CN103816804B - A kind of method of low-concentration organic in original position water phase separated - Google Patents
A kind of method of low-concentration organic in original position water phase separated Download PDFInfo
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- CN103816804B CN103816804B CN201210465823.2A CN201210465823A CN103816804B CN 103816804 B CN103816804 B CN 103816804B CN 201210465823 A CN201210465823 A CN 201210465823A CN 103816804 B CN103816804 B CN 103816804B
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Abstract
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.Be immersed in by membrane module in feed liquid to be separated, in feed liquid to be separated and membrane module, extractant carries out extraction and exchanges in the fenestra of membrane module, and component to be separated is to enrichment in extractant; And then realize being separated of low-concentration organic and aqueous phase.The present invention utilizes perforated membrane as support, combines supported liquid membrane and Membrane Materials two processes, has both advantages, avoid both shortcomings simultaneously.
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 at 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, then 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 the effective ways overcoming Product inhibiton.Original position separation refers to and completes reaction and separation processes two processes simultaneously, and its advantage comprises: will have inhibiting product separation in course of reaction, can improve total recovery and disposal ability, reduces consersion unit investment; Can directly utilize reaction heat for separation process in exothermic reaction; Conventional original position isolation technics comprises extraction, absorption, air lift technology etc. and membrane technology comprises Membrane Materials, infiltration evaporation, membrane extraction and liquid film etc.
Patent 201110039036 proposes a kind of process and device of acetone butanol fermentation separation coupling, this invention make use of extraction and distillation technology, effectively can eliminate the product inhibition of acetone/butanol fermentation, improve Product yields and raw material availability, and can effectively reduce energy consumption and cost.Liquid-liquid extraction speed is fast, and separation factor is high, but usually will use a large amount of extractant, extractant and the easy emulsification of reaction system, and extractant often has suppression or toxic action to catalyst (or thalline).Large-scale application during these problems hinder extraction to be separated in position.
Patent 200710062809.7 proposes CO
2circulating gas-lifting on-line separation coupling prepares the method and apparatus of ethanol.Utilize CO
2circulating gas-lifting reduces production concentration, and designs multiple ON-LINE SEPARATION device, strengthening unit operations, extends the Batch fermentation time and improves alcohol production intensity, effectively reducing production cost, improve production efficiency.Air lift process and Membrane Materials similar, simple to operate, easily amplify, be suitable for original position lock out operation, but this process be subject to system to be separated itself VLE restriction, separation factor is usually all lower.
And for using the membrane process of dense film, such as infiltration evaporation, membrane extractions etc., are removing the research field of a small amount of organic solvent in water, although also there is corresponding patent document, such as patent 200710130936.6 improves the ethyl alcohol in situ separating method of biomass ferment strength; Patent 03105055.7, organic acid On-line testing and concentrating method etc. in organic acid fermentation process, but there is no the commercialization film of corresponding maturation, slower development.
Liquid film technology is solid film comparatively, selective all higher with flux, but stability awaits improving.Researcher, from membrane material and operating condition membrane structure aspect development of new membrane module, improves stability.Patent 95201509 proposes 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, gap between inner-outer sleeve tube wall and the corresponding strip liquor of the hollow difference of inner sleeve, film phase carrier solution and feed solution flow passage.This invention film is mutually uniform and stable, and mass transfer rate is fast, and concentration effect is good.But combine the above-mentioned liquid film that extraction and back-extraction gets process, design comparison is complicated, and fluid mobility status is complicated, 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 the method providing 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 carries out extraction and exchanges in the fenestra of membrane module, and component to be separated is to enrichment in extractant; And then realize being separated of low-concentration organic and aqueous phase.
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 fill organic extractant.
Described hollow-fibre membrane is placed in tubular membrane component film assembly, membrane module is immersed in feed liquid to be separated, with carrier gas purge or vacuum state can be kept inside doughnut in separation process, in feed liquid to be separated and membrane module, extractant carries out extraction and exchanges in the fenestra of membrane module, and component to be separated is to enrichment in extractant; Component to be separated, in the volatilization of doughnut inner surface, as concentrated product after condensation, and then realizes being separated of low-concentration organic and aqueous phase.
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 film.Described tubular membrane is hydrophilic film.Described extractant is the organic solvent compared with strong-hydrophobicity higher than component boiling point to be separated.
By carrier gas purge or make it be in vacuum state inside described doughnut, must ensure that both sides pressure reduction is lower than " liquid immerses pressure ", makes organic solvent not penetrate fenestra.Its value size depends on the size shape of hollow-fibre membrane fenestra and the hydrophobe degree 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 exchanges with occurring to extract with extractant in the fenestra of tubular membrane, and component to be separated is to enrichment in extractant; Owing to possessing carrier gas purge or certain vacuum degree inside doughnut, component to be separated volatilizees, as concentrated product after condensation at doughnut inner surface.
The advantage that the present invention has:
The present invention utilizes perforated membrane as support, combines supported liquid membrane and Membrane Materials two processes, has both advantages, avoid both shortcomings simultaneously.First, owing to there being the existence of perforated membrane, can reduce the alternate extractant caused of carrying secretly and lose, use hydrophilic film material to contact with feed liquid in addition, 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; 3rd, due to the enrichment of component to be separated in extractant, and the boiling point of extractant own is higher, to a certain degree improves the separative efficiency of Membrane Materials; Finally, operationally see, invention components is directly immersed in feed liquid to be separated, externally only has a pipeline, and very little on feed liquid impact, structure is simple, is easy to amplify.The present invention is on supported liquid membrane stability study basis, and binding film still-process, consumption of organic solvent is few, stable, can be the separation of low-concentration organic in aqueous phase and provides new solution.
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.
The Membrane Materials that Fig. 3 provides for the embodiment of the present invention and air lift steam evaporation rate comparison diagram.
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.
Detailed description of the invention
Embodiment 1
Solvent selection:
The butanol solution of configuration 18g/L, with profit volume ratio for 1:2 adds extractant, to be statically placed in 37 degree of insulating boxs 24 hours, to measure the concentration of butanols and water in aqueous phase and oil phase respectively after stirring.Calculate the distribution coefficient of butanols in two-phase and separation factor.Distribution coefficient and separation factor calculate according to the following formula:
K in formula
dBrepresent the distribution coefficient of butanols, C
bWrepresent the concentration of butanols in aqueous phase, C
bOrepresent the concentration of butanols in oil phase, α
bWrepresent separation factor, C
wWrepresent the concentration of water in aqueous phase, 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 determines 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, the extractant that namely distribution coefficient is higher in general distribution coefficient and separation factor, its separation factor is general lower.
Then calculate 1-amylalcohol respectively 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, the distribution coefficient of the extractants such as jacoll-20, jacoll-24, jacoll95BJ and separation factor.
From Fig. 1 and Fig. 2, most of extractant can play the effect of concentrated butanols, and separation factor is generally more than 200.Component to be separated is concentrated through extraction and evaporation two processes, because evaporation process depends on the vapour pressure difference of component to be separated itself and water, and is separated restriction by original position, and operating condition on its impact not quite.Therefore, the screening of extractant determines the efficiency of the method to a great extent.
Embodiment 2
Preparation packed density is respectively the ratio at 0.02,0.09,0.18(and doughnut cross section and tubular membrane interface) membrane module, using pure water as volatile medium, the change of investigation packed density on the impact of film disposal ability, and contrasts with air lift.The results are shown in Figure 3.
Membrane Materials film itself does not have centrifugation to solution, but disposal ability is subject to membrane structure impact.As seen from the figure, when the speed of purging is lower, the volatile quantity of each Water Under vapour is basically identical, because now steam evaporation rate is higher relative to carrier gas purge speed, carrier gas obtains identical vapour quantity.Along with carrier gas purge 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 Membrane Materials 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 degree, 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, in feed liquid, butanol concentration reduces fast.
Claims (5)
1. the method for low-concentration organic in original position water phase separated, is characterized in that: be immersed in by membrane module in feed liquid to be separated, and in feed liquid to be separated and membrane module, extractant carries out extraction and exchanges in the fenestra of membrane module, and component to be separated is to enrichment in extractant; And then realize being separated of low-concentration organic and aqueous phase;
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 fill organic extractant.
2. by the method for low-concentration organic in original position water phase separated according to claim 1, 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, with carrier gas purge or vacuum state can be kept inside doughnut in separation process, in feed liquid to be separated and membrane module, extractant carries out extraction and exchanges in the fenestra of membrane module, and component to be separated is to enrichment in extractant; Component to be separated, in the volatilization of doughnut inner surface, as concentrated product after condensation, and then realizes being separated of low-concentration organic and aqueous phase.
3., by the method for low-concentration organic in original position water phase separated according to claim 2, it is characterized in that: described hollow-fibre membrane and tubular membrane aperture are between 0.002 to 20 micron.
4., by the method for low-concentration organic in original position water phase separated according to claim 1, it is characterized in that: described tubular membrane can be hydrophilic or hydrophobic membrane, hollow-fibre membrane is hydrophilic film.
5., by the method for low-concentration organic in original position water phase separated according to claim 4, it is characterized in that: described tubular membrane is hydrophilic film.
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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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| CN2213563Y (en) * | 1995-01-27 | 1995-11-29 | 天津纺织工学院 | Sleeve type hollow fibre supported liquid film assemblage |
| 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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| US7341663B2 (en) * | 2004-12-16 | 2008-03-11 | The United States Of America As Represented By The Secretary Of Agriculture | Spiral-wound liquid membrane module for separation of fluids and gases |
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Patent Citations (5)
| 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 |
| 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 (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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