CN101274876A - Method for adsorptive separating 2, 3-butanediol from fermentation liquor by using hydrophobic zeolite - Google Patents
Method for adsorptive separating 2, 3-butanediol from fermentation liquor by using hydrophobic zeolite Download PDFInfo
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- CN101274876A CN101274876A CNA2008100248656A CN200810024865A CN101274876A CN 101274876 A CN101274876 A CN 101274876A CN A2008100248656 A CNA2008100248656 A CN A2008100248656A CN 200810024865 A CN200810024865 A CN 200810024865A CN 101274876 A CN101274876 A CN 101274876A
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- butyleneglycol
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- hydrophobic silicalite
- desorption
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- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 47
- 238000000855 fermentation Methods 0.000 title claims abstract description 35
- 230000004151 fermentation Effects 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 32
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 229910021536 Zeolite Inorganic materials 0.000 title abstract description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title abstract description 5
- 239000010457 zeolite Substances 0.000 title abstract description 5
- 230000000274 adsorptive effect Effects 0.000 title 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000003795 desorption Methods 0.000 claims abstract description 19
- 239000007788 liquid Substances 0.000 claims description 79
- 238000001179 sorption measurement Methods 0.000 claims description 28
- 238000010521 absorption reaction Methods 0.000 claims description 16
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 14
- 239000011521 glass Substances 0.000 claims description 14
- 239000006228 supernatant Substances 0.000 claims description 12
- 230000003068 static effect Effects 0.000 claims description 11
- 229960004756 ethanol Drugs 0.000 claims description 10
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- 241000193830 Bacillus <bacterium> Species 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 6
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- 229910021641 deionized water Inorganic materials 0.000 claims description 6
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- 238000000926 separation method Methods 0.000 abstract description 8
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- 238000004821 distillation Methods 0.000 description 13
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- HNSDLXPSAYFUHK-UHFFFAOYSA-N 1,4-bis(2-ethylhexyl) sulfosuccinate Chemical compound CCCCC(CC)COC(=O)CC(S(O)(=O)=O)C(=O)OCC(CC)CCCC HNSDLXPSAYFUHK-UHFFFAOYSA-N 0.000 description 1
- PKAUICCNAWQPAU-UHFFFAOYSA-N 2-(4-chloro-2-methylphenoxy)acetic acid;n-methylmethanamine Chemical compound CNC.CC1=CC(Cl)=CC=C1OCC(O)=O PKAUICCNAWQPAU-UHFFFAOYSA-N 0.000 description 1
- YLWILEVNDBDRIU-UHFFFAOYSA-N 3-hydroxybutan-2-one;4-hydroxybutan-2-one Chemical compound CC(O)C(C)=O.CC(=O)CCO YLWILEVNDBDRIU-UHFFFAOYSA-N 0.000 description 1
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- 241000370738 Chlorion Species 0.000 description 1
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000588749 Klebsiella oxytoca Species 0.000 description 1
- 201000008225 Klebsiella pneumonia Diseases 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 206010035717 Pneumonia klebsiella Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 244000126002 Ziziphus vulgaris Species 0.000 description 1
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- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a method for absorbing and separating 2, 3-butanediol in fermentation broth by applying hydrophobic zeolite. Hydrophobic zeolite is applied to absorbing 2, 3-butanediol from pretreated 2, 3-butanediol fermentation broth obtained from fungus fermentation, and anhydrous ethanol is applied to desorption and 2, 3-butanediol is obtained after removing ethanol in the desorption solution. The method of the invention has simple process, high separation efficiency, no impurities and low energy consumption and solves the bottleneck which restrains the current fermentation production process of 2, 3-butanediol, thus having comparatively good industrial application prospect.
Description
Technical field
The invention belongs to technical field of biochemical industry, be specifically related to a kind of employing hydrophobic silicalite fractionation by adsorption 2 from microbial fermentation solution, the method for 3-butyleneglycol.
Background technology
2, the 3-butyleneglycol is widely used in a plurality of fields (Syu M J.ApplMicrobiol Biotechnol, 2001,55 (1): 10～18) such as chemical industry, food, fuel and aerospace.Its dewatered product methylethylketone is a kind of lower boiling solvent, can be applicable to industries such as coating, binding agent, lubricant, dyestuff, printing ink, can be used as the intermediate of organic synthesis spices, oxidation inhibitor etc. simultaneously again; Dewatered product 1,3-butadiene after the esterification is a kind of important petrochemical complex basic organic material and synthetic rubber monomer; Concentrate the octane isomer that forms after the dehydrogenation with methylethylketone, can be used to produce senior aviation with oily; Its high value derivative 3-oxobutanol (acetoin) and dimethyl diketone are widely used in industries such as food, spices and makeup; Simultaneously because of its calorific value higher (27,200kJ/kg), same ethanol (29,100kJ/kg) suitable, can be used as fuel dope and use (Garg S, Jain A.Bioresour Technol, 1995,51 (2): 103-109).
Some bacterium of occurring in nature has product 2, the ability of 3-butyleneglycol, comprise that mainly Klebsiella (Klebisella), series bacillus belong to (Paenibacillus), enterobacter (Enterobacter) and serratia (AfscharA S such as (Serratia), Vaz Rossell C E, Jonas R, et al.J Biotechnol, 1993,27 (3): 317～329).In the century in the past, people are to these bacterium living beings Synthetic 2s, the 3-butyleneglycol has carried out system and deep research, make their biosynthesizing 2, the fermentation final concentration of 3-butyleneglycol has reached higher level (reaching as high as 113g/L) (Olson B H, Johnson M J.JBacteriol, 1948,55 (2): 209～222; Yu E K C, Saddler J N.Appl Environ Microbiol, 1983,46 (3): 630～635; Zeng A P, Biebl H, Deckwer W D.Appl Microbiol Biotechnol, 1991,34 (4): 463-468).Yet product 2, the separation and Extraction of 3-butyleneglycol is a restriction Production by Microorganism Fermentation 2 always, one of bottleneck of 3-butyleneglycol development, this is because 2, the 3-butyleneglycol has oneself factor such as higher boiling point, very strong wetting ability and contains some other impurity in the fermented liquid usually, this makes that from fermented liquid with 2, the 3-butyleneglycol is separated very difficulty.The more separation method of research has at present: underpressure distillation (rectifying), pervaporation, membrane distillation, vacuum membrane distillation and organic solvent extraction.Rectifying is the difference of utilizing each component volatilization ability in the mixture, mixture is constantly separated, but because composition is very complicated in the fermented liquid, before reaching distillation temperature, some soluble parts in the fermented liquid will be condensed into the long-pending piece of thicker oily, thereby slow down 2, therefore the vaporator rate of 3-butyleneglycol should not adopt the method for rectifying to extract.Pervaporation promptly utilizes concentration gradient, carries out the components selection diffusion by nonporous membrane; The evaporative process that membrane distillation is promptly undertaken by porous hydrophobic membrane, and vacuum membrane distillation is the combination of the two.(Qureshi N such as Qureshi, Meagher M M, Hutkins R W.Sep SciTechnol, 1994,29 (13): 1733-1748) once in the vacuum membrane distillation process, used a kind of poly tetrafluoroethylene with microvoid structure, this film can allow water vapour to pass through smoothly, but can stop 2, the 3-butyleneglycol passes through, and adopts this method to make 2, the final quality concentration of 3-butyleneglycol reaches 430g/L, but there is big difficulty in this process later separation.In addition, than higher, film cost height, and exist film to pollute, be difficult to problems such as cleaning is so be difficult in industrial being used widely to the requirement of equipment for pervaporation, membrane distillation, vacuum membrane distillation.The extraction agent that uses in the organic extraction has normal butane, diethyl etherate etc., Tsao (Tsao G T.Final report, USDOE, Contract No:EG-77-S-02-4298,1978-07-31) find to use in the recyclable fermented liquid of diethyl etherate 75% 2, the 3-butyleneglycol, but this method because of the solvent usage quantity the big and more high laboratory scale that is only limited to of cost, and be not suitable for large-scale industrial production.
Absorption is a kind of Solid-Phase Extraction isolation technique of less energy-consumption.Adsorption be since the molecule of solid surface or atom because of discontinuity equalization has remaining surface energy.When some materials collision solid surface, be subjected to the attraction of these unbalanced forces and be trapped on the solid surface, make be adsorbed molecule adsorbent surface concentration be higher than the solution body mutually in concentration.The sorbent material that mainly adopts with absorption method processing fermented liquid has gac, modified-cellulose and resin etc.The charcoal absorption performance is preferable, but its regeneration difficulty (needing superheated vapour and comparatively high temps).Polymeric adsorbent is applied and forms a kind of adsorption separation technology of uniqueness in every field, but existing resin choice is not high.Hydrophobic silicalite is a kind of novel adsorption and separation material, U.S. combinating carbide company had at first made report (Grow R W in 1977, Flanigen E M.USP 4061724 (1977)), it has hydrophobic, close organic character, can select absorb organic molecule in the presence of water.Hydrophobic silicalite has very high water, thermostability simultaneously, anti-strong acid and weakly alkaline chemical etching, and the organism desorption temperature that is adsorbed is not high, is difficult for generating residue and stops up the duct.After prolonged and repeated absorption-desorption operation, the regenerated temperature is not higher than 800 ℃.Because the heat and the hydrothermal stability of silicon zeolite are higher than 850 ℃, the original characterization of adsorption in regeneration back can recover, and replaces activated carbon to use in many occasions, and overall economic efficiency is preferably arranged.
Summary of the invention
The objective of the invention is at 2; there are problems such as energy consumption height, cost height in the sepn process of 3-butyleneglycol; a kind of adsorption separation technology is provided; utilize the adsorption of hydrophobic silicalite, 2 in the separate fermentation liquid, 3-butyleneglycol; separate 2 to reduce ordinary method; energy consumption and cost in the 3-butyleneglycol process are convenient to 2, the large-scale production of 3-butyleneglycol.
Purpose of the present invention can reach by following measure:
A kind ofly utilize in the hydrophobic silicalite fractionation by adsorption fermented liquid 2, the method for 3-butyleneglycol, with strain fermentation make 2, after the pre-treatment of 3-butyleneglycol fermentation liquid with hydrophobic silicalite to 2, the 3-butyleneglycol adsorbs, absorption back dehydrated alcohol desorption, desorption liquid obtains 2 after removing ethanol, the 3-butyleneglycol.Absorption and desorption process can adopt static treatment or dynamichandling.
Wherein bacterial classification is the bacterium that Klebsiella (Klebisella), series bacillus belong to (Paenibacillus), bacillus (Bacillus), enterobacter (Enterobacter), serratia (Serratia).2, in the 3-butyleneglycol fermentation liquid 2, the concentration of 3-butyleneglycol depends on bacterial classification and fermenting process, is preferably 30～200g/L.
Before fermented liquid adsorbs, need carry out some conventional pre-treatment, as filtration, flocculation, micro-filtration or centrifugal etc., removing the thalline in the fermented liquid, and regulate fermented liquid pH with NaOH or KOH, making its pH is 6.0～8.0.
Hydrophobic silicalite used in the present invention is preferably FX-I type hydrophobic silicalite, FX-II type hydrophobic silicalite or MFI type hydrophobic silicalite.The diameter of hydrophobic silicalite there is no too big requirement, but considers consumption and adsorption effect, is preferably 2.0～3.0mm.
The absorption of hydrophobic silicalite and desorption process can be divided into and adopt two kinds of static treatment or dynamichandling, all be to utilize hydrophobic silicalite absorption 2, utilize alcohol desorption behind the 3-butyleneglycol again, its difference is only different for the equipment that absorption and desorption are utilized, and has brought the operation steps difference thus.Wherein static treatment is: with pretreated 2,3-butyleneglycol fermentation liquid adds in the contactor that contains hydrophobic silicalite and adsorbs, wherein adsorption conditions is: in hydrophobic silicalite and the fermented liquid 2, the mass ratio of 3-butyleneglycol is 1: 1.0～2.0, the vibration rotating speed is 100～250r/min (shaking table), temperature is 25～80 ℃, and adsorption time is 2～6h; The centrifugal abandoning supernatant in absorption back, the dehydrated alcohol that adds 0.5～1.0 times of reason fermentating liquid volume of living in carries out desorb at similarity condition, centrifugation after the desorb, supernatant liquor is desorption liquid.Contactor sealing or opening all can during static treatment; Alr mode adopts the constant temperature cradle vibrate or adopts the constant temperature magnetic agitation.Wherein dynamichandling is: hydrophobic silicalite is packed in the adsorption column, with pretreated 2,3-butyleneglycol fermentation liquid cycles through the lasting 4～6h of adsorption column and adsorbs, then with the fermented liquid that does not adsorb in the deionized water rinsing glass column, carry out continuous wash-out 1～2h with dehydrated alcohol again, collect elutriant and be desorption liquid.Static treatment and dynamichandling are distilled the desorption liquid that obtains at last, collect 80 ℃ of cuts, are 2 after the residual fraction drying, the 3-butyleneglycol.
With the static treatment is example, and a kind of concrete process is: pretreated contained 2, and the fermented liquid of 3-butyleneglycol is delivered to contactor and adsorbs, and adsorption conditions is: the hydrophobic silicalite particle diameter is 2.0～3.0mm; In hydrophobic silicalite particle and the fermented liquid 2, the mass ratio of 3-butyleneglycol is 1.0～2.0 before handling; The vibration rotating speed is 100～250r/min; Temperature range is 25～80 ℃; Adsorption time is 2～6h.The centrifugal supernatant liquor of abandoning, the dehydrated alcohol of 0.5～1.0 times of reason fermentating liquid volume of living in of adding, the similarity condition desorb, the supernatant liquor distillation is got in centrifugation, collects 80 ℃ of cuts and recycles, and residual cut promptly obtains 2 after drying, 3-butyleneglycol product.
With the dynamichandling is example, and a kind of concrete process is: with 30～50g, particle diameter is that the hydrophobic silicalite of 2.0～3.0mm is packed into
The glass column of 10mm * 500mm, after with the flow velocity of 5～8mL/min 200～400mL fermented liquid being cycled through glass column 4～6h, with the fermented liquid of absorption not in the deionized water rinsing glass column of 2 times of column volumes, carry out continuous wash-out with dehydrated alcohol more then, elution speed is 6～10mL/min, elution time is 1～2h, and wash-out finishes, and collects elutriant, distill, collect 80 ℃ of cuts and recycle, residual cut promptly obtains 2 after drying, 3-butyleneglycol product.
Beneficial effect of the present invention:
The present invention is used for 2 of separate fermentation liquid, during the 3-butyleneglycol, the separation efficiency height, have higher 2, the 3-butyleneglycol rate of recovery, and energy consumption is lower, technology is simple and easy to amplify, and helps 2, the large-scale production of 3-butyleneglycol; Simultaneously, zeolite is nontoxic, tasteless, to not influence of environment, and fabulous acid resistance, thermostability and water vapour stability are arranged; Easily regeneration, and can keep original characterization of adsorption after the regeneration, can repeat repeatedly to use; Therefore, the present invention is used for 2 of separate fermentation liquid, and the 3-butyleneglycol has better industrial application prospects.
Embodiment
The invention will be further elaborated by the following examples.
In the embodiment of the invention, described fermented liquid adds for adopting microorganism strains to criticize formula stream that glucose fermentation obtains, possesses the required nutritive ingredient of microorganism growth in the fermention medium, as carbon sources such as glucose, nitrogenous sources such as yeast extract paste, corn steep liquor or urea, negatively charged ion such as positively charged ions such as sodium, potassium, ammonia, magnesium, calcium and phosphate radical, sulfate radical, chlorion, and trace elements such as zinc, iron, manganese, copper, cobalt, boron and molybdenum.When fermentation stops, 2, the concentration of 3-butyleneglycol is 30～200g/L.Residual substrate glucose and product 2 in the fermented liquid, 3-butyleneglycol and various by product such as ethanol, lactic acid and acetate etc. adopt DIONEX summitP680 high performance liquid chromatograph to measure.Chromatographic column is an Aminex HPX-87H post (Bio-Rad), and column temperature is 60 ℃, and detector is a SHODEX RI-101 refractive power differential detector, and moving phase is 0.005mol/L H
2SO
4, flow velocity is 0.2mL/min, sample size is 20 μ L.
Embodiment 1 adopts FX-I type hydrophobic silicalite Static Adsorption
Step 1: collect 200mL by acid-producing Klebsiella bacterium (Klebsiella oxytoca) CCTCC M 207023 (from application number be 200710021641.5, publication number is the bacterial classification that CN101063095A, name are called preservation in the patent application document of " a kind of acid-producing Klebsiella bacterium and application thereof ") fermentation make 2,3-butyleneglycol fermentation liquid (wherein 2, the concentration of 3-butyleneglycol is 125g/L), fermented liquid is obtained clear liquid through flocculation after removing thalline, regulate pH with NaOH, making its pH is 7.0.
Step 2: pretreated contained 2, and the fermented liquid of 3-butyleneglycol is transferred in the 500mL triangular flask and adsorbs, and the commercial FX-I type of 30g hydrophobic silicalite (Shanghai Zhuoyue Chemical Science Co., Ltd is housed in the triangular flask; Its mean pore size 0.56nm, sphere, particle diameter is 2.0～3.0mm, tap density 0.62～0.72g/mL, crush strength 〉=25N); (rotating speed is 120r/min to the constant temperature cradle vibrate; Temperature is 25 ℃); The centrifugal supernatant liquor of abandoning behind the absorption 5h.
Step 3: add the 100mL dehydrated alcohol in the precipitation of step 2 gained, ((rotating speed is 120r/min to the constant temperature cradle vibrate to similarity condition; Temperature is 25 ℃)) desorb 5h, the supernatant liquor distillation is got in centrifugation, collect 80 ℃ of cuts (ethanol) and recycle, residual cut 23mL is through liquid chromatographic detection 2, and 3-butyleneglycol concentration is 989g/L, and without any impurity, 2, the rate of recovery of 3-butyleneglycol is 91.0%.
Embodiment 2 adopts FX-I type hydrophobic silicalite dynamic adsorption
Step 1: collect 300mL by Klebsiella pneumonia (Klebsiella pneumoniae) CICC 10011 (administrative center provides by the preservation of Chinese industrial microbial strains) fermentation make 2,3-butyleneglycol fermentation liquid (wherein 2, the concentration of 3-butyleneglycol is 92.4g/L), fermented liquid is obtained clear liquid through centrifugal after removing thalline, regulate pH with NaOH, making its pH is 7.0.
Step 2: with the commercial FX-I type of 35g hydrophobic silicalite (Shanghai Zhuoyue Chemical Science Co., Ltd; Its mean pore size 0.56nm, sphere, particle diameter is 2.0～3.0mm, tap density 0.62～0.72g/mL, crush strength 〉=25N) pack into
The glass column of 10mm * 500mm, 300mL fermented liquid step 1 is pretreated with the flow velocity of 5mL/min cycles through glass column 40min.
Step 3: after the fermented liquid that does not adsorb in deionized water rinsing step 2 glass column of 2 times of column volumes, carry out continuous wash-out with dehydrated alcohol again, elution speed is 8mL/min, elution time is 1.5h, wash-out finishes, and collects elutriant, distills, collecting 80 ℃ of cuts (ethanol) recycles, residual cut 26.5mL is through liquid chromatographic detection 2, and 3-butyleneglycol concentration is 980g/L, and without any impurity, 2, the rate of recovery of 3-butyleneglycol is 93.6%.
Embodiment 3 adopts FX-II type hydrophobic silicalite Static Adsorption
Step 1: collect 200mL by enterobacter cloacae (Enterobacter cloacae) CICC 10014 (administrative center provides by the preservation of Chinese industrial microbial strains) fermentation make 2,3-butyleneglycol fermentation liquid (wherein 2, the concentration of 3-butyleneglycol is 100.8g/L), obtain clear liquid after fermented liquid removed by filter thalline, regulate pH with KOH, making its pH is 7.0.
Step 2: pretreated contained 2, and the fermented liquid of 3-butyleneglycol is transferred in the 500mL triangular flask and adsorbs, and the commercial FX-II type of 25g hydrophobic silicalite (Shanghai Zhuoyue Chemical Science Co., Ltd is housed in the triangular flask; Its mean pore size 0.56nm, sphere, particle diameter is 2.0～3.0mm, tap density 0.62～0.72g/mL, crush strength 〉=40N); (rotating speed is 150r/min to the constant temperature cradle vibrate; Temperature is 37 ℃); The centrifugal supernatant liquor of abandoning behind the absorption 4h.
Step 3: add the 100mL dehydrated alcohol in the precipitation of step 2 gained, ((rotating speed is 150r/min to the constant temperature cradle vibrate to similarity condition; Temperature is 37 ℃)) desorb 4h, the supernatant liquor distillation is got in centrifugation, collect 80 ℃ of cuts (ethanol) and recycle, residual cut 19mL is through liquid chromatographic detection 2, and 3-butyleneglycol concentration is 990g/L, and without any impurity, 2, the rate of recovery of 3-butyleneglycol is 93.3%.
Embodiment 4 adopts FX-II type hydrophobic silicalite dynamic adsorption
Step 1: collect 300mL by Paenibacillus polymyxa (Paenibacillus polymyxa) CICC 10010 (administrative center provides by the preservation of Chinese industrial microbial strains) fermentation make 2,3-butyleneglycol fermentation liquid (wherein 2, the concentration of 3-butyleneglycol is 87.2g/L), fermented liquid is obtained clear liquid through micro-filtration after removing thalline, regulate pH with KOH, making its pH is 7.0.
Step 2: with the commercial FX-II type of 31g hydrophobic silicalite (Shanghai Zhuoyue Chemical Science Co., Ltd; Its mean pore size 0.56nm, sphere, particle diameter is 2.0～3.0mm, tap density 0.62～0.72g/mL, crush strength 〉=40N) pack into
The glass column of 10mm * 500mm, 300mL fermented liquid step 1 is pretreated with the flow velocity of 6mL/min cycles through glass column 50min.
Step 3: after the fermented liquid that does not adsorb in deionized water rinsing step 2 glass column of 2 times of column volumes, carry out continuous wash-out with dehydrated alcohol again, elution speed is 6mL/min, elution time is 1.8h, wash-out finishes, and collects elutriant, distills, collecting 80 ℃ of cuts (ethanol) recycles, residual cut 25mL is through liquid chromatographic detection 2, and 3-butyleneglycol concentration is 985g/L, and without any impurity, 2, the rate of recovery of 3-butyleneglycol is 94.1%.
Embodiment 5 adopts MFI type hydrophobic silicalite Static Adsorption
Step 1: collect 200mL by subtilis (Bacillus subtilis) CICC 10026 (administrative center provides by the preservation of Chinese industrial microbial strains) fermentation make 2,3-butyleneglycol fermentation liquid (wherein 2, the concentration of 3-butyleneglycol is 84.6g/L), fermented liquid is obtained clear liquid through flocculation after removing thalline, regulate pH with NaOH, making its pH is 7.0.
Step 2: pretreated contained 2, and the fermented liquid of 3-butyleneglycol is transferred in the 500mL triangular flask and adsorbs, and the commercial MFI type of 20g hydrophobic silicalite (the Shanghai fine science and trade of good horse Development Co., Ltd, mean pore size is 0.6nm) is housed in the triangular flask; (rotating speed is 150r/min to the constant temperature cradle vibrate; Temperature is 37 ℃); The centrifugal supernatant liquor of abandoning behind the absorption 4h.
Step 3: add the 100mL dehydrated alcohol in the precipitation of step 2 gained, ((rotating speed is 150r/min to the constant temperature cradle vibrate to similarity condition; Temperature is 37 ℃)) desorb 4h, the supernatant liquor distillation is got in centrifugation, collect 80 ℃ of cuts (ethanol) and recycle, residual cut 15mL is through liquid chromatographic detection 2, and 3-butyleneglycol concentration is 990g/L, and without any impurity, 2, the rate of recovery of 3-butyleneglycol is 87.8%.
Embodiment 6 adopts MFI type hydrophobic silicalite dynamic adsorption
Step 1: collect 300mL by serratia marcescens (Serratia marcescens) CICC 10187 (administrative center provides by the preservation of Chinese industrial microbial strains) fermentation make 2,3-butyleneglycol fermentation liquid (wherein 2, the concentration of 3-butyleneglycol is 97.5g/L), fermented liquid is obtained clear liquid through flocculation after removing thalline, regulate pH with KOH, making its pH is 7.0.
Step 2: (the Shanghai fine science and trade of good horse Development Co., Ltd, mean pore size is 0.56nm) packs into the commercial MFI type of 35g hydrophobic silicalite
The glass column of 10mm * 500mm, 300mL fermented liquid step 1 is pretreated with the flow velocity of 6mL/min cycles through glass column 50min.
Step 3: after the fermented liquid that does not adsorb in deionized water rinsing step 2 glass column of 2 times of column volumes, carry out continuous wash-out with dehydrated alcohol again, elution speed is 9mL/min, elution time is 1h, wash-out finishes, and collects elutriant, distills, collecting 80 ℃ of cuts (ethanol) recycles, residual cut 28mL is through liquid chromatographic detection 2, and 3-butyleneglycol concentration is 985g/L, and without any impurity, 2, the rate of recovery of 3-butyleneglycol is 94.2%.
Claims (9)
1, a kind ofly utilizes in the hydrophobic silicalite fractionation by adsorption fermented liquid 2, the 3-butyleneglycol-method, it is characterized in that with strain fermentation make 2, after the pre-treatment of 3-butyleneglycol fermentation liquid with hydrophobic silicalite to 2, the 3-butyleneglycol adsorbs, after using dehydrated alcohol desorption, desorption liquid to remove ethanol, the absorption back obtains 2, the 3-butyleneglycol.
2, method according to claim 1 is characterized in that described bacterial classification is the bacterium of Klebsiella, series bacillus genus, bacillus, enterobacter or serratia.
3, method according to claim 1 is characterized in that described pre-treatment is that 3-butyleneglycol fermentation liquid is removed thalline with 2, regulates pH value to 6.0～8.0 with the clear liquid that obtains again.
4, method according to claim 1 is characterized in that described hydrophobic silicalite is FX-I type hydrophobic silicalite, FX-II type hydrophobic silicalite or MFI type hydrophobic silicalite.
5, method according to claim 4, the diameter that it is characterized in that described hydrophobic silicalite is 2.0～3.0mm.
6, method according to claim 1 is characterized in that described absorption and desorption process adopt static treatment or dynamichandling.
7, method according to claim 6, it is characterized in that described static treatment is: with pretreated 2,3-butyleneglycol fermentation liquid adds in the contactor that contains hydrophobic silicalite and adsorbs, wherein adsorption conditions is: in hydrophobic silicalite and the fermented liquid 2, the mass ratio of 3-butyleneglycol is 1: 1.0～2.0, temperature is 25～80 ℃, and adsorption time is 2～6h; The centrifugal abandoning supernatant in absorption back, the dehydrated alcohol that adds 0.5～1.0 times of reason fermentating liquid volume of living in carries out desorb at similarity condition, centrifugation after the desorb, supernatant liquor is desorption liquid.
8, method according to claim 6, it is characterized in that described dynamichandling is: hydrophobic silicalite is packed in the adsorption column, with pretreated 2,3-butyleneglycol fermentation liquid cycles through the lasting 4～6h of adsorption column and adsorbs, then with the fermented liquid that does not adsorb in the deionized water rinsing glass column, carry out continuous wash-out 1～2h with dehydrated alcohol again, collect elutriant and be desorption liquid.
9, according to claim 1,7 or 8 described methods, it is characterized in that described desorption liquid is distilled, collect 80 ℃ of cuts, be 2 after the residual fraction drying, the 3-butyleneglycol.
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