CN102351646B - Method for separating ethanol from fermentation liquor - Google Patents
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- CN102351646B CN102351646B CN201110275497.4A CN201110275497A CN102351646B CN 102351646 B CN102351646 B CN 102351646B CN 201110275497 A CN201110275497 A CN 201110275497A CN 102351646 B CN102351646 B CN 102351646B
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Abstract
The invention discloses a method for separating ethanol from fermentation liquor, wherein the ethanol fermentation liquor is subjected to solid-liquid separation to obtain clear liquid, the clear liquid passes through an adsorption column filled with macroporous adsorption resin, the ethanol is selectively adsorbed, the saturated macroporous adsorption resin is subjected to hot air heating desorption and vacuum suction desorption, the vapor of the ethanol and water is collected and condensed to obtain high-concentration ethanol solution, and the desorbed adsorbent is subjected to regeneration treatment for reuse. The method can relieve the inhibition of ethanol on yeast cells during fermentation, and reduce energy consumption for ethanol separation.
Description
Technical field
The invention belongs to bioseparation technology field, be specifically related to a kind of from fermented liquid the method for separating alcohol.
Background technology
Ethanol is a kind of reproducible clean energy, makes fuel by the gasoline-gasohol of adding ethanol, can significantly reduce the consumption of oil and the discharge of carbonic acid gas.Because the content of oxygen in ethanol is high, can make the more abundant of fuel combustion, the discharge of carbon monoxide and hydrocarbons in minimizing combustion processes.Along with consuming excessively and the continuous enhancing of environmental consciousness of petroleum resources, the substitute energy of development take ethanol as fuel, can alleviating energy crisis and alleviate environmental pollution, and its development prospect is very wide.
Ethanol Production by Fermentation exists obvious product and suppresses phenomenon.Microorganism changes according to the condition such as bacterial classification, temperature the tolerance of ethanol, but the massfraction of usually ethanol is while reaching 5～8%, will be to the obvious restraining effect of microorganisms.The people such as Jones (Jones R, Tezel F H, Thibault J, et al.Adsorption separation of ethanol from water for bio-ethanol production[C] .AIChE Annual Meeting, Cincinnati, OH, United states, 2005.) find that the fermenting process of ethanol will stop when alcohol concn in fermented liquid is higher than 8% time.This reason has limited the raising of alcohol concn in the raising of sugar degree in proferment feed liquid and fermented liquid, thereby has increased raw material saccharification and dehydrated alcohol and produce the energy consumption of process.
Patent (CN101891590A) disclose a kind of in fermentation, isolate fermented liquid in the method for ethanol.Its method is: first fermentation liquid is sent into separating tank, by vacuum pump by ethanol, CO
2, air and part water vapour isolates fermentation liquid, mash turns back to fermentor tank relaying supervention ferment, when controlled fermentation in mash alcohol concn lower than 2%, thereby remove the restraining effect of ethanol to thalline in fermenting process.Isolated ethanol mixed gas is heated to 80-100 ℃, enters in adsorption column and adsorbs, and the high concentration ethanol that desorption produces obtains dehydrated alcohol through dehydration again.The method can be got up the fermentation process coupled with separation of ethanol, but operating procedure condition is harsher.
Patent (CN101024846A) discloses a kind of method and apparatus of preparing fuel alcohol by fermented liquid steam phase adsorption separation.Its method is: fermented liquid is adsorbed by silicon zeolite adsorption bed vapor phase through slightly heating up in a steamer after concentrated, and the high concentration ethanol steam that desorption obtains is dried after agent water suction and obtains alcohol fuel.Compared with tradition distillation, this tripping device can reduce separation of ethanol energy consumption approximately 30%, can not be coupled together with ethanol fermentation in technique but install, and cannot eliminate the low problem of ethanol fermentation process efficiency.
United States Patent (USP) (US19800195917) discloses a kind of method of separating alcohol.Its method is: adopt granular carbon pyropolymer as sorbent material, the ethanol in aqueous ethanolic solution is adsorbed, then adopt organic solvent to carry out desorption under certain pressure, 95 ℃ of conditions, fraction collection desorption liquid, thereby the ethanol of acquisition high density.The method has been used organic solvent to carry out desorption under the condition of pressurization, and desorption temperature is higher, thereby its processing condition are harsher, and cost is higher, and this separating technology is difficult to be coupled with fermenting process.
On the other hand, adopt method separating alcohol energy consumption from fermented liquid of distillation higher, account for 40% of alcohol production energy consumption.Low and the separation of ethanol energy consumption height of fermentation efficiency is the high major cause of current Ethanol Production by Fermentation process costs.
Summary of the invention
Technical problem to be solved by this invention be to provide a kind of from fermented liquid the method for separating alcohol, the method can be removed the restraining effect of ethanol to yeast cell, reduces the energy consumption of separation of ethanol process simultaneously.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of from fermented liquid the method for separating alcohol, ethanol fermentation liquid obtains clear liquid through solid-liquid separation, clear liquid is by being equipped with the adsorption column of macroporous adsorbent resin, ethanol is by the absorption of selectivity, macroporous adsorbent resin after saturated is through warm air beating desorption and vacuum take-off desorption, the steam of collecting second alcohol and water obtains the ethanolic soln of high density through condensation, the sorbent material after desorption is reused through manipulation of regeneration.
As the preferred technical scheme of the present invention, the present invention's method of separating alcohol from fermented liquid comprises the steps:
(1) adsorption operations: ethanol fermentation liquid obtains clear liquid through solid-liquid separation, clear liquid with the flow velocity of 0.5～3BV/h by the adsorption column of macroporous adsorbent resin is housed, ethanol is by the absorption of selectivity, the adsorption operations time is 10～60min, does not flow out from the other end of adsorption column containing the effluent liquid of ethanol;
(2) desorption manipulation: after adsorption column absorption is saturated, stop charging, by the drain in adsorption column, add thermal desorption to passing into warm air in adsorption column, when bed temperature reaches 50～80 ℃, stop passing into warm air, adopt vacuum take-off mode desorption, vacuum pressure is-0.06～-0.1MPa, and the vacuum take-off operating time is 5～60min, and the steam of collecting the second alcohol and water that adds thermal desorption and the generation of vacuum take-off desorption obtains the ethanolic soln of high density through condensation;
(4) regenerative operation: after desorption finishes, pass into hot water with the flow velocity of 0.5～3BV/h in adsorption column, the impurity of absorption with macroporous adsorbent resin is resolved to regeneration, the regenerative operation time is 10～60min;
(5) cooling operation: to regeneration after adsorption column in cooling with the flow velocity water flowing of 0.5～3BV/h, be 10～60min cooling time, adsorption column can be used for adsorption operations next time after being cooled to normal temperature.
Wherein, described ethanol fermentation liquid is obtained by yeast fermentation, and fermentation raw material is biomass material, comprises corn, cassava or sugarcane.
Wherein, described solid-liquid separation is centrifugal or filters.
Wherein, the clear liquid that ethanol fermentation liquid obtains through solid-liquid separation, wherein the mass percent concentration of ethanol is 4～12%.
Wherein, described adsorption column is more than 2, and guaranteeing has 1 adsorption column all the time in adsorption operation condition.Described adsorption column is preferably 4, and when wherein any one while carrying out adsorption operations, other 3 can be respectively in desorption, regeneration and cooling operation, with guarantee lock out operation continuously, stable carrying out.
Wherein, described macroporous adsorbent resin is take crosslinked polystyrene-Vinylstyrene as skeleton, with the very strong polar resin of a kind of wetting ability of sulfonic acid group.Monomer whose is vinylbenzene, and linking agent is divinylbenzene, and pore-creating agent is toluene, and dispersion agent is gelatin, and particle size range is 0.4mm-1.2mm.In vacuum desorption process, can guarantee that on resin, most of moisture is not got off by desorption, and can, by water direct invasion, just can complete the regeneration of resin with hot water.The pore size distribution of this resin is narrower, is about 20-30nm, to the macromolecular substance in the middle of fermented liquid, as the materials such as protein do not adsorb, therefore higher to the Ethanol Adsorption selectivity in fermented liquid.
Wherein, condensing temperature is 0～-10 ℃.
Wherein, regenerative operation passes into the hot water regeneration of 40～70 ℃.
Wherein, this separation method is directly used in conjunction with zymotechnique, fermentation unit, equipment for separating liquid from solid is connected to formation Integrated process technique with adsorption column separation device.
In the present invention, adsorption operations, the flow direction of liquid is at the bottom of post from capital; Desorption manipulation, the flow direction of warm air be at the bottom of post to capital, vacuum suction gas flow to be to capital at the bottom of post; Regenerative operation, hot water flow is to being at the bottom of post from capital; Cooling operation, cold water flow is to being at the bottom of post from capital.
The present invention is the ethanol adopting in adsorption column Adsorption Concentration fermented liquid, can remove the restraining effect of ethanol to yeast cell in fermenting process, and reduce the energy consumption of separation of ethanol process.
The sorbent material that the present invention uses is macroporous adsorbent resin, there is the skeleton structure of crosslinked polystyrene, belonging to polar resin, be spherical particle, thereby operating process resistance is less, simultaneously, this resin polarity is stronger, thereby has stronger water-retentivity, and desorption finishes not yet complete drying of rear resin, add water and can infiltrate immediately, regenerate convenient.In adsorption operations process, the ethanol in fermented liquid, by the absorption of selectivity, does not flow out from the other end of adsorption column containing the effluent liquid of ethanol, after sorbent material absorption is saturated, stops charging, and by the drain in adsorption column, turns to desorption manipulation.First passing into warm air heats bed, make bed become comparatively loose simultaneously, when bed temperature reaches 50～80 ℃, close hot-air inlets valve, open vacuum pump, adsorbent ethanol is parsed under vacuum condition, the steam of the second alcohol and water that warm air blowoff and vacuum desorption get off enters condensing works, second alcohol and water is condensed into liquid, thereby obtains the ethanolic soln of high density.
Of the present invention one large advantage can be coupled with fermentation exactly, can also be coupled with rectifying simultaneously, realizes efficiently integrated that ethanol fermentation separates.Because operating procedure of the present invention is charging at normal temperatures, therefore can be coupled together with fermentation.In ethanol fermentation process, fermented liquid is after yeast thalline is removed in centrifugal or filtration, enter technique of the present invention, after ethanol is adsorbed by selectivity, do not turn back to fermentor tank relaying supervention ferment containing effluent liquid and the isolated thalline of ethanol, can in the process of fermentation, product ethanol constantly be removed from fermented liquid like this, avoid the ethanol of high density to the restraining effect of yeast cell, improve fermentation rate.Meanwhile, technique of the present invention also can integrate with rectification process, and ethanol is carried out to further concentrated purification.The high concentration ethanol steam producing in desorption manipulation process can be used as the feeding liquid of rectifying tower, and this will significantly reduce the load of reboiler, reduces equipment and the process cost of downstream separation.
Accompanying drawing explanation
Fig. 1 is process flow diagram of the present invention.
In figure, ethanol fermentation liquid is after centrifugation goes out yeast cell, and clear liquid passes into the flow velocity of 0.5～3BV/h in the adsorption column that macroporous adsorbent resin is housed, and ethanol, by the absorption of selectivity, does not turn back to fermentor tank relaying supervention ferment containing the effluent liquid of ethanol.Absorption 10～60min, after adsorption column absorption is saturated, stops charging, and by the drain in post.Warm air is passed in post bed is heated, Exhaust Gas is condensed into liquid through condenser, in the time that bed temperature is raised to 60～80 ℃, stop passing into warm air, open vacuum pump, under the pressure of-0.06～-0.1MPa (table), the ethanol of absorption is carried out to desorption, the steam of generation is condensed into the ethanolic soln of high density through condenser.After desorption 5～60min, when phlegma substantially no longer flows out, desorption finishes, in the adsorption column after desorption, add hot water with the flow velocity of 0.5～3BV/h, maintain 10～60min, recovery stream fluid enters storage tank, after allotment, can be back in fermentor tank, resin regeneration is complete, can be used for adsorption operations next time.4 adsorption columns are set, and when wherein any one during in adsorbed state, other 3 can be respectively in desorption, regeneration and the state of cooling, with guarantee lock out operation continuously, stable carrying out.
Embodiment
According to following embodiment, the present invention may be better understood.But, those skilled in the art will readily understand, the described concrete content of embodiment is only for the present invention is described, and should also can not limit the present invention described in detail in claims.
Embodiment 1: the preparation of ethanol fermentation liquid.
Ethanol fermentation tank adopts the self-suction fermentor of air lift type, first at 120 ℃, carries out in-situ sterilization 30 minutes with steam, then is adjusted to 35 degree.The component of fermented liquid comprises glucose, KH
2pO
4, MgSO
4.7H
2o, yeast extract paste, (NH
4)
2sO
4, CaCl
2, the concentration range of these components is as shown in table 1.These components are first dissolved with tap water, are made into certain density solution, then put into high-pressure sterilizing pot, and sterilizing 30 minutes at 120 ℃ is poured in fermentor tank after being cooled to room temperature.
Table 1 fermented liquid moiety
The selected bacterial classification of ethanol fermentation is the industrial high-temperature-resistant Active Dry Yeast (themophilic alcohol active dry roast (TH-AADY)) that Angel Yeast Co.,Ltd produces, high-temperature resistant is 40-42 ℃, acidproof (pH=2.5), resistance to ethanol (w (C
2h
5o)=0.13), resistance to dense sugar (w (C
6h
12o
6)=0.6).Dry yeast consumption is the 0.1%-0.2% of fermentating liquid volume.First in temperature is the tap water of 37 ℃, dissolves and bring back to life 15～20 minutes, then directly dropping in fermented liquid and ferment.
In fermenting process, from fermented liquid, sample 20ml every 4h, measure the pH of fermented liquid, yeast mass concentration, glucose quality concentration and ethanol mass concentration, in fermented liquid, add glucose according to take off data, make more than its mass concentration maintains 30g/L, regulate the pH of fermented liquid to be in 4.2-4.8 with the strong aqua of 5N simultaneously, guarantee to ferment and normally carry out continuously; After 40 hours, stop stream and add glucose, continue fermentation to approximately 70 hours, lower tank, the fermented liquid obtaining, through centrifugal or Plate Filtration, obtains fermentation clear liquid.In final clear liquid, the concentration of ethanol is 10～12wt%.
Embodiment 2:
Ethanol fermentation liquid is through the centrifugal clear liquid that obtains, in clear liquid, ethanol mass percentage concentration is 8%, clear liquid with the flow velocity of 1BV/h from top to bottom by macroporous adsorbent resin (XA-02 is housed, purchased from Nanjing TongKai ZhaoYe biotechnology Co.,Ltd, identical below) adsorption column, ethanol, by the absorption of selectivity, does not turn back to fermentor tank relaying supervention ferment containing the effluent liquid of ethanol.Absorption 50min stops charging, and by the drain in post.Warm air is passed in post bed is heated from bottom to top, Exhaust Gas is condensed into liquid through condenser, in the time that bed temperature rises to 70 ℃, open vacuum pump, under the pressure of-0.08MPa (table), the ethanol of absorption is carried out to desorption, the steam of generation is condensed into the ethanolic soln of high density through condenser.After desorption 30min, when phlegma substantially no longer flows out, desorption finishes, and ethanol yield reaches 92%, and in desorption liquid, the mean concns of ethanol is 35wt%.To 60 ℃ of hot water that add 0.5BV in the adsorption column after desorption, maintain 10min, then pass into hot water with the flow velocity of 1BV/h, recovery stream fluid enters storage tank, after allotment, can be back in fermentor tank, and the impurity adsorbing after 30min is substantially by wash-out, and resin regeneration is complete.To regeneration after adsorption column in cooling with the flow velocity water flowing of 2BV/h, after 30min, adsorption column is down to normal temperature, can be used for adsorption operations next time.
Embodiment 3:
Ethanol fermentation liquid is through the centrifugal clear liquid that obtains, in clear liquid, ethanol mass percentage concentration is 6%, clear liquid with the flow velocity of 2BV/h from top to bottom by macroporous adsorbent resin (XA-02) adsorption column is housed, ethanol, by the absorption of selectivity, does not turn back to fermentor tank relaying supervention ferment containing the effluent liquid of ethanol.Absorption 30min stops charging, and by the drain in post.Warm air is passed in post bed is heated from bottom to top, Exhaust Gas is condensed into liquid through condenser, in the time that bed temperature rises to 60 ℃, open vacuum pump, under the pressure of-0.09MPa (table), the ethanol of absorption is carried out to desorption, the steam of generation is condensed into the ethanolic soln of high density through condenser.After desorption 30min, when phlegma substantially no longer flows out, desorption finishes, and ethanol yield reaches 93%, and alcohol concn is 33wt%.To 50 ℃ of hot water that add 0.7BV in the adsorption column after desorption, maintain 10min, then pass into hot water with the flow velocity of 2BV/h, recovery stream fluid enters storage tank, after allotment, can be back in fermentor tank, and the impurity adsorbing after 30min is substantially by wash-out, and resin regeneration is complete.To regeneration after adsorption column in cooling with the flow velocity water flowing of 1BV/h, after 50min, adsorption column is down to normal temperature, can be used for adsorption operations next time.
Embodiment 4:
Ethanol fermentation liquid is through the centrifugal clear liquid that obtains, in clear liquid, ethanol mass percentage concentration is 10%, by clear liquid with the flow velocity of 1.5BV/h from top to bottom by macroporous adsorbent resin (XA-02) adsorption column is housed, ethanol, by the absorption of selectivity, does not turn back to fermentor tank relaying supervention ferment containing the effluent liquid of ethanol.Absorption 40min stops charging, and by the drain in post.Warm air is passed in post bed is heated, Exhaust Gas is condensed into liquid through condenser, in the time that bed temperature rises to 55 ℃, open vacuum pump, under the pressure of-0.07MPa (table), the ethanol of absorption is carried out to desorption, the steam of generation is condensed into the ethanolic soln of high density through condenser.After desorption 50min, when phlegma substantially no longer flows out, desorption finishes, and ethanol yield reaches 91%, and alcohol concn is 36.5wt%.To 70 ℃ of hot water that add 0.6BV in the adsorption column after desorption, maintain 10min, then pass into hot water with the flow velocity of 2.5BV/h, recovery stream fluid enters storage tank, after allotment, can be back in fermentor tank, and the impurity adsorbing after 20min is substantially by wash-out, and resin regeneration is complete.To regeneration after adsorption column in cooling with the flow velocity water flowing of 2.5BV/h, after 20min, adsorption column is down to normal temperature, can be used for adsorption operations next time.
Claims (8)
1. the method for a separating alcohol from fermented liquid, it is characterized in that, ethanol fermentation liquid obtains clear liquid through solid-liquid separation, clear liquid is by being equipped with the adsorption column of macroporous adsorbent resin, ethanol is by the absorption of selectivity, macroporous adsorbent resin after saturated is through warm air beating desorption and vacuum take-off desorption, and the steam of collecting second alcohol and water obtains the ethanolic soln of high density through condensation, and the sorbent material after desorption is reused through manipulation of regeneration;
Described macroporous adsorbent resin is take crosslinked polystyrene-Vinylstyrene as skeleton, with the polar resin of sulfonic acid group;
From fermented liquid, the method for separating alcohol specifically comprises the steps:
(1) adsorption operations: ethanol fermentation liquid obtains clear liquid through solid-liquid separation, clear liquid with the flow velocity of 0.5～3BV/h by the adsorption column of macroporous adsorbent resin is housed, ethanol is by the absorption of selectivity, and the adsorption operations time is 10～60min, does not flow out from the other end of adsorption column containing the effluent liquid of ethanol;
(2) desorption manipulation: after adsorption column absorption is saturated, stop charging, by the drain in adsorption column, add thermal desorption to passing into warm air in adsorption column, when bed temperature reaches 50～80 ℃, stop passing into warm air, adopt vacuum take-off mode desorption, vacuum pressure is-0.06～-0.1MPa, and the vacuum take-off operating time is 5～60min, and the steam of collecting the second alcohol and water that adds thermal desorption and the generation of vacuum take-off desorption obtains the ethanolic soln of high density through condensation;
(3) regenerative operation: after desorption finishes, pass into hot water with the flow velocity of 0.5～3BV/h in adsorption column, the impurity of absorption with macroporous adsorbent resin is resolved to regeneration, the regenerative operation time is 10～60min;
(4) cooling operation: to regeneration after adsorption column in cooling with the flow velocity water flowing of 0.5～3BV/h, be 10～60min cooling time, adsorption column can be used for adsorption operations next time after being cooled to normal temperature.
According to claim 1 from fermented liquid the method for separating alcohol, it is characterized in that, described ethanol fermentation liquid is obtained by yeast fermentation, fermentation raw material is biomass material, comprises corn, cassava or sugarcane.
According to claim 1 from fermented liquid the method for separating alcohol, it is characterized in that, described solid-liquid separation is centrifugal or filters.
According to claim 1 from fermented liquid the method for separating alcohol, it is characterized in that, the clear liquid that ethanol fermentation liquid obtains through solid-liquid separation, wherein the mass percent concentration of ethanol is 4～12%.
According to claim 1 from fermented liquid the method for separating alcohol, it is characterized in that, described adsorption column is more than 2, guaranteeing has 1 adsorption column all the time in adsorption operation condition.
According to claim 1 from fermented liquid the method for separating alcohol, it is characterized in that, condensing temperature is 0～-10 ℃.
According to claim 1 from fermented liquid the method for separating alcohol, it is characterized in that, regenerative operation passes into the hot water regeneration of 40～70 ℃.
According to claim 1 from fermented liquid the method for separating alcohol, it is characterized in that, this separation method is directly used in conjunction with zymotechnique, fermentation unit, equipment for separating liquid from solid is connected to formation Integrated process technique with adsorption column separation device.
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| CN104928150A (en) * | 2015-06-30 | 2015-09-23 | 许成荫 | Grinding-pressure biofuel production apparatus |
| CN104962467A (en) * | 2015-06-30 | 2015-10-07 | 许成荫 | Compression type biofuel production equipment |
| CN104928149A (en) * | 2015-06-30 | 2015-09-23 | 许成荫 | Biofuel production device |
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| US4359593A (en) * | 1981-11-27 | 1982-11-16 | National Distillers & Chemical Corp. | Process for recovering ethanol from dilute aqueous solutions employing solid sorbent |
| US5919991A (en) * | 1996-07-03 | 1999-07-06 | Subbiah; Ven | Solid phase extraction of phenethyl alcohol |
| DE102006010994A1 (en) * | 2006-03-09 | 2007-09-13 | Wacker Chemie Ag | Process for the enzymatic preparation of chiral alcohols |
| CN101024846B (en) * | 2006-12-14 | 2011-05-04 | 复旦大学 | Method and apparatus for preparing fuel alcohol by fermented liquid steam phase adsorption separation |
| CN101225017A (en) * | 2008-01-24 | 2008-07-23 | 复旦大学 | Method and device for producing fuel alcohol by fermentation liquor distillation-free whole molecular sieve adsorptive separation |
| CN102051329B (en) * | 2009-10-27 | 2013-05-01 | 中国石油化工股份有限公司 | Biomass ferment-separation coupling device and method for preparing ethanol |
| CN101891590B (en) * | 2010-08-05 | 2013-03-13 | 湖南农业大学 | Method for producing anhydrous ethanol from fermentation liquid by gas adsorption |
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