.2%CO, 33.7%H
2, 30.1%CO
2, 2%N
2Pass in the continuously stirring fermentor tank (3 liters of NBS Bioflo) that aqueous phase is suspended with Clostridium autoethanogenum with the synthetic gas of methane and to ferment.Aqueous phase contains the necessary VITAMIN of microorganism growth, trace elements and inorganic salt etc.Gas residence time (ratio of reactor volume and gas flow rates under the standard conditions) remains on 8.3 minutes, the fermented liquid residence time (liquid reactor volume and fresh nutrient solution add the ratio of speed) 21h, 37 ℃ of temperature of reactor, 1 normal atmosphere of reaction pressure, stirring velocity is 580rpm, and the pH value is 5.03.
The fermented liquid that fermentation obtains pumps into membrane sepn cell separator separation of bacterial, and bacterium is back in the fermentor tank.Ethanol, acetic acid (salt) content in the aqueous ethanolic solution that employing gas chromatograph analytical separation goes out.Utilize the ethanol in the rectifying still separating alcohol aqueous solution, the residue raffinate is back to bio-reactor at the bottom of the rectifying still.
Escaping gas passes into separating alcohol and water in the interchanger in the fermented liquid, and wherein interchanger is connected with-10 ℃ of icy salt solutions as cold medium, and aqueous ethanolic solution is delivered in the rectifying still, and fermentation tail gas enters detection, CO
2Remove and the recycling program.
With CO, H in the bio-reactor air inlet of mass spectrograph on-line monitoring and the tail gas
2, CO
2Content etc. component.The ratio that fermentation tail gas is listed according to table one is through removing CO
2Rear and fresh synthetic gas mixes, and then enters bio-reactor and ferments; Fermentation tail gas alkali lye Adsorption CO
2, the co 2 removal rate reaches 90%.
Table one: the result of fermentation tail gas reuse after enrichment is processed.
* nonreactive gas refers to N
2, CH
4Deng the gaseous component that does not participate in fermentation reaction.
From table one as seen, when fermentation tail gas is treated carry out reuse after, CO and H
2Transformation efficiency obviously improve, the poor conversion of the two obviously reduces.When the reclamation rate of fermentation tail gas is 80%, CO and H
2Comprehensive transformation efficiency be increased to 83.1%, H by about 67.5%
2Be reduced to 6.6% with the transformation efficiency difference of CO by 15%.At this moment, get after testing: ethanol content 26g/L, acetic acid (salt) content 2.5g/L in the fermented liquid.
Use method of the present invention to reclaim reducing gas, CO and H
2Comprehensive transformation efficiency can reach 83%, H
2Can be reduced to 6.6% with CO transformation efficiency difference, the ratio of ethanol and acetic acid (salt) reaches 10: 1 in the product, takes full advantage of the gas phase substrate, has improved ratio and the output of ethanol in the product.In addition, the CO of recovery
2Can do industrial goods and use, such as chemical reagent processing etc.
Embodiment 2
Except specified otherwise, synthetic gas fermentation whole process is with embodiment 1.
Advance fermentor cultivation from seed, the second alcohol and water that separates from evolving gas returns fermentor tank; Cell separator and nutritive medium are reinforced not to be opened.
Behind the fermentation 78h, alcohol concn is 2.5% (mass concentration, lower same) in the fermented liquid; To from evolving gas, be delivered to purifying in the ethanol rectifier unit by isolated second alcohol and water.Alcohol concn changes in the analysis monitoring fermented liquid, when the concentration of ethanol in the fermented liquid less than 1.0% the time, will from evolving gas, be delivered to fermentor tank by isolated second alcohol and water, stop to gather the second alcohol and water of separation.Keep in the fermented liquid alcohol concn at 3.5% following continuing fermentation 520h, during the second alcohol and water of separating is switched in rectification process and defeated being back between the bioreactor for treatment.In the whole fermenting process, be 2.41g/1.h (by every liter of fermented liquid per hour) by separating the second alcohol and water in the evolving gas and carrying out the ethanol average productivity that rectifying obtains, synthetic gas fermenting alcohol average productivity is 1.41g/1.h (every liter fermented liquid hour).
In the whole fermented liquid process, the cell retrieving arrangement is not opened.Reduced the part energy consumption.The ethanol mean concns that tail gas condensing obtains is 21%.The fermented liquid that contains 2-3% ethanol with processing is compared, composition simple (being mainly water and ethanol) in the phlegma, the energy consumption that has greatly alleviated ethyl alcohol purification.
Claims (10)
1. a gas phase fermenting substrate is produced the method for ethanol, comprises step:
(1) will contain CO and/or H
2Synthetic gas pass into to cultivate in the bio-reactor that microorganism is arranged and ferment, obtain the gas of fermented liquid and effusion fermented liquid;
(2) from the gas of effusion fermented liquid, isolate the second alcohol and water, obtain fermentation tail gas;
(3) CO in the fermentation tail gas that obtains of separating step (2)
2With the CO in the enrichment fermentation tail gas and/or H
2
(4) fermentation tail gas after the processing that step (3) is obtained reacts with passing in the bio-reactor after fresh synthesis gas mixes.
2. method according to claim 1 is characterized in that, described method further comprises step (5): the bacterium in the fermented liquid that separating step (1) obtains is back to isolated bacterium in the bio-reactor and reuses.
3. method according to claim 2 is characterized in that, described method further comprises step (6): the organic solution of isolating bacterium in the step (5) is carried out rectifying obtain product ethanol, the residue raffinate is back in the bio-reactor.
4. method according to claim 3, it is characterized in that, described method further comprises step (7): the second alcohol and water of separating in the step (2) is carried out rectifying obtain product ethanol, or the second alcohol and water of separating in the step (2) is switched in rectification process and defeated being back between the bioreactor for treatment.
5. each described method is characterized in that according to claim 1-4, and in the step (3), the fermentation tail gas that the step with 40%～80% (2) obtains carries out CO
2Separating treatment.
6. method according to claim 5 is characterized in that, in the step (3), the fermentation tail gas that the step with 80% (2) obtains carries out CO
2Separating treatment.
7. each described method is characterized in that according to claim 1-4, and the method for isolating the second alcohol and water in the step (2) from the gas of effusion fermented liquid is condensation method, membrane separation process or solvent absorption.
8. each described method is characterized in that according to claim 1-4, CO in the separate fermentation tail gas in the step (3)
2Method adopt physical separation method or chemical reaction method, wherein physical separation method is rectification method, physisorphtion or membrane separation process.
9. each described method according to claim 1-4, it is characterized in that described microorganism is Wu Shi bacillus aceticus, food methylbutyric bacillus, clostridium aceticum, acetone clostridium butylicum, hot clostridium aceticum, mucus Eubacterium, Young clostridium, Clostridium autoethanogenum or peptostreptococcus productus.
10. each described method is characterized in that according to claim 1-4, and described bio-reactor is trickle-bed reactor, continuous-stirring reactor or airlift reactor, and the pressure in the described bio-reactor keeps more than or equal to a normal atmosphere.
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| CN103911280A (en) * | 2014-04-16 | 2014-07-09 | 河南农业大学 | Coupling film equipment capable of fermenting and separating synthetic gas simultaneously |
| WO2018231663A1 (en) | 2017-06-12 | 2018-12-20 | Aldous, David | Methods and apparatus for recycling tail gas in syngas fermentation to ethanol |
| CN111533406A (en) * | 2020-05-26 | 2020-08-14 | 冯丹丹 | An injectable repair box containing alcohol sludge |
| CN112654712A (en) * | 2018-09-25 | 2021-04-13 | 积水化学工业株式会社 | Method for producing organic substance |
| CN112755743A (en) * | 2021-01-11 | 2021-05-07 | 宁夏首朗吉元新能源科技有限公司 | Tail gas recovery equipment and method for ferroalloy industrial tail gas fermentation |
| CN112812930A (en) * | 2021-02-05 | 2021-05-18 | 清华大学 | System and process for producing oxygen-containing organic matters from carbon dioxide and coal |
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| CN112812930A (en) * | 2021-02-05 | 2021-05-18 | 清华大学 | System and process for producing oxygen-containing organic matters from carbon dioxide and coal |
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