CN1165623C - Two-step microbial fermentation process of producing propylene glycol - Google Patents
Two-step microbial fermentation process of producing propylene glycol Download PDFInfo
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- CN1165623C CN1165623C CNB011387696A CN01138769A CN1165623C CN 1165623 C CN1165623 C CN 1165623C CN B011387696 A CNB011387696 A CN B011387696A CN 01138769 A CN01138769 A CN 01138769A CN 1165623 C CN1165623 C CN 1165623C
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Abstract
The present invention relates to a technology for producing 1, 3-propanediol by two-step microorganism fermentation method, which belongs to the technical field of biological engineering. The present invention is characterized in that first, an aerobic microbe strain is used for fermenting carbohydrate such as glucose, starch saccharification liquid, cellulose enzymolysis liquid, etc. for generating glycerin; then, another anaerobic microorganism strain is used for converting the glycerin into the 1, 3-propanediol, wherein thalli in fermentation liquid obtained in the first fermentation step can be removed through centrifugation or filtration, clear liquid can directly enter the second fermentation step or can be used as batch flowing adding liquid for the second fermentation step after being concentrated, and parts of thalli can be cycled during the continuous fermentation; the fermentation liquid of the first fermentation step can also not be centrifugated, and after being sterilized, the fermentation liquid can be used in the second fermentation step. The present invention has the advantages that raw materials at a low price are utilized; the characteristics of each fermentation step is fully exerted; the glycerin separation expense is saved; the production cost is lowered, the whole fermentation time is shortened, the production efficiency is improved, and the present invention provides an economic and practicable fermentation process for the industrialization of the 1, 3-propanediol production by the microorganism fermentation method.
Description
Technical field
The invention belongs to technical field of bioengineering, specially refer to two-step microbial fermentation and produce 1, the method for ammediol.
Background technology
As everyone knows, 1, ammediol is a kind of important chemical material, can be used as organic solvent and is applied to industries such as printing ink, printing and dyeing, coating, lubricant, antifreezing agent, goes back the useful as drug synthetic intermediate.1, the topmost purposes of ammediol will be the macromolecular material as the synthetic excellent performance of polymer monomer.1, ammediol can substitute ethylene glycol, 1, the 2-propylene glycol, and 1, intermediates such as 4-butyleneglycol and neopentyl glycol are used to produce how pure polyester and extend agent as carbochain.With 1, ammediol and terephthalic acid synthetic polyester PTT (polytrimethylene terephthalate) are that monomer synthetic polymer P ET (polyethylene terephthalate), PBT (polybutylene terephthalate) have better performance than with ethylene glycol, butyleneglycol, good continuous printing and dyeing that present as need not to add any speciality chemical in the tint permanence of recovery of elasticity, uvioresistant, ozone and the oxynitride of nylon sample, low static, low water absorption, the panchromatic scope and biodegradable etc.PTT is considered to the new polyester material of the workability of the high-performance of a kind of PET of having concurrently and PBT, have broad application prospects, but expensive at present price has hindered its widespread use.
Present 1, the production method of ammediol mainly is a chemical synthesis, is raw material with ethene as Shell Co. Ltd, under high temperature (280 ℃), become oxyethane as catalyst oxidation with silver, hydrogenation and carbon monoxide change into the 3-hydroxy propanal then, are hydrogenated to product 1 at last, ammediol; Degussa company then is raw material with the propylene, is propenal with molybdenum as catalyst oxidation under 350 ℃, 0.2Mpa, and rehydration is the 3-hydroxy propanal, is hydrogenated to 1 then, ammediol (USP5008473).These two kinds of methods all need be carried out under high temperature and valuable catalyst action, and product removes 1, and ammediol also has 1 outward, 2-propylene glycol and the close by product of character such as dimer, tripolymer thereof, and it is difficult to cause product separation to be purified, and production cost is corresponding higher.
The microbial method glycerine converting is 1, and the research of ammediol starts from 1881, but just causes people's attention gradually up to the eighties in 20th century.Compare with chemical synthesis, it has mild condition, easy and simple to handle, characteristics such as by product is few, non-environmental-pollution.Present 1, the microorganisms producing method of ammediol is broadly divided into three classes: the one, and be 1 with intestinal bacteria with the glycerine disproportionation, (USP 5254467 for ammediol; EP 0373230 A1); The 2nd, be that substrate produces 1 with genetic engineering bacterium with glucose, (PCT/US 96/06705 for ammediol; USP 5599689; USP6025184; WO 96/35796; WO 9821340; WO 9821339; ZL 96195288); The 3rd, with production glycerine and production 1, two strain bacterium mixed culture (USP 5599689) of ammediol.These methods respectively have relative merits, and the transformation efficiency of first method and production concentration are all higher, but glycerine is on the high side, influence 1, the cost of ammediol; Second method can reduce raw materials cost, but the throughput of genetic engineering bacterium and stability thereof are also not ideal; The third method helps to reduce the time of two-step fermentation, but because the growth conditions of two kinds of bacterium is not quite similar, as produce glycerol stock (as yeast saccharomyces cerevisiae (Saccharomyces cerevisiae), zygosaccharomyces (Zygosaccharomyces), pichia spp (Pichia), candiyeast (Candida), debaryomyces hansenii (Hansenula), Dbaly yeast (Debaryomyces sp.), kluyveromyces (Kluyveromyces), aspergillus (Aspergillus), genus bacillus (Bacillus), Mucor (Mucor) etc.) under aerobic condition, grow usually, and produce 1, the ammediol bacterium is (as klebsiella (Klebsiella), lemon bacterium (Citrobacter) and clostridium (Clostridia) etc.) growth under anaerobic usually, therefore be difficult to obtain comparatively ideal effect.
Summary of the invention
The objective of the invention is to utilize cheap starch, Mierocrystalline cellulose to make raw material, after enzymolysis obtains glucose solution, produce 1 by two-step fermentation again, ammediol, i.e. the first step employing aerobic fermentation is a glycerine with conversion of glucose, it is 1 with transformation of glycerol that second step was adopted anaerobically fermenting, ammediol, be Production by Microorganism Fermentation 1, ammediol provides a kind of practicable technology, and fermentation period is long, transformation efficiency is low and a production cost high-technology difficult problem to solve.
Technical scheme
The invention provides a kind of two-step microbial fermentation and produce 1, the method of ammediol, at first use a kind of aerobic microbiological cell that carbohydrate such as glucose, starch saccharificating liquid, cellulase hydrolysis liquid are converted into glycerine, the glycerine that to go up in the step fermented liquid by another kind of anaerobion cell further is converted into 1, ammediol again.The resulting fermented liquid of the first step glycerol fermentation is removed or the recycle thalline with centrifugal or filtering method, batch formula stream liquid feeding that centrifuged supernatant or filtering filtrate directly enter the fermentation of second step or ferments as second step after evaporation concentration; The first step fermented liquid also can not centrifugally carry out the fermentation of second step again after sterilization, and does not need to add yeast powder, yeast extract or vitamin B12.
The step that realizes the inventive method is as follows:
1) preparation of saccharification liquid: in starch and 1: 2.5 ratio of water preparation starch fluid, add an amount of high temperature resistant liquefaction enzyme (α-Dian Fenmei) (4～6u/g starch),, be cooled to 60 ℃ then, transfer pH4.0～4.5 in 90～100 ℃ of stirring liquefaction 60min; The amount of pressing 200u/g starch adds saccharifying enzyme (beta-amylase), and saccharification was filtered after 24 hours under 60 ℃ of constant temperature, got saccharification liquid.
2) preparation of cellulase hydrolysis liquid: adopt the tangerine bar of farm crop such as corn, wheat, straw after air-dry, to be cut into the 2cm segment, (soak with chemical Treatment as 3% liming, 1%NaOH solution delignification etc.), again in conjunction with (121 ℃ of pyroprocessing, 1 hour), tangerine bar drying and crushing after the processing is crossed the 1mm sieve aperture.At pH4.8, in the 0.05mol/l citrate buffer solution, add above-mentioned crushed material (5%) and cellulase (50～100IU/100ml), stir down in 45 ℃ and 100rpm, carry out enzyme digestion reaction and can make cellulase hydrolysis liquid in 50～70 hours.
3) preparation of substratum: must possess the required nutritive ingredient of microorganism growth in the substratum, as carbon sources such as glucose or glycerine, nitrogenous source and phosphoric acid salt (phosphorus source) and vitriol (sulphur source) etc. such as urea, ammonium salt, yeast extract or yeast powder.Also need positively charged ion and trace elements such as zinc, iron, manganese, copper, cobalt, boron and molybdenum such as sodium, potassium, magnesium, calcium in addition, every kind of content of elements is greatly in the scope of 0.01mg/L～50mg/L.Substratum must be sterilized down at 121 ℃ and can be used in 15～20 minutes.
4) seed culture: carry out in shaking bottle, shaking speed is 100～300 rev/mins, and temperature is 27～40 ℃, and incubation time is 9～30 hours.
5) fermentation culture: can carry out in fermentor tank, the fermentor tank inoculum size is 5%～20%, and rotating speed of agitator is 100～400 rev/mins, and temperature is 27～40 ℃.Can lead to nitrogen or air in the fermenting process in fermentor tank, air flow is 0.2～4vvm.Fermentation mode can be that batch fermentation, batch formula stream add fermentation or continuously ferments, the time that intermittence or batch formula stream add fermentation is 10～200 hours, advanced person's fermentation of in the ranks having a rest when continuously fermenting, when treating in the fermented liquid that thalline reaches certain density (is 2～5 as optical density(OD) under the 650nm), stream adds fermention medium and carries out the perseverance cultivation again, and dilution rate is 0.01～0.5h
-1The first step glycerol fermentation glucose concn can be in 10%～50% scope, and pH is controlled in 3.5～5.5 scopes, and the rate of consumption of glucose can reach 80%～95%, and the concentration of product glycerine can reach 5%～30%; In second step 1, ammediol ferment glycerin starting point concentration is 2%～15%, and pH is 6～8, product 1, and the concentration of ammediol can reach 10～85g/L.When continuously fermenting, the first step glycerol fermentation and second step 1, the thalline concentrated solution after the fermented liquid of ammediol fermentation separates with centrifugal or filter method can be in 10%～90% ratio recycle; The centrifuged supernatant of the first step fermented liquid or filtering filtrate can directly enter the fermentation of second step; The first step fermented liquid also can not centrifugally carry out the fermentation of second step again after sterilization, and does not need to add yeast powder, yeast extract or vitamin B12.Starch saccharificating liquid or cellulase hydrolysis liquid and the first step fermented liquid can go on foot batch formula stream liquid feeding (containing glucose or glycerol concentration is 40%～90%) of fermentation respectively as the first step and second after evaporation concentration.
Advantage of the inventive method and beneficial effect have been to give full play to the characteristics of each step fermentation, aerobic bacteria and anerobe can both be grown under optimum separately condition, thereby improve glycerine and 1, the productive rate of ammediol, and saved the isolating expense of glycerine, reduced production cost, shortened whole fermentation time, improved production efficiency, be Production by Microorganism Fermentation 1, the industrialization of ammediol is laid a good foundation.It is the production of raw material that this technology both had been suitable for glucose, and being suitable for starch or Mierocrystalline cellulose again is the production of raw material; Can in a bio-reactor, operate, also can operate with two reactors in series; Also can be applicable to glycerine and 1 in addition, the coproduction of ammediol.
Embodiment
Below be described in detail most preferred embodiment of the present invention:
1) bacterial classification: the first step used bacterial classification that ferments is candida krusei (Candida krusei) in the embodiment of the invention, is a kind of aerobic osmophilic yeast; The bacterial classification of second step fermentation is Cray Bai Shi bacillus (Klebsiella pneumoniae), is a kind of anerobe.They are all available from Chinese common micro-organisms DSMZ (CGMCC), and culture presevation number is respectively AS2.1708 and AS1.1736.
2) substratum: divide two kinds of seed culture medium and fermention mediums, division is as follows:
2.1 candida krusei
A. seed culture medium:
Glucose: 10%, corn steep liquor: 3 ‰, urea: 3 ‰, pH4.0～4.5
B. fermention medium:
Glucose: 25%, corn steep liquor: 2.5 ‰, urea: 2.5 ‰, pH4.0～4.5
2.2 Cray Bai Shi bacillus:
A. seed culture medium: (1000ml):
Glycerine: 20g K
2HPO
43H
2O:4.56g
KH
2PO
4：1.3g (NH
4)
2SO
4：2.0g
MgSO
47H
2O:2g yeast powder: 1g
CaCO
3: 2g trace element TE1:2ml
0.5%FeSO
4Solution: 1ml 2%CaCl
2Solution: 1ml
Trace element TE1 forms (1000ml):
Saturated hydrochloric acid: 0.9ml ZnCl
2: 70mg
MnCl
2·4H
2O：100mg H
3BO
3：60mg
CoCl
2·6H
2O：200mg NiCl
2·6H
2O：25mg
NaMoO
4·2H
2O：35mg CuCl
2·2H
2O：20mg
B. fermention medium is formed (1000ml):
(NH
4)SO
4：6.61g KH
2PO
4：1.36g
MgCl
26H
2O:0.26 citric acid: 0.42g
Yeast powder: 1g trace element TE2:5ml
Trace element TE2 forms (1000ml):
Saturated hydrochloric acid: 10ml ZnCl
26H
2O:0.68g
FeCl
3·6H
2O：5.4g MnCl
2·4H
2O：0.17g
CoCl
2·6H
2O：0.47g H
3BO
3：0.06g
NaMoO
4·2H
2O：0.005g CuCl
2·2H
2O：0.47g
It is 7.0 that seed and fermention medium all need to regulate pH before sterilization.
3) fermenting process: divide two kinds of seed culture and fermentation culture, wherein seed culture is carried out in the triangular flask of a 500mL, and liquid amount is 200mL, and shaking speed is 200 commentaries on classics/min; Fermentation culture can be carried out in automatic fermenter, and working volume is 5L, and actual liquid amount is 3L, and inoculum size is 10%, and rotating speed is controlled to be 300 commentaries on classics/min, and the air flow 0.4vvm of air or nitrogen regulates pH with 2mol/L sodium hydroxide.
A. the first step fermentation: the seed culture temperature is 35 ℃, and incubation time is 24hr; When batch fermentation is cultivated in pure glucose or the W-Gum saccharification liquid concentration of glucose be 25%, pH and temperature are controlled to be 4.0 and 35 ℃ respectively, in the fermenting process in fermentor tank blowing air stop fermentation when remaining sugar concentration is 1% left and right sides to keep aerobic condition.
B. second step fermentation: the seed culture temperature is 37 ℃, and incubation time is 12hr; Batch fermentation is cultivated preceding with the centrifugal thalline of removing of the first step fermented liquid, in clear liquid, add the cultivation composition, regulating the pH value is 7.0, sterilization cooling back inoculation, the glycerine starting point concentration is adjusted to 7%, pH and temperature are respectively 7.0 and 37 ℃, and logical nitrogen is to keep anaerobic condition in fermentor tank in the fermenting process, and fermentation proceeds to till the glycerine consumption fully.
Resulting result is as follows for most preferred embodiment of the present invention:
Pure glucose solution with 25% is that raw material carries out two-step fermentation, and when the first step fermentation proceeded to 70 hours, remaining glucose concn was 0.76g/L, contains 69.3g/L glycerine and 1.26g/L ethanol in the fermented liquid, and the molar yield of glycerine is 54.2%; The second step fermentation has been carried out 15 hours, and in the fermented liquid 1, the concentration of ammediol is 24.39g/L, the concentration of ethanol and acetate respectively 8.56 and 3.74g/L, 1, and the ammediol molar yield is 42.2%.
With the W-Gum saccharification liquid that contains 25% glucose is that raw material carries out two-step fermentation, and the first step fermentation has been carried out 54 hours, and remaining glucose concn is 11.6g/L, contains 49.9g/L glycerine and 7.35g/L ethanol in the fermented liquid, and the molar yield of glycerine is 39.1%; The second step fermentation has been carried out 31 hours, and in the fermented liquid 1, the concentration of ammediol is 13.18g/L, the concentration of ethanol and acetate respectively 10.95 and 4.14g/L, 1, and the ammediol molar yield is 22.8%.
Claims (1)
1. one kind is utilized the grape sugar and starch, enzymolysis solutions such as Mierocrystalline cellulose produce 1 through two-step microbial fermentation, the method of ammediol, in temperature, under pH and the mixing speed constant condition, carry out intermittence, batch formula stream adds or continuously ferments, at first use yeast saccharomyces cerevisiae (Saccharomyces cerevisiae), zygosaccharomyces (Zygosaccharomyces), pichia spp (Pichia), candiyeast (Candida), debaryomyces hansenii (Hansenula), Dbaly yeast (Debaryomyces sp.), kluyveromyces (Kluyveromyces), aspergillus (Aspergilius), genus bacillus (Bacillus), (aerobic bacteria such as Mucor is a glycerine with conversion of glucose to Mucor, then use Cray Bai Shi bacillus (Klebsiella), lemon bacterium (Citrobacter) and clostridium anerobes such as (Clostridia) further are converted into 1 with glycerine, ammediol, the inoculum size of bacterial classification is 5%～20% in the fermenting process, the fermentor tank rotating speed of agitator is 100～400 rev/mins, temperature is 27～40 ℃, the air flow of nitrogen or air is 0.2～4vvm, pH is controlled between 3.5～5.5 in the first step glycerol fermentation, the rate of consumption of glucose reaches 80%～95%, and the concentration of product glycerine reaches 5%～30%; In second step 1, the glycerine starting point concentration is 2%～15% in the ammediol fermentation, and pH is 6.0～8.0, product 1, and the concentration of ammediol reaches 10～85g/L;
This inventive method is characterised in that:
A) the resulting fermented liquid of the first step glycerol fermentation needn't be removed thalline, and mend direct heating sterilization back
Added for second step 1, the ammediol needed trace element that ferments, the fermentation of second step is carried out in inoculation,
And do not need to add yeast powder, yeast extract or vitamin B12; Or the first step glycerol fermentation
Liquid is removed thalline with centrifugal or filtering method, and adding second step fermentation is required in clear liquid
Nutritive ingredient and bacterial classification proceed the second step fermentation;
B) criticize formula stream and add when fermentation, the used stream liquid feeding of the first step glycerol fermentation be dense glucose solution or
The spissated starch saccharificating liquid of person, cellulase hydrolysis liquid, wherein the concentration of glucose is
In 40%～90%, second step 1, the stream liquid feeding of ammediol fermentation is to send out through the glycerine of evaporation concentration
Ferment liquid, wherein the concentration of glycerine is 40%～90%;
When c) continuously fermenting, the first step glycerol fermentation and second step 1, the fermented liquid of ammediol fermentation is used
Thalline concentrated solution after centrifugal or filter method separates is with 10%～90% ratio recycle;
D) the used raw material of two-step fermentation is carbon water such as glucose, starch saccharificating liquid, cellulase hydrolysis liquid
Compound, wherein glucose content is between 10%～50%.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB011387696A CN1165623C (en) | 2001-12-05 | 2001-12-05 | Two-step microbial fermentation process of producing propylene glycol |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011387696A CN1165623C (en) | 2001-12-05 | 2001-12-05 | Two-step microbial fermentation process of producing propylene glycol |
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| CN1357628A CN1357628A (en) | 2002-07-10 |
| CN1165623C true CN1165623C (en) | 2004-09-08 |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1327001C (en) * | 2005-06-03 | 2007-07-18 | 清华大学 | Method for producing 1,3-propylene glycol through using glycerin of by-product from biologic diesel oil |
| CN1329518C (en) * | 2005-04-07 | 2007-08-01 | 东南大学 | Method for producing 1,3-propylene glycol through ferment in high cell density by using bacteria in intestinal tract |
| CN100427605C (en) * | 2005-06-17 | 2008-10-22 | 清华大学 | Mehtod for producing 1,3-propanediol and 2,3-cis-butanediol from crude starch material |
| CN101343643B (en) * | 2008-09-05 | 2010-12-15 | 清华大学 | High production method for glycerol with multi-step zymotechnics |
| CN102154385A (en) * | 2011-02-23 | 2011-08-17 | 安徽立兴化工有限公司 | Method for preparing 1,3-propylene glycol by controlling pH value with polyethylene polyamine and fermenting |
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| CN1807610B (en) * | 2006-01-23 | 2011-01-26 | 迟乃玉 | Method for producing low temperature cellulase using microbe fermentation |
| CN100463968C (en) * | 2006-01-27 | 2009-02-25 | 华侨大学 | Process for preparing 1,3-propylene glycol and dihydroxy acetone by bio-catalytic conversion of glycerol |
| US8129157B2 (en) * | 2006-03-31 | 2012-03-06 | William Marsh Rice University | Anaerobic fermentation of glycerol |
| CN100355899C (en) * | 2006-04-14 | 2007-12-19 | 清华大学 | Pretreatment method for filtering fermentation liquor of bacteria of possessing capsula |
| AR072446A1 (en) | 2008-03-02 | 2010-09-01 | Dow Global Technologies Inc | IMPROVED HYDROGENATION PROCESS |
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| CA2922120C (en) * | 2013-09-03 | 2022-09-06 | Myriant Corporation | A process for manufacturing acrylic acid, acrylonitrile and 1,4-butanediol from 1,3-propanediol |
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| CN108070622A (en) * | 2016-11-11 | 2018-05-25 | 湖南尔康制药股份有限公司 | A kind of method that biological fermentation process prepares 1,3- propylene glycol |
| CN112111534B (en) * | 2020-09-09 | 2022-08-16 | 大连理工大学 | Method for preparing 1, 3-propanediol coupled phage through microbial fermentation production |
| CN114806961A (en) * | 2022-05-18 | 2022-07-29 | 苏州苏震生物工程有限公司 | Fermentation medium and method for producing bio-based 1, 3-propylene glycol |
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2001
- 2001-12-05 CN CNB011387696A patent/CN1165623C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1329518C (en) * | 2005-04-07 | 2007-08-01 | 东南大学 | Method for producing 1,3-propylene glycol through ferment in high cell density by using bacteria in intestinal tract |
| CN1327001C (en) * | 2005-06-03 | 2007-07-18 | 清华大学 | Method for producing 1,3-propylene glycol through using glycerin of by-product from biologic diesel oil |
| CN100427605C (en) * | 2005-06-17 | 2008-10-22 | 清华大学 | Mehtod for producing 1,3-propanediol and 2,3-cis-butanediol from crude starch material |
| CN101343643B (en) * | 2008-09-05 | 2010-12-15 | 清华大学 | High production method for glycerol with multi-step zymotechnics |
| CN102154385A (en) * | 2011-02-23 | 2011-08-17 | 安徽立兴化工有限公司 | Method for preparing 1,3-propylene glycol by controlling pH value with polyethylene polyamine and fermenting |
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