CN102634543A - Method for producing 1,3-propylene glycol by using microbial fermentation - Google Patents
Method for producing 1,3-propylene glycol by using microbial fermentation Download PDFInfo
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- CN102634543A CN102634543A CN2012101353124A CN201210135312A CN102634543A CN 102634543 A CN102634543 A CN 102634543A CN 2012101353124 A CN2012101353124 A CN 2012101353124A CN 201210135312 A CN201210135312 A CN 201210135312A CN 102634543 A CN102634543 A CN 102634543A
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Abstract
The invention provides a method for producing 1,3-propylene glycol by using microbial fermentation. The method takes glycerol as a raw material and uses microbial fermentation to produce 1,3-propylene glycol, wherein the used microbe strain is one of Klebsiella pneumoniae, Klebsiella acid-producing bacillus or clostridia butyricum, and liquid ammonia is used for adjusting the pH value of a fermentation liquid in the fermentation process. By using the method, the pH value in the fermentation process can be well controlled, and the by-product obtained by the reaction has wide application.
Description
Technical field
The present invention relates to microbial fermentation and produce 1, the method for ammediol belongs to the synthetic field of biochemical industry.
Background technology
The existing microbial fermentation that utilizes produces 1; The method of ammediol; Be be raw material with glycerine, utilize microbial fermentation to produce 1, ammediol, the bacterial classification of use have Cray Bai Shi pneumobacillus, Cray Bai Shi to produce in acidfast bacilli or the clostridium butyricum etc. any; It is 1 that these bacteriums all have under anaerobism or little oxygen consumption condition transformation of glycerol, the ability of ammediol.No matter be which kind of bacterial classification, the substratum of general fermentation mainly is a G & W, and is equipped with the inorganic salt of potassium hydrogenphosphate, potassium primary phosphate, ammonium sulfate or the like.
The existing strain fermentation such as Cray Bai Shi bacillus that utilizes produces 1, during ammediol, also can obtain 2, and 3-butyleneglycol and some organic acids are like Succinic Acid, lactic acid, acetic acid etc.Fermented preceding 3 ~ 5 hours, living weight increases but does not have the tunning generation.Along with the continuation of fermenting process, glycerine constantly is consumed, and product constantly accumulates.Along with the continuous accumulation of tunning, organic acids such as by product Succinic Acid, lactic acid, acetic acid also can constantly accumulate, and therefore, the pH value of fermented liquid can change, and fermenting process is produced inhibition.For fermenting process is carried out smoothly, therefore the pH value that needs the control fermented liquid, when the pH of fermented liquid value reduces, need constantly add the alkali neutralization in certain limit.Normally used alkali is sodium hydroxide.Sodium hydroxide is liquid, mixes with the liquid liquid that is mixed into of fermented liquid, and mixing time is long and inhomogeneous, has the possibility of local meta-acid or inclined to one side alkali in the short period of time.In addition, after fermentation reaction finishes, in the fermented liquid organic acid of by-product actual be that form with Soduxin, Sodium.alpha.-hydroxypropionate, sodium-acetate exists.
In the fermented liquid 1, ammediol can obtain purified product through extraction, in leaching process, can obtain 2,3-butyleneglycol and mixing organic salt.2, the 3-butyleneglycol directly can utilize, and can be used as commodity selling, or is used for preparing methylethylketone.And the purposes of organic acid sodium salt is few, as 1, and the sub product of ammediol fermentative prodn, these whereabouts of mixing organic salt are the problems that industrialization must solve.
Summary of the invention
Technical problem to be solved by this invention provides a kind of microbial fermentation and produces 1; The method of ammediol; Require to use in the fermenting process of this method, can control well in the fermenting process, and it is wide to react the purposes of the sub product that obtains because produce the reduction of the pH value that acid causes.
For solving the problems of the technologies described above, the invention provides a kind of microbial fermentation and produce 1, the method for ammediol, be raw material with glycerine, utilize microbial fermentation to produce 1, ammediol uses liquefied ammonia to regulate the pH value of fermented liquid during the fermentation.
For the purpose of the brief description problem, below microbial fermentation of the present invention is produced 1, the method for ammediol all abbreviates present method as.
Present method is to use liquefied ammonia to regulate the pH value of fermented liquid during the fermentation; Oneself gasification became ammonia when liquefied ammonia got in the fermentor tank, and ammonia is blended in the pressurized air, under the effect of stirring; Can promptly be distributed to the every nook and cranny of fermentor tank; With the fermented liquid thorough mixing, therefore more accurate sooner to the adjusting meeting of the pH value of fermented liquid, make the controlling well of pH value of fermentation reaction.
Use liquefied ammonia to regulate the pH value of fermented liquid, make that the sub product in the end product that ferments all exists with ammonium salts, like ammonium succinate, DL-Lactic acid ammonium salt, ammonium acetate etc.The ammonium salt of mixed organic acid is compared with sodium salt, and purposes is widely arranged.The ammonium salt of mixed organic acid can be used as the fodder additives of ruminating animals such as cattle and sheep.Mixing organic salt also can continue to purify and obtain organic acid.
Said organic acid is respectively Succinic Acid, lactic acid, acetic acid, and wherein Succinic Acid is the intermediate product of tricarboxylic acid cycle, and it can directly be utilized by organism and obtain energy.Lactic acid is a kind of acid that organism produces in the anaerobic metabolism process, and it is regarded as by FDA (Food and Drug Adminstration) (FDA) is the foodstuff additive that are perfectly safe, so be safe as feed.Acetic acid also be safe can absorbed a kind of organic acid.Ammonium can be used as the non-protein nitrogen(NPN) source.So the ammonium salt of mixed organic acid as the fodder additives of ruminating animal, is compared with ammonium sulfate, and better effectiveness is arranged.
In sum, use present method, the controlling well of the pH value in the fermenting process, the sub product that obtains of many uses can solve microbial fermentation production 1, the whereabouts problem of the mixing organic salt that ammediol obtains well.
The microbial strains of using in present method is that Cray Bai Shi pneumobacillus, Cray Bai Shi produce any in acidfast bacilli or the clostridium butyricum.
Present method comprises following concrete steps:
(1) fermention medium ferments in fermentor tank through sterilization back access bacterial classification, and the medium pH value is 6.5 ~ 8.5, and leavening temperature is 32 ~ 38 ℃;
(2) feed the pressurized air of 0.1 ~ 0.8VVM in the fermenting process, mixing speed 80 ~ 250rpm, and keep fermentor tank pressure 0.01 ~ 0.07MPa, and ferment and flow glycerol adding after 3 ~ 5 hours, flowing the speed that adds is 5 ~ 50g/L*h;
(3) in the fermenting process, when fermented liquid pH value reduces to 6.5, regulate the pH value of fermented liquid, make the pH value of fermented liquid maintain 6.5 ~ 7.0 through adding liquefied ammonia.
As the optimization of present method, said liquefied ammonia adds through the compressed-air actuated inlet pipe that is positioned at the fermentor tank bottom, on the pipeline of carrying liquefied ammonia, is provided with the SV of control liquefied ammonia flow.
Liquefied ammonia adds from the compressed air inlet pipe that is located at fermentor tank bottom, liquefied ammonia and pressurized air are mixed after adding equably, liquefied ammonia becomes behind the gaseous state along with pressurized air can mix rapidly with fermented liquid, thus the pH value of regulating fermented liquid faster and more accurately.
The amount that liquefied ammonia adds is not a steady state value.3 ~ 5 hours fermentation initial stages, acid was not produced in a large amount of breedings of bacterium, the no considerable change of pH value of fermented liquid.Control the SV of liquefied ammonia flow and do not open this moment.Begin to produce acid after about 3 ~ 5 hours, the pH value of fermented liquid descends, and when pH reduced to 6.5, the SV of control liquefied ammonia flow began to open and close, and opens and closes frequency and changes according to the pH value.
As the further optimization of present method, said fermentor walls is provided with the pH transmitter, and said pH transmitter is chain with the SV of control liquefied ammonia flow, the pH value of regulating fermented liquid through automatic control system.
The pH transmitter is chain with the SV of control liquefied ammonia flow; Through automatic control system (like DCS or PLC system); Can more accurately and timely regulate the pH value of fermented liquid: when the pH of fermented liquid value diminished, SV opened and closed frequent, strengthened the inlet amount of liquefied ammonia; When the pH of fermented liquid value approached neutrality, SV opened and closed frequency and diminishes, and does not even open, and keeps pH value constant purpose thereby reach.
Embodiment
Further specify the present invention through specific embodiment below.
Embodiment 1
Microbial fermentation produces 1, the method for ammediol, be raw material with glycerine, utilize Cray Bai Shi pneumobacillus fermentative prodn 1, ammediol uses liquefied ammonia to regulate the pH value of fermented liquid during the fermentation.Specifically may further comprise the steps:
(1) fermention medium ferments in fermentor tank through sterilization back access bacterial classification, and the medium pH value is 6.5, and leavening temperature is 32 ℃;
(2) pressurized air of feeding 0.1VVM in the fermenting process, fermentor tank mixing speed 80rpm, and keep fermentor tank pressure 0.01MPa, and to ferment and flow glycerol adding after 3 hours, the speed of stream glycerol adding is 5g/L*h;
(3) in the fermenting process, when fermented liquid pH value reduces to 6.5, regulate the pH value of fermented liquid, the pH value of fermented liquid is maintained between 6.5 ~ 7.0 through adding liquefied ammonia.
Liquefied ammonia adds through the compressed-air actuated inlet pipe that is positioned at the fermentor tank bottom, on the pipeline of carrying liquefied ammonia, is provided with the SV of control liquefied ammonia flow.
On fermentor walls, be provided with the pH transmitter, said pH transmitter is chain with the SV of control liquefied ammonia flow, the pH value of regulating fermented liquid through the DCS automatic control system.
Embodiment 2
Microbial fermentation produces 1, the method for ammediol, be raw material with glycerine, utilize Cray Bai Shi to produce acidfast bacilli fermentative prodn 1, ammediol uses liquefied ammonia to regulate the pH value of fermented liquid during the fermentation.Specifically may further comprise the steps:
(1) fermention medium ferments in fermentor tank through sterilization back access bacterial classification, and the medium pH value is 8.5, and leavening temperature is 38 ℃;
(2) pressurized air of feeding 0.8VVM in the fermenting process, fermentor tank mixing speed 250rpm, and keep fermentor tank pressure 0.07MPa, and to ferment and flow glycerol adding after 5 hours, the speed of stream glycerol adding is 50g/L*h;
(3) in the fermenting process, when fermented liquid pH value reduces to 6.5, regulate the pH value of fermented liquid, the pH value of fermented liquid is maintained between 6.5 ~ 7.0 through adding liquefied ammonia.
Liquefied ammonia adds through the compressed-air actuated inlet pipe that is positioned at the fermentor tank bottom, on the pipeline of carrying liquefied ammonia, is provided with the SV of control liquefied ammonia flow.
On fermentor walls, be provided with the pH transmitter, said pH transmitter is chain with the SV of control liquefied ammonia flow, the pH value of regulating fermented liquid through the PLC automatic control system.
Embodiment 3
Microbial fermentation produces 1, the method for ammediol, be raw material with glycerine, utilize Cray Bai Shi pneumobacillus fermentative prodn 1, ammediol uses liquefied ammonia to regulate the pH value of fermented liquid during the fermentation.Specifically may further comprise the steps:
(1) fermention medium ferments in fermentor tank through sterilization back access bacterial classification, and the medium pH value is 7.0, and leavening temperature is 35 ℃;
(2) pressurized air of feeding 0.5VVM in the fermenting process, fermentor tank mixing speed 160rpm, and keep fermentor tank pressure 0.04MPa, and to ferment and flow glycerol adding after 4 hours, the speed of stream glycerol adding is 30g/L*h;
(3) in the fermenting process, when fermented liquid pH value reduces to 6.5, regulate the pH value of fermented liquid, the pH value of fermented liquid is maintained between 6.5 ~ 7.0 through adding liquefied ammonia.
Liquefied ammonia adds through the compressed-air actuated inlet pipe that is positioned at the fermentor tank bottom, on the pipeline of carrying liquefied ammonia, is provided with the SV of control liquefied ammonia flow.
On fermentor walls, be provided with the pH transmitter, said pH transmitter is chain with the SV of control liquefied ammonia flow, the pH value of regulating fermented liquid through the PLC automatic control system.
In the present embodiment, also can replace Cray Bai Shi pneumobacillus to come fermentative prodn 1, ammediol with clostridium butyricum.
Claims (5)
1. a microbial fermentation produces 1, the method for ammediol, be raw material with glycerine, utilize microbial fermentation to produce 1, ammediol is characterized in that: use liquefied ammonia to regulate the pH value of fermented liquid during the fermentation.
2. microbial fermentation according to claim 1 produces 1, and the method for ammediol is characterized in that: the microbial strains of use is that Cray Bai Shi pneumobacillus, Cray Bai Shi produce any in acidfast bacilli or the clostridium butyricum.
3. microbial fermentation according to claim 1 and 2 produces 1, and the method for ammediol comprises following concrete steps:
(1) fermention medium ferments in fermentor tank through sterilization back access bacterial classification, and the medium pH value is 6.5 ~ 8.5, and leavening temperature is 32 ~ 38 ℃;
(2) feed the pressurized air of 0.1 ~ 0.8VVM in the fermenting process, mixing speed 80 ~ 250rpm, and keep fermentor tank pressure 0.01 ~ 0.07MPa, and ferment and flow glycerol adding after 3 ~ 5 hours, flowing the speed that adds is 5 ~ 50g/L*h;
(3) in the fermenting process, when fermented liquid pH value reduces to 6.5, regulate the pH value of fermented liquid, make the pH value of fermented liquid maintain 6.5 ~ 7.0 through adding liquefied ammonia.
4. microbial fermentation according to claim 3 produces 1, and the method for ammediol is characterized in that: said liquefied ammonia adds through the compressed-air actuated inlet pipe that is positioned at the fermentor tank bottom, on the pipeline of carrying liquefied ammonia, is provided with the SV of control liquefied ammonia flow.
5. microbial fermentation according to claim 4 produces 1; The method of ammediol; It is characterized in that: said fermentor walls is provided with the pH transmitter, and said pH transmitter is chain with the SV of control liquefied ammonia flow, the pH value of regulating fermented liquid through automatic control system.
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| CN2012101353124A CN102634543A (en) | 2012-05-04 | 2012-05-04 | Method for producing 1,3-propylene glycol by using microbial fermentation |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108118072A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of method for promoting microorganism conversion production 1,3-PD |
| CN111116258A (en) * | 2019-11-28 | 2020-05-08 | 张家港美景荣化学工业有限公司 | Organic potassium composition containing polyhydric alcohol and preparation method thereof |
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| CN85104377A (en) * | 1984-11-19 | 1986-12-10 | 帝国化学工业公司 | The production method of single cell protein and sucrose |
| CN1239511A (en) * | 1996-11-13 | 1999-12-22 | 金克克国际有限公司 | Method for prodn. of 1,3-propanediol by recombinant organisms |
| CN101553572A (en) * | 2006-02-24 | 2009-10-07 | 东丽株式会社 | Method of producing chemical product and continuous fermentation apparatus |
| CN101603057A (en) * | 2009-07-20 | 2009-12-16 | 北京理工大学 | A kind of biological process synthesizes 1, the method for ammediol |
| CN102181502A (en) * | 2011-05-17 | 2011-09-14 | 内蒙古阜丰生物科技有限公司 | Method for improving yield of L-threonine produced by fermentation |
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2012
- 2012-05-04 CN CN2012101353124A patent/CN102634543A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85104377A (en) * | 1984-11-19 | 1986-12-10 | 帝国化学工业公司 | The production method of single cell protein and sucrose |
| CN1239511A (en) * | 1996-11-13 | 1999-12-22 | 金克克国际有限公司 | Method for prodn. of 1,3-propanediol by recombinant organisms |
| CN101553572A (en) * | 2006-02-24 | 2009-10-07 | 东丽株式会社 | Method of producing chemical product and continuous fermentation apparatus |
| CN101603057A (en) * | 2009-07-20 | 2009-12-16 | 北京理工大学 | A kind of biological process synthesizes 1, the method for ammediol |
| CN102181502A (en) * | 2011-05-17 | 2011-09-14 | 内蒙古阜丰生物科技有限公司 | Method for improving yield of L-threonine produced by fermentation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108118072A (en) * | 2016-11-29 | 2018-06-05 | 中国石油化工股份有限公司 | A kind of method for promoting microorganism conversion production 1,3-PD |
| CN111116258A (en) * | 2019-11-28 | 2020-05-08 | 张家港美景荣化学工业有限公司 | Organic potassium composition containing polyhydric alcohol and preparation method thereof |
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Application publication date: 20120815 |