CN102618586A - Method for producing biological butanol by using tung nutshells - Google Patents
Method for producing biological butanol by using tung nutshells Download PDFInfo
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Abstract
The invention discloses a method for producing biological butanol by using tung nutshells. The method comprises the following steps of: (1) collection and pretreatment of the tung nutshells; (2) hydrolysis of the tung nutshells, to the specific, adding dilute sulphuric acid with the mass concentration of 1-5% in screened tung nutshell powder according to the ratio of the mass of the screened tung nutshell powder to the volume of the dilute sulphuric acid of 1:5-9, hydrolyzing for 1-3 hours at the temperature of 120-180 DEG C, obtaining hydrolysate of the nutshells, and controlling the concentration of the total sugar in the hydrolysate to be 35-45g/L; (3) preparation of a hydrolysate fermentation medium; and (4) fermentation of the hydrolysate of the tung nutshells, to be specific, transferring the prepared medium in the step (3) into a fermentation tank, then inoculating a strain cultured in advance with the inoculating amount of 5%-10% of the volume of the fermented hydrolysate medium, carrying out anaerobic fermentation for 72-120 hours at the temperature of 35-40 DEG C, and obtaining the biological butanol. By utilization of the method, the utilization ratio of the tung nutshells can be increased, and the resource waste and environmental pollution can be reduced.
Description
Technical field
The present invention relates to a kind of tung oil tree shell and produce the method for biological butanol.
Background technology
Tung oil tree (Vernicia fordii Hemsley) belongs to the Euphorbiaceae tung tree, is the middle subtropical zone deciduous tree, is that original China and cultivation utilize long essential industry oil plant seeds.In the Hunan, areas such as Hubei, Guizhou, Chongqing, Sichuan, Guangxi, Guangdong, Yunnan, Shaanxi, Henan, Anhui, Jiangsu, Zhejiang, Jiangxi, Fujian, Taiwan all have cultivation to distribute, wherein the neighboring region with Hunan, Chongqing, Guizhou, Hubei is the producing region, center.The main products of tung oil tree is a tung oil, is one of best siccative oil, in industry, has extensive use.The tung oil tree shell is the by product of tung nut processing tung oil, accounts for the 40-55% of tung nut fresh weight.For a long time, the tung oil tree shell is abandoned waste by people mostly, the gas with foreign flavor polluted air that the tung oil tree shell that is dropped produces in degradation process, the liquid of generation and solid pollution water source.
Crude oil in China import interdependency in 2011 is up to 55.3%, and expecting 2015 crude oil in China import interdependencies will be above 65.0%.To fossil energy, particularly the high degree of dependence of petroleum resources is just restricting the Sustainable development of China's economy, affects the strategic security of country.Along with becoming increasingly conspicuous of environmental problems such as the exhaustion of petroleum resources and Greenhouse effect, efficiently utilizing renewable raw materials to produce the energy has become one of emphasis of whole world concern with chemical.Alcohols is one type of important platform chemical, and wherein most of alcohol can transform through microbial fermentation and get, and therefore, alcohols is considered to have the biofuel and the bio-based chemical of development potentiality.Butanols is a kind of important platform chemical, is mainly used in to make softening agent or be used as solvent, extraction agent etc.In recent years, the researchist finds that calorific value, octane value and the gasoline of butanols is suitable, and MTBE commonly used in its oxygen level and the gasoline is close; Can corrosion pipeline, be difficult for suction, be convenient to pipe-line transportation; Steam forces down, and is safe, and can with gasoline with any than mixing.So butanols has become by a kind of novel biological fuel [Durre, P., Biobutanol:an attractive biofuel.Biotechnol.J.2007,2, (12), 1525-34.] that has potentiality of countries in the world enterprise and research institution's strong interest.The use of butanols fuel can reduce the consumption of fossil oil and the discharging of greenhouse gases effectively.
At present, mainly through chemical synthesis production, its raw material sources are in petroleum chemicals for butanols.Utilize microbial fermentation to produce butanols and aspect a lot of, the incomparable advantage of chemical synthesis is arranged; Microbial fermentation is that the suitability for industrialized production of butanols has been opened up new road, and famous ABE fermentation method (acetone-butanols-ethanol) once was second largest in the world biological fermentation engineering.ABE fermentation rule is to be raw material with grain, obtains acetone, butanols, ethanol (mass ratio 3:6:1) through fermentation, after rectifying, makes acetone, butanols and alcohol product more respectively.Along with the rising steadily of oil price, butylic fermentation industry has welcome the opportune moment of recovery industry in recent years.
Because it is raw material that the development of first-generation bioenergy is based on grain, this can bring bioenergy and grain to strive ground, and people's problem of striving grain.Therefore, press for the technology that other raw material of development and use produces the thing energy next life at present, i.e. s-generation bioenergy technology.The characteristics of s-generation bioenergy technology are that to utilize non-grain crop be that biomass such as cellulose family are produced large energy product (like bio-ethanol, biological butanol etc.).At present, the trial that has had domestic and international investigator to report to utilize various biomass to produce butanols, the biomass of report are agricultural wastes mostly, like large and small wheat straw stalk, corn straw, maize peel, corn cob etc.Yet it is very rare to utilize forestry waste to produce the report of thing butanols next life.
Summary of the invention
The objective of the invention is to improve the method that a kind of tung oil tree shell is produced biological butanol.
The objective of the invention is to realize through following technical scheme: a kind of tung oil tree shell is produced the method for biological butanol, may further comprise the steps:
(1) the tung oil tree shell is collected and pre-treatment: after the tung oil tree shell is collected, dry or dry, after kibbler was pulverized, mistake >=100 mesh sieves got sieving tung oil tree shell powder;
(2) tung oil tree shell hydrolysis: in sieving tung oil tree shell powder quality: the ratio of dilute sulphuric acid volume=1:5-9 (preferred 1:6) adds the dilute sulphuric acid (preferred mass concentration is 2% dilute sulphuric acid) that mass concentration is 1-5% in sieving tung oil tree shell powder; At 120-180 ℃ of hydrolysis 1-3 hour; Get tung oil tree shell hydrolyzed solution, total sugar concentration is 35-45g/L in the control tung oil tree shell hydrolyzed solution;
(3) preparation of hydrolyzed solution fermention medium: tung oil tree shell hydrolyzed solution is cooled to room temperature, filters and remove solid substance, be mixed with fermention medium;
(4) tung oil tree shell hydrolyzed solution fermentation: prepared culture medium in the step (3) is changed in the fermentor tank, inoculate cultured in advance bacterial classification then, the inoculum size of bacterial classification is for the 5%-10% of fermentation hydrolyzed solution culture volume, at 35-40 ℃ of anaerobically fermenting 72-120 hour;
The used bacterial classification that ferments can be clostridium acetobutylicum (Clostridium acetobutylicum DSM 792; Preserve the center available from German microbial strains), Bai Shi clostridium (Clostridium beijerinckii NCIMB 8052; Available from Something English industry and marine bacteria DSMZ), or clostridium acetobutylicum and Bai Shi clostridial equal-volume mixture.
Further; Step (3); The preparation of said fermention medium: in tung oil tree shell hydrolyzed solution, adding sodium acetate is 3.0-5.0g/L (preferred 4.0g/L) until sodium acetate concentration; Adding potassium primary phosphate is 0.75-0.95g/L (preferred 0.85g/L) until the biphosphate potassium concn, and adding potassium hydrogenphosphate is 0.75-0.95g/L (preferred 0.85g/L) until potassium hydrogenphosphate concentration, and adding sal epsom is 0.20-0.30g/L (preferred 0.25g/L) until magnesium sulfate concentration; Adding manganous sulfate is 0.01-0.03g/L (preferred 0.02g/L) until manganous sulfate concentration; Adding ferric sulfate is 0.01-0.03g/L (preferred 0.02g/L) until ferric sulfate concentration, uses ammoniacal liquor to regulate the pH value and is 6.5-7.0,110-120 ℃ of sterilization 15-25 minute.
Research shows, clostridium acetobutylicum in the fusobacterium
(Clostridium acetobutylicum),The Bai Shi clostridium
(Clostridium beijerinckii)Can the fermentative prodn butanols
[Keis, S.; Shaheen, R.; Jones; D. T.; Emended descriptions of Clostridium acetobutylicum and Clostridium beijerinckii, and descriptions of Clostridium saccharoperbutylacetonicum sp. nov. and Clostridium saccharobutylicum sp. nov [J]. Int. J. Syst. Evol. Microbiol. 2001,51; (Pt 6), 2095-103.]Clostridium acetobutylicum
(Clostridium acetobutylicum)Be to hang down GC content; Can form spore; A kind of gram positive bacterium of strictly anaerobic, it can with various sugar (as: glucose sugar, semi-lactosi, cellobiose, seminose, wood sugar and pectinose) be substrate carry out fermentation and acid (acetate and butyric acid) and solvent (acetone, butanols and ethanol) [
Ezeji, T.; Qureshi, N.; Blaschek; H. P.; Butanol production from agricultural residues:Impact of degradation products on Clostridium beijerinckii growth and butanol fermentation. Biotechnol. Bioeng. 2007; 97, (6), 1460-1469.]; And the Bai Shi clostridium
(Clostridium beijerinckii)Substrate spectrum wideer with the pH optimum range, ratio clostridium acetobutylicium on fermenting
(Clostridium acetobutylicum)Have more the industrial application potentiality [
Ezeji, T. C.; Qureshi, N.; Blaschek, H. P., Butanol fermentation research:upstream and downstream manipulations. The Chemical Record 2004,4, (5), 305-314.].
Meta-bolites (acetate, butyric acid, acetone, butanols, ethanol etc.) to after carbohydrate (wood sugar, glucose and pectinose) in the gained tung oil tree shell hydrolyzed solution of the present invention and the fermentation uses performance liquid chromatography (High performance Liquid Chromatography; HPLC) isolation identification adopts external standard method to carry out quantitative analysis.Concrete grammar is following: take out the sample in the fermenting process, carry out the centrifuging and taking supernatant; Supernatant filters with Millipore Millex-GP PES (SLGP033RB) 0.22 μ m needle-based strainer; The full-automatic sample introduction of supernatant after the filtration gets into Agilent1200 HPLC (Agilent Technologies company) system, with the rare H of 0.05mM
2SO
4As moving phase; Flow velocity 0.5mL/min; Use Bio-Rad Aminex HPX-87H ion exchange column (7.8 * 300 mm, Bio-Rad company), applied sample amount 5 μ L; Column temperature is controlled at 15 ℃, uses differential refraction detector (Refractive index (RI) detector) to carry out signal detection down at 30 ℃.
The present invention's tung oil tree shell is produced the method for biological butanol, for the butanols microbial fermentation provides a new approach, not only can solve China's energy starved problem, the problem of striving grain with the people that also can avoid being brought because of traditional butylic fermentation production.In addition, along with the purposes of tung oil in national economy is increasingly extensive, the continuous growth of output will have a large amount of by product tung oil tree shell outputs every year.Utilize the present invention, fully these tung oil tree shell resources of development and utilization when improving tung oil tree by product utilization ratio, reduce the wasting of resources and environmental pollution.
Embodiment
Below in conjunction with embodiment the present invention is described further.
Embodiment 1
Present embodiment may further comprise the steps:
(1) collection of tung oil tree shell and pre-treatment: after the collection of tung oil tree shell, dry, after kibbler is pulverized, cross 100 mesh sieves, take by weighing the tung oil tree shell powder 1.0kg that sieves;
(2) hydrolysis of tung oil tree shell: adding 6L mass concentration is 2% dilute sulphuric acid in tung oil tree shell powder, and packing into behind the mixing has in the autoclave of refrigerating unit, 160 ℃ of hydrolysis 1 hour, gets tung oil tree shell hydrolyzed solution; Through detecting, total sugar content is 40.6g/L in the tung oil tree shell hydrolyzed solution;
(3) preparation of hydrolyzed solution fermention medium: after treating that tung oil tree shell hydrolyzed solution is cooled to room temperature in the step (2); Filter and remove solid substance; In hydrolyzed solution, adding sodium acetate sodium acetate content in hydrolyzed solution again is 4.0g/L, and the biphosphate potassium content is 0.85g/L in adding potassium primary phosphate to the hydrolyzed solution, and adding potassium hydrogenphosphate potassium hydrogenphosphate content in hydrolyzed solution is 0.85g/L; Adding sal epsom sal epsom content in hydrolyzed solution is 0.25g/L; Adding manganous sulfate manganous sulfate content in hydrolyzed solution is 0.02g/L, and adding ferric sulfate ferric sulfate content in hydrolyzed solution is 0.02g/L, and using ammoniacal liquor to regulate the pH value is 6.8; 115 ℃ of sterilizations 20 minutes, process fermention medium;
(4) tung oil tree shell hydrolyzed solution fermentation: prepared culture medium in the step (3) is changed in the fermentor tank; The cultured in advance clostridium acetobutylicum of aseptic technique inoculation (Clostridium acetobutylicum DSM 792; Preserve the center available from German microbial strains); The inoculum size of bacterial classification is 5% of fermentation hydrolyzed solution culture volume, 37 ℃ of anaerobically fermentings 120 hours.
The assay of solvent in the present embodiment gained tunning (butanols, ethanol and acetone): take out the sample in the fermenting process, carry out the centrifuging and taking supernatant; Supernatant filters with Millipore Millex-GP PES (SLGP033RB) 0.22 μ m needle-based strainer; The full-automatic sample introduction of supernatant after the filtration gets into Agilent 1200 HPLC (Agilent Technologies company) system, with the rare H of 0.05mM
2SO
4As moving phase; Flow velocity 0.5mL/min uses Bio-Rad Aminex HPX-87H ion exchange column (7.8 * 300mm, Bio-Rad company); Applied sample amount 5 μ L; Column temperature is controlled at 15 ℃, uses differential refraction detector (Refractive index (RI) detector) to carry out signal detection at 30 ℃, adopts external standard method to carry out quantitative analysis.
Fermentation result: after fermentation in 120 hours, produce butanols 7.6g/L, ethanol 1.3g/L, acetone 3.2g/L, total solvent 12.1g/L; Wherein the ratio of butanols reaches 62.8%.
Embodiment 2
The difference of present embodiment and embodiment 1 is: step (4), used fermented bacterium are Bai Shi clostridium (Clostridium beijerinckii NCIMB 8052 is available from Something English industry and marine bacteria DSMZ).
Fermentation result: after fermentation in 120 hours, produce butanols 8.3 g/L, ethanol 1.1g/L, acetone 2.9g/L, total solvent 12.3g/L; Wherein the ratio of butanols reaches 67.5%.
Embodiment 3
The difference of present embodiment and embodiment 1 is: step (4); Used fermented bacterium is clostridium acetobutylicum (Clostridium acetobutylicum DSM 792; Preserve the center available from German microbial strains) and Bai Shi clostridium (Clostridium beijerinckii NCIMB 8052 is available from Something English industry and marine bacteria DSMZ) equal-volume mixture.
Fermentation result: after fermentation in 120 hours, produce butanols 9.8g/L, ethanol 1.1g/L, acetone 3.4g/L, total solvent 14.3g/L; Wherein the ratio of butanols reaches 68.5%.
Claims (3)
1. the method that the tung oil tree shell is produced biological butanol is characterized in that, may further comprise the steps:
(1) the tung oil tree shell is collected and pre-treatment: after the tung oil tree shell is collected, dry or dry, after kibbler was pulverized, mistake >=100 mesh sieves got sieving tung oil tree shell powder;
(2) tung oil tree shell hydrolysis: in sieving tung oil tree shell powder quality: the ratio of dilute sulphuric acid volume=1:5-9 adds mass concentration in sieving tung oil tree shell powder be the dilute sulphuric acid of 1-5%; 120-180 ℃ hydrolysis 1-3 hour; Get tung oil tree shell hydrolyzed solution, total sugar concentration is 35-45g/L in the control tung oil tree shell hydrolyzed solution;
(3) preparation of hydrolyzed solution fermention medium: tung oil tree shell hydrolyzed solution is cooled to room temperature, filters, remove solid substance, be mixed with fermention medium;
(4) tung oil tree shell hydrolyzed solution fermentation: prepared culture medium in the step (3) is changed in the fermentor tank, inoculate cultured in advance bacterial classification then, the inoculum size of bacterial classification is for the 5%-10% of fermentation hydrolyzed solution culture volume, at 35-40 ℃ of anaerobically fermenting 72-120 hour;
The used bacterial classification that ferments is clostridium acetobutylicum (Clostridium acetobutylicum DSM 792), Bai Shi clostridium (Clostridium beijerinckii NCIMB 8052), or clostridium acetobutylicum and Bai Shi clostridial equal-volume mixture.
2. tung oil tree shell according to claim 1 is produced the method for biological butanol; It is characterized in that: step (3); The preparation of said fermention medium: in tung oil tree shell hydrolyzed solution, adding sodium acetate is 3.5-4.5g/L until sodium acetate concentration; Adding potassium primary phosphate is 0.75-0.95g/L until the biphosphate potassium concn, and adding potassium hydrogenphosphate is 0.75-0.95 g/L until potassium hydrogenphosphate concentration, and adding sal epsom is 0.20-0.30g/L until magnesium sulfate concentration; Adding manganous sulfate is 0.01-0.03g/L until manganous sulfate concentration; Adding ferric sulfate is 0.01-0.03g/L until ferric sulfate concentration, uses ammoniacal liquor to regulate the pH value and is 6.5-7.0,110-120 ℃ of sterilization 15-25 minute.
3. tung oil tree shell according to claim 1 and 2 is produced the method for biological butanol; It is characterized in that: the preparation of said fermention medium: in tung oil tree shell hydrolyzed solution, adding sodium acetate is 4.0g/L until sodium acetate concentration; Adding potassium primary phosphate is 0.85g/L until the biphosphate potassium concn, and adding potassium hydrogenphosphate is 0.85g/L until potassium hydrogenphosphate concentration, and adding sal epsom is 0.25g/L until magnesium sulfate concentration; Adding manganous sulfate is 0.02g/L until manganous sulfate concentration; Adding ferric sulfate was 0.02g/L until ferric sulfate concentration, and using ammoniacal liquor to regulate the pH value is 6.8,115 ℃ of sterilizations 20 minutes.
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| CN102876731A (en) * | 2012-10-25 | 2013-01-16 | 中南林业科技大学 | Method for producing biological butanol by rice hull |
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| CN101333545A (en) * | 2008-08-05 | 2008-12-31 | 上海凯赛生物技术研发中心有限公司 | Method for producing bio butanol |
| CN101353632A (en) * | 2008-01-11 | 2009-01-28 | 上海凯赛生物技术研发中心有限公司 | A strain of Clostridium acetobutylicum, screening method and use thereof |
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| CN101353632A (en) * | 2008-01-11 | 2009-01-28 | 上海凯赛生物技术研发中心有限公司 | A strain of Clostridium acetobutylicum, screening method and use thereof |
| CN101333545A (en) * | 2008-08-05 | 2008-12-31 | 上海凯赛生物技术研发中心有限公司 | Method for producing bio butanol |
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| CN102876731A (en) * | 2012-10-25 | 2013-01-16 | 中南林业科技大学 | Method for producing biological butanol by rice hull |
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