CN100469746C - Technique of extracting 1,3-dihydroxypropane prepared by fermentation method - Google Patents
Technique of extracting 1,3-dihydroxypropane prepared by fermentation method Download PDFInfo
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- CN100469746C CN100469746C CNB2007100655588A CN200710065558A CN100469746C CN 100469746 C CN100469746 C CN 100469746C CN B2007100655588 A CNB2007100655588 A CN B2007100655588A CN 200710065558 A CN200710065558 A CN 200710065558A CN 100469746 C CN100469746 C CN 100469746C
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Abstract
This invention relates to a pick up method for producing 1, 3-propanediol, which utilizes the character that inorganic salt is easy to be crystallized and the organic salt in the 1, 3-propanediol ferment solution is not easy to be crystallized to add suitable volume of inorganic acid in the ferment solution to replace the organic salts to organic acid and generate inorganic salts, concentrate the ferment solution to crystallize the inorganic salts and separate it out so as to separate itself from the ferment solution, and the concentrated ferment solution becomes a mixture of 1, 3-propanediol, amber acid, lactic acid, acetic acid, glycerin and 2, 3-butanediol to be vacuum-rectified to get a product with various compositions advantaged that either the salts in the ferment solution are taken off, or products of amber acid, lactic acid, acetic acid and inorganic salts are got.
Description
Technical field
The invention belongs to technical field of chemical separation, a kind of fermentative Production 1 is provided especially, the extraction process of ammediol from 1, extracts 1 in the ammediol fermented liquid, ammediol and 2, and the 3-butyleneglycol obtains several organic acid technologies simultaneously.
Background technology
1, ammediol is mainly produced polyester material as monomer, generates Poly(Trimethylene Terephthalate) with terephthalic acid.Also can produce some other biodegradable polyesters material in addition, as 1, ammediol and 1, polymkeric substance (the Liu Y. that 4-cyclohexanedimethanol and succsinic acid polymerization obtain, Ranucci E., Lindblad M.S., Albertsson is Biodegradable Polymers from Renewable Sources:Polyester-carbonates Based on1 A.2001.New, 3-Propylene-co-1,4-Cyclohexanedimethylene Succinate.J.Polym.Sci.Part are A.39:2508-2519).1, ammediol can be produced by traditional chemical synthesis process.It is method (the Arntz D. of raw material that industrial process has the propenal of Degussa company, Haas T., M ü ller A., Wiegand is untersuchung zur hydratisierung von acrolein.Chem.Ing.Tech.63:733-735 N.1991Kinetische) and the oxyethane of Shell company be method (the Slaugh L.H. of raw material, Powell J.B., Forschner T.C., Semple, T.C., Weider, P.R.1995.Process for preparing 1,3-propanediol.United StatesPatent.5,463,146).People have developed gradually and have utilized Production by Microorganism Fermentation 1, the method for ammediol in recent years.Because microbe fermentation method utilizes glycerine etc. can be raw material in the production-goods source, and chemical method utilizes petrochemical material, and along with the big ups and downs of international petroleum price, make the price of petroleum chemicals raise gradually, but biofuel and the pure industrial expansion of lipid acid fat then make the price of by-product glycerin reduce gradually, so Production by Microorganism Fermentation 1, ammediol show advantage economically gradually.
With glycerine or glucose is substrate, with Cray Bai Shi pneumobacillus (Klebsiella pneumoniae), when Cray Bai Shi product acidfast bacilli bacterial strains such as (Klebsiella oxytoca) ferments, thalline also produces organic acid (Qi Wentao such as acetate, lactic acid and succsinic acid when producing PDO, repair the will dragon. the glycerine disproportionation produces 1, the metabolism of ammediol process and gene regulating mechanism progress, Chinese biological engineering magazine, 2003,23:64-68), for keeping the pH in the fermenting process stable, need stream to add the organic acid that neutralizations such as NaOH or KOH produce.Contain K in the fermention medium simultaneously
2HPO
4, KH
2PO
4, (NH
4)
2SO
4And MgSO
4Deng inorganic salts (Zhang Jian, Zhao Hongying, Liu Hongjuan, etc., glucose as cosubstrate fermentative production 1, the research of ammediol, modern chemical industry, 2002,22:32-35), contain a large amount of salts when making fermentation ends in the fermented liquid.These salt fusing points are low, be difficult for Crystallization Separation, could be but in later separation work, must remove with 1 in the fermented liquid, ammediol extracts, can adopt ion-exchange and electrodialytic mode the salt in the fermented liquid to be removed (Hao Jian, Liu De China 1, the desalination of ammediol fermented liquid electroosmose process, process engineering journal at present, 2005,5:36-39).But this method is not effectively recycled salt, and our rule has been saved the electrodialysis process in the extraction of former back, is extracting 1, and ammediol and 2 in the time of the 3-butyleneglycol, is effectively separated acetate, lactic acid and succsinic acid.Improve fermentative Production 1, the overall efficiency of ammediol.Reduce discharging wastes, reduced environmental pollution.
Summary of the invention
The purpose of this invention is to provide a kind ofly from 1, extract 1.3-propylene glycol and 2 in the ammediol fermented liquid, the 3-butyleneglycol obtains several organic acid technologies simultaneously.Add cheap mineral acid in the fermented liquid, organic acid salt is replaced as organic acid, generate inorganic acid salt simultaneously.Fermented liquid is concentrated, make the inorganic acid salt crystallization separate out, separate the solid salt then.At this moment spissated fermented liquid is 1, ammediol, 2, and the mixture of alcohols such as 3-butyleneglycol and acids such as acetate, lactic acid and succsinic acid by rectification under vacuum, separates mixture, obtains the pure product of each component.Described a kind of from 1, separation and Extraction organic acid technological process is in the ammediol fermented liquid:
1. the total yield volumetric molar concentration of organic acid salt in the mensuration fermented liquid, according to the total concn of salt, the mineral acid of molar equivalents such as adding.
2. fermented liquid concentrates, and makes the inorganic acid salt crystallization separate out, and separates the inorganic salt crystallization.
3. spissated fermented liquid carries out vacuum distilling, and each component is separated, and obtains 1, ammediol product, glycerine, 2, the pure product of 3-butyleneglycol, acetate, lactic acid and succsinic acid or the mixture of several components.
Described 1, the ammediol fermented liquid comprises: Cray Bai Shi pneumobacillus Klebsiella pneumoniae is called gas bacillus Aerobacter aerogenes previously; Cray Bai Shi produces acidfast bacilli Klebsiella oxytoca; Cray Bai Shi plants living bacillus Klebsiella planticola; Flocculation enterobacteria Enterobacter agglomerans; C. freundii Citrobacter freundii; Many nutritive muds bacillus Ilyobacter polytropus; Clostridium butylicum Clostridiumbutyricu; Clostridium pasteurianum Clostridium Pasteurianum; Short lactobacillus Lactobacillus brevis; Lactobacillus buchneri Lactobacillus buchneri; And strain fermentation glycerine such as lactobacillus reuteri Lactobacillus reuteri intestinal bacteria Escherichia coli, glucose and their mixture produce 1, the ammediol fermented liquid
Described mineral acid comprises: sulfuric acid; Hydrochloric acid; Phosphoric acid; Cheap mineral acid such as nitric acid.
Beneficial effect of the present invention: will be difficult to be transformed into organic acid by the isolating organic acid salt of crystallization mode, and add mineral acid and generate inorganic acid salt, inorganic acid salt is by condensing crystal, and organic acid separates with other liquid ingredients by rectifying.Save the electrodialysis process in the extraction process of former back, greatly reduced production cost, simplified back extraction operation, simultaneously to greatest extent the various main ingredients in the fermented liquid have been carried out Separation and Recovery, increase benefit, reduced discharging wastes, reduced environmental pollution.
Embodiment
The invention provides a kind ofly, extract 1 in the ammediol fermented liquid from 1, ammediol and 2, the 3-butyleneglycol obtains several organic acid technologies simultaneously.Add mineral acid in the fermented liquid, make that the organic acid salt in the fermented liquid is transformed into organic acid and inorganic acid salt, make the inorganic acid salt crystallization separate out by concentrating, concentrated solution by rectifying with organic acid and 1, ammediol, glycerine, 2, components such as 3-butyleneglycol are separated, and obtain the product of each component.From 1, separation and Extraction organic acid technological process is in the ammediol fermented liquid:
1. the concentration of each organic acid salt in the detection fermented liquid calculates total volumetric molar concentration, adds mineral acid, makes organic acid salt just be transformed into organic acid fully;
2. fermented liquid concentrates, to water-content be 0.1～10% (w/w), make the inorganic acid salt crystallization separate out, and separate with concentrated solution;
3. concentrated solution separates by the mode of rectification under vacuum, and vacuum tightness makes tower still temperature not be higher than 200 ℃.
Embodiment 1
(1) fermented liquid: the fermented liquid that Cray Bai Shi pneumobacillus aerobic fermentation is produced.Specifically consist of: 1, ammediol 67g/L, succsinic acid 11g/L, lactic acid 15g/L, acetic acid 5g/L, glycerine 11g/L, ethanol 3g/L, 2,3-butyleneglycol 22g/L.Wherein organic acid salt is represented with organic acid concentration, and each salt is sodium salt.
(2) add mineral acid: the sulfuric acid 21.5g of every liter of fermented liquid adding 98%.
(3) the 1L fermented liquid is concentrated into 150mL, separating sodium sulfate crystal.
(4) concentrated solution carries out rectification under vacuum: vacuum tightness 20mmHg post, and periodical operation, disposable the putting into of tower still concentrates fermentation concentrated solution 1L, reflux ratio 6:1, control tower still fermentation concentrated solution is in boiling state, and range of temperature is 60～180 ℃; Cat head Fractional Collections product, each section sample composition composition sees Table 1.
Table 1 batch rectifying result
Embodiment 2
(1) fermented liquid: Cray Bai Shi produces the fermented liquid that the acidfast bacilli anaerobically fermenting is produced.Specifically consist of: 11, ammediol 50g/L, succsinic acid 4g/L, lactic acid 8g/L, acetic acid 9g/L, glycerine 30g/L, ethanol 13g/L, 2,3-butyleneglycol 8g/L
(2) add mineral acid: the hydrochloric acid 25mL of every liter of fermented liquid adding 37%.
(3) the 1L fermented liquid is concentrated into 150mL, separating sodium sulfate crystal.
(4) concentrated solution carries out rectification under vacuum: vacuum tightness 2mmHg post, and periodical operation, disposable the putting into of tower still concentrates fermentation concentrated solution 1L, reflux ratio 6:1, control tower still fermentation concentrated solution is in boiling state, and range of temperature is 60～180 ℃; Cat head Fractional Collections product, each section sample composition composition sees Table 1.
Table 1 batch rectifying result
Claims (3)
1. fermentative Production 1, and the extraction process of ammediol is characterized in that: technology is:
(1) the total yield volumetric molar concentration of organic acid salt in the mensuration fermented liquid, according to the total concn of salt, the mineral acid of molar equivalents such as adding;
(2) fermented liquid concentrates, and makes the inorganic acid salt crystallization separate out, and separates the inorganic salt crystallization;
(3) spissated fermented liquid carries out vacuum distilling, and each component is separated, and obtains 1, ammediol product, glycerine, 2, the pure product of 3-butyleneglycol, acetate, lactic acid and succsinic acid or the mixture of several components.
2. technology according to claim 1, it is characterized in that: described fermented liquid is: Cray Bai Shi pneumobacillus, Cray Bai Shi produce acidfast bacilli, Cray Bai Shi plants living bacillus, flocculation enterobacteria, C. freundii, many nutritive muds bacillus, clostridium butylicum, clostridium pasteurianum, short lactobacillus, Lactobacillus buchneri, and lactobacillus reuteri strain fermentation glycerine, glucose and their mixture produce 1, any in the ammediol fermented liquid.
3. according to the described technology of claim 1, it is characterized in that: mineral acid is: any in sulfuric acid, hydrochloric acid, phosphoric acid, the nitric acid.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101376620B (en) * | 2007-08-30 | 2012-05-30 | 黑龙江辰能生物工程有限公司 | Desalination process for producing 1,3-propanediol by fermentation method |
| CN101255451B (en) * | 2008-03-27 | 2012-05-16 | 清华大学 | Method for producing lactic acid by using glycerol |
| CN101497556B (en) * | 2009-01-20 | 2013-02-27 | 东南大学 | Method for separating and extracting 1,3-propanediol by solid superacid catalyst reaction |
| CN102795966B (en) * | 2011-05-24 | 2014-09-03 | 江苏恒祥化工有限责任公司 | Method for controlling polymerization in rectification process of 1,4-cyclohexanedimethanol |
| CN102321680B (en) * | 2011-06-07 | 2014-07-23 | 大连理工大学 | Dihydric alcohol and organic acid co-production and separation method |
| CN105400831B (en) * | 2015-12-07 | 2019-02-05 | 清华大学 | Utilize the method for recombination Corynebacterium glutamicum coproduction 1,3-PD and glutamic acid |
| CN106399204B (en) * | 2016-11-24 | 2020-08-14 | 大连理工大学 | Microbial mixed flora for producing 1, 3-propylene glycol by fermentation and fermentation method |
| CA3076745A1 (en) * | 2017-10-02 | 2019-04-11 | Metabolic Explorer | Method for producing organic acid salts from fermentation broth |
| CN108057121A (en) * | 2017-12-28 | 2018-05-22 | 广东伊茗药业有限公司 | One kind makes the stability-enhanced pharmaceutical composition of ambroxol hydrochloride |
| CN108893497A (en) * | 2018-07-18 | 2018-11-27 | 大连理工大学 | A kind of many cells system and fermentation process changing aeration condition regulation product |
| CN112479868A (en) * | 2020-11-26 | 2021-03-12 | 广州国宏新材料有限公司 | Method and device for extracting organic acid from mixed salt obtained by separating fermentation liquor |
| CN112617268A (en) * | 2021-01-07 | 2021-04-09 | 贵州山珍宝绿色科技开发有限公司 | A bead containing Passion fruit and fructus Rosae Normalis |
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