CN109852639A - A method of using novel eutectic solvent pretreated straw fermentation butyl alcohol - Google Patents
A method of using novel eutectic solvent pretreated straw fermentation butyl alcohol Download PDFInfo
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Abstract
The invention discloses a kind of methods using novel eutectic solvent pretreated straw fermentation butyl alcohol, belong to technical field of bioengineering.The present invention is hydrogen bond donor with lactic acid and ethylamine hydrochloride is the novel donor eutectic solvent pretreated straw of hydrogen bond receptor synthesis, then adds cellulase degradation, recycles enzymolysis liquid as carbon source, fermentation butyl alcohol.Hemicellulose removal rate (73.2%) with higher and lignin removing rate's (55.7%) during pretreated water rice straw, total sugar concentration is up to 59g/L after enzymatic hydrolysis, and wherein concentration of glucose is 58.3gL–1, choline chloride: formic acid is used compared to before: ionic liquid (42g/L) tool of acetic acid has a distinct increment.Whole process has many advantages, such as that at low cost, the three wastes are few.And pretreated stalk hydrolyzate can be used to fermenting and producing butanol.
Description
Technical field
The present invention relates to a kind of methods using novel eutectic solvent pretreated straw fermentation butyl alcohol, belong to bioengineering
Technical field.
Background technique
Demand of the world today to non-renewable energy resources such as petroleum, natural gas and coals is increasingly increasing.The stone of the seventies
Oily crisis causes common concern of the countries in the world to future source of energy shortage problem.Traditional energy, coal, oil and natural gas are equal
It is non-renewable energy resources, the development difficulty of remaining reserves is increasing.Moreover, China is large agricultural country, lignocellulosic material
Quite abundant, agricultural crop straw cellulose rich in and hemicellulose are a kind of renewable resources of preciousness, but at me
State, has considerable agricultural crop straw to be thrown aside or burned, and not only causes the waste of resource, also easily causes environmental pollution.?
In this case, biomass energy receives the extensive pass of people as a kind of renewable energy cheap, from a wealth of sources
Note.Currently, the utilization of biomass is in Rapid development stage, for example utilize biomass liquid fuel was prepared or gaseous fuel；Together
When can also by biomass catalyzing degrade obtain high valuable chemicals.
During biomass economy, biomass pretreatment is the committed step that it is efficiently utilized.Biomass is pretreated
The component parameter of biomass can be changed in journey: such as reduction content of lignin reduces cellulose crystallity, these parameters directly affect
To cellulase hydrolysis.Therefore, it in order to realize the effective use of biomass, develops efficient biomass pretreatment method and compels in eyebrow
Eyelash.Currently, preprocess method mainly has the combined method of physical method, chemical method, bioanalysis and first three methods.Wherein chemical method
It is the research emphasis of various countries researcher with physical method.Chemical method is mainly the catalysis using the chemical reagent such as acid, alkali, organic solvent
Effect or dissolution, destroy the crystal structure of cellulose, make hemicellulose degradation or dissolution, and expand lignin to eliminate
Protective effect to cellulose, increases the porosity and specific surface area of lignocellulose biomass, improves connecing for cellulose and enzyme
Probability is touched, higher enzymolysis efficiency is obtained.
In recent years, ionic liquid is as a kind of novel dissolvent emerged, has good dissolubility, designability and can
The advantages that recyclability, is widely used in biomass pretreatment.But " the green aspect " of ionic liquid receives pole recently
It is all reported in big query, possible toxicity and the current document of low-down biological degradability.In order to overcome these
Disadvantage and the good characteristic for keeping ionic liquid, Abbott et al. (J.Am.Chem.Soc., 2004,126,9142-9147) are first
It is secondary to report a kind of novel ionic liquid: eutectic solvent.Compared with traditional acid-base pretreatment method, eutectic solvent is pre-
Environmental pollution, saccharification efficiency height are not only reduced during processing rice straw, but also have the characteristics that be easily recycled, this
Just significantly reduce pretreatment cost and protection environment.2014, and Xia et al. (RSC Adv., 2014,4,10586-
10596) choline eutectic solvent is handled cellulose and switchgrass by the first again, this is for the first time to be applied to eutectic solvent
Lignocellulose biomass pretreatment.2017, Ni etc. established dihydrogen bond donor eutectic solvent (choline chloride: formic acid: second
Acid) pretreated water rice straw method, treatment effect is more obvious than general eutectic solvent.But that there is also costs is inclined for this method
Height, the removal rate of hemicellulose is not still high, thus the concentration of final glucose be not achieved it is very high.
Summary of the invention
In order to solve the above technical problems, the present invention improves biology to further decrease the synthesis cost of eutectic solvent
The cellulose accessibility of matter stalk, we have developed the novel eutectic solvents based on ethylamine hydrochloride and lactic acid, and combine secondary
Sodium chlorate preprocessing biomass stalk, gained hydrolyzate can be with directly come fermenting and producing butanol, to production of butanol bacterial strain without suppression
Production is used.
The first purpose of the invention is to provide a kind of sides using novel eutectic solvent pretreated straw fermentation butyl alcohol
Method includes the following steps:
(1) eutectic solvent synthesizes: ethylamine hydrochloride and ammonium lacate are mixed according to molar ratio 1:0.5~2,60~
0.5~3h or more is reacted under 100oC, obtains eutectic solvent；
(2) stalk pretreatment: at 110~130oC, by stalk and the eutectic solvent of step (1) synthesis according to quality
It is mixed than 1:8~12, is separated by solid-liquid separation after reacting 0.5~3h, using 0.5~10% after obtained solid washing is dry
Liquor natrii hypochloritis carry out 6~72h of immersion, be dried to obtain pretreated straw after immersion；
(3) it digests: buffer solution being added in the pretreated straw obtained to step (2) and is mixed, fiber is then added
Plain enzyme is digested, and enzymolysis liquid is obtained；
(4) ferment: the enzymolysis liquid obtained using step (3) is carbon source through fermentation butanol.
Further, the additive amount of the cellulase is 40~60FPUg-1.In the present invention, the additive amount of enzyme
It is to be added with total solid content.
Further, the temperature of the enzymatic hydrolysis is 45~55oC.
Further, the buffer is citric acid-sodium citrate buffer.
Further, the citric acid-sodium citrate buffer concentration is 45~55mM.
Further, the mass ratio of the pretreated straw and buffer solution is 1:5~20.
Further, the stalk is one of rice straw, wheat stalk, corn stover, cane residuals or more
Kind combination.
Further, the fermentation is the fermenting and producing butanol using sugared clostridium butylicum as strain.
Further, the culture medium of the fermentation further includes 8~12gL of Dried Corn Steep Liquor Powder-1, CaCO32~6gL-1, (NH4)2SO41~4gL-1, K2HPO40.3~0.6gL-1, MnSO4·H20.01~0.03gL of O-1。
Further, the inoculum concentration of the clostridium butylicum is 8~15%, and cultivation temperature is 35~38oC.
The beneficial effects of the present invention are:
With lactic acid be hydrogen bond donor and ethylamine hydrochloride is the novel donor eutectic solvent of hydrogen bond receptor synthesis, is being located in advance
Hemicellulose removal rate (73.2%) with higher and lignin removing rate's (55.7%) during rice straw are managed, after enzymatic hydrolysis
Total sugar concentration is up to 59g/L, and wherein concentration of glucose is 58.3gL–1, choline chloride: formic acid: acetic acid is used compared to before
Ionic liquid (42g/L) tool has a distinct increment.Whole process has many advantages, such as that at low cost, the three wastes are few.And pretreated straw
Stalk hydrolyzate can be used to fermenting and producing butanol.
Detailed description of the invention
Fig. 1 is the cellulase saccharification result of different eutectic solvent pretreated water rice straws；
Fig. 2 is to utilize rice straw enzymolysis liquid fermenting and producing butanol result.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples, so that those skilled in the art can be with
It more fully understands the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
Glucose content is measured using high performance liquid chromatography (HPLC).
Embodiment 1: novel eutectic solvent (ethylamine hydrochloride: lactic acid) pretreated water rice straw
Taking 100g ethylamine hydrochloride is hydrogen bond receptor, and lactic acid is hydrogen bond donor (molar ratio is shown in Table 1), and 10g rice straw are added
Stalk (eutectic solvent is 10:1 with rice straw mass ratio), mixture, is then centrifuged by stir process 2h at 140 DEG C, uses
Deionized water washing precipitating 3 times.After drying to constant weight, sieving.
The citric acid-sodium citrate buffer solution that pH4.8,50mM is added in treated stalk is formed into mixed system, rice
Stalk final mass concentration is 10% (w/v), is addedCellulase digested, at 50 DEG C and
It is digested for 24 hours on the shaking bath of 150rpm.
1 synthesizing new eutectic solvent method of table
Simultaneously synthesizing to have different ethylamine hydrochlorides and lactic acid molar ratio, the ionic liquid of Ji Shuiwei hydrogen bond donor is (specific
Method is shown in Table the effect for 1) and its handling rice straw (effect is as shown in Figure 1).As shown in Figure 1, ethylamine hydrochloride and ammonium lacate
The eutectic solvent of 1:1 molar ratio synthesis has best pretreating effect, and final total sugar concentration is 22.66gL–1.In addition,
Using processing method same as described above, using ethylene glycol and glycerol as hydrogen acceptor, according to ethylamine hydrochloride: ethylene glycol/glycerol is rubbed
You handle rice straw at ionic liquid than being 1:1 reaction, and finally obtained total sugar concentration is respectively 12.26 and 12.02gL–1, effect is also good without the effect of ethylamine hydrochloride and lactic acid eutectic solvent.
Embodiment 2: novel eutectic solvent (ethylamine hydrochloride: lactic acid) combines liquor natrii hypochloritis's pretreated water rice straw
Taking 100g ethylamine hydrochloride is hydrogen bond receptor, and lactic acid is hydrogen bond donor (molar ratio and synthetic method are shown in Table 1), is added
(for 10:1), the stir process 2h at 140 DEG C then will mixing for eutectic solvent and rice straw mass ratio for 10g rice straw
Object centrifugation, is washed with deionized precipitating 3 times.After drying to constant weight, sieving.Again with 0.5% sodium hypochlorite in immersion treatment 6h,
The rice straw after eutectic solvent and sodium hypochlorite combination processing can be obtained after drying sieving.By treated, stalk is added
The citric acid-sodium citrate buffer solution of pH4.8,50mM form mixed system, and rice straw final mass concentration is 10% (w/
V), it is addedCellulase digested, digested for 24 hours on the shaking baths of 50 DEG C and 150rpm, always
Sugared concentration reaches 59.2gL–1, wherein concentration of glucose is 58.3gL–1。
Embodiment 3: pretreated water rice straw hydrolyzate fermenting and producing butanol is utilized
The citric acid-sodium citrate buffer solution of pH4.8,50mM is added in the rice straw for taking a certain amount of combination pretreated,
And it is addedCellulase, make final solid-to-liquid ratio 1:10, on the shaking baths of 50 DEG C and 150rpm
For 24 hours, centrifugation obtains rice straw hydrolyzate to enzymatic hydrolysis, and is added as follows at being distributed into culture medium: Dried Corn Steep Liquor Powder 10gL-1,
CaCO3 4g·L-1, (NH4)2SO4 2g·L-1, K2HPO4 0.5g·L-1, MnSO4·H2O 0.01g·L-1.PH to 6.5 is adjusted,
115 DEG C of sterilizing 20min.It is inoculated with the Clostridium saccharobutylicum DSM 13864 (10%, v/v) of activation,
Anaerobic culturel at 37 DEG C.The result of fermented and cultured 72h is as shown in Figure 2, wherein butanol yield is 10.16gL-1, yield isSpace-time yield is 0.14gL-1·h-1。
Embodiment 4: novel eutectic solvent (ethylamine hydrochloride: lactic acid) combines sodium hypochlorite pretreated water rice straw
100g ethylamine hydrochloride: lactic acid (molar ratio 1:1) is taken, 20g rice straw (eutectic solvent and rice straw are added
Stalk mass ratio is 5:1), mixture, is then centrifuged by stir process 2h at 140 DEG C, precipitating is washed with deionized 3 times.It dries
It does to constant weight, is sieved.Again with 10% sodium hypochlorite in immersion treatment 6h, can be obtained after drying sieving eutectic solvent and time
Rice straw after sodium chlorate combination processing.Treated stalk is added to the citric acid-sodium citrate buffering of pH4.8,50mM
Liquid forms mixed system, and rice straw final mass concentration is 10% (w/v), is addedCellulase into
Row enzymatic hydrolysis, digests for 24 hours, final total sugar concentration is in 60.5gL on 50 DEG C and 150rpm of shaking bath-1。
Embodiment 5: novel eutectic solvent (ethylamine hydrochloride: lactic acid) combines sodium hypochlorite pretreated water rice straw
100g ethylamine hydrochloride: lactic acid (molar ratio 1:1) is taken, 5g rice straw (eutectic solvent and rice straw are added
Stalk mass ratio is 20:1), mixture, is then centrifuged by stir process 2h at 140 DEG C, precipitating is washed with deionized 3 times.It dries
It does to constant weight, is sieved.Again with 0.5% sodium hypochlorite in immersion treatment 6h, can be obtained after drying sieving eutectic solvent and
Rice straw after sodium hypochlorite combination processing.The citric acid-sodium citrate that pH4.8,50mM is added in treated stalk is delayed
Fliud flushing forms mixed system, and rice straw final mass concentration is 10% (w/v), is addedCellulase
It is digested, is digested for 24 hours on 50 DEG C and 150rpm of shaking bath, final total sugar concentration is in 55.3gL-1。
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention
It encloses without being limited thereto.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in the present invention
Protection scope within.Protection scope of the present invention is subject to claims.
Claims (10)
1. a kind of method using novel eutectic solvent pretreated straw fermentation butyl alcohol, which comprises the steps of:
(1) eutectic solvent synthesizes: ethylamine hydrochloride and ammonium lacate being mixed according to molar ratio 1:0.5~2,60~100
0.5~3h is reacted at DEG C, obtains eutectic solvent；
(2) stalk pretreatment: at 110~130 DEG C, by stalk and the eutectic solvent of step (1) synthesis according to mass ratio 1:5
~20 are mixed, and are separated by solid-liquid separation after reacting 0.5~3h, and 0.5~10% time is used after obtained solid washing is dry
Sodium chlorate carries out 6~72h of immersion, is dried to obtain pretreated straw after immersion；
(3) it digests: buffer solution being added in the pretreated straw obtained to step (2) and is mixed, cellulase is then added
It is digested, obtains enzymolysis liquid；
(4) ferment: the enzymolysis liquid obtained using step (3) is carbon source through fermentation butanol.
2. the method according to claim 1, wherein the additive amount of the cellulase is 40~60FPUg-1。
3. the method according to claim 1, wherein the temperature of the enzymatic hydrolysis is 45~55 DEG C.
4. the method according to claim 1, wherein the buffer is that citric acid-sodium citrate buffering is molten
Liquid.
5. according to the method described in claim 4, it is characterized in that, the citric acid-sodium citrate buffer concentration is
45~55mM.
6. the method according to claim 1, wherein the mass ratio of the pretreated straw and buffer solution is
1:5~20.
7. the method according to claim 1, wherein the stalk is rice straw, wheat stalk, corn stalk
One of stalk, cane residuals or multiple combinations.
8. the method according to claim 1, wherein the fermentation is the fermentation using sugared clostridium butylicum as strain
Produce butanol.
9. according to the method described in claim 8, it is characterized in that, the culture medium of the fermentation further includes Dried Corn Steep Liquor Powder 8
~12gL-1, CaCO32~6gL-1, (NH4)2SO41~4gL-1, K2HPO40.3~0.6gL-1, MnSO4·H2O
0.01~0.03gL-1。
10. according to the method described in claim 8, it is characterized in that, the inoculum concentration of the clostridium butylicum be 8~15%, training
Supporting temperature is 35~38 DEG C.
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| CN110540508A (en) * | 2019-08-30 | 2019-12-06 | 齐鲁工业大学 | Eutectic solvent and application thereof in extracting lignin |
| CN111154817A (en) * | 2020-02-19 | 2020-05-15 | 中国科学院过程工程研究所 | Method for efficiently separating lignocellulose and carrying out enzymolysis by using ionic liquid-high-boiling-point alcohol composite system |
| CN111961220A (en) * | 2020-08-21 | 2020-11-20 | 齐鲁工业大学 | Method for efficiently separating straw components by adopting novel eutectic solvent |
| CN113322525A (en) * | 2021-07-02 | 2021-08-31 | 东华大学 | Method for extracting refined dry hemp fiber through one-step ramie degumming based on eutectic solvent |
| CN113603899A (en) * | 2021-07-12 | 2021-11-05 | 华南理工大学 | Method for pretreating lignocellulose by using Lewis base to assist neutral eutectic solvent |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110540508A (en) * | 2019-08-30 | 2019-12-06 | 齐鲁工业大学 | Eutectic solvent and application thereof in extracting lignin |
| CN110540508B (en) * | 2019-08-30 | 2021-01-01 | 齐鲁工业大学 | Eutectic solvent and application thereof in extracting lignin |
| CN111154817A (en) * | 2020-02-19 | 2020-05-15 | 中国科学院过程工程研究所 | Method for efficiently separating lignocellulose and carrying out enzymolysis by using ionic liquid-high-boiling-point alcohol composite system |
| CN111961220A (en) * | 2020-08-21 | 2020-11-20 | 齐鲁工业大学 | Method for efficiently separating straw components by adopting novel eutectic solvent |
| CN111961220B (en) * | 2020-08-21 | 2022-04-12 | 齐鲁工业大学 | Method for efficiently separating straw components by adopting novel eutectic solvent |
| CN113322525A (en) * | 2021-07-02 | 2021-08-31 | 东华大学 | Method for extracting refined dry hemp fiber through one-step ramie degumming based on eutectic solvent |
| CN113603899A (en) * | 2021-07-12 | 2021-11-05 | 华南理工大学 | Method for pretreating lignocellulose by using Lewis base to assist neutral eutectic solvent |
| CN113603899B (en) * | 2021-07-12 | 2023-03-21 | 华南理工大学 | Method for pretreating lignocellulose by using Lewis base to assist neutral eutectic solvent |
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