CN102911854A - Separation and purification device and separation and purification method for butanol and acetone - Google Patents
Separation and purification device and separation and purification method for butanol and acetone Download PDFInfo
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Abstract
Disclosed are a separation and purification device and a separation and purification method for butanol and acetone. The separation and purification device comprises a fermentation device and a gas stripping and pervaporation coupling purification device. The separation and purification method implemented by the separation and purification device includes culturing acetone and butanol producing strains at first, and then fermenting the acetone and butanol producing strains to obtain butanol and acetone; performing online separation and purification for the acetone and butanol by gas stripping and pervaporation coupling purification; performing gas stripping for gas generated by the acetone and butanol producing strains during fermentation, filling the gas into a fermentation system to form bubbles, performing gas stripping for the butanol and the acetone in fermentation liquor of the acetone and butanol producing strains, and performing condensation gas stripping by a condensing plant to obtain butanol and acetone; purifying the butanol and the acetone by pervaporation membranes; and recycling permeate of the pervaporation membranes in a condensing mode or directly filling the permeate into a next-stage separation device. Raw material liquid used in the pervaporation process is lower-layer water-phase condensate obtained by gas stripping. The separation and purification device and the separation and purification method have the advantages that the butanol and acetone separation and purification efficiency is effectively improved, and novel technical support is provided for separating and purifying butanol, acetone and products of the butanol and the acetone which are produced by existing biological methods.
Description
Technical field
The present invention relates to the device and method of a kind of separation and purification butanols and acetone, belong to biological technical field.
Background technology
Butanols can obtain by microbe fermentation method as a kind of important substituting liquid energy and chemical, sees document for details: D ü rre, P. Biobutanol:an attractive biofuel. Biotechnol. J. 2:1525 – 1534,2007.But during with clostridium acetobutylicum or Bai Shi clostridium fermentative production butanols, can produce acetone simultaneously, the butanol concentration of terminal point is no more than 2.0%(w/v usually in the fermented liquid), acetone concentration is no more than 1.0%(w/v).And the boiling point of butanols is 117.7 ℃, is higher than 100 ℃ of the boiling points of water.Therefore, if utilize traditional rectifying or distillation and separation method, its separation costs is high, infeasible economically, be difficult to realize suitability for industrialized production (Matsumura, M., Kataoka, H., Sueki, M., Araki, K. Energy saving effect of pervaporation using oleyl alcohol liquid membrane in butanol purification. Bioprocess Eng. 3:93-100,1988).
Substitutability isolation technique such as liquid-liquid extraction, air lift, absorption etc. can produce the product butanols that suppresses to cell by constantly removing during the fermentation and reclaiming, and improve fermentation efficiency, are to improve the effective technology that biological process is produced butanols.But utilize at present these isolation technique to separate, main problem is that separation efficiency is low, and separated product concentration is low, therefore, needs development new technologies to the product purification of dewatering, and improves separation efficiency.
Therefore, the present invention utilizes air lift-infiltration gasification coupling method of purification to carry out the separation and purification of tunning butanols and acetone, can effectively obtain butanols and the acetone of high density, reduces separation costs.Wherein, the advantage of air lift-infiltration gasification coupling method of purification is, by coupling fermentation system ON-LINE SEPARATION butanols and acetone, compare with other ON-LINE SEPARATION recovery technologies, simple to operate, to the cell toxicological harmless, product separation cleaning inclusion-free, advantage (the Ezeji TC such as target product and cell natural separation, Qureshi N, Blaschek HP. Production of acetone, butanol and ethanol by Clostridium beijerinckii BA101 and in situ recovery by gas stripping. World J Microbiol Biotechnol. 19:595-603,2003).Utilize Pervaporation membrane to the highly selective of butanols and acetone, purifying air lift condensation method separates butanols and the acetone product that obtains, and can obtain butanols and the acetone of high density.Its advantage is, utilize before traditional membrane separation technique separating butanol, need expensive ultra-filtration membrane isolated cell from fermented liquid, if cellular segregation is not thorough, easily cause the film of whole device to pollute, cause production cost sharply to increase (Qureshi, N., Meagher, M.M., Huang, J.C., Hutkins, R.W. Acetone butanol ethanol (ABE) recovery by pervaporation using silicalite-silicone composite membrane from fed-batch reactor of Clostridium acetobutylicum. J. Membr. Sci. 187:93-102,2001).And the present invention can save the cost of isolated cell, and has solved the pollution problem of Pervaporation membrane.Up to the present, have no use air lift-infiltration gasification coupling method of purification carries out separation and purification to butanols and acetone report and Patents.
Summary of the invention
The invention provides the device and method of a kind of High-efficient Production and separation and purification butanols and acetone.
For achieving the above object, the invention provides the constructional device of separation and purification butanols and acetone as follows:
The device of a kind of separation and purification butanols and acetone is the device of a kind of air lift-infiltration gasification coupling purifying plant and fermentation unit coupling, and device comprises two portions: fermentation unit and air lift-infiltration gasification coupling purifying plant;
Fermentation unit is formed by connecting by seed culture tank, pump G, bio-reactor, pump A and cell fixation device; Air lift-infiltration gasification coupling purifying plant comprises air lift condensing works and infiltration gasification condensing works; The air lift condensing works is comprised of prolong, phlegma storage tank A, subcooling thermostatic bath, pump B, pump C and pump E; Infiltration gasification condensing works is formed by connecting by pump D, constent temperature heater, storage tank A, membrane cisterna, storage tank B, vacuum pump, cold-trap, pump F and phlegma storage tank B.
Utilize the method for said apparatus separation and purification butanols and acetone, produce bacterium by cultivating first acetone-butanol, produce the bacterium fermentation with acetone-butanol again and obtain butanols and acetone; Adopt air lift-infiltration gasification coupling method of purification from fermented liquid ON-LINE SEPARATION purifying butanols and acetone; Wherein air lift-infiltration gasification coupling method of purification concrete steps are as follows:
Air lift is produced the self-produced gas that bacterium produces with acetone-butanol in the fermenting process, the stock liquid of air lift condensation process is the fermented liquid that acetone-butanol is produced bacterium, gas enters in the fermentation system and to form bubble and carry out air lift, the butanols and the acetone that raise by the condensing works condensing air; Re-use Pervaporation membrane purification butanols and acetone, the stock liquid of infiltration gasification condensation process is lower floor's water of the phlegma that obtains of air lift; Pervaporation membrane see through liquid, the next stage tripping device is reclaimed or directly enters in condensation.
In the method for the invention, acetone-butanol production bacterium is that the acetone-butanols such as clostridium acetobutylicum, Bai Shi clostridium, intestinal bacteria or clostridium tyrobutyricum are produced bacterial strain.
Preferred acetone-butanol is produced the bacterium fermentation system and is comprised the cell fixation device, and use therein sorbing material is selected from least a in wooden unit, pottery, sponge, towel, resin, activated carbon, the zeolite.
Preferred in air lift-infiltration gasification coupling method of purification: used gas is that acetone-butanol is produced self-produced gas such as carbonic acid gas and the hydrogen that bacterium produces in the fermenting process, stock liquid in the air lift condensation process is that the acetone-butanol that contains butanols and acetone is produced the fermented liquid of bacterium, and gas enters and forms bubble in the fermentation system and carry out air lift;
Preferred in air lift-infiltration gasification coupling method of purification: Pervaporation membrane is organic hydrophobic membrane and the organic-inorganic hybrid films of highly selective, the stock liquid of infiltration gasification condensation process is lower floor's water of the phlegma that obtains of air lift, permeate device condensation or the direct condensation of liquid nitrogen, temperature is-30-+15 ℃ during the device condensation, keeps vacuum tightness at 5 – 200kPa in permeate one side.
By method of the present invention, do not increasing facility investment and saving under the prerequisite of purification energy consumption, Effective Raise production and the separating-purifying efficient of butanols and acetone, provide new technical support for producing butanols and acetone take biological process at present as main liquid biofuel and production and the separating-purifying of bio-based chemical.
Description of drawings
Fig. 1 be among the present invention for the production of with the apparatus structure schematic diagram of separation and purification butanols and acetone.
Fig. 2 is the graph of a relation of butanol concentration in phlegma and the fermented liquid in the air lift process.
Fig. 3 is the graph of a relation of acetone concentration in phlegma and the fermented liquid in the air lift process.
Fig. 4 is the stereoscan photograph figure of PDMS polymeric membrane.
Fig. 5 is the stereoscan photograph figure of the hybrid films of PDMS/20%ZSM-5.
Fig. 6 is the stereoscan photograph figure of the hybrid films of PDMS/80%ZSM-5.
Among Fig. 1: 1 seed culture tank; 2 bio-reactors; 3 cell fixation devices; 4 pump A; 5 pump B; 6 pump C; 7 pump D; 8 prolongs; 9 phlegma storage tank A; 10 subcooling thermostatic baths; 11 pump E; 12 pump F; 13 pump G; 14 constent temperature heaters; 15 storage tank A; 16 membrane cisternas; 17 storage tank B; 18 cold-traps; 19 vacuum pumps; 20 phlegma storage tank B.
Embodiment
Be described in detail the specific embodiment of the present invention below in conjunction with technical scheme and accompanying drawing.
The first step is cultivated acetone-butanol and is produced bacterium
At first, as shown in Figure 1, in seed culture tank 1, cultivate acetone-butanol with seed culture medium and produce bacterium.
Described acetone-butanol is produced bacterium to be not particularly limited, can enumerate clostridium acetobutylicum (Clostridium acetobutylicum), Bai Shi clostridium (Clostridium beijerinckii), intestinal bacteria (Escherichia coli) or clostridium tyrobutyricum (Clostridium tyrobutyricum) etc. and produce the engineering bacteria of acetone-butanol, preferred clostridium acetobutylicum.
Described seed culture medium is before using, and after passing into first nitrogen or other rare gas elementes and carrying out deoxygenation in 10 minutes and process, again 121 ℃ of sterilizations 30 minutes, behind the cool to room temperature, the access acetone-butanol is produced bacterium.
Acetone-butanol is produced bacterium cultivate the most active logarithmic phase of growth.Cultivate logarithmic phase for acetone-butanol is produced bacterium, incubation time is 12-18h, is preferably 15h; Culture temperature is 35-39 ℃, is preferably 37 ℃.
Second step, acetone-butanol are produced the bacterium fermentation and are obtained butanols and acetone
Then, with containing of obtaining in the above-mentioned steps seed liquor that acetone-butanol produces bacterium from seed culture tank 1 after pump 13 is linked into fermention medium the stirring type bioreactor 2, by ejector priming 4, fermented liquid is circulated in stirring type bioreactor 2 and cell fixation device 3, and (cell can be adsorbed by the sorbing material in the cell fixation device 3, realize cell fixation), begin fermentation.
Fermention medium is to produce the material that bacterium provides nutrition (carbon source) for acetone-butanol, can glucose as the carbon source in the fermention medium, also can starch, molasses, cassava or cellulosic hydrolysate (such as the stalk hydrolyzed solution) etc. be the carbon source in the fermention medium.
Described fermention medium, passed into nitrogen or other rare gas elementes 2 h and carries out the deoxygenation processing after 30 minutes 121 ℃ of sterilizations before the access acetone-butanol is produced bacterial classification, and behind the cool to room temperature, the access acetone-butanol is produced bacterium.
Acetone-butanol is produced the access amount of bacterium and can suitably be adjusted according to the amount of fermention medium, is generally the 5-10%(volume percent of substratum).
Leavening temperature is 35-39
oC is preferably 37
oC.PH in the fermenting process is controlled at more than 5.0, when pH is lower than 5.0, adds aqueous sodium hydroxide solution or ammoniacal liquor in the substratum, when pH greater than 5.0 the time, do not need to adjust.
In the 3rd step, utilize air lift-infiltration gasification coupling method of purification ON-LINE SEPARATION purifying butanols and acetone from fermented liquid
For air lift-infiltration gasification coupling method of purification, at first utilize the volatility of butanols and acetone and gas to the absorption principle of butanols and acetone, first by air lift method ON-LINE SEPARATION purifying butanols and acetone from fermented liquid, namely ferment on one side and produce butanols and acetone, one side is separation and purification butanols and acetone (fermentation coupling air lift) from fermented liquid, thereby butanols and acetone in the fermented liquid constantly are removed, reduce butanols and acetone to the murder by poisoning of cell.Then, utilize butanols, acetone and water dissolve in Pervaporation membrane and the difference of diffusibility, and what butanols and acetone were more is dissolved on the film, and diffuses through film, in the opposite side gasification of film and be drawn out of, obtain butanols and the acetone of high density.
For air lift condensing works in air lift-infiltration gasification coupling method of purification, after the butanols in the stirring type bioreactor 2 reaches finite concentration, ejector priming 5 beginning air lifts, start simultaneously subcooling thermostatic bath 10 for air lift prolong 8 provides the low temperature cold lime set, the butanols that obtains and the phlegma of acetone are in phlegma storage tank 9.
The used stock liquid of air lift is the fermented liquid that acetone-butanol is produced bacterium, enter the gas that is used for extraction butanols and acetone in the fermentation system and be preferably any self-produced gas that the fermenting process acetone-butanol is produced the bacterium generation, normally carbonic acid gas and hydrogen, do not need to provide external gas, so just can save input cost.
Like this, the butanol concentration that separates in the phlegma that obtains after the air lift can be brought up to about 15%, and acetone concentration is brought up to about 4%.
The condition optimization of air lift condenser system is as follows in air lift-infiltration gasification coupling method of purification: gas flow rate is 1-20 L/min, and gas flow direction is for making progress or passing through prolong downwards; The prolong that uses in the air lift condenser system is straight type or serpentine condenser, and condensing temperature is-15
oC-+15
oC.
The phlegma of butanols and acetone is standing demix in phlegma storage tank 9, and the upper strata is the organic phase of enrichment butanols, and butanol concentration is about 80%, and acetone concentration is about 4%; Lower floor is water, and butanol concentration is about 8%, and acetone concentration is about 4%.Upper organic phase is directly pumped into recovery in the phlegma storage tank 20 by pump 11, and then ejector priming 6 pumps into the lower floor's phlegma in the air lift phlegma storage tank 9 in the storage tank 15, as the stock liquid of infiltration gasification, carries out the pervaporation separation operation.Starting simultaneously constent temperature heater 14 heats for the stock liquid in the storage tank 15, make the side circulation of the stock liquid film in membrane cisterna 16 in the storage tank 15 by pump 7, starting simultaneously vacuum pump 19 makes the film opposite side form certain vacuum tightness, butanols in the stock liquid, the matter selective such as acetone and water ground sees through film with the steam form, see through liquid and be recovered in the storage tank 17 in the cold-trap 18, by pump 12 the collection liquid pump in the storage tank 17 is entered in the storage tank 20 at last, mix with the upper organic phase that air lift is collected.
The lower layer of water heat phase to 25 of the phlegma that air lift is obtained
oC-90
oPermeate gasification between the C, preferred 80
oC.Liquid nitrogen is chosen in the condensation of permeate usually, also can choose condensing works and carry out condensation, if choose the condensing works condensation, condensing temperature is at-30-+15 ℃, the preferential 5 – 200kPa of the vacuum tightness of permeate one side.
Lower floor's water of the phlegma that air lift is obtained carries out pervaporation separation, butanol concentration can be brought up to about 50% by 8%, and acetone concentration is brought up to 16-17% by 4%.
As mentioned above, the fermenting process toxic that realized air lift of the present invention-infiltration gasification coupling method of purification suppresses constantly removing and efficient recovery and the dual purpose that concentrates of product butanols and acetone, improved the production efficiency of butanols and acetone, reduced the cost recovery of butanols and acetone, improved the economic return of fermentative Production butanols and acetone, be suitable for applying.
Below in conjunction with embodiment the present invention is specified.But the present invention is not subjected to the restriction of following embodiment, in the scope of aim, can do suitable change to the present invention before and after meeting the present invention.
In following Comparative Examples and embodiment, each experiment material and method are as follows:
Acetone-butanol is produced bacterium: clostridium acetobutylicum (Clostridium acetobutylicum), buy in U.S. ATCC strain library (ATCC number:55025-E604).
Seed culture medium: contain glucose 30 g, yeast powder 2 g, Tryptones 4 g, potassium primary phosphate 0.5 g, dipotassium hydrogen phosphate 0.5 g, ammonium acetate 2.2 g and mineral mixture in every liter of substratum.Wherein, consisting of of mineral mixture: contain 7 Magnesium sulfate heptahydrates, 0.1 g, 7 ferrous sulfate hydrates, 0.015 g, 2 hydration calcium chloride, 0.015 g, 1 anhydrous manganese, 0.01 g, cobalt chloride 0.02 g and zinc sulfate 0.002 g in every liter of substratum.
Fermention medium: contain glucose 80 g, yeast powder 1 g, potassium primary phosphate 0.5g, dipotassium hydrogen phosphate 0.5 g, ammonium acetate 2.2 g, mineral mixture and VITAMIN in every liter of substratum.Wherein, consisting of of mineral mixture: contain 7 Magnesium sulfate heptahydrates, 0.2 g, 7 ferrous sulfate hydrates, 0.01 g, 1 anhydrous manganese, 0.01 g and sodium-chlor 0.01 g in every liter of substratum; Consisting of of VITAMIN: contain para-amino benzoic acid 0.001 g, VITMAIN B1 0.001 g and vitamin H 0.00001 g in every liter of substratum.
Acetone-butanol is produced cultivation and the fermentation of bacterium: seed culture medium is before using, and logical nitrogen deoxygenation 10 minutes is then 121
o C sterilization 30 minutes, behind the cool to room temperature, bacterium is produced in access.With produce bacterium in seed culture tank 1 after cultivating 15h under 37 ℃ the condition, prepare to be linked in the fermention medium.Fermention medium is before using, 121
oThen C sterilization 30 minutes passes into nitrogen deoxygenation 2h, behind the cool to room temperature, will contain the seed liquor of producing bacterium (fermention medium volume 10%) by pump 13 and pump in the stirring type bioreactor 2 37
oBegin fermentation under the condition of C, open simultaneously pump 4 make contain the fermention medium of producing bacterium and use cotton fibre to be sorbing material at cell fixation device 3() and stirring type bioreactor 2 in circulate the realization cell fixation.Fermention medium is not initially regulated the pH value, and after fermented liquid pH was lower than 5.0, auto-feeding aqueous sodium hydroxide solution or ammoniacal liquor were adjusted to pH more than 5.0.
The preparation of Pervaporation membrane: polydimethylsiloxane (PDMS) is from being purchased from Dow corning company (Dow corning).Zeolite nano material (ZSM-5) is bought from U.S. Zeolyst International.ZSM-5 is first 80 ℃ of lower oven dry 24 hours.Base gel solution in the polydimethylsiloxane (PDMS) and solidifying agent mix in the ratio of 10:1.For the preparation of single PDMS polymeric membrane, directly descended centrifugal 5 minutes at 8000 rev/mins, carry out subsequent operations.For the PDMS hybrid films of adding the ZSM-5 material, choose respectively 20% and 80% in the ZSM-5(embodiment of the invention 2 and 3 with the specified wt ratio) mix with the mixed PDMS preparation liquid of 10:1 ratio in mass ratio, turn lower centrifugal 5 minutes 8000, carry out subsequent operations.Subsequent operations with supersound process preparation liquid 15 minutes or vacuumize processing, is removed the bubble in the preparation liquid for first, then with scraper preparation liquid is evenly spread upon on the sheet glass, will be put into the sheet glass of preparation liquid 3 hours film forming in 100 ℃ the baking oven.From baking oven, take out at last sheet glass, peel off the Pervaporation membrane for preparing, be fixed in the membrane cisterna, be used for the pervaporation separation operation.
Conventional vapor-phase chromatography is used in the analysis of butanols, and conventional liquid phase chromatography or DNS method are used in the concentration determination of glucose.
If no special instructions, employed experimental technique is ordinary method, and material therefor, reagent etc. all can be bought from biological or chemical company.
Comparative Examples 1: the fermentation of butanols and acetone---without lock out operation
Carry out as stated above cultivation and fermentation that acetone-butanol is produced bacterium.After producing bacterium access stirring type bioreactor 2, active cell immobilization device 3 is until fermentation ends.The result is as shown in table 1, and butanols and the acetone endpoint concentration in fermented liquid is respectively 1.6%(w/v) and 0.8%(w/v).
Comparative Examples 2: traditional air lift method is separated
Carry out as stated above cultivation and fermentation that acetone-butanol is produced bacterium.After producing bacterium access stirring type bioreactor 2, start the air lift condensing works that is used for air lift, until fermentation ends.The condensed product that air lift obtains is collected, left standstill, and phlegma is without layering.Traditional Method carries out air lift, adopts fermentation and air lift to carry out simultaneously, and acellular immobilization device; In addition, Traditional Method does not embed other separation methods yet.In addition, traditional air lift method etc. is all identical with embodiment 1.The result is as shown in table 1.The result shows that the gas stripping efficiency of Traditional Method and Butanol Recycling concentration are very low, and the butanol concentration that is recovered in the phlegma is 7.0%(w/v), acetone concentration is 1-2%(w/v) about.
Table 1
Comparative Examples 3: traditional pervaporation separation
Carry out as stated above cultivation and fermentation that acetone-butanol is produced bacterium.When Traditional Method permeates gasification with the fermentation coupling, need to be between fermentation unit and infiltration gasification installation, the access ultra-filtration equipment is used for filtration cell, namely first with the cell in the fermented liquid and separation of fermentative broth, and then permeate gasification, so the waste that can cause energy and device to drop into of isolated cell process, in addition, if cellular segregation is not thorough, very easily cause obstruction or the pollution of follow-up Pervaporation membrane, whole device can't be moved.The result is as shown in table 1.The result shows that the concentration of traditional pervaporation separation butanols is 9.8%(w/v), the butanol concentration that obtains than traditional air lift is slightly high, acetone concentration is 2%(w/v) about.
Embodiments of the invention all adopt air lift-infiltration gasification coupling method of purification separating-purifying, and are specific as follows:
Embodiment 1: the air lift of usefulness PDMS polymeric membrane-infiltration gasification coupling method of purification separating-purifying
Carry out as stated above cultivation and fermentation that acetone-butanol is produced bacterium.After beginning fermentation in the stirring type bioreactor 2, ejector priming 4 active cell immobilization systems, until fermentation ends, starting simultaneously subcooling thermostatic bath 10 provides the low temperature cold lime set for air lift prolong 8.The self-produced gas that the production bacterium produces during the fermentation forms bubble by fermentation system and enters in the stirring type bioreactor 2, as air lift gas.Air lift butanols and acetone steam out passes through prolong 8 rear condensations, contains phlegma standing demix in phlegma storage tank 9 of butanols and acetone, and the upper strata is directly pumped in the phlegma storage tank 20 by pump 11.Then lower floor's water is heated to 80 with constent temperature heater 14
oC, ejector priming 7 permeates gasification, and starting simultaneously vacuum pump 19 provides vacuum tightness 70kPa in a side of Pervaporation membrane, sees through condensation in the butanols of film and the storage tank 17 of acetone steam in cold-trap 18.By pump 12 phlegma is pumped in the storage tank 20 at last, mix with the upper organic phase that air lift obtains.After the glucose concn in the fermention medium drops to 1g/L, add the concentrated glucose of 600 g/L in the fermention medium, continue fermentation, altogether add about glucose 400g.
For air lift-infiltration gasification coupling method of purification, the parameter of air lift condenser system all is set to: for from bottom to up, vertically place by prolong through the direction of prolong for gas stream, and prolong control temperature is 0-2 ℃, and gas flow rate is 1.5 L/min.Employed Pervaporation membrane is the polydimethylsiloxane polymeric membrane, and the stereoscan photograph of film as shown in Figure 4.The flow velocity of stock liquid is 0.5L/min, and the vacuum tightness of film opposite side is 70kPa, and condensing mode is liquid nitrogen condensation.
Behind air lift-infiltration gasification coupling method of purification separating-purifying, butanols and acetone concentration in air lift product, infiltration gasification product and the final product are as shown in table 1.
Compare with Comparative Examples 1, use the cell fixation system in the fermentation system, not only can improve the total cell concn in the fermentation system, improve the production intensity of butanols and acetone, and in adopting air lift-infiltration gasification coupling method of purification separating-purifying process, butanols and acetone can constantly be separated in fermented liquid, reduce them to the toxic action of cell.Therefore, the concentration of butanols and acetone is respectively 45.1% and 16.2% in the final product among the embodiment 1, compares with Comparative Examples 1 and wants high a lot.
Different from traditional air lift method in the Comparative Examples 2, after the concentration of butanols in fermented liquid reaches 5 g/L, start for the air lift condensing works, when the concentration of butanols in fermented liquid is lower than 5 g/L, close this air lift condensing works.And traditional air lift method just starts the air lift condensing works when beginning to ferment, until fermentation ends, and air lift when fermented liquid butanols and acetone concentration are very low, the selectivity of butanols and acetone is very low, causes that to reclaim in the phlegma concentration of butanols and acetone very low.Because the butanol concentration in the phlegma that stripping recovery obtains and the butanol concentration in the fermented liquid are in close relations to be that butanol concentration in the phlegma raises with the rising of the butanol concentration in the fermented liquid, as shown in Figure 2.Usually in fermented liquid, the concentration ratio of butanols and acetone probably is 2:1, and the acetone in the phlegma that stripping recovery obtains also raises with the rising of the acetone concentration in the fermented liquid, as shown in Figure 3.As shown in Figures 2 and 3, when the butanols in the fermented liquid was identical with acetone concentration, cell concn was higher in the fermented liquid, and butanols and acetone concentration in the phlegma are lower, i.e. the existence of cell has negative impact to butanols and acetone gas stripping efficiency.Therefore, compare with Comparative Examples 2, cell is fixed on the cell density that can reduce in the cell fixation device in the fermented liquid, improve the gas stripping efficiency among the present invention, improve and reclaim butanols and the acetone concentration of purifying in the phlegma.The present invention begins air lift after butanol concentration arrives 5g/L, guarantee whole lock out operation to the highly selective of butanols, so the butanol concentration in the phlegma doubles abovely than Traditional Method, and acetone concentration also improves accordingly.
Compare with Comparative Examples 3, the present invention utilizes the polydimethylsiloxane polymeric membrane that the lower floor's aqueous phase butanols in the air lift phlegma and acetone are further permeated the gasification purification, the butanol concentration of acquisition 45.1% and 16.2% acetone concentration, the phlegma upper organic phase that the final sum air lift obtains is mixed, and obtains end product butanol concentration 58.2% and acetone concentration 10.1%.And in the Comparative Examples 3, usually directly from fermented liquid, extract butanols and acetone with the infiltration evaporating method, and between fermentation system and infiltration gasification, increase the cellular segregation system, namely increase the equipment investment cost, waste energy again.Therefore, the more efficient and economically feasible of method of the present invention.
Embodiment 2: the air lift of usefulness PDMS/20%ZSM-5 hybrid films-infiltration gasification coupling method of purification separating-purifying
Carry out cultivation and the fermentation that acetone-butanol is produced bacterium by the method in the example 1.For air lift-infiltration gasification coupling method of purification separating-purifying process, the Pervaporation membrane that uses is mixed substrate membrane containing nano-grade molecular sieve, and it consists of 20% ZSM-5 nanosized zeolitic material and the rear crosslinked film forming of polydimethylsiloxane mixing.Nano zeolite is hydrophobicity, can increase film to the selectivity of butanols, improves the concentration of butanols in permeate.The stereoscan photograph of the hybrid films of PDMS/20%ZSM-5 such as Fig. 5.
In addition, additive method is identical with embodiment 1, and the parameter of air lift-infiltration gasification coupling purifying plant is also identical with embodiment 1.
The result is as shown in table 1.The concentration of butanols and acetone is respectively 62.3% and 10.5% in the final product of the present invention, compares with Comparative Examples 1 and wants high a lot.Butanols and acetone concentration in the phlegma that obtains by the air lift separation and purification are respectively 17.6% and 4.0%, compare with Comparative Examples 2 to exceed about one times.The butanols and the acetone concentration that obtain after pervaporation separation is purified are respectively 50.7% and 16.8%, compare with Comparative Examples 3, the butanol concentration height 5 times, the acetone concentration height 8 times.Phlegma upper organic phase that the final sum air lift obtains is mixed, and obtains that butanols and acetone concentration are respectively 62.3% and 10.5% in the end product.The single polydimethylsiloxane polymeric membrane performance that explanation uses the mixing basement membrane that contains 20% nanosized zeolitic material to use in than embodiment 1 in infiltration gasification is better, and is higher to the selectivity of butanols, to the selectivity of acetone without considerable change.
Embodiment 3: the air lift of usefulness PDMS/80%ZSM-5 hybrid films-infiltration gasification coupling method of purification separating-purifying
Carry out cultivation and the fermentation that acetone-butanol is produced bacterium by the method in the example 1.For air lift-infiltration gasification coupling method of purification separating-purifying process, the Pervaporation membrane that uses is mixed substrate membrane containing nano-grade molecular sieve, and it consists of 80% nanosized zeolitic material and the rear crosslinked film forming of polydimethylsiloxane mixing.Compare with embodiment 2, improve nano zeolite shared ratio to 80% in film, purpose is the hydrophobicity that increases film, improves hybrid films to the selectivity of butanols, improves the concentration of butanols in permeate.The stereoscan photograph of the hybrid films of PDMS/80%ZSM-5 such as Fig. 6.
The result is as shown in table 1.The present invention obtains the end product butanols and acetone concentration is respectively 66.2% and 10.6%, compares with Comparative Examples 1 and wants high a lot.Butanols and acetone concentration that the present invention separates in the phlegma obtain by air lift are respectively 15.5% and 4.2%, compare with Comparative Examples 2 double about.Butanols and acetone concentration that the pervaporation separation purification obtains are respectively 56.2% and 17.0%, compare with Comparative Examples 3, and butanol concentration is high more than 5 times, and acetone concentration is high more than 8 times.The phlegma upper organic phase that the final sum air lift obtains is mixed, and obtains end product butanols and acetone concentration and is respectively 66.2% and 10.6%.Explanation uses the mixed base film properties that contains 20% zeolite nano particle that uses among single polydimethylsiloxane polymeric membrane that the mixing basement membrane that contains 80% zeolite uses in than embodiment 1 and the embodiment 2 better in infiltration gasification, selectivity to butanols is higher, to the acetone selectivity without considerable change.
As shown in Table 1, the present invention is by air lift-infiltration gasification coupling method of purification, contains butanols about 58-66% and about 10% acetone in the final product that separating-purifying obtains.Wherein, take by to air lift the time suitable air lift strategy behind 5g/L, to begin air lift when the butanol concentration in the fermented liquid, compare with the traditional air lift in the Comparative Examples 2, in the air lift process, can separate the butanol concentration that obtains is 15%-17%, double with separating the butanol concentration that obtains in the Comparative Examples 2, acetone concentration is corresponding improve also.In the pervaporation separation purification process, by using different mould materials, can obtain different separating effects.Wherein use the hybrid films of PDMS/80%ZSM-5, finally can separate the final product of the acetone that obtains containing 66.2% high-concentration butanol and 10.6%, the butanol concentration that obtains with tradition infiltration evaporating method in the Comparative Examples 3 is high more than 6 times, and acetone concentration is high about 5 times.
As from the foregoing, tradition is the acetone butanol fermentation of integrated separation not, and butanols and acetone concentration are respectively 1.6% and 0.8% in the fermented liquid that obtains.Butanols in the phlegma that traditional air lift method obtains and acetone concentration be respectively 7.0% and 1-2% about.The butanols that traditional infiltration evaporating method obtains and acetone concentration are respectively 9.8% and 2%.The present invention is by containing butanols in the product of finally collecting and acetone concentration is respectively about 58-66% and 10%.Owing to containing the butanols of high concentration in the final product, very easily by simple processed such as rectifying, distillation or membrane sepn obtain pure butanols.Infiltration gasification in air lift of the present invention-infiltration gasification coupling method of purification is for improving butanols purification concentration, and the energy consumption that reduces whole fermentation separating technology is most important.Compare with traditional rectifying separation, the energy expenditure that air lift-infiltration gasification coupling method of purification needs is about 40% of traditional rectifying separation.And, guaranteeing that follow-up butanols and acetone purifies and separates can less energy-consumption in being rich in the solution of high-concentration butanol, high-level efficiency is carried out.Therefore, the present invention can improve butanols and acetone production and organic efficiency and reduce the energy consumption of separating-purifying, produces butanols and acetone provides new technology for biological process, has very large industrial application value.
Claims (9)
1. the device of a separation and purification butanols and acetone is the device of a kind of air lift-infiltration gasification coupling purifying plant and fermentation unit coupling, it is characterized in that, device comprises two portions: fermentation unit and air lift-infiltration gasification coupling purifying plant;
Fermentation unit is by seed culture tank (1), pump G(13), bio-reactor (2), pump A(4) and cell fixation device (3) be formed by connecting;
Air lift-infiltration gasification coupling purifying plant comprises air lift condensing works and infiltration gasification condensing works; The air lift condensing works is by prolong (8), phlegma storage tank A(9), subcooling thermostatic bath (10), pump B(5), pump C(6) and pump E(11) form; Infiltration gasification condensing works is by pump D(7), constent temperature heater (14), storage tank A(15), membrane cisterna (16), storage tank B(17), vacuum pump (19), cold-trap (18), pump F(12) and phlegma storage tank B(20) be formed by connecting.
2. device claimed in claim 1 is for separating of the method for purifying butanols and acetone, and the method is cultivated first acetone-butanol and produced bacterium in seed culture tank, produce bacterium with acetone-butanol and produce butanols and acetone in fermentation unit; Adopt again air lift-infiltration gasification coupling purifying plant ON-LINE SEPARATION purifying butanols and acetone from fermented liquid; It is characterized in that:
Air lift is produced the gas that bacterium produces with acetone-butanol in the fermenting process, gas is passed into form bubble in the fermentation unit, and butanols and acetone that acetone-butanol is produced in the fermented liquid carry out air lift, the butanols and the acetone that raise by the condensing works condensing air; Re-use Pervaporation membrane purification butanols and acetone, the stock liquid of infiltration gasification condensation process is lower floor's water that the air lift condensation process obtains phlegma; Pervaporation membrane see through liquid, the next stage tripping device is reclaimed or directly enters in condensation.
3. method according to claim 2 is characterized in that, described Pervaporation membrane is hydrophobic organic membrane or organic-inorganic hybrid films.
4. according to claim 2 or 3 described methods, it is characterized in that, it is clostridium acetobutylicum, Bai Shi clostridium, intestinal bacteria or clostridium tyrobutyricum that acetone-butanol is produced bacterium.
5. according to claim 2 or 3 described methods, it is characterized in that, fermentation unit comprises the cell fixation device, and use therein sorbing material is selected from least a in wooden unit, pottery, sponge, towel, resin, activated carbon, the zeolite.
6. method according to claim 4 is characterized in that, acetone-butanol is produced the bacterium fermentation unit and comprised the cell fixation device, and use therein sorbing material is selected from least a in wooden unit, pottery, sponge, towel, resin, activated carbon, the zeolite.
7. according to claim 2 or 3 or 6 described methods, it is characterized in that, the stock liquid temperature of air lift condensation process is leavening temperature, and condensing temperature is-15-+15 ℃; The stock liquid temperature of infiltration gasification condensation process is+20-+100 ℃, device condensation or the direct condensation of liquid nitrogen, and temperature is-30-+15 ℃ during the device condensation, vacuum tightness is 5 – 200kPa.
8. method according to claim 4 is characterized in that, the stock liquid temperature of air lift condensation process is leavening temperature, and condensing temperature is-15-+15 ℃; The stock liquid temperature of infiltration gasification condensation process is+20-+100 ℃; Device condensation or the direct condensation of liquid nitrogen, temperature is-30-+15 ℃ during the device condensation, vacuum tightness is 5 – 200kPa.
9. method according to claim 5 is characterized in that, the stock liquid temperature of air lift condensation process is leavening temperature, and condensing temperature is-15-+15 ℃; The stock liquid temperature of infiltration gasification condensation process is+20-+100 ℃; Device condensation or the direct condensation of liquid nitrogen, temperature is-30-+15 ℃ during the device condensation, vacuum tightness is 5 – 200kPa.
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