CN105585430B - A kind of method that 2,3 butanediols are extracted from zymotic fluid - Google Patents
A kind of method that 2,3 butanediols are extracted from zymotic fluid Download PDFInfo
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- CN105585430B CN105585430B CN201410563689.9A CN201410563689A CN105585430B CN 105585430 B CN105585430 B CN 105585430B CN 201410563689 A CN201410563689 A CN 201410563689A CN 105585430 B CN105585430 B CN 105585430B
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Abstract
The invention discloses the method that one kind extracts 2,3 butanediols from zymotic fluid, including following content：（1）Pulping component, synergist and a small amount of zymotic fluid are well mixed in the basic conditions, fermentation liquor pretreatment agent is obtained；（2）By in fermentation liquor pretreatment agent addition zymotic fluid, then hybrid reaction adjusts pH, and standing separation is collected liquid phase, obtains pretreated zymotic fluid；（3）Soluble inorganic salt is added to pretreated zymotic fluid, is dissolved and is well mixed, be subsequently adding low-carbon alcohols and/or polyalcohol, after being sufficiently mixed, stratification takes supernatant, and refined extraction obtains 2,3 butanediols.The inventive method can effectively remove the large biological molecule such as thalline dissolution albumen, lipid in zymotic fluid, be conducive to the implementation of the refined mode such as next step aqueous two-phase extraction, rectifying, it is adaptable to large-scale production and application.
Description
Technical field
The invention belongs to biological chemical field, it is related to a kind of biological fermentation process to prepare the separation and Extraction side of 2,3-butanediol
Method.
Background technology
2,3-butanediol can substitute traditional platform chemicals as a kind of potential platform chemicals, for big rule
Mould synthesizes MEK（Fine solvent）With 1,3- butadiene（It is widely used in the fields such as synthetic rubber, polyester and polyurethane）.
In addition, 2,3-butanediol can also be used to prepare ink, perfume, fumigant, humidizer, softening agent, plasticizer, explosive and medicine
Thing chiral support etc., the oxidation product 3-Hydroxybutanone and diacetyl of 2,3-butanediol can be used as flavorant；Meanwhile, because
Its calorific value is higher, suitable with ethanol, methyl alcohol, therefore can be used as fuel additive；Polyurethane foam can be generated after the esterification of 2,3- butanediols
The precursor of foam；2,3-butanediol generates 2,3-butanediol diacetate esters with acetic acidreaction, and the ester improves local flavor in being added to cream；
2,3-butanediol is also added in white wine in China, to improve the local flavor of white wine.2,3- butanediol dehydrogenations become biacetyl, double
Acetyl is in the food industry as a kind of flavouring agent with very high value.The L-type isomers of 2,3- butanediols can be used for freeze proof
Agent.2,3- butanediol esters compound can be used as the precursor for making medicine and cosmetics.Other potential purposes are included for making ink
Water, plasticizer, wetting agent.The synthesis of current 2,3-butanediol is main to be used with the chemical method that petroleum cracking thing is source, but with
A large amount of consumption of petroleum resources and climbing up and up for non-renewable resources price, the friendly biological-based chemicals of development environment
Biorefinery technology has turned into transforms mode of economic growth, ensures ecological chain benign cycle, realizes the sustainable development of socio-economy
Strategic Demand.
During biofermentation prepares 2,3-butanediol, generally using glucose as carbon source, therefore fermentation process in
Accessory substance is more, and zymotic fluid system is more complicated, increased the difficulty that 2,3-butanediol product is extracted, purified.2,3- butanediols
With double hydroxyls, hydrophily is extremely strong, 180 DEG C of atmospheric boiling point, equal using modes such as conventional vacuum distillation, pervaporation, film evaporations
Good extraction effect can not be played.It is mainly manifested in before reaching 2,3-butanediol boiling point, some soluble portions in zymotic fluid
Thicker oily kettle point will be condensed into residual, so as to slow down the evaporation rate of 2,3-butanediol.
With the development of aqueous two phase extraction technique, the method for aqueous two-phase extraction is also widely used in dividing for biofermentation products
From, purifying.CN 200710010203.9 discloses a kind of two aqueous phase extraction method of the separating 2,3-butanediol from zymotic fluid,
It is characterized in that to adding inorganic salts and hydrophilic organic thing to form new aqueous two-phase in the zymotic fluid of 2,3-butanediol, so as to reach
The purpose of 2,3- butanediols in extract and separate zymotic fluid.Although can be right with the double-aqueous phase system that ethanol and dipotassium hydrogen phosphate are constituted
2,3-butanediol plays preferable concentrated effect, but in actual application, the addition of ethanol can cause albumen in bacterium solution
The flocculation of composition, its separating effect is unsatisfactory.CN200810024865.6 discloses a kind of using hydrophobic silicalite absorption point
The method of 2,3-butanediol in zymotic fluid, it is characterised in that after 2,3-butanediol fermentation liquor pretreatment obtained in strain fermentation
2,3-butanediol is adsorbed with hydrophobic silicalite, is desorbed with absolute ethyl alcohol after absorption, desorption liquid obtains 2 after removing ethanol,
3- butanediols.Hydrophobic silicalite is a kind of new adsorption and separation material, with hydrophobic, organophilic property, can be in water
In the presence of select organic molecule.Although 2,3-butanediol is an organic molecular species, because it contains two hydroxyls, easily
Hydrogen bond is formed, and molecule is relatively small, with stronger hydrophily, therefore theory absorption of the hydrophobic silicalite to 2.3- butanediols
Amount is very low, and prospects for commercial application is unsatisfactory.
The separation method of current 2,3-butanediol, mainly according to the characterization of molecules of 2,3-butanediol, with physics or change
Mode, is targetedly concentrated, is purified, but is shown from achievement in research at this stage, and its actual separating effect is simultaneously
It is undesirable, main reason is that in the zymotic fluid of 2,3-butanediol, carbohydrate, fermentation byproduct, thalline dissolution albumen, lipid etc. are raw
Between thing macromolecular, under certain condition with stronger combination effect, therefore only voucher one processing mode be extremely difficult to it is bright
Aobvious separating effect.
The content of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of method that 2,3-butanediol is extracted from zymotic fluid.This hair
Bright method can effectively remove the large biological molecule such as thalline dissolution albumen, lipid in zymotic fluid, form more homogeneous, pure water
Phase, is conducive to the implementation of the refined mode such as next step aqueous two-phase, rectifying, it is adaptable to large-scale production and application.
The method that 2,3-butanediol is extracted from zymotic fluid of the invention, including following content：
（1）Pulping component, synergist and a small amount of zymotic fluid are well mixed in the basic conditions, fermentation liquor pretreatment is obtained
Agent；
（2）By in fermentation liquor pretreatment agent addition zymotic fluid, regulation pH is 8~10, hybrid reaction, and it is 4 then to adjust pH
~6, standing separation collects liquid phase, obtains pretreated zymotic fluid；
（3）Aqueous two-phase extraction is carried out to pretreated zymotic fluid, process is as follows：Being added to pretreated zymotic fluid can
Soluble inorganic salt, dissolves and is well mixed, and is subsequently adding low-carbon alcohols and/or polyalcohol, and after being sufficiently mixed, stratification takes
Clear liquid, refined extraction obtains 2,3-butanediol.
In the inventive method, handled zymotic fluid comes from glucose as substrate, is obtained not through microbial fermentation
By the zymotic fluid of any treatment, the 2,3-butanediol containing 20~200g/L in described zymotic fluid, wherein containing necessarily having
The accessory substances such as machine acid, mycoprotein.
In the inventive method, step（1）Described pulping component can using bentonite, organoclay, kaolin, illite,
One or more in montmorillonite or sepiolite, the mesh number of pulping component is 100 ~ 300 mesh, and pulping component needs to be done before adding
Dry treatment, drying condition is：Dried 10~24 hours at 100~300 DEG C.
In the inventive method, step（1）Described synergist is sulfonated lignite, low viscous sanlose, height glue
One or more in carboxymethyl cellulose sodium salt, CMS, vinyl sulfonate copolymers or polyanion cellulose etc..
In the inventive method, step（1）Described pulping component is 5 with synergist mass ratio:1~50：1；Zymotic fluid is pre-
Pulping component and the solid-to-liquid ratio of zymotic fluid are 1 in inorganic agent:10~1:2（g:mL）.
In the inventive method, step（1）The pH of described alkalescence condition is 8 ~ 10；Step（1）With（2）Regulation pH is 8 ~ 10
NaOH or calcium hydroxide are can select, also dependent on synergist cationic composition, corresponding sodium salt or calcium salt is selected；Step
（2）Middle regulation pH is the middle strong acid such as 4 ~ 6 optional dilute sulfuric acid, phosphoric acid.
In the inventive method, step（2）The addition of described fermentation liquor pretreatment agent, according to pulping component with mix after
The solid-to-liquid ratio 1 of zymotic fluid:100~1:10（g:mL）Add.
In the inventive method, step（2）The described hybrid reaction time is 0.5~2 hour,
In the inventive method, step（3）Described soluble inorganic salt is the strong base-weak acid salt with higher solubility, such as
One or more in dipotassium hydrogen phosphate, disodium hydrogen phosphate or potassium dihydrogen phosphate.
In the inventive method, step（3）Described low-carbon alcohols and/or polyalcohol are selected from ethanol, ethylene glycol, propyl alcohol, isopropyl
Two or more in alcohol, butanol or BDO, wherein at least contains BDO, low-carbon alcohols and/or polynary
The 10%~30% of the percent by volume of 1,4- butanediols in alcohol.
Have the following advantages that compared with prior art：
（1）Clay minerals used in pulping composition, itself adsorbs ability in elecrtonegativity, with ion exchange, from
And can have adsorption-flocculation to act on the large biological molecules such as somatic cells, thalline dissolution albumen, lipid；Usual clay minerals
Mixed effect in water phase is poor, therefore limited to the suction-operated of large biological molecule in zymotic fluid.This programme is with pH conditions
The coherent conditions of the pulping composition in water phase such as control bentonite, organoclay, i.e., improve the dispersion of pulping composition under the conditions of pH high
Degree, it is easy to suspension is formed, so as to increase its adsorption effect to large biological molecule in zymotic fluid；Make its spontaneous under low ph condition
Flocculation, is beneficial to solid phase separation.
（2）The polymer molecule with synergistic effect is added during fermentation liquor pretreatment, under the conditions of pH high, can be strengthened
The decentralization of clay component, hydration effect；Under low ph condition, the crosslinked action of pulping composition can be strengthened, so as to improve gather
The effect of sedimentation.In the presence of polymer molecule, suction-operated of the clay component to large biological molecule in zymotic fluid is enhanced,
So that some low molecular proteins are easier removal, pretreating effect is improve.
（3）Low-carbon alcohols and/or polyalcohol comprising a certain amount of BDO, alcohols are with the addition of during aqueous two-phase extraction
Being can be to the concentration of 2,3-butanediol, in collectively residing in phase clear liquid, simultaneously because BDO boiling point by hydrogen bond
Higher than 2,3-butanediol such that it is able to play the effect that 2,3-butanediol yield is improved in distillation process.
（4）The inventive method obtains more pure fermentation clear liquid by effective fermentation liquor pretreatment step, reduces
Subsequent extracted difficulty, while being optimized to aqueous two-phase extraction scheme, is more beneficial for distillation operation, it is possible to increase 2,3- fourths
The yield of glycol, is more beneficial for commercial Application.
Specific embodiment
The detailed process and effect of the inventive method are illustrated with reference to embodiment, but is not limited to following implementation
Example.
Strain used is Klebsiella in the present embodiment（Klebsiella pneumoniae）From CNPC
Fushun Petrochemical Research Institute of work limited company patent strain, through China General Microbiological DSMZ（CGMCC）,
Deposit number：0798.Zymotic fluid is obtained through batch stream plus glucose sugar fermentation by the strain, and its 2,3-butanediol concentration is 80g/
L.Bentonite, organoclay used in embodiment, mesh number are 300 mesh, using preceding in 90 DEG C of baking ovens, have carried out 24h's
Dried process.
Embodiment 1
（1）It is prepared by fermentation liquor pretreatment liquid：Commercialization bentonite 50g, polyanion cellulose 1g are weighed, 500mL is dissolved in
Zymotic fluid.PH is adjusted to 9 with 10mol/L NaOH, system is turned into suspension.
（2）Fermentation liquor pretreatment：By in 500 mL fermentation liquor pretreatments agent addition 2L zymotic fluids, 10mol/L hydroxides are used
Sodium adjusts pH to 9, mixes 0.5h, forms homogeneous system；PH is adjusted to by 4, stratification with 2mol/L sulfuric acid；By filtering
Solid phase is gone, zymotic fluid clear liquid is obtained.
（3）Aqueous two-phase extraction：Zymotic fluid clear liquid 1L is taken, dipotassium hydrogen phosphate 300g, stirring to dissolving is added；Will by 40mL1,
4- butanediols and 160mL ethanol are added in zymotic fluid as extraction, after mixing fully, stand 24h；Upper organic phase is taken to enter
Row just stays treatment.
（4）Upper organic phase 420mL is taken, air-distillation is carried out, 80 DEG C or so there are a large amount of ethanol to steam, 180 DEG C or so steamings
Go out 2,3- butanediols 165mL.The overall recovery of 2,3- butanediols is 82%.
Embodiment 2
（1）It is prepared by fermentation liquor pretreatment liquid：Commercialization organoclay 50g, CMS 10g are weighed, 250mL fermentations are dissolved in
Liquid.PH is adjusted to 10 with 10mol/L NaOH, system is turned into suspension.
（2）Fermentation liquor pretreatment：By in 500 mL fermentation liquor pretreatments agent addition 4.75L zymotic fluids, 10mol/L hydrogen-oxygens are used
Change sodium regulation pH to 10, mix 2h, form homogeneous system；PH is adjusted to by 5, stratification with 2mol/L sulfuric acid；Through filtering
Solid phase is removed, zymotic fluid clear liquid is obtained.
（3）Aqueous two-phase extraction：Zymotic fluid clear liquid 3.5L is taken, disodium hydrogen phosphate 2000g, stirring to dissolving is added；Will be by
80mL1,4- butanediol and 720mL ethanol are added in zymotic fluid as extraction, after mixing fully, stand 24h；Taking upper strata has
Machine mutually carries out rectification process.
（4）Upper organic phase 2.8L is taken, air-distillation is carried out, 80 DEG C or so there are a large amount of ethanol to steam, and 180 DEG C or so steam
2,3- butanediols 342mL.The overall recovery of 2,3- butanediols is 84.97%.Embodiment 3
（1）It is prepared by fermentation liquor pretreatment liquid：Commercialization bentonite 50g, viscous carboxymethyl cellulose sodium salt 5g high are weighed, is dissolved in
200mL zymotic fluids.PH is adjusted to 10 with 10mol/L NaOH, system is turned into suspension.
（2）Fermentation liquor pretreatment：By in 200 mL fermentation liquor pretreatments agent addition 2.8L zymotic fluids, 10mol/L hydrogen-oxygens are used
Change sodium regulation pH to 9, mix 1h, form homogeneous system；PH is adjusted to by 5, stratification with 2mol/L sulfuric acid；By filtering
Solid phase is gone, zymotic fluid clear liquid is obtained.
（3）Aqueous two-phase extraction：Zymotic fluid clear liquid 1.5L is taken, potassium carbonate 300g, stirring to dissolving is added；Will be by 40mL1,4-
Butanediol and 160mL methyl alcohol are added in zymotic fluid as extraction, after mixing fully, stand 24h；Taking upper organic phase is carried out
Just stay treatment.
（4）Upper organic phase 510mL is taken, air-distillation is carried out, 68 DEG C or so there are a large amount of methyl alcohol to steam, 180 DEG C or so steamings
Go out 2,3- butanediols 205mL.The overall recovery of 2,3- butanediols is 84.8%.
Comparative example 1
According to method disclosed in CN 200710010203.9,2.5L zymotic fluids are taken, fermented by the way of membrane filtration
Liquid is pre-processed, and carries out aqueous two-phase extraction（The double-aqueous phase system that selection is made up of dipotassium hydrogen phosphate and ethanol）.In distillation process
Still there is coking phenomenon in bottom, and the overall recovery of 2,3-butanediol is 52%.
Comparative example 2
According to method disclosed in CN 200710010203.9,2.5L zymotic fluids are taken, fermented by the way of membrane filtration
Liquid is pre-processed, according to step in embodiment 1（3）Carry out aqueous two-phase extraction（Selection is by dipotassium hydrogen phosphate, ethanol, 1,4- butanediols
The double-aqueous phase system of composition, wherein dipotassium hydrogen phosphate, BDO, the addition of ethanol be respectively 300g, 40mL,
160mL）.Still there is coking phenomenon in bottom in distillation process, and the overall recovery of 2,3-butanediol is 70%.
Comparative example 3
According in embodiment 1（1）（2）The step of carry out fermentation liquor pretreatment after, directly carry out atmospheric distillation.Distillation process
In, after rectification temperature is more than 85 DEG C, viscosity gradually increases in kettle, obvious coking occurs and manifests.During water is steamed,
The complete coking in bottom, does not obtain 2,3-butanediol rectifying product.
Claims (10)
1. it is a kind of from zymotic fluid extract 2,3-butanediol method, it is characterised in that including following content：（1）By pulping group
Divide, synergist and a small amount of zymotic fluid are well mixed in the basic conditions, obtain fermentation liquor pretreatment agent；（2）Zymotic fluid is located in advance
Reason agent is added in zymotic fluid, and regulation pH is 8~10, hybrid reaction, and it is 4~6 then to adjust pH, and standing separation collects liquid phase, obtains
To pretreated zymotic fluid；（3）Soluble inorganic salt is added to pretreated zymotic fluid, is dissolved and is well mixed, then
Low-carbon alcohols and/or polyalcohol are added, after being sufficiently mixed, stratification takes supernatant, and refined extraction obtains 2,3-butanediol；Step
Suddenly（1）Described pulping component is using the one kind or several in bentonite, organoclay, kaolin, illite, montmorillonite or sepiolite
Kind, the mesh number of pulping component is 100 ~ 300 mesh；Step（1）Described synergist is sulfonated lignite, low viscous sodium carboxymethylcellulose
One kind or several in salt, viscous carboxymethyl cellulose sodium salt high, CMS, vinyl sulfonate copolymers or polyanion cellulose
Kind；Step（3）Described low-carbon alcohols and/or polyalcohol are selected from ethanol, ethylene glycol, propyl alcohol, isopropanol, butanol or 1,4- butanediols
In two or more, wherein at least contains BDO.
2. in accordance with the method for claim 1, it is characterised in that：Handled zymotic fluid comes from glucose as substrate,
Through the zymotic fluid without any treatment that microbial fermentation is obtained, 2%~20% 2,3- fourths two are contained in described zymotic fluid
Alcohol.
3. in accordance with the method for claim 1, it is characterised in that：Step（1）Described pulping component needs to be done before adding
Dry treatment, drying condition is：Dried 10~24 hours at 100~300 DEG C.
4. in accordance with the method for claim 1, it is characterised in that：Step（1）Described pulping component and synergist mass ratio
It is 5:1~50：1.
5. in accordance with the method for claim 1, it is characterised in that：Step（1）Pulping group in described fermentation liquor pretreatment agent
It is 1 to divide with the solid-to-liquid ratio of zymotic fluid:10~1:2, g:mL.
6. in accordance with the method for claim 1, it is characterised in that：Step（1）The pH of described alkalescence condition is 8 ~ 10.
7. in accordance with the method for claim 1, it is characterised in that：Step（2）The addition of described fermentation liquor pretreatment agent,
According to pulping component and the solid-to-liquid ratio 1 for mixing after fermentation liquid:100~1:10, g:mL.
8. in accordance with the method for claim 1, it is characterised in that：Step（2）The described hybrid reaction time is 0.5~2 small
When.
9. in accordance with the method for claim 1, it is characterised in that：Step（3）Described soluble inorganic salt is phosphoric acid hydrogen two
One or more in potassium, disodium hydrogen phosphate or potassium dihydrogen phosphate.
10. in accordance with the method for claim 1, it is characterised in that：Step（3）1 in described low-carbon alcohols and/or polyalcohol,
The 10%~30% of the percent by volume of 4- butanediols.
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| CN201410563689.9A CN105585430B (en) | 2014-10-22 | 2014-10-22 | A kind of method that 2,3 butanediols are extracted from zymotic fluid |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB574094A (en) * | 1943-05-06 | 1945-12-20 | Robert Alan Walmesley | Improvements in or relating to the recovery of butylene glycol from carbohydrate fermentation mashes |
| CN101693735A (en) * | 2009-10-30 | 2010-04-14 | 大连理工大学 | Method for extracting protein and enzyme by aqueous two-phase extraction technology |
| CN104003844A (en) * | 2014-05-23 | 2014-08-27 | 大连理工大学 | Method for separating 2,3-butanediol from fermentation broth by coupling of extraction and fermentation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8704016B2 (en) * | 2012-05-23 | 2014-04-22 | Orochem Technologies, Inc. | SMB process for the purification of ethanol and butanediol with integrated regeneration |
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2014
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB574094A (en) * | 1943-05-06 | 1945-12-20 | Robert Alan Walmesley | Improvements in or relating to the recovery of butylene glycol from carbohydrate fermentation mashes |
| CN101693735A (en) * | 2009-10-30 | 2010-04-14 | 大连理工大学 | Method for extracting protein and enzyme by aqueous two-phase extraction technology |
| CN104003844A (en) * | 2014-05-23 | 2014-08-27 | 大连理工大学 | Method for separating 2,3-butanediol from fermentation broth by coupling of extraction and fermentation |
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