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CN1357628A - Two-step microbial fermentation process of producing propylene glycol - Google Patents

Two-step microbial fermentation process of producing propylene glycol Download PDF

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Publication number
CN1357628A
CN1357628A CN 01138769 CN01138769A CN1357628A CN 1357628 A CN1357628 A CN 1357628A CN 01138769 CN01138769 CN 01138769 CN 01138769 A CN01138769 A CN 01138769A CN 1357628 A CN1357628 A CN 1357628A
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fermentation
liquid
glucose
propanediol
glycerol
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CN1165623C (en
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修志龙
刘海军
张代佳
徐友海
贾凌云
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Research Inst Of Jilin Petro-Chemical Branch China National Petroleum Co Ltd
Dalian University of Technology
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Research Inst Of Jilin Petro-Chemical Branch China National Petroleum Co Ltd
Dalian University of Technology
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Abstract

本发明属于生物工程技术领域,特别涉及到一种两步微生物发酵法生产1,3－丙二醇的技术。本发明的特征在于首先使用一种好氧微生物菌种发酵如葡萄糖、淀粉糖化液、纤维素酶解液等碳水化合物产生甘油,进而再通过另一种厌氧微生物菌种将甘油转化为1,3－丙二醇,其中第一步发酵所得到的发酵液可离心或过滤除去菌体,清液可直接进入第二步发酵或者经浓缩后作为第二步发酵的批式流加液,部分菌体可在连续发酵时循环使用;第一步发酵液也可不离心经灭菌后再进行第二步发酵。本发明的优点是利用廉价原料,充分发挥了每一步发酵的特点,节省了甘油分离的费用,降低了生产成本,缩短了整个发酵时间,提高了生产效率,为微生物发酵法生产1,3－丙二醇的工业化提供了经济可行的发酵工艺。The invention belongs to the technical field of bioengineering, and in particular relates to a technology for producing 1,3-propanediol through a two-step microbial fermentation method. The present invention is characterized in that first, an aerobic microbial strain is used to ferment carbohydrates such as glucose, starch saccharification liquid, and cellulose enzymatic hydrolysis liquid to produce glycerol, and then another anaerobic microbial strain is used to convert glycerol into 1, 3-Propanediol, wherein the fermentation liquid obtained from the first step of fermentation can be centrifuged or filtered to remove bacteria, and the clear liquid can directly enter the second step of fermentation or be concentrated as a batch feeding liquid for the second step of fermentation, part of the bacteria It can be recycled during continuous fermentation; the first step fermentation liquid can also be sterilized without centrifugation, and then the second step fermentation can be carried out. The invention has the advantages of utilizing cheap raw materials, giving full play to the characteristics of each step of fermentation, saving the cost of glycerin separation, reducing production costs, shortening the entire fermentation time, improving production efficiency, and providing 1,3- The industrialization of propylene glycol provides an economically viable fermentation process.

Description

Two-step microbial fermentation produces 1, the method for ammediol
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, ammediol (PCT/US96/06705 with glucose; USP5599689; USP6025184; WO96/35796; WO9821340; WO9821339; ZL96195288); The 3rd, with production glycerine and production 1, two strain bacterium mixed culture (USP5599689) 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 (B-amylase), and saccharification was filtered after 24 hours under 60 ℃ of constant temperature, got saccharification liquid.
2) 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.
3) 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.
4) 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 (containing glucose or glycerol concentration is 40%～99%) and carries out the perseverance cultivation again.The 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.
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)

1.一种利用葡萄糖和淀粉、纤维素等酶解液经两步微生物发酵生产1，3-丙二醇的方法，在温度、pH和搅拌转速恒定的条件下，进行间歇、批式流加或连续发酵，首先用酿酒酵母(Saccharomyces cerevisiae)、接合酵母(Zygosaccharomyces)、毕赤酵母(Pichia)、假丝酵母(Candida)、汉逊酵母(Hansenula)、德巴利酵母(Debaryomyces sp.)、克鲁维酵母(Kluyveromyces)、曲霉(Aspergillus)、芽孢杆菌(Bacillus)、毛霉(Mucor)等好氧菌将葡萄糖转化为甘油，继而用克雷伯氏杆菌(Klebsiella)、柠檬菌(Citrobacter)和梭状芽孢杆菌(Clostridia)等厌氧菌将甘油进一步转化为1，3-丙二醇，发酵过程中菌种的接种量为5％～20％，发酵罐搅拌桨转速为100～400转/分钟，温度为27～40℃，氮气或空气的通气量为0.2～4vvm，第一步甘油发酵中pH控制在3.5～5.5之间，葡萄糖的消耗率达到80％～95％，产物甘油的浓度达到5％～30％；第二步1，3-丙二醇发酵中甘油初始浓度为2％～15％，pH为6.0～8.0，产物1，3-丙二醇的浓度达到10～85g/L；1. A method for producing 1,3-propanediol through two-step microbial fermentation using enzymatic hydrolysis solutions such as glucose, starch, and cellulose. Under conditions of constant temperature, pH and stirring speed, intermittent, batch fed or continuous Fermentation, first with Saccharomyces cerevisiae, Zygosaccharomyces, Pichia, Candida, Hansenula, Debaryomyces sp. Aerobic bacteria such as Kluyveromyces, Aspergillus, Bacillus and Mucor convert glucose into glycerol, and then Klebsiella, Citrobacter and Clostridium Anaerobic bacteria such as Clostridia (Clostridia) further convert glycerol into 1,3-propanediol. The temperature is 27-40°C, the ventilation rate of nitrogen or air is 0.2-4vvm, the pH of the first glycerin fermentation is controlled between 3.5-5.5, the consumption rate of glucose reaches 80%-95%, and the concentration of product glycerin reaches 5%. ~30%; in the second step of 1,3-propanediol fermentation, the initial concentration of glycerol is 2%-15%, the pH is 6.0-8.0, and the concentration of the product 1,3-propanediol reaches 10-85g/L; 该发明方法的特征在于：The inventive method is characterized in that: a)第一步甘油发酵所得到的发酵液不必去除菌体，直接加热灭菌后补加第二步1，3-丙二醇发酵所需要的微量元素，接种进行第二步发酵，而不需要添加酵母粉、酵母浸膏或维生素B12；a) The fermentation liquid obtained from the first step of glycerol fermentation does not need to remove the bacteria, directly heats and sterilizes and then adds the trace elements required for the second step of 1,3-propanediol fermentation, and inoculates for the second step of fermentation without adding Yeast powder, yeast extract or vitamin B12; b)第一步甘油发酵液用离心或过滤的方法除去菌体，向清液中加入第二步发酵所需要的营养成分和菌种继续进行第二步发酵；b) The first step of glycerol fermentation liquid is centrifuged or filtered to remove the thallus, and the nutrients and bacterial species required for the second step of fermentation are added to the clear liquid to continue the second step of fermentation; c)批式流加发酵时，第一步甘油发酵所用的流加液是浓葡萄糖溶液或者浓缩的淀粉糖化液、纤维素酶解液，其中葡萄糖的浓度为40％～90％，第二步1，3-丙二醇发酵的流加液是经蒸发浓缩的甘油发酵液，其中甘油的浓度为40％～90％；c) During batch fed-batch fermentation, the feed liquid used in the first step of glycerin fermentation is concentrated glucose solution or concentrated starch saccharification liquid, cellulose enzymatic hydrolysis liquid, wherein the concentration of glucose is 40% ~ 90%, the second step The feeding liquid for 1,3-propanediol fermentation is evaporated and concentrated glycerin fermentation liquid, wherein the concentration of glycerol is 40%-90%; d)连续发酵时，第一步甘油发酵和第二步1，3-丙二醇发酵的发酵液用离心或过滤方法分离后的菌体浓缩液以10％～90％的比例循环利用；d) During continuous fermentation, the bacterial cell concentrate after the first step of glycerol fermentation and the second step of 1,3-propanediol fermentation is separated by centrifugation or filtration to recycle at a ratio of 10% to 90%; e)两步发酵所用的原料是葡萄糖、淀粉糖化液、纤维素酶解液等碳水化合物，其中葡萄糖含量在10％～50％之间。e) The raw materials used in the two-step fermentation are carbohydrates such as glucose, starch saccharification liquid, and cellulose hydrolysis liquid, wherein the content of glucose is between 10% and 50%.
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WO2006128381A1 (en) * 2005-06-03 2006-12-07 Tsinghua University Method for preparing 1,3-propanediol by using glycerine as the by-product of the biological diesel oil
WO2006133637A1 (en) * 2005-06-17 2006-12-21 Tsinghua University Method for preparing 1,3-propanediol and 2,3-tuanediol by the coarse starch material
CN100355899C (en) * 2006-04-14 2007-12-19 清华大学 Pretreatment method for filtering fermentation liquor of bacteria of possessing capsula
CN100463968C (en) * 2006-01-27 2009-02-25 华侨大学 A method for preparing 1,3-propanediol and dihydroxyacetone from biocatalyzed conversion of glycerol
CN1807610B (en) * 2006-01-23 2011-01-26 迟乃玉 Method for producing low temperature cellulase using microbe fermentation
CN101941767B (en) * 2009-07-10 2012-03-07 中国石油天然气股份有限公司 A kind of processing method of 1,3-propanediol concentrated bacterial liquid
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CN105705647A (en) * 2013-09-03 2016-06-22 麦兰特公司 A process for manufacturing acrylic acid, acrylonitrile and 1,4-butanediol from 1,3-propanediol
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WO2006128381A1 (en) * 2005-06-03 2006-12-07 Tsinghua University Method for preparing 1,3-propanediol by using glycerine as the by-product of the biological diesel oil
WO2006133637A1 (en) * 2005-06-17 2006-12-21 Tsinghua University Method for preparing 1,3-propanediol and 2,3-tuanediol by the coarse starch material
EP1897955A4 (en) * 2005-06-17 2010-12-15 Univ Tsinghua PROCESS FOR THE PREPARATION OF 1,3-PROPANEDIOL AND 2,3-BUTANEDIOL FROM RAW STARCH MATERIAL
US7968319B2 (en) 2005-06-17 2011-06-28 Tsinghua University Method for producing 1,3-propanediol and 2,3-butanediol from raw starch material
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 A method for preparing 1,3-propanediol and dihydroxyacetone from biocatalyzed conversion of glycerol
CN101415830B (en) * 2006-03-31 2014-02-05 莱斯大学 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
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