CN102766020B - Method for producing ethanol, acetone and butanol by permeabilization, vaporization, coupling and rectification of ABE (Acetone, Butanol and Ethanol) fermentation liquor - Google Patents
Method for producing ethanol, acetone and butanol by permeabilization, vaporization, coupling and rectification of ABE (Acetone, Butanol and Ethanol) fermentation liquor Download PDFInfo
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- CN102766020B CN102766020B CN201210225327.XA CN201210225327A CN102766020B CN 102766020 B CN102766020 B CN 102766020B CN 201210225327 A CN201210225327 A CN 201210225327A CN 102766020 B CN102766020 B CN 102766020B
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Abstract
The invention provides a method for producing bulk biologic chemicals: ethanol, acetone and butanol by permeabilization, vaporization, coupling and rectification of an ABE (Acetone, Butanol and Ethanol) fermentation liquor. The method comprises the steps of: step A, separating and condensing the ABE fermentation liquor containing ethanol, acetone, butanol and butyric acid through a permeabilization and vaporization film, and obtaining a gas mixture containing ethanol, acetone, butanol, butyric acid and water on the permeable side; and step B, enabling the gas mixture to enter a rectification device directly to be subjected to rectification and separation without condensation so as to obtain ethanol, acetone and butanol products. According to the method provided by the invention, the ABE mixture on the permeable side after permeabilization and vaporization is enabled to enter the rectifying tower directly in form of gas, therefore, the energy consumption of product in the production process is greatly reduced, and the production efficiency is improved.
Description
Technical field
The invention belongs to infiltration vaporization coupling rectifying separation purification technique field, be specifically related to a kind of ABE fermented liquid and through infiltration vaporization coupling rectifying, produce the method for ethanol, acetone and butanols.
Background technology
Butanols, acetone and ethanol are important Organic Chemicals.Butanols is mainly used in the production of acrylate, methacrylic ester and n-butyl phthalate, also can be used as the solvent of resin, paint and tackiness agent simultaneously, the extraction agent of grease, spices and pharmaceutical industry and ore dressing defoamer.In addition, research shows, butanols or a kind of efficient liquid biofuel, and its character approaches hydro carbons very much, good with the compatibleness of gasoline, has higher energy density and fuel value, and lower vapour pressure and corrodibility are easy to carry.Acetone is widely used in plastics, coating and pharmaceutical industries, is the main raw material of producing dihydroxyphenyl propane, methyl methacrylate.Ethanol has good dissolving power, can be used as the production of medical disinfectant, automobile fuel and multiple industrial chemicals.
Acetone butanol fermentation refers to that microorganism (normally clostridium acetobutylicum or Bai Shi clostridium and mutant strain thereof) under anaerobic utilizes the process of biomass material fermentation production of acetone (Acetone), butanols (Butanol) and the ethanol (Ethanol) of starch, glucide and rich cellulose and hemicellulose, is called for short ABE fermentation.
Compare with chemical synthesis, Production by Microorganism Fermentation butanols is still lacked competitiveness relatively, and its major cause is that production cost is too high.Cause the reason of fermentative Production high cost to mainly contain following several respects: one, raw materials cost is high; Two, principal product butanols has toxicity, forms product and suppresses; Three, production concentration is low, and separation and Extraction energy consumption is large.
In ABE industrial fermentation process, generally comprise and produce acid (acetic acid and butyric acid) and produce two stages of solvent (ethanol, acetone and butanols); When butanol concentration reaches 14.5g/L, the generation of solvent will stop, and has a strong impact on the utilization ratio of transformation efficiency and the equipment of raw material; Meanwhile, lower solvent strength makes later separation extraction process become the process of energy consumption maximum in butylic fermentation production process, therefore, how to seek effective means and reduces product inhibition, reduces sepn process cost and becomes the focus in butylic fermentation research.Wherein ABE fermented liquid through infiltration evaporation separated concentrated be one of technology of paying close attention to the most of vast researcher.As patent CN102304106 has described a kind of method that hemicellulose biomass ferment is produced butanols, acetone, butyric acid and furfural that is rich in.This technique is compared with traditional butylic fermentation production technique, greatly reduces the energy consumption of raw materials cost and separated from solvent leaching process, thereby has reached the object that reduces industrial production cost.But the component that infiltration evaporation sees through side in this patent needs first to enter rectifying tower after condensation again and refines, wherein to see through the heat-processed energy consumption of feed liquid in the condensation of side feed liquid and rectifying tower still higher for infiltration evaporation.
Summary of the invention
The invention provides a kind of ABE fermented liquid infiltration vaporization coupling rectifying and produce the method for ethanol, acetone and butanols, comprise: steps A, the ABE fermented liquid that contains ethanol, acetone, butanols and butyric acid carries out separated concentrated through infiltrating and vaporizing membrane, see through side and obtain the gaseous mixture containing ethanol, acetone, butanols, butyric acid and water; With step B, described gaseous mixture directly enters rectifier unit and carries out rectifying separation without condensation, obtain ethanol, acetone and butanols product.
In embodiments of the invention, rectifier unit described in preferred steps B comprises the first rectifying tower, Second distillation column and the 3rd rectifying tower.Wherein, in a concrete embodiment, described gaseous mixture is in the first rectifying tower after rectifying separation, and the mixture that tower top obtains acetone and ethanol enters Second distillation column, tower middle part side line recovered water, the mixture that obtains butanols and butyric acid at the bottom of tower enters the 3rd rectifying tower; At the bottom of the tower top of Second distillation column and tower, obtain respectively acetone and ethanol; At the bottom of the tower top of the 3rd rectifying tower and tower, obtain respectively butanols and butyric acid.And in another concrete embodiment, described gaseous mixture is in the first rectifying tower after rectifying separation, the mixture that tower top obtains acetone and ethanol enters Second distillation column, and the mixture that obtains water, butanols and butyric acid at the bottom of tower enters the 3rd rectifying tower; At the bottom of the tower top of Second distillation column and tower, obtain respectively acetone and ethanol; At the bottom of the tower top of the 3rd rectifying tower and tower, obtain respectively water and butyric acid, tower middle part side line extraction butanols.
In the present invention, in preferred steps A, infiltration evaporation feed liquid side feed temperature is between 30 ~ 75 ℃, and seeing through wall pressure is 50 ~ 650Pa.More preferably, infiltration evaporation feed liquid side feed temperature is between 55 ~ 60 ℃, and seeing through wall pressure is 100 ~ 550Pa.
In the present invention, Pervaporation Technology is under the poor promotion of vapor partial pressure, interactional different according to solvent and mould material, optionally through object component, reaches separated concentrated object, has the feature energy-conservation, efficient, selectivity is high.Infiltrating and vaporizing membrane in aforesaid method can be any one infiltrating and vaporizing membrane that can play the materials such as concentrated butanols and acetone, as with octamethylcyclotetrasiloxane, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, polydimethylsiloxane, poly-trimethyl silicane propine, polypropylene, polystyrene, polyvinylidene difluoride (PVDF), tetrafluoroethylene and Mierocrystalline cellulose, and the infiltrating and vaporizing membrane of one or more making in described material material modified.Wherein, more preferably, infiltrating and vaporizing membrane described in steps A is for take silicon rubber/polyvinylidene fluoride permeable vaporizing composite membrane that water prepared as solvent, and wherein silicon rubber is above-mentioned polydimethylsiloxane.
Accompanying drawing explanation
Fig. 1 is the schematic flow sheet of the embodiment of the present invention 1, and wherein each Reference numeral is explained as follows: 1-fermentor tank, 2-micro-filtration, 3-feed pump, 4-infiltration evaporation storage tank, 5-feed pump, 6-infiltration evaporation membrane separation apparatus, 7-the first rectifying tower, 8-feed pump, 9-Second distillation column, 10-feed pump, 11-the 3rd rectifying tower, 12-acetone storage tank, 13-ethanol storage tank, 14-butanols storage tank, 15-butyric acid storage tank, 16-surge tank, 17-vacuum pump.
Embodiment
Embodiment 1
Take Semen Maydis powder as fermentation substrate carries out ABE fermentation, acetone, butanols and ethanol are produced in infiltration vaporization coupling rectifying; 1 to describe production stage specific as follows by reference to the accompanying drawings.
Fermentation: this step is carried out in fermentor tank 1 as shown in Figure 1; Be that Clostridium acetobutylicumABE1101 bacterial strain be take Semen Maydis powder and as carbon source, carried out anaerobically fermenting and obtain the fermented liquid that contains acetone, butanols and ethanol.Wherein this fermentation step comprises again preparation and two steps of inoculation of substratum.The preparation of substratum: take Semen Maydis powder as fermentation substrate preparing natural substratum, in substratum, Semen Maydis powder is 60g/L; The natural medium of preparation is transferred to high-temperature sterilization in fermentor tank, after temperature in fermentor tank is down to 40 ℃, passes into aseptic nitrogen and build oxygen-free environment.Inoculation: access activated bacterial classification under aseptic technique in above-mentioned substratum, inoculum size is the volume of volume/substrate cultivation base of 1:10(bacteria culture fluid), under 37 ℃ of constant temperatures, ferment, in fermenting process, timing sampling is analyzed the variation of substrate and the variation of product solvent in fermented liquid.
The microbial strains used during the fermentation can be clostridium acetobutylicum as above, can be also Bai Shi clostridium and mutant strain thereof, can also be the product butanols bacterial strain obtaining by other approach screenings.The fermentation substrate of fermenting process can be the biomass of the glucides such as glucose, wood sugar, molasses or cassava, wheat, corn or other rich in starch, can be also sweet sorghum stalk, sweet corn stem stalk, corn cob, bagasse, apple residue, jerusalem artichoke or other liquid glucoses that is rich in the juice after the squeezings such as hemicellulose and cellulosic biomass or obtains through methods such as acidolysis, enzymolysis.Fermentation mode in aforesaid method can be a batch fermentation, and fed-batch fermentation can be also to continuously ferment.
Micro-filtration degerming: this step is carried out in micro-filtration 2 as shown in Figure 1; In previous step, after 40h fermentation, butanols massfraction in fermented liquid detected and reach 0.82%; Now, open fermentor tank bleeder valve, in fermentor tank, the fermented liquid of the Multiple components such as mycetome, carbohydrate and solvent flows out fermentor tank with the speed of 70L/h and enters micro-filtration, in micro-filtration 2, thalline returns to fermentor tank after being concentrated, and the fermented liquid of removing after thalline and other solid substances enters infiltration evaporation storage tank 4.The microfiltration membrane of using in micro-filtration 2 can be that any one can play and filters microfiltration membrane of removing thalline, as the microfiltration membrane of one or more making with in the inorganic materials such as the organic materialss such as Mierocrystalline cellulose, polyethylene, polypropylene, polystyrene, tetrafluoroethylene, polyvinylidene difluoride (PVDF), polyacrylonitrile, polyester, polysulfones or zirconium white, titanium oxide, aluminum oxide, silicon-dioxide.
Infiltration evaporation is separated concentrated: this step is carried out in infiltration evaporation membrane separation apparatus 6 as shown in Figure 1; Acetone in fermented liquid, butanols and ethanol equal solvent are concentrated after infiltrating and vaporizing membrane, in infiltration evaporation storage tank, feed temperature maintains 60 ℃, system vacuum degree maintains 450Pa left and right, the infiltrating and vaporizing membrane using in infiltration evaporation membrane separation apparatus is for take silicon rubber/polyvinylidene fluoride permeable vaporizing composite membrane that water prepared as solvent, feed liquid enters after infiltration evaporation membrane separation apparatus, the feed liquid that does not see through film is returned to infiltration evaporation storage tank 4, see through side and obtain the gas containing acetone, butanols, ethanol, butyric acid and water, be wherein rich in acetone, butanols and ethanol.
Rectifying: this step is carried out in rectifying tower 7,9 and 11 as shown in Figure 1; The gas that is rich in acetone, butanols and ethanol that infiltration evaporation obtains through side directly enters the first rectifying tower 7 without condensation, tower top arranges condenser, during beginning, overhead condensation is taked the mode of total reflux, the mode of taking partial condensation to reflux after 0.5h, the liquid of trim the top of column crosses with the gaseous mixture that sees through the rising of side from infiltration evaporation, constantly carry out mass-and heat-transfer effect, thereby complete fine separation process; The first rectifying tower 7 tower top temperatures are 23 ℃, and reflux ratio is 3:1, and cut is the mixture of ethanol and acetone, and it is refining that overhead fraction enters Second distillation column 9; Second distillation column is also taked the refining mode of partial reflux, and reflux ratio is 2:1, and tower top temperature is 15 ℃, and tower reactor temperature is 45 ℃, overhead extraction acetone, and purity is 98.2%, tower reactor extraction ethanol, purity is 95.5%; In the tower middle part of the first rectifying tower 7 side line recovered water (not shown in figure 1); The tower reactor temperature of the first rectifying tower 7 is 58 ℃, and at the bottom of tower, component is the mixture of butanols and butyric acid, and it is refining that it enters the 3rd rectifying tower 11; The 3rd rectifying tower is also taked partial reflux mode, and its reflux ratio is 3:2, and tower top temperature is 25 ℃, and tower reactor temperature is 95 ℃, overhead extraction butanols, and its purity is 99.5%, and tower reactor obtains butyric acid, and butyric acid is as the by product in the present invention, and its output is very little.
The acetone obtaining in the present invention, butanols and alcohol concn all meet national standard; The present invention provides a good method for industrial production ethanol, acetone and butanols.
The inventive method is compared with the method that ethanol, acetone and butanols are produced in existing ABE fermented liquid infiltration vaporization coupling rectifying, and not only Energy Intensity Reduction 30%, and facility investment reduces approximately 10%.
Embodiment 2
The mode of the rectifying part of this embodiment is different from embodiment 1, and this embodiment is not illustrated by drawings.Infiltration evaporation sees through the gaseous mixture containing acetone, butanols, ethanol, butyric acid and water that side obtains in the first rectifying tower after rectifying separation, the mixture that tower top obtains acetone and ethanol enters Second distillation column, and the mixture that obtains water, butanols and butyric acid at the bottom of tower enters the 3rd rectifying tower; At the bottom of the tower top of Second distillation column and tower, obtain respectively acetone and ethanol; At the bottom of the tower top of the 3rd rectifying tower and tower, obtain respectively water and butyric acid, tower middle part side line extraction butanols.
Claims (5)
1. the method for ethanol, acetone and butanols is produced in an ABE fermented liquid infiltration vaporization coupling rectifying, comprise: steps A, the ABE fermented liquid that contains ethanol, acetone, butanols and butyric acid carries out separated concentrated through infiltrating and vaporizing membrane, see through side and obtain the gaseous mixture containing ethanol, acetone, butanols, butyric acid and water; With step B, described gaseous mixture directly enters rectifier unit and carries out rectifying separation without condensation, obtain ethanol, acetone and butanols product;
Wherein, rectifier unit described in step B comprises the first rectifying tower, Second distillation column and the 3rd rectifying tower;
Described gaseous mixture is in the first rectifying tower after rectifying separation, and the mixture that tower top obtains acetone and ethanol enters Second distillation column, tower middle part side line recovered water, and the mixture that obtains butanols and butyric acid at the bottom of tower enters the 3rd rectifying tower; At the bottom of the tower top of Second distillation column and tower, obtain respectively acetone and ethanol; At the bottom of the tower top of the 3rd rectifying tower and tower, obtain respectively butanols and butyric acid;
Wherein the tower top temperature of the first rectifying tower is 23 ℃, and reflux ratio is 3:1; The tower top temperature of Second distillation column is 15 ℃, and tower reactor temperature is 45 ℃, and reflux ratio is 2:1; The tower top temperature of the 3rd rectifying tower is 25 ℃, and tower reactor temperature is 95 ℃, and reflux ratio is 3:2.
2. method according to claim 1, is characterized in that, in steps A, infiltration evaporation feed liquid side feed temperature is between 30～75 ℃, and seeing through wall pressure is 50～650Pa.
3. method according to claim 2, is characterized in that, in steps A, infiltration evaporation feed liquid side feed temperature is between 55～60 ℃, and seeing through wall pressure is 100～550Pa.
4. method according to claim 1, it is characterized in that, infiltrating and vaporizing membrane described in steps A is with octamethylcyclotetrasiloxane, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, polydimethylsiloxane, poly-trimethyl silicane propine, polypropylene, polystyrene, polyvinylidene difluoride (PVDF), tetrafluoroethylene and Mierocrystalline cellulose, and the infiltrating and vaporizing membrane of one or more making in described material material modified.
5. method according to claim 4, is characterized in that, infiltrating and vaporizing membrane described in steps A is for take silicon rubber/polyvinylidene fluoride permeable vaporizing composite membrane that water prepared as solvent.
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| CN201210225327.XA CN102766020B (en) | 2012-06-29 | 2012-06-29 | Method for producing ethanol, acetone and butanol by permeabilization, vaporization, coupling and rectification of ABE (Acetone, Butanol and Ethanol) fermentation liquor |
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| CN103910605B (en) * | 2013-12-27 | 2016-04-27 | 江苏九天高科技股份有限公司 | The technique of a kind of infiltration evaporation system and refined biological propyl carbinol thereof |
| CN103772144B (en) * | 2014-01-27 | 2016-08-17 | 南京工业大学 | A kind of method utilizing osmotic gasification-rectification integrated separation acetone-butanol alcohol fermentation liquid |
| CN104771924B (en) * | 2015-04-15 | 2016-06-08 | 中国科学院广州能源研究所 | A kind of devices and methods therefor of furfural preparation coupling ethanol rectification |
| CN110002960B (en) * | 2019-05-05 | 2020-06-23 | 北京化工大学 | Device and method for separating ABE fermentation pervaporation liquid |
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| CN101397236A (en) * | 2008-11-19 | 2009-04-01 | 河北工业大学 | Rectification technique for separating ethanol, acetone and butanol fermentation mash |
| WO2010077070A2 (en) * | 2008-12-30 | 2010-07-08 | 서울대학교산학협력단 | Organic electroluminescence device and method of manufacturing same |
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