CN102787144A - Process for producing acetone and butanol by biomass fermentation and pervaporation membrane coupling - Google Patents
Process for producing acetone and butanol by biomass fermentation and pervaporation membrane coupling Download PDFInfo
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Abstract
The invention relates to a process for producing acetone and butanol by biomass fermentation and pervaporation membrane coupling, in particular to a production process of coupling a pervaporation membrane and ABE (acetone, butanol and ethanol) fermentation, separating ABE in situ on line and utilizing an extraction tower to obtain an anhydrous solvent. Fermentation liquor in a fermentation tank is pumped out, and is filtered by an ethanol-permselective membrane to obtain a concentrated solution, the concentrated solution is sent into the extraction tower and is separated into an organic phase and a water phase in the extraction tower, after the water phase is pumped into a water phase storage tank, the organic phase does not pass a mash tower but directly enters a butanol tower and follow-up rectifying tower groups to obtain anhydrous butanol, acetone and ethanol, the water phase in the water phase storage tank passes a pervaporation ethanol-permselective membrane assembly, dialysate is pumped into the extraction tower, and the cycle is repeated. According to the process disclosed by the invention, the fermentation process is coupled with the pervaporation technology, the extraction tower is added behind the pervaporation assembly, the inhibitory action of the butanol in the fermentation process is reduced, energy consumption in the separation process is saved, and the competitiveness of a biomass fermentation method for producing the butanol is improved.
Description
Invention field
The present invention relates to the technology that a kind of biomass ferment-acetone-butanol is produced in the infiltrating and vaporizing membrane coupling; Be specifically related to a kind of infiltration evaporation coupling of will fermenting and produce the ABE fermenting process; Online original position is separated ABE, and utilizes infiltration evaporation alcohol permselective membrane and extraction tower to obtain the technology of anhydrous solvent.
Background technology
Along with world petroleum resource is in short supply day by day, countries in the world are all in the development and use of actively seeking renewable resource.Biofuel has caused the attention of various countries as important renewable energy, and the ratio that expects the year two thousand twenty bio-fuel-oil will rise to 30%, and aggregate demand will reach 87,000,000,000 gallons.
Yet the preparation of propylene synthesis method is mainly adopted in the production of butanols at present, and this method is to be feedstock production butanols product with the propylene in the oil.Exhaustion day by day along with petroleum resources utilizes the new butanol production method of renewable biomass development of resources to become the focus of international concern.Fermentation method is the production of butanol technology that is expected to replace the propylene synthesis method of generally acknowledging.Yet, the feedback inhibition that two main difficult problems that run in the fermentative Production butanols process promptly are tunnings with separate the too high problem of energy consumption that concentrates.After feedback inhibition is meant that the concentration of some meta-bolites reaches certain limit; Because the purpose product has the noncompetitive inhibition effect to microbial growth; Thereby cause fermentation reaction to be difficult to normally carry out, the purpose product no longer increases, and the purpose production concentration is crossed low phenomenon in the product fermented liquid.Just because of this, the concentration of ABE is merely 1～2% (product of butylic fermentation is generally butanols, acetone and ethanol, and the three is abbreviated as ABE, and wherein butanols, acetone, alcoholic acid ratio are 6:3:1) in the butylic fermentation liquid.It is too high that so low butanol concentration causes the concentrated energy consumption of subsequent product separation.It is reported that adopt traditional distillation method also high to the combustion heat energy that butylic fermentation liquid concentrates required ability loss-rate butanols itself, especially wine with dregs column distillation concentration process is brought up to 500g/L with solvent strength, consumed energy almost accounts for 50% of whole distillation energy consumption.Just because of this, for many years, the preparation of propylene synthesis method is adopted in the production of butanols always.This shows; The effective stripping technique of development of new; Can solve product feedback inhibition and the concentrated too high problem of energy consumption of product in the fermentation to produce biological fuel process, be the key that realize that the industrialization of biofuel butanols is produced, significant to the Technological Economy property that improves the fermentative prodn butanols.
At present, utilize infiltration evaporation coupling original position acetone, butanols and alcoholic acid patent to have 201010136813.5,201010162856.0.Patent 201010136813.5 optionally is provided with a microfiltration membrane separator before infiltrating and vaporizing membrane, the suspended solid in microorganism cells and the fermented liquid is held back, thereby the pollution of reduction infiltrating and vaporizing membrane improves separation efficiency.Patent 201010162856.0, fermentation liquid are sent into by last fermentor tank before next fermentor tank, and the liquid phase part in the fermentation liquid separates butanols through the infiltration evaporation membrane separation unit earlier, and the fermentation liquid behind the separating butanol is sent into next fermentor tank again.There is bibliographical information utilization fermentation-infiltration evaporation coupling technique to alleviate inhibition both at home and abroad; Improve the butanols productive rate; Heitmann et al. (2012) for example, Wouter et al. (2012) utilizes the solvent in ionic liquid supporting liquid sheet and the PDMS membrane sepn fermented liquid respectively.But these reports all do not relate to the application of the phenomenon of phase separation of acetone-butanol solvent.The characteristics that the present invention utilizes the ABE liquid concentrator to occur being separated increase extraction tower after infiltration evaporation technology, be separated at the solvent of extraction tower middle and high concentration.The concentration of organic phase solvent wherein; Can reach the concentration (500g/L) after the wine with dregs tower concentrates; Thereby in follow-up rectifying, omit the wine with dregs tower, and extraction tower does not increase energy consumption, so with respect to CN101805754A and CN101851641A; This technology can cut down the consumption of energy and the water consumption, and then obtains anhydrous solvent.
Summary of the invention
The object of the present invention is to provide a kind of technology of producing acetone-butanol, removed that ABE improves the productive rate of acetone-butanol to the restraining effect of thalline in the fermenting process with fermentation infiltration evaporation coupling technique.
Another object of the present invention is to provide a kind of infiltration evaporation and extraction tower of utilizing, obtain high density acetone-butanol alcoholic acid method, reduced follow-up distillation procedure step, reduce the consumption of energy, realize energy-saving and emission-reduction.
The invention provides a kind of continuously fermenting and produce the technology of anhydrous solvent with infiltration evaporation membrane sepn coupling, it is characterized in that technological process is following:
(1) will pass through pretreated biomass as fermentation substrate, inoculation ABE bacterial classification ferments;
(2) fermented liquid in the fermentor tank is inputed to the evaporation alcohol permselective membrane separator through pump, see through liquid and obtain acetone, butanols and alcoholic acid liquid concentrator through the condensing surface collection, trapped fluid is back in the fermentor tank;
(3) acetone, butanols and alcoholic acid penetrating fluid are through in the pump input extraction tower, and penetrating fluid is divided into organic phase and water in extraction tower;
(4) above-mentioned water is crossed pump input water basin, and above-mentioned organic phase directly gets into a fourth tower and follow-up rectifying tower group without the wine with dregs tower, and less water removes acquisition anhydrous propanone, butanols and ethanol in the realization organic phase; Water in the water basin is realized concentrating of aqueous phase small amount of acetone, butanols and alcohol mixeding liquid through the evaporation alcohol permselective membrane separator, gets into extraction tower subsequently again, carries out subsequent operations.
Evaporation alcohol permselective membrane separator of the present invention is made up of one or more evaporation alcohol permselective membrane separator, and the per-meate side of each unit evaporation alcohol permselective membrane separator is passed through the pipeline serial or parallel connection in the vacuum pump main pipe rail.
Evaporation alcohol permselective membrane of the present invention is organic membrane, mineral membrane or hybrid organic-inorganic film; Its membrane module form is rolling, tubular type, plate and frame or tubular fibre formula.
The material of hybrid organic-inorganic film of the present invention is a kind of among PDMS-Silicalite-1, PDMS-ZSM-5 or the PTMSP-Silicalite; The material of organic membrane is Zylox, gather trimethyl silicane propine, Vestolen PP 7052, pvdf or tetrafluoroethylene; The material of mineral membrane can be Silicalite-1 or ZSM-5.
Extraction tower of the present invention is a kind of in spraying and extracting tower, sieve-tray tower, rotating disc contactor and the pulse-column.
Biomass of the present invention can be lignocellulose (the for example stalk of various farm crop such as wheat stalk, corn straw, bagasse, grass class and deciduous tree or acerose wood chips); Also can be starchy material (for example one or both in corn, cassava, Ipomoea batatas, yam, the root of kudzu vine), also can be saccharide raw material (for example molasses, Chinese sorghum juice).The pretreatment process of lignocellulose adopts physics and chemistry pre-treatment such as Chemical Pretreatment such as conventional diluted acid or steam explosion to get final product.The hydrolysis temperature of lignocellulose is 45-50 ℃, and the temperature of acetone butanol fermentation is 37-40 ℃.Preferred acetone butanol fermentation mikrobe is C.acetobutylicum ATCC824, and C.butylicum 23592, and C.acetobutylicum 170, C.acetobutylicum P260, C.beijerinckii ATCC55025.
A kind of technology of utilizing fermentation infiltration evaporation coupling technique to produce acetone-butanol provided by the invention will ferment, evaporation alcohol permselective membrane separator and rectifying combination; Realized the separation of tunning acetone-butanol alcoholic acid original position; Reduced the restraining effect of acetone-butanol ethanol, improved butylic fermentation intensity organism of fermentation; While also is provided with extraction tower after the evaporation alcohol permselective membrane separator, fully effectively utilized through the evaporation alcohol permselective membrane separator and seen through liquid ground phenomenon of phase separation afterwards, has reduced the separation costs of follow-up solvent.Technology provided by the invention has been saved energy consumption and the water consumption in the production process with the zymotechnique and the infiltrating and vaporizing membrane sepn process close-coupled of glucose acetone-butanol in the hydrolyzed solution, has reduced the production cost of being produced the fuel butanols by biomass.
Description of drawings
Fig. 1 is that fermentation infiltration evaporation rectification integrated technique is produced the process flow diagram of acetone-butanol scheme one;
Reference numeral
1. feed supplement jar 2. fresh feed pumps 3. fermentor tanks 4. fresh feed pumps 5. evaporation alcohol permselective membrane assemblies 6. condensing surfaces 7. tensimeters 8. vacuum pumps 9. fresh feed pumps 10. extraction towers 11. fresh feed pumps 12. valves 13. water basins 14. fresh feed pumps 15. evaporation alcohol permselective membrane assemblies 16. condensing surfaces 17. tensimeters 18. vacuum pumps 19. fresh feed pumps 20. 1 fourth towers
Embodiment
Below in conjunction with embodiment the present invention is further specified, theme protection domain involved in the present invention is not limited only to these embodiment.
1 one kinds of corn straw fermentation-infiltration evaporations of embodiment coupling technique is produced the technology of acetone-butanol
Corn straw is processed slip and is got into feed supplement jar 1 after steam explosion processing, acid hydrolysis, enzymic hydrolysis; Open fresh feed pump 2 and get into fermentor tank 3; Behind the microbe inoculation 37 ℃ the fermentation 72h after; When total solvent concentration in the liquid phase in the jar when detection reaches 18g/L, open fresh feed pump 4, fermented liquid is delivered into evaporation alcohol permselective membrane assembly 5; Be composed in series by two plate and frame evaporation alcohol permselective membrane separators in the infiltration evaporation assembly, the infiltrating and vaporizing membrane of employing is hybrid organic-inorganic film (PDMS-Silicalite-1).Simultaneously, open vacuum pump 8, vacuum meter 7 vacuum tightnesss maintain 500Pa, and the penetrating fluid device 6 that is condensed is collected, and acetone, butanols and the total ethanol concentration of collecting gained reach 150g/L, and the feed liquid of holding back is returned in the fermentor tank 3; After overcoupling separates 12h, suspend coupling and separate, stream adds the identical stalk hydrolysis sugar liquid of penetrating fluid volume that obtains with the infiltration evaporation membrane sepn in fermentor tank from feed supplement jar 1, continues fermentation.Open fresh feed pump 9 simultaneously, collect the penetrating fluid that obtains in the condensing surface 6 and get into extraction tower 10, extraction tower is the spraying and extracting tower, in extraction tower, is divided into organic phase and water; Aqueous-phase concentration is about 100g/L in the extraction tower, through fresh feed pump 11, opens valve 12 and gets into water basin 13 paths; Organic phase concentration in the extraction tower reaches 500g/L, through fresh feed pump 11, opens valve 12 and gets into a fourth tower 20 paths, obtains anhydrous butanols, acetone and ethanol; Water in the water basin 13 is crossed fresh feed pump 14 input evaporation alcohol permselective membrane assemblies 15; Open vacuum pump 18; Vacuum gauge pressure 500pa treats that the extraction tower organic phase all gets into a fourth tower 20, and condensing surface 16 is collected penetrating fluid and got into extraction tower 12 through fresh feed pump 19; So circulation obtains anhydrous butanols, acetone and ethanol at last.After coupling separates 12h, suspend coupling and separate, stream adds the identical stalk hydrolysis sugar liquid of penetrating fluid volume that obtains with the infiltration evaporation membrane sepn in fermentor tank from feed supplement jar 1, continues fermentation.When in the fermentor tank 2 when the concentration of total solvent reaches 18g/L, the open vacuum pump, the separation that is coupled once more, penetrating fluid gets into condensing surface and is collected, and so circulates 10 times.
This example has realized corn straw hydrolysis sugar liquid semicontinuous fermentation production acetone-butanol; Not only significantly reduced the restraining effect of the acetone-butanol solvent of fermentation generation to microorganism cells; And owing to behind the evaporation alcohol permselective membrane assembly, increased extraction tower, made full use of the phase separation property of evaporation alcohol permselective membrane penetrating fluid, effectively reduced the energy consumption of concentration process; Compare with traditional batch fermentation-still-process; The production intensity of butanols improves, owing to omit the wine with dregs tower, can save the rectifying energy consumption.
2 one kinds of fermentation of corn starch of embodiment-infiltration evaporation coupling technique is produced the technology of acetone-butanol
With the Semen Maydis powder is the preparation of raw material substratum, and 121 ℃ of boiling gelatinizations 90 minutes obtain maize powder medium; Get into feed supplement jar 1; Open fresh feed pump 2 and get into fermentor tanks 3, behind the microbe inoculation behind 37 ℃ of fermentation 60h, when total solvent concentration in the liquid phase in the jar when detection reaches 20g/L; Open fresh feed pump 4; Fermented liquid is delivered into evaporation alcohol permselective membrane assembly 5, and membrane module is made up of a tubular fibre evaporation alcohol permselective membrane separator, and the infiltrating and vaporizing membrane of selecting for use is mineral membrane Silicalite-1 or ZSM-5.Simultaneously, open vacuum pump 9, vacuum meter 8 vacuum tightnesss maintain 500Pa, and the penetrating fluid device 6 that is condensed is collected, and acetone, butanols and the total ethanol concentration of collecting gained reach 400g/L, and the feed liquid of holding back is returned in the fermentor tank 3; After separating 12h, suspend infiltration evaporation and separate, stream adds the identical stalk hydrolysis sugar liquid of penetrating fluid volume that obtains with the infiltration evaporation membrane sepn in fermentor tank from feed supplement jar 1, continues fermentation.Open fresh feed pump 9 simultaneously, collect the penetrating fluid that obtains in the condensing surface 6 and get into extraction tower 10, extraction tower is a sieve-tray tower, in extraction tower, is divided into organic phase and water; Aqueous-phase concentration is about 280g/L in the extraction tower, through fresh feed pump 11, opens valve 12 and gets into water basin 13 paths; Organic phase concentration in the extraction tower reaches 700g/L, through fresh feed pump 11, opens valve 12 and gets into a fourth tower 20 paths, obtains anhydrous butanols, acetone and ethanol; Water in the water basin 13 is crossed fresh feed pump 14 input evaporation alcohol permselective membrane assemblies 15; Open vacuum pump 18; Vacuum gauge pressure 500pa treats that the extraction tower organic phase all gets into a fourth tower 20, and condensing surface 16 is collected penetrating fluid and got into extraction tower 12 through fresh feed pump 19; So circulation obtains anhydrous butanols, acetone and ethanol at last.After overcoupling separates 12h, suspend coupling and separate, stream adds the identical stalk hydrolysis sugar liquid of penetrating fluid volume that obtains with the infiltration evaporation membrane sepn in fermentor tank from feed supplement jar 1, continues fermentation.When in the fermentor tank 2 when the concentration of total solvent reaches 20g/L, the open vacuum pump, the separation that is coupled once more, penetrating fluid gets into condensing surface and is collected, and so circulates 10 times.
This example has realized Semen Maydis powder semicontinuous fermentation production acetone-butanol; Not only significantly reduced the restraining effect of the acetone-butanol solvent of fermentation generation to microorganism cells; And owing to behind evaporation alcohol permselective membrane, increased extraction tower, made full use of the phase separation property of high density penetrating fluid, effectively reduced the energy consumption of concentration process; Compare with traditional batch fermentation-still-process, the production intensity of butanols improves.3 one kinds of corn straws of embodiment continuously ferment-and the infiltration evaporation coupling technique produces the technology of acetone-butanol
Corn straw is processed slip and is got into feed supplement jar 1 after steam explosion processing, acid hydrolysis, enzymic hydrolysis; Open fresh feed pump 2 and get into fermentor tanks 3, behind the microbe inoculation behind 37 ℃ of fermentation 20h, when total solvent concentration in the liquid phase in the jar when detection reaches 5g/L; Open fresh feed pump 4; Fermented liquid is delivered into evaporation alcohol permselective membrane assembly 5, and membrane module is composed in parallel by two rolling evaporation alcohol permselective membrane separators, uses infiltrating and vaporizing membrane to be the pvdf organic membrane.Simultaneously, open vacuum pump 9, vacuum meter 8 vacuum tightnesss maintain 500Pa, collect the penetrating fluid that obtains in the condensing surface 6 and get into extraction tower 10, and extraction tower is a rotating disc contactor, in extraction tower, is divided into organic phase and water; Aqueous-phase concentration is about 80g/L in the extraction tower, through fresh feed pump 11, opens valve 12 and gets into water basin 13 paths; Organic phase concentration in the extraction tower reaches 500g/L, through fresh feed pump 11, opens valve 12 and gets into a fourth tower 20 paths, directly gets into a fourth tower, obtains anhydrous butanols, acetone and ethanol; Water in the water basin 13 is crossed fresh feed pump 14 input evaporation alcohol permselective membrane assemblies 15; Open vacuum pump 18; Vacuum gauge pressure 500pa treats that the extraction tower organic phase all gets into a fourth tower 20, and condensing surface 16 is collected penetrating fluid and got into extraction tower 12 through fresh feed pump 19; So circulation obtains anhydrous butanols, acetone and ethanol at last.
This example has realized the corn straw production acetone-butanol that continuously ferments; Not only significantly reduced the restraining effect of the acetone-butanol solvent of fermentation generation to microorganism cells; And owing to behind evaporation alcohol permselective membrane, increased extraction tower, made full use of the phase separation property of evaporation alcohol permselective membrane penetrating fluid, effectively reduced the energy consumption of concentration process; Compare with traditional batch fermentation-still-process, the production intensity of butanols is improved simultaneously.
4 one kinds of Semen Maydis powder of embodiment continuously ferment-and the infiltration evaporation coupling technique produces the technology of acetone-butanol
With the Semen Maydis powder is the preparation of raw material substratum, and 121 ℃ of boiling gelatinizations 90 minutes obtain maize powder medium; Get into feed supplement jar 1; Open fresh feed pump 2 and get into fermentor tanks 3, behind the microbe inoculation behind 37 ℃ of fermentation 20h, when total solvent concentration in the liquid phase in the jar when detection reaches 5g/L; Open fresh feed pump 4; Fermented liquid is delivered into evaporation alcohol permselective membrane assembly 5, and membrane module is composed in parallel by three tubular type evaporation alcohol permselective membrane separators, and used infiltrating and vaporizing membrane is organic membrane Vestolen PP 7052 or hybrid organic-inorganic film PTMSP-Silicalite-1.Simultaneously, open vacuum pump 9, vacuum meter 8 vacuum tightnesss maintain 500Pa, and the penetrating fluid device 6 that is condensed is collected, and acetone, butanols and the total ethanol concentration of collecting gained reach 200g/L, and the feed liquid of holding back is returned in the fermentor tank 3; From feed supplement jar 1, in fermentor tank, flow simultaneously and add the identical stalk hydrolysis sugar liquid of penetrating fluid volume that obtains with the infiltration evaporation membrane sepn, the continuation fermentation.Open fresh feed pump 9 simultaneously, collect the penetrating fluid that obtains in the condensing surface 6 and get into extraction tower 10, extraction tower is a pulse-column, in extraction tower, is divided into organic phase and water; Aqueous-phase concentration is about 100g/L in the extraction tower, through fresh feed pump 11, opens valve 12 and gets into water basin 13 paths; Organic phase concentration in the extraction tower reaches 520g/L, through fresh feed pump 11, opens valve 12 and gets into a fourth tower 20 paths, obtains anhydrous butanols, acetone and ethanol; Water in the water basin 13 is crossed fresh feed pump 14 input evaporation alcohol permselective membrane assemblies 15; Open vacuum pump 18; Vacuum gauge pressure 500pa treats that the extraction tower organic phase all gets into a fourth tower 20, and condensing surface 16 is collected penetrating fluid and got into extraction tower 12 through fresh feed pump 19; So circulation obtains anhydrous butanols, acetone and ethanol at last.
This example has realized the Semen Maydis powder production acetone-butanol that continuously ferments; Not only significantly reduced the restraining effect of the acetone-butanol solvent of fermentation generation, and, made full use of the phase separation property of evaporation alcohol permselective membrane penetrating fluid owing to behind evaporation alcohol permselective membrane, increased extraction tower to microorganism cells; Omitted the big wine with dregs tower of energy consumption; Effectively reduce the energy consumption of concentration process, compare with traditional batch fermentation-still-process, the production intensity of butanols improves.
Claims (8)
1. biomass ferment-infiltrating and vaporizing membrane is coupled and produces the technology of acetone-butanol, it is characterized in that this technology key step comprises:
(1) will pass through pretreated biomass as fermentation substrate, inoculation ABE bacterial classification ferments;
(2) fermented liquid in the fermentor tank is inputed to the evaporation alcohol permselective membrane separator through pump, penetrating fluid is collected through condensing surface and is obtained acetone, butanols and alcoholic acid liquid concentrator; Trapped fluid is back to fermentor tank;
(3) acetone that obtains in the step (2), butanols and alcoholic acid liquid concentrator are imported in the extraction tower through pump, liquid concentrator is divided into organic phase and water in extraction tower;
(4) water that obtains in the step (3) is crossed pump and be drained in the water basin, organic phase directly gets into a fourth tower and follow-up rectifying tower group without the wine with dregs tower, and less water removes acquisition anhydrous propanone, butanols and ethanol in the realization organic phase; Water in the water basin concentrates through infiltration evaporation alcohol permselective membrane assembly, and liquid concentrator gets into extraction tower and is separated again, so circulation.
2. technology according to claim 1 is characterized in that, in the fermented liquid of extracting out in the fermentor tank described in the step (2), the concentration of acetone, butanols and total ethanol solvent reaches 18-20g/L.
3. technology according to claim 1 is characterized in that, the total solvent mass concentration of acetone, butanols and the ethanol liquid concentrator that obtains through the condensing surface collection described in the step (2) reaches 100-400g/L.
4. technology according to claim 1 is characterized in that, the total solvent mass concentration reaches 500-700g/L in the organic phase that extraction tower obtains described in the step (3), and aqueous phase total solvent mass concentration reaches 80-280g/L.
5. technology according to claim 1; It is characterized in that; Evaporation alcohol permselective membrane separator described in the step (2) is made up of one or more evaporation alcohol permselective membrane separator, and the per-meate side of each unit evaporation alcohol permselective membrane separator is passed through the pipeline serial or parallel connection in the vacuum pump main pipe rail.
6. according to the technology described in the claim 1, it is characterized in that evaporation alcohol permselective membrane is organic membrane, mineral membrane or hybrid organic-inorganic film described in the step (2); Its membrane module form is rolling, tubular type, plate and frame or tubular fibre formula.
7. according to the technology described in the claim 6, it is characterized in that the material of hybrid organic-inorganic film is a kind of among PDMS-Silicalite-1, PDMS-ZSM-5 and the PTMSP-Silicalite-1; The material of organic membrane is Zylox, gather trimethyl silicane propine, Vestolen PP 7052, pvdf or tetrafluoroethylene; The material of mineral membrane is Silicalite-1 or ZSM-5.
8. according to the technology described in the claim 1, it is characterized in that extraction tower described in the step (3) is a kind of in spraying and extracting tower, sieve-tray tower, rotating disc contactor and the pulse-column.
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| CN102911854A (en) * | 2012-09-29 | 2013-02-06 | 大连理工大学 | Separation and purification device and separation and purification method for butanol and acetone |
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