CN1951887A - Method for separating 1,3-propanediol from fermentation liquor - Google Patents
Method for separating 1,3-propanediol from fermentation liquor Download PDFInfo
- Publication number
- CN1951887A CN1951887A CN 200510047497 CN200510047497A CN1951887A CN 1951887 A CN1951887 A CN 1951887A CN 200510047497 CN200510047497 CN 200510047497 CN 200510047497 A CN200510047497 A CN 200510047497A CN 1951887 A CN1951887 A CN 1951887A
- Authority
- CN
- China
- Prior art keywords
- fermented liquid
- ammediol
- accordance
- separating
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a removing method of 1, 3-propylene glycol from ferment liquid of 1, 3-propylene glycol, which comprises the following steps: adjusting pH value of ferment liquid not more than 5.5; heating; stewing; sedimenting; fetching supernatant; heating the supernatant; condensing; dehydrating; separating to remove evolved salt; decompressing; rectifying; collecting the fraction of 1, 3-propylene glycol. The invention reinforces flocculation effect, which is convenient to separate.
Description
Technical field
The invention belongs to biological technical field, relate to microbial fermentation product separation technology, specially refer to and from fermented liquid, separate 1, the method for ammediol.
Background technology
1, ammediol (1,3-PD) be a kind of important chemical material, all have a wide range of applications at aspects such as making trevira, urethane, hot melt adhesive, powder coating, antifreezing agent, wrapping material and organic synthesis intermediate, wherein making high performance trevira PTT is present main purposes.1, ammediol can be produced by chemical method route and biological process route, adopt biotechnology to produce 1, ammediol, with its Green Chemistry is feature, have the reaction conditions gentleness, easy and simple to handle, by product is few, environmental pollution is little, can utilize characteristics such as renewable resource, becomes one of focus of new millennium biochemical industry research.
1, the fermented liquid of ammediol is the very complicated mixed system of a composition, main component comprises product 1, ammediol, microbial cells, organic acid salt, inorganic salt, glycerine, water, protein and other mesostate etc., because product 1, the ammediol molecule contains two hydroxyls, its wetting ability is stronger than ethanol, the concentration of product is 30～70g/L in the fermented liquid at present, to from rare fermented liquid, just become very difficult by the Separation and Recovery product, product recovery rate is low, and separation costs is very high.
The first step of fermentation liquor treatment is removed thalline exactly and is obtained clarified broth.Because thalli granule is tiny, the fermented liquid outward appearance is form of emulsion, except that containing particle tiny bacterial cell and cell debris, also contains protein and other jelly.The direct filtration degerming almost is impossible, and at present methods that adopt centrifugal, membrane filtering method or additional flocculating agents make thalline produce to a certain degree flocculation more, are convenient to filtration sterilization.Bactofugation needs the high speed centrifugation apparatus, degerming fully, and product loss is big.The problem that membrane filtration exists is that separating power is little, disengaging time is long, is prone to film contamination and plugging etc.Additional flocculating agents can only make the part thalline produce flocculation sediment, and the salt that exists in the fermented liquid can not separate out in crystallization, can bring very big difficulty to subsequent processes.
In order more effectively from fermented liquid, to separate 1, the ammediol product, the scientific worker has made unremitting effort for this reason both at home and abroad, has proposed many processing methodes.Adopt the liquid-liquid extraction method from fermented liquid, to separate 1 as people such as Janusz J, ammediol, and its application potential done evaluation (Biotechnology Techiques1999 13:127-130), the result shows, be difficult to choose suitable solvent, extraction does not reach the ideal separating effect.On this research basis, they have further studied reaction, extraction again and have separated 1, the method for ammediol.Its method is in the presence of acid catalyst, 1, the reaction of ammediol and acetaldehyde generates condenses, uses benzene kind solvent (toluene, ethylbenzene, dimethylbenzene etc.) extraction then, again through remove solvent, hydrolysis obtains 1, ammediol.This process steps is loaded down with trivial details, and operational condition is difficult to control, and product yield is not high yet.
At US 6, in 603,048, people such as David Richard Corbin have proposed a kind of zeolite molecular sieve absorption separation method, select the suitable molecular sieve and the program desorb of employing to reach isolating purpose, the selected zeolite of this method is mesopore synthetic zeolite H-ZSM-5, and the fermented liquid behind the separate microorganism cell adsorbs by adsorption column, carries out the substep desorb with the Different concentrations of alcohol aqueous solution, this zeolite molecular sieve not only adsorbs 1, ammediol also adsorb glycerine simultaneously, and loading capacity is low.The subject matter that this method exists is that product selectivity is not high, and loading capacity is too little, and practical application also has certain difficulty.US 6,479, and 716 have proposed ion exchange chromatography separates 1, ammediol, and this method has adopted the technology that is similar to moving-bed (SMB), Separation and Recovery 1 from fermented liquid effectively, ammediol.Resin is a polystyrolsulfon acid type storng-acid cation exchange resin, and treatment step comprises fermentation liquor pretreatment, fractionation by adsorption, desorb and purifying.This method primary recovery is not high, and the efficient of whole process is not high yet, and isolating product purity has only 50%～90%, and a large amount of waste water of regeneration of resin processing meeting generation, and scale operation exists many practical difficulties.At present fermentative Production 1, problem such as cost height that ammediol later separation purifying exists, separating power is little, and the salt crystallization appears in underpressure distillation and viscous substance hinders evaporation etc., Chinese patent CN1460671A proposed a kind of from fermented liquid Separation and Recovery 1, the method of ammediol, specific practice is that germ-carrying fermented liquid direct evaporation is concentrated to 1/2～1/20 of original volume, add a certain proportion of alcoholic solvent such as methyl alcohol, ethanol, propyl alcohol or acetone etc., filter or the centrifugal clear liquid that obtains, behind the distillating recovering solvent, rectification under vacuum obtains product 1, ammediol again.This method is because concentrated solution also has the water of a great deal of to exist, and used solvent all is hydrophilic, character in this alcohol (ketone) aqueous systems such as thalline and albumen does not have big change, centrifugal or filtration sterilization is still very difficult, the clear liquid color that obtains is darker, and the salt that exists in the fermented liquid do not removed fully, and the problem that salt crystallization that vacuum distillation process occurs and viscous substance hinder evaporation is not effectively solved.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, what a kind of simple, good separating effect was provided separates 1, the method for ammediol from fermented liquid.
Steps such as the inventive method comprises that mainly microbial cells separates, fermented liquid clarify, dewaters, desalination (comprising removal impurity), purifying products specifically comprise:
(1) with 1, the pH value of ammediol fermented liquid is transferred to 1.5～5.5, is preferably 2.0～4.0, is heated to 80～100 ℃, keeps 0.5～5.0h, leaves standstill cooling and natural subsidence;
(2) fermented liquid of separating step (1) gained is removed thalline and insoluble solid, obtains clear liquid;
(3) clear liquid that step (2) is obtained heats thickening, separates out crystalline salt simultaneously;
(4) concentrated solution of separating step (3) gained is removed the salt of separating out;
(5) step (4) is separating obtained concentrated solution collects 1, the ammediol cut by underpressure distillation.
The present invention is handled 1, and in the ammediol fermented liquid 1, the content of ammediol is 30～80g/L, and it is 6.0～8.0 that fermentation stops the pH value.
Usually the pH value that stops fermented liquid is 6.0～8.0, and thalline and albumen do not produce flocculation with this understanding, and salt can not separated out in crystallization yet, and the operation of degerming desalination is difficulty very.But this fermented liquid is under the condition of pH value≤5.5, and thalline and albumen can produce throwing out, improve filtration velocity greatly, and after fermented liquid removed water, salt wherein also can be separated out in crystallization.
The inventive method can be selected one or more mineral acids for use when regulating the pH value of fermented liquid, one or more in sulfuric acid, nitric acid, hydrochloric acid and the phosphoric acid in the preferred mineral acid, and the concentration of mineral acid is preferably 2～10N.The concentration of acid is unsuitable excessive when adding acid, otherwise can be when adding partial concn excessive, make some the sensitive materials generation oxidations in the fermented liquid, deepen the color of fermented liquid.
Heating described in the step (3) concentrates adopts distillating method to remove moisture usually, both can adopt the air distillation dehydration, also can adopt the underpressure distillation dehydration.For quicker, dehydration more up hill and dale, can adopt the dehydration of rough vacuum condition, system vacuum degree 500mmHg～80mmHg is preferably 400mmHg～200mmHg.
Step (2) and the separation method that to pass through filtration or centrifugation described in (4).
Underpressure distillation described in the step (5) can be adopted the method for high vacuum rectification, and its vacuum degree control is preferably in 15mmHg～8mmHg at 20mmHg～5mmHg, steams lighter component earlier, collects to be rich in 1, and the cut of ammediol is the finished product.
Can also add a certain amount of auxiliary agent in step (1), described auxiliary agent generally is powdered carbon or the atlapulgite with vesicular structure, has the effect that filter is adsorbed and helped in decolouring simultaneously.According to the characteristic of reason fermented liquid of living in, gac is preferably selected the macroporous type powdered carbon for use, and granularity is more than 100 orders, is preferably more than 120 orders, and add-on accounts for the 0.5wt%～5.0wt% of fermented liquid weight, is preferably 1.0wt%～3.0wt%.For atlapulgite, then select acid atlapulgite for use, granularity is more little, and effect is good more, and 1.0wt%～8.0wt% that add-on accounts for fermented liquid weight is advisable, and is preferably 1.5wt%～6.0wt%.
Flocculation process should guarantee that thalline and the albumen in the fermented liquid can flocculate to greatest extent heat-up time under the temperature that requires, guarantee that again decolorizing adsorbent reaches the good adsorption effect.
The present invention compared with prior art has the following advantages: microbial cells, proteic flocculation and decolouring are finished in same step in (1), the fermented liquid of the present invention, thalline and albumen are flocculated more effectively, and combine the advantage of heating demulsification type, strengthened flocculating effect, made the degerming process become more simple and effective; (2), the inventive method can make the salt crystallization that exists in the fermented liquid separate out, just can remove easily by filtration or centrifugation, thereby solved the salt crystallization of vacuum distillation process appearance and the problem that viscous substance hinders evaporation effectively, made the separation purification process be convenient to more implement.
Embodiment
The present invention is described in further detail below by embodiment.
Embodiment 1
The handled fermented liquid of present embodiment is to be substrate with glycerine, adopt the klebsiella fermentation and obtain 1, the ammediol fermented liquid, 1, the content of ammediol is 70.7 g/L, it is 7.0 that fermentation stops the pH value.
Get the above-mentioned fermented liquid of 500ml,, add the powdered carbon of 1.2wt%, be heated to 95 ℃ under stirring with the sulphur acid for adjusting pH value to 4.0 of 8N, constant temperature 0.8h, the standing sedimentation of lowering the temperature naturally, the complete sedimentation after-filtration of waiting to flocculate obtains water white fermentation clear liquid.The water in the clear liquid is removed in air distillation, wherein contained salt is crystalloid and separates out, remove by filter salt, obtain containing 1, the concentrated solution of ammediol, underpressure distillation under the vacuum tightness of 10mmHg then, collect 100～108 ℃ 1, the ammediol cut, the purity that obtains product is 99.1wt%, rate of recovery 82.2wt%.
Embodiment 2
Used 1 in the present embodiment, in the ammediol fermented liquid, 1, ammediol content is 51.2g/L, it is 7.0 that fermentation stops the pH value.
Get the above-mentioned fermented liquid of 500ml,, add the powdered carbon of 2.0wt%, be heated to 90 ℃ under stirring with the salt acid for adjusting pH value to 3.0 of 6N, constant temperature 1h, the standing sedimentation of lowering the temperature naturally, the complete sedimentation after-filtration of waiting to flocculate obtains water white fermentation clear liquid.The water in the clear liquid is removed in underpressure distillation, operation vacuum tightness is 200mmHg, 65～70 ℃ of service temperatures remove by filter the salt that crystallization goes out then, obtain containing 1, the concentrated solution of ammediol, underpressure distillation under the vacuum tightness of 10mmHg, collect 100～108 ℃ 1, the ammediol cut, the purity that obtains product is 99.3wt%, rate of recovery 84.5wt%.
Embodiment 3
Used 1 in the present embodiment, in the ammediol fermented liquid, 1, ammediol content is 63.3g/L, it is 7.4 that fermentation stops the pH value.
Get the above-mentioned fermented liquid of 500ml,, add the powdered activated carclazyte of 4.0wt%, be heated to 82 ℃ under stirring with the sulphur acid for adjusting pH value to 5.0 of 4N, constant temperature 3.5h, the standing sedimentation of lowering the temperature naturally, the complete sedimentation after-filtration of waiting to flocculate obtains fermentation clear liquid.Underpressure distillation dewaters, operation vacuum tightness is 100mmHg, 51～56 ℃ of service temperatures remove by filter the salt that crystallization goes out then, obtain containing 1, the concentrated solution of ammediol, underpressure distillation under the vacuum tightness of 6mmHg, collect 95～98 ℃ 1, the ammediol cut, the purity that obtains product is 99.0wt%, rate of recovery 81.5wt%.
Claims (10)
1, a kind of from fermented liquid separation and Extraction 1, the method for ammediol, its step comprises:
(1) with 1, the pH value of ammediol fermented liquid is transferred to 1.5～5.5, is heated to 80～100 ℃, and after keeping 0.5～5.0h, standing sedimentation;
(2) fermented liquid of separating step (1) gained is removed thalline and insoluble solid, gets 85 to clear liquid;
(3) clear liquid that step (2) is obtained heats thickening, separates out crystalline salt simultaneously;
(4) concentrated solution of separating step (3) gained is removed the salt of separating out;
(5) step (4) is separating obtained concentrated solution collects 1, the ammediol cut by underpressure distillation.
2, in accordance with the method for claim 1, it is characterized in that describedly 1, in the ammediol fermented liquid 1, the content of ammediol is 30～80g/L, and it is 6.0～8.0 that fermentation stops the pH value.
3, in accordance with the method for claim 1, it is characterized in that being used in the step (1) regulating the used acid of fermented liquid pH value and be one or more of sulfuric acid, nitric acid, hydrochloric acid and phosphoric acid, its concentration is 2～10N.
4,, it is characterized in that regulating in the step (1) pH value to 2.0～4.0 of fermented liquid according to claim 1 or 3 described methods.
5, in accordance with the method for claim 1, it is characterized in that the heating described in the step (3) concentrates the dehydration of employing rough vacuum condition, system vacuum degree 500mmHg～80mmHg.
6, in accordance with the method for claim 1, it is characterized in that step (2) and separating described in (4) are the methods by filtration or centrifugation.
7, in accordance with the method for claim 1, it is characterized in that the method for the underpressure distillation employing high vacuum rectification described in the step (5), its vacuum degree control is at 20mmHg～5mmHg.
8, in accordance with the method for claim 1, it is characterized in that in step (1), adding auxiliary agent; Described auxiliary agent is powdered carbon or the atlapulgite with vesicular structure.
9, in accordance with the method for claim 8, it is characterized in that the used gac of step (1) is the macroporous type powdered carbon, granularity is more than 100 orders, and add-on accounts for the 0.5wt%～5.0wt% of fermented liquid weight.
10, in accordance with the method for claim 8, it is characterized in that the used atlapulgite of step (1) is acid atlapulgite, add-on accounts for the 1.0wt%～8.0wt% of fermented liquid weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100474973A CN100413832C (en) | 2005-10-19 | 2005-10-19 | Method for separating 1,3-propanediol from fermentation liquor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100474973A CN100413832C (en) | 2005-10-19 | 2005-10-19 | Method for separating 1,3-propanediol from fermentation liquor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1951887A true CN1951887A (en) | 2007-04-25 |
| CN100413832C CN100413832C (en) | 2008-08-27 |
Family
ID=38058467
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100474973A Active CN100413832C (en) | 2005-10-19 | 2005-10-19 | Method for separating 1,3-propanediol from fermentation liquor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100413832C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101891591A (en) * | 2010-07-16 | 2010-11-24 | 张家港华美生物材料有限公司 | Method for separating and extracting 1,3-propylene glycol from fermentation liquor |
| CN102040475A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Method for purifying 1,3-propylene glycol |
| CN102040476A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Method for separating and purifying 1,3-propylene glycol from fermentation liquor |
| 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 |
| CN106117012A (en) * | 2016-06-22 | 2016-11-16 | 苏州苏震生物工程有限公司 | A kind of separation and recovery method of fermentation liquid electrodialysis desalination dense room liquid |
| CN108261794A (en) * | 2018-01-15 | 2018-07-10 | 山东祥瑞药业有限公司 | A kind of 1,3-PD zymotic fluid desalting system and method |
| CN115282630A (en) * | 2022-08-10 | 2022-11-04 | 安徽海蓝生物科技有限公司 | Concentration and crystallization process and concentration and crystallization equipment for solution in production process of L (+) -tartaric acid |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6361983B1 (en) * | 1999-09-30 | 2002-03-26 | E. I. Du Pont De Nemours And Company | Process for the isolation of 1,3-propanediol from fermentation broth |
| CN1304345C (en) * | 2004-10-13 | 2007-03-14 | 清华大学 | Method for separation and extraction of 1,3-propylene glycol and its byproducts from fermentation liquid |
-
2005
- 2005-10-19 CN CNB2005100474973A patent/CN100413832C/en active Active
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN102040475A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Method for purifying 1,3-propylene glycol |
| CN102040476A (en) * | 2009-10-21 | 2011-05-04 | 中国石油化工股份有限公司 | Method for separating and purifying 1,3-propylene glycol from fermentation liquor |
| CN102040475B (en) * | 2009-10-21 | 2013-07-24 | 中国石油化工股份有限公司 | Method for purifying 1,3-propylene glycol |
| CN102040476B (en) * | 2009-10-21 | 2014-01-08 | 中国石油化工股份有限公司 | Method for separating and purifying 1,3-propylene glycol from fermentation liquor |
| CN101891591A (en) * | 2010-07-16 | 2010-11-24 | 张家港华美生物材料有限公司 | Method for separating and extracting 1,3-propylene glycol from fermentation liquor |
| CN106117012A (en) * | 2016-06-22 | 2016-11-16 | 苏州苏震生物工程有限公司 | A kind of separation and recovery method of fermentation liquid electrodialysis desalination dense room liquid |
| CN106117012B (en) * | 2016-06-22 | 2018-07-31 | 苏州苏震生物工程有限公司 | A kind of separation and recovery method of the dense room liquid of zymotic fluid electrodialysis desalination |
| CN108261794A (en) * | 2018-01-15 | 2018-07-10 | 山东祥瑞药业有限公司 | A kind of 1,3-PD zymotic fluid desalting system and method |
| CN115282630A (en) * | 2022-08-10 | 2022-11-04 | 安徽海蓝生物科技有限公司 | Concentration and crystallization process and concentration and crystallization equipment for solution in production process of L (+) -tartaric acid |
| CN115282630B (en) * | 2022-08-10 | 2023-10-31 | 安徽海蓝生物科技有限公司 | Concentration crystallization process and concentration crystallization equipment for solution in L (+) -tartaric acid production process |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100413832C (en) | 2008-08-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100413832C (en) | Method for separating 1,3-propanediol from fermentation liquor | |
| CN102238990B (en) | Method for purifying an alcohol from a fermentation broth using a falling film, a wiped film, a thin film or a short path evaporator | |
| CN102040476B (en) | Method for separating and purifying 1,3-propylene glycol from fermentation liquor | |
| US8859808B2 (en) | Method for obtaining lactic acid with a high degree of purity from fermentative liquor | |
| CN100487129C (en) | Clean production process of tetracycline antibiotics | |
| CN102363594B (en) | Method for separating and purifying succinic acid from fermentation broth | |
| CN102676606A (en) | Process for clarifying and removing impurities from fermentation liquor of xylose mother liquid | |
| CN102659612A (en) | Process for purifying L-phenylalanine | |
| CN103948106A (en) | Purification technology and equipment of high-enriched roxburgh rose juice and application thereof | |
| CN105566136A (en) | Method for separating and extracting 4-hydroxyisoleucine from fermentation liquor | |
| CN102241707A (en) | Method for extracting L-arabinose and preparing xylitol | |
| WO2023010982A1 (en) | Preparation method for bio-based 1,3-propanediol | |
| CN101586129A (en) | Method of preparing sodium gluconate from xylose crystallization mother liquor | |
| US5851405A (en) | Process for clarifying vinasse | |
| CN101665448A (en) | Method for extracting coronatine from fermentation liquor by using membrane separation technique | |
| Hatti-Kaul | Downstream processing in industrial biotechnology | |
| CN102432643A (en) | Separation method of rhamnolipid by using ultrafiltration membrane | |
| CN101607889A (en) | A kind of chromatography separating method of citric acid | |
| CN100386297C (en) | Method for removing bacterial body and protein and pigment from 1,3-propanediol fermentation liquor | |
| CN105712841B (en) | A kind of method of the propane diols of the separation and Extraction from zymotic fluid 1,3 | |
| CN109456146A (en) | A method of the separation preparation high-purity 1,2,4- butantriol from Recombinant E. coli Fermentation Broth | |
| CN100509757C (en) | Purification method of *N-L-arginine | |
| CN101875598B (en) | Separation method of 1,3-propylene glycol fermentation liquid | |
| US20200299218A1 (en) | Process for the recovery of ketones and glycols from fermentation | |
| CN103193896B (en) | A kind of preparation method of Konjac Glucomannan and the thin-film evaporator adopted thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |