CN103816804A - Method for separating low-concentration organic substances in aqueous phases in in-situ manner - Google Patents
Method for separating low-concentration organic substances in aqueous phases in in-situ manner Download PDFInfo
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- CN103816804A CN103816804A CN201210465823.2A CN201210465823A CN103816804A CN 103816804 A CN103816804 A CN 103816804A CN 201210465823 A CN201210465823 A CN 201210465823A CN 103816804 A CN103816804 A CN 103816804A
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Abstract
The invention belongs to the field of biochemical engineering, and particularly relates to a method for separating low-concentration organic substances in aqueous phases in an in-situ manner. The method comprises the following steps: immersing membrane components in feed liquid to be separated, performing extraction and exchange in membrane holes of the membrane components by extraction agents in the feed liquid to be separated and the membrane components, enriching constituents to be separated towards the extraction agents, and further separating the low-concentration organic substances from the aqueous phases. Through the adoption of the method, porous membranes are used as support, two courses of liquid membrane supporting and membrane distillation are combined, so that the method has the advantages of the two courses and avoids the disadvantages of the two courses at the same time.
Description
Technical field
The invention belongs to biological chemical field, be specifically related to the method for low-concentration organic in a kind of original position water phase separated.
Background technology
In a lot of chemistry or bioprocess, due to toxicity or the feedback inhibition of product itself, its final concentration is lower.This phenomenon of biofermentation products is especially obvious, and end-product is generally all below 10wt%.If amino acid is 1-5wt%, antibiotic is 0.1-3wt%, and biological butanol is usually less than 1wt%.If the boiling point of product own is higher, not volatile, low concentration can cause rectifying high expensive.The exploitation of the separation purifying technique of high efficiency, low cost is the important channel of increasing economic efficiency.
Original position isolation technics is to overcome the effective ways that product suppresses.Original position separates and refers to and complete two processes of reaction and separation processes simultaneously, and its advantage comprises: in course of reaction, will have inhibiting product separation, and can improve total recovery and disposal ability, and reduce consersion unit investment; In exothermic reaction, can directly utilize reaction heat for separation process; Conventional original position isolation technics comprises that extraction, absorption, air lift technology etc. and membrane technology comprise film distillation, infiltration evaporation, membrane extraction and liquid film etc.
Patent 201110039036 has proposed a kind of process and device of acetone butanol fermentation separation coupling, this invention has utilized extraction and distillation technology, product inhibition, raising product output and the raw material availability of acetone/butanol fermentation can be effectively eliminated, and energy consumption and cost can be effectively reduced.Liquid-liquid extraction speed is fast, and separation factor is high, but conventionally will use a large amount of extractants, the easy emulsification of extractant and reaction system, and extractant often has and suppresses or toxic action catalyst (or thalline).These problems hinder the large-scale application extracting in separating in position.
Patent 200710062809.7 proposes CO
2circulating gas-lifting on-line separation coupling is prepared the method and apparatus of ethanol.Utilize CO
2circulating gas-lifting reduces production concentration, and designs multiple ON-LINE SEPARATION device, and strengthening unit operations extends batch fermentation time and improves alcohol production intensity, effectively reduces production cost, has improved production efficiency.Air lift process and film distillation are similar, simple to operate, easily amplify, and are suitable for original position lock out operation, but this process is subject to the VLE restriction of system to be separated itself, and separation factor is conventionally all lower.
And for the membrane process that uses dense film, such as infiltration evaporation, membrane extraction etc., in the research field that removes a small amount of organic solvent in water, although also there is corresponding patent documentation, for example patent 200710130936.6 improves the ethyl alcohol in situ separating method of biomass ferment strength; Patent 03105055.7, in organic acid fermentation process, organic acid, at line drawing and concentrating method etc., but does not have the commercialization film of corresponding maturation, slower development.
Liquid film technology is compared with solid film, selective and flux is all higher, but stability awaits raising.Researcher, from membrane material and operating condition membrane structure aspect development of new membrane module, improves stability.Patent 95201509 has proposed a kind of sleeve type hollow fibre liquid film assembly, it is characterized in that the doughnut in liquid film supporting module is made up of sleeve type hollow fibre, space outside sleeve pipe, the corresponding strip liquor of the hollow difference of gap between inner-outer sleeve tube wall and inner sleeve, film phase carrier solution and feed liquid flow channel.This invention film is mutually uniform and stable, and mass transfer rate is fast, and concentration effect is good.But, combine extraction and back-extraction and get the above-mentioned liquid film of process, design comparison complexity, fluid mobility status complexity, needs the many conveying equipments of multi-pipeline, and needs multiple organic solvent.Moreover, the product after back extraction still needs further separation.The manufacture difficulty of the doughnut of internal and external casing is higher in addition.
Summary of the invention
Content of the present invention is to provide the method for low-concentration organic in a kind of original position water phase separated.
For achieving the above object, the technical solution used in the present invention is:
A method for low-concentration organic in original position water phase separated, is immersed in membrane module in feed liquid to be separated, and in feed liquid to be separated and membrane module, extractant extracts exchange in the fenestra of membrane module, and component to be separated is to enrichment in extractant; And then realize separating of low-concentration organic and water.
Described membrane module is made up of hollow-fibre membrane and tubular membrane; Hollow-fibre membrane is placed in tubular membrane, and two intermembrane spaces are filled organic extractant.
Described hollow-fibre membrane is placed in tubular membrane component film assembly, membrane module is immersed in feed liquid to be separated, in separation process, doughnut inner side can purge or maintenance vacuum state with carrier gas, in feed liquid to be separated and membrane module, extractant extracts exchange in the fenestra of membrane module, and component to be separated is to enrichment in extractant; Component to be separated is in doughnut inner surface volatilization, after condensation, as concentrated product, and then realizes separating of low-concentration organic and water.
Described hollow-fibre membrane and tubular membrane aperture are between 0.002 to 20 micron.Described tubular membrane can be hydrophilic or hydrophobic membrane, and hollow-fibre membrane is hydrophilic membrane.Described tubular membrane is hydrophilic membrane.Described extractant be higher than component boiling point to be separated compared with the organic solvent of strong-hydrophobicity.
Described doughnut inner side purges or makes it in vacuum state by carrier gas, must guarantee that both sides pressure reduction, lower than " liquid immerses and presses ", makes organic solvent can not penetrate fenestra.Its value size depends on the size shape of hollow-fibre membrane fenestra and the close hydrophobicity of material.
Concrete extractant is as oleyl alcohol, n-octyl alcohol, benzene, carbon tetrachloride, alcohol, kerosene, hexane, cyclohexane and ethyl acetate etc.
Technique separation principle of the present invention: feed liquid to be separated with in the fenestra of tubular membrane, there is extraction exchange with extractant, component to be separated is to enrichment in extractant; Because doughnut inner side possesses carrier gas purging or certain vacuum degree, component to be separated is in the volatilization of doughnut inner surface, after condensation as concentrated product.
The present invention has advantages of:
The present invention utilizes perforated membrane as support, combines supported liquid membrane and two processes of film distillation, has advantages of both, has avoided both shortcomings simultaneously.First, owing to there being the existence of perforated membrane, can reduce the alternate extractant loss causing of carrying secretly, use in addition hydrophilic film material to contact with feed liquid, first feed liquid infiltrates membrane material, and mass transfer occurs in inner side fenestra, can reduce extractant and run off.Secondly, the consumption of extractant is considerably less, and extractant exists only between tubular membrane and hollow-fibre membrane, and consumption can reduce along with the increase of packed density; The 3rd, due to the enrichment of component to be separated in extractant, and the boiling point of extractant own is higher, has to a certain degree improved the separative efficiency of film distillation; Finally, from operation, assembly of the present invention is directly immersed in feed liquid to be separated, externally only has a pipeline, very little, simple in structure on feed liquid impact, is easy to amplify.The present invention on supported liquid membrane stability study basis, binding film still-process, consumption of organic solvent is few, stable, can be the separation of low-concentration organic in water new solution is provided.
Accompanying drawing explanation
The distribution coefficient figure of the extractant that Fig. 1 provides for the embodiment of the present invention.
The separation factor figure of the extractant that Fig. 2 provides for the embodiment of the present invention.
Film distillation and air lift steam evaporation rate comparison diagram that Fig. 3 provides for the embodiment of the present invention.
The original position separating effect figure that Fig. 4 provides for the embodiment of the present invention.
The original position separation schematic diagram of Fig. 5 for providing for the embodiment of the present invention.
The membrane module schematic diagram of Fig. 6 for providing for the embodiment of the present invention.
The specific embodiment
Solvent selection:
The butanol solution of configuration 18g/L, adds extractant take profit volume ratio as 1:2, be statically placed in 37 degree insulating boxs 24 hours after stirring, measures respectively the concentration of butanols and water in water and oil phase.Calculate distribution coefficient and the separation factor of butanols in two-phase.Distribution coefficient and separation factor are calculated according to the following formula:
K in formula
dBrepresent the distribution coefficient of butanols, C
bWrepresent the concentration of butanols in water, C
bOrepresent the concentration of butanols in oil phase, α
bWrepresent separation factor, C
wWrepresent the concentration of water in water, C
wOrepresent the concentration of water in oil phase.Distribution coefficient characterizes the distribution condition of material to be separated in two-phase.Distribution coefficient has determined the extracting power of extract, and separation factor characterizes the multiple that component to be separated is concentrated in extractant.
Good extractant have simultaneously high distribution coefficient and high score from.But there is " trade off " phenomenon in general distribution coefficient and separation factor, i.e. the higher extractant of distribution coefficient, its separation factor is generally lower.
Then calculate respectively 1-amylalcohol according to said process, 1-hexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, 1-decyl alcohol, 1-tip-nip, oleic acid, methyl oleate, ethyl oleate, butyl oleate, jacoll-20, jacoll-24, the distribution coefficient of the extractants such as jacoll95BJ and separation factor.
From Fig. 1 and Fig. 2, most of extractant can play the effect of concentrated butanols, and separation factor generally exceedes 200.Component to be separated is concentrated through extraction and two processes of evaporation, because evaporation process depends on the vapour pressure difference of component to be separated itself and water, and is subject to original position separation limit, and operating condition is little on its impact.Therefore, the screening of extractant has determined the efficiency of the method to a great extent.
Embodiment 2
Preparation packed density is respectively the ratio that 0.02,0.09,0.18(is doughnut cross section and tubular membrane interface) membrane module, using pure water as volatile medium, the impact of variation on film disposal ability of investigation packed density, and contrasting with air lift.The results are shown in Figure 3.
Film distillation does not have centrifugation with film itself to solution, but disposal ability is subject to membrane structure impact.As seen from the figure, in the time that purging speed is lower, the volatile quantity of each Water Under vapour is basically identical, and higher because the now relative carrier gas of steam evaporation rate purges speed, carrier gas obtains identical vapour quantity.Along with carrier gas purging speed increases, high packed density has the disposal ability higher than low packed density.Along with the increase of packed density, the volatilization efficiency of film distillation can be identical with air lift even higher.
Embodiment 3
By the membrane module shown in Fig. 5 and 6, with 500mL feed liquid, initial butanol concentration is 6g/L, as separate object, temperature 37 is spent, and use packed density is the polyether sulphone hollow fibre film of 0.09 micron, doughnut inwall adopts steam blowing pattern, and throughput is 120L/h, and condensation temperature is minus 20 degrees.Tubular membrane is Kynoar, and intermembranous extractant is oleyl alcohol.The results are shown in Figure 4.Visible in figure, along with separation process is carried out, butanol concentration fast reducing in feed liquid.
Claims (7)
1. a method for low-concentration organic in original position water phase separated, is characterized in that: membrane module is immersed in feed liquid to be separated, and in feed liquid to be separated and membrane module, extractant extracts exchange in the fenestra of membrane module, and component to be separated is to enrichment in extractant; And then realize separating of low-concentration organic and water.
2. by the method for low-concentration organic in original position water phase separated claimed in claim 1, it is characterized in that: described membrane module is made up of hollow-fibre membrane and tubular membrane; Hollow-fibre membrane is placed in tubular membrane, and two intermembrane spaces are filled organic extractant.
3. by the method for low-concentration organic in the original position water phase separated described in claim 1 or 2, it is characterized in that: described hollow-fibre membrane is placed in tubular membrane component film assembly, membrane module is immersed in feed liquid to be separated, in separation process, doughnut inner side can purge or maintenance vacuum state with carrier gas, in feed liquid to be separated and membrane module, extractant extracts exchange in the fenestra of membrane module, and component to be separated is to enrichment in extractant; Component to be separated is in doughnut inner surface volatilization, after condensation, as concentrated product, and then realizes separating of low-concentration organic and water.
4. by the method for low-concentration organic in original position water phase separated claimed in claim 3, it is characterized in that: described hollow-fibre membrane and tubular membrane aperture are between 0.002 to 20 micron.
5. by the method for low-concentration organic in original position water phase separated claimed in claim 1, it is characterized in that: described tubular membrane can be hydrophilic or hydrophobic membrane, hollow-fibre membrane is hydrophilic membrane.
6. by the method for low-concentration organic in original position water phase separated claimed in claim 5, it is characterized in that: described tubular membrane is hydrophilic membrane.
7. by the method for low-concentration organic in original position water phase separated claimed in claim 1, it is characterized in that: described extractant be higher than component boiling point to be separated compared with the organic solvent of strong-hydrophobicity.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110302682A (en) * | 2019-06-30 | 2019-10-08 | 浙江工业大学 | A kind of method and apparatus based on doughnut liquid film separation methyl linolenate |
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| CN106830157A (en) * | 2017-01-19 | 2017-06-13 | 河南理工大学 | The device and method of nonionic surface active agent in extract and separate soil washed liquid |
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| CN2213563Y (en) * | 1995-01-27 | 1995-11-29 | 天津纺织工学院 | Sleeve type hollow fibre supported liquid film assemblage |
| US20060131235A1 (en) * | 2004-12-16 | 2006-06-22 | The United States Of America, As Represented By The Secretary Of Agriculture | Spiral-wound liquid membrane module for separation of fluids and gases |
| CN101121639A (en) * | 2007-07-13 | 2008-02-13 | 天津大学 | Membrane distillation dehydration method for polyatomic alcohol water solution produced from corn |
| CN101417209A (en) * | 2007-10-22 | 2009-04-29 | 天津海之凰科技有限公司 | Energy-saving pressure-reduction distillation device and method |
| CN101659495A (en) * | 2008-08-29 | 2010-03-03 | 北京清大国华环保科技有限公司 | Membrane distillation bioreactor device and method |
| CN102408140A (en) * | 2010-09-25 | 2012-04-11 | 中国石油化工股份有限公司 | Method for removing and recycling volatile alcohol organic matters in water |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN2213563Y (en) * | 1995-01-27 | 1995-11-29 | 天津纺织工学院 | Sleeve type hollow fibre supported liquid film assemblage |
| US20060131235A1 (en) * | 2004-12-16 | 2006-06-22 | The United States Of America, As Represented By The Secretary Of Agriculture | Spiral-wound liquid membrane module for separation of fluids and gases |
| CN101121639A (en) * | 2007-07-13 | 2008-02-13 | 天津大学 | Membrane distillation dehydration method for polyatomic alcohol water solution produced from corn |
| CN101417209A (en) * | 2007-10-22 | 2009-04-29 | 天津海之凰科技有限公司 | Energy-saving pressure-reduction distillation device and method |
| CN101659495A (en) * | 2008-08-29 | 2010-03-03 | 北京清大国华环保科技有限公司 | Membrane distillation bioreactor device and method |
| CN102408140A (en) * | 2010-09-25 | 2012-04-11 | 中国石油化工股份有限公司 | Method for removing and recycling volatile alcohol organic matters in water |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110302682A (en) * | 2019-06-30 | 2019-10-08 | 浙江工业大学 | A kind of method and apparatus based on doughnut liquid film separation methyl linolenate |
| CN110302682B (en) * | 2019-06-30 | 2021-10-01 | 浙江工业大学 | Method and device for separating methyl linolenate based on hollow fiber liquid membrane |
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