CN101514349A - Method for preparing fuel ethanol from bamboo fibers - Google Patents
Method for preparing fuel ethanol from bamboo fibers Download PDFInfo
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- CN101514349A CN101514349A CNA200810080614XA CN200810080614A CN101514349A CN 101514349 A CN101514349 A CN 101514349A CN A200810080614X A CNA200810080614X A CN A200810080614XA CN 200810080614 A CN200810080614 A CN 200810080614A CN 101514349 A CN101514349 A CN 101514349A
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- formic acid
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Abstract
The invention discloses a method for preparing fuel ethanol from bamboo fibers. The method comprises the following steps that: waste from bamboo (or other non-wood biomass) processing is used as a raw material, the raw material is cut, dried, crushed and passed through a 80-mesh sieve, the powder passing through the 80-mesh sieve is fine bamboo powder and the powder failing to pass through the 80-mesh sieve is coarse bamboo powder; the coarse bamboo powder is cooked in a mixed liquid of formic acid, acetic acid and water for hydrolyzing hemicellulose and delignification, and fibers are obtained and subjected to hydrolysis by an organic acid to form a reducing monosaccharide; the fine bamboo powder is hydrolyzed directly by the organic acid to form the reducing monosaccharide; the reducing monosaccharide obtained from the hydrolysis of the hemicelluloses, the fibers and the fine bamboo powder are detoxicated by an excess amount of Ca(OH)2, the pH of the mixture is reduced, and the fuel ethanol is obtained after fermentation and rectification. The method for producing the fuel ethanol ensures the yield of the fuel ethanol, reduces the energy consumption for hydrolysis, and allows the organic acid used for hydrolysis to be recycled. In addition, the process of the fuel ethanol preparation using the method requires less water, and reduces environmental pollution and cost.
Description
Technical field
The present invention relates to a kind ofly prepare the method for alcohol fuel by bamboo fiber, promptly is raw material with the bamboo wood, obtains reducing sugar with organic acid hydrolysis bamboo fibers, and the reducing sugar of gained is fermented obtains alcohol fuel again.Wherein, used organic acid can be recycled.
Technical background
Along with the increase of world population and the raising of various countries' industrialization degree, the energy and environmental problem have become the focus that the whole world is paid close attention to.Fossil energy materials such as oil, coal and Sweet natural gas are petered out; be the protection environment and realize the target of human kind sustainable development, from renewable resources particularly Wooden Biomass production chemical products with high added-value become the important development strategy of many countries and the hot fields of scientific research.Biomass energy is reproducible clean energy, utilizes biomass to produce Chemicals such as alcohol fuel for the concurrent ferment of raw material hydrolysis and is subjected to extensive concern just day by day.
The technology that employing contains the farm crop preparing ethanol by fermentation of sugar and starch etc. has reached its maturity, and widespread use.Yet along with world population increases, the staple food supply anxiety is the method expansion on a large scale of feedstock production alcohol fuel with food crop, and therefore adopting wood fibre is raw material, and it is significant to produce alcohol fuel by biomass by hydrolyzation.The three big components of forming Wooden Biomass are polymkeric substance such as Mierocrystalline cellulose, hemicellulose and lignin, and wherein Mierocrystalline cellulose and hemicellulose can be converted into ethanol, and theoretical yield can similar with grain (greater than 400L/t).On total amount, Mierocrystalline cellulose, hemicellulose and lignin are only the resource of renewable biomass the most widely that exists in the world.Bamboo belongs to grass, and Mierocrystalline cellulose and hemicellulose level are higher, and content of lignin is lower, and the phenolic acids secondary substance is also less.China has abundant bamboo plant resource as bamboo kingdom.Bamboo grove is widely distributed, and growth is fast, and it is short to cut down the phase, and the output height is the important Forest Types of China.Therefore, bamboo can become the high-quality of producing alcohol fuel and abundant desirable feedstock.
Since the seventies in 20th century, the whole world has started the research boom of one cleaning substitute energy, the alcohol fuel that wherein derives from biomass energy with its recyclability, nonstaining property, do not cause Greenhouse effect and improve the characteristics such as explosion-proof performance of automobile and be acknowledged as one of renewable energy source of prospects for commercial application is arranged most, obtained extensive studies.Wood Adhesives from Biomass is that ethanol will be fermentable raw material-reducing sugar with Wood Adhesives from Biomass at first.Main at present mineral acid (rare or dense) and the enzymic hydrolysis filamentary material of adopting produces reducing sugar.
1. acid-hydrolysis method
Acid hydrolysis can be divided into dilute acid hydrolysis and concentrated acid hydrolysis, and dilute acid hydrolysis is a five-carbon sugar with hydrolysis of hemicellulose earlier usually at a lower temperature, and then adds acid hydrolysis residual solids under comparatively high temps, obtains hydrolysate glucose.The transformation efficiency of dilute acid hydrolysis sugar has only 50%, and has more depolymerization product can stop yeast fermentation to generate ethanol.Vitriol oil hydrolysis has 90% Mierocrystalline cellulose and hemicellulose to be converted into fermentable sugars approximately, but the acid in the hydrolysis is difficult to reclaim, and produces a large amount of gypsum with in the lime and back, and its value is very low.
2. enzyme hydrolysis method
Enzymic hydrolysis is a biochemical reaction, and biological material is put into hydrolysis reactor through after the pre-treatment, adds cellulase.Katalysis by cellulase is cellulose hydrolysis the monose that can ferment.This hydrolytic process reaction conditions gentleness does not generate poisonous degraded product.But because cost height, the hydrolysis time of production of cellulose enzyme are long at present, and productive rate relies on effects of pretreatment, equipment that pre-treatment need be bigger and higher running cost to a great extent.
Summary of the invention
The object of the present invention is to provide a kind of is the method for feedstock production alcohol fuel with the bamboo wood, and promptly with organic acid hydrolysis bamboo fine powder (or organic acid handled bamboo meal) preparation reducing sugar, the hydrolyzed solution that ferments then obtains alcohol fuel.
Conception of the present invention
The biomass by hydrolyzation process be exactly hemicellulose and cellulose degradation be the process of pentose and glucose.But under hot conditions, pentose and glucose are also unstable, can further be degraded to by products such as furfural and hydroxymethylfurfural, and follow-up microbial fermentation is brought disadvantageous effect.Therefore, hydrolytic process should reduce production of by-products as far as possible when improving sugared concentration.
Compare with Mierocrystalline cellulose, the hydrolysis ratio of hemicellulose is easier to carry out.When temperature during at 100-105 ℃, add certain density organic acid boiling, can stripping be enclosed in Mierocrystalline cellulose xylogen on every side, hemicellulose is degraded to pentose simultaneously, pentose and lignin are dissolved in the organic acid soln simultaneously, thin up, the lignin precipitation leaches, and gets the wood sugar concentrated solution after filtrate is concentrated.Isolated solid residue Mierocrystalline cellulose adds catalyzer hydrolysis at normal temperatures with organic acid again after the boiling, distills out organic acid and promptly obtains reducing sugar.Consider factors such as fermentation costs and equipment, pentose is become alcohol fuel with shehatae candida with fermentation by saccharomyces cerevisiae with follow-up cellulose hydrolysis gained reducing sugar.The lignin that reclaims can continue to prepare the chemical of other high added value or act as a fuel burning etc.
The present invention imagination when boiling bamboo meal with organic acid formic acid and acetate, hydrolysis bamboo fine powder and use formic acid during by the Mierocrystalline cellulose of bamboo meal preparation, and make catalyzer with hydrochloric acid.
Technical scheme
1, the present invention is starting material with mao bamboon tankage (also being applicable to other non-timber biomass), and it is blocked, dries, pulverizes, crosses 80 mesh sieves.By 80 mesh sieves be the bamboo fine powder, what cross 80 mesh sieves is the bamboo meal.
2, the bamboo meal is added in the pulp digester, with the mixed solution (liquid-solid ratio is 10: 1) of formic acid, acetate and water (ratio is 10/70/20) at 100-105 ℃ of following boiling 2h.Hydrolysis of hemicellulose is that wood sugar is dissolved in the acid solution, and lignin also is dissolved in the acid solution, and acid solution thin up lignin precipitation is separated out, and gets the pentose concentrated solution after cooking liquor is concentrated, and the gained solid residue is a cellulose components.
Above-mentioned gained solid residue Mierocrystalline cellulose adds 60 ℃ of hydrolysis 6h of 4% hydrochloric acid with 85% formic acid, and the formic acid underpressure distillation obtains reducing sugar after reclaiming.
3, the bamboo fine powder is added in the hydrolysis reactor, add 85% formic acid and 4% hydrochloric acid at 25: 1 at 60 ℃ of following hydrolysis 6h, after formic acid and salt acid recovery, obtain reducing sugar with liquid-solid ratio.
4, above-mentioned gained reducing sugar is mixed, after the detoxification treatment, with yeast saccharomyces cerevisiae and shehatae candida, 30 ℃ of fermentations 48 hours.
Description of drawings
Fig. 1 bamboo fiber prepares the alcohol fuel schematic flow sheet
Specific implementation method
The present invention will be further described below by example, but do not influence protection scope of the present invention:
Embodiment 1
The mao bamboon tankage are blocked, dry, pulverize.Cross 80 mesh sieves, by 80 mesh sieves be the bamboo fine powder, be not the bamboo meal by the person.Take by weighing 400 gram bamboo meal and add in the digestion reactors, add the mixed solution of formic acid/acetic acid/water (10/70/20) at 10: 1 with liquid-solid ratio, 105 ℃ of boiling 2h, filter 50.2% filter residue (main component is a Mierocrystalline cellulose); Have behind the filtrate thin up precipitation separate out, filter 16% xylogen; Test contains 20% piperylene after the concentrating filter liquor.
Embodiment 2
Embodiment 1 gained Mierocrystalline cellulose is added in the hydrolysis reactor, add 85% formic acid and 4% hydrochloric acid at 25: 1 at 60 ℃ of following hydrolysis 6h with liquid-solid ratio, underpressure distillation can obtain 55% reducing sugar after reclaiming formic acid.
Embodiment 3
Bamboo fine powder 400 grams that take by weighing among the embodiment 1 preparation add in the hydrolysis reactors, add 85% formic acid and 4% hydrochloric acid at 25: 1 at 60 ℃ of following hydrolysis 6h with liquid-solid ratio, after formic acid and hydrochloric acid underpressure distillation are reclaimed, obtain 72.7% reducing sugar.
Embodiment 4
With embodiment 1,2,3 gained reductive hydrolysis liquid glucoses, with Ca (OH)
2Adjust pH is used H again to 9-10 (excessive alkaline process overliming)
2SO
4Recall to pH5.5.With hydrolysis sugar liquid 150ml after the detoxification treatment and the yeast saccharomyces cerevisiae bacterial classification concentrated solution 50mL mixed fermentation behind the multiplication culture, ferment after 48 hours, fermented liquid is drawn off, the bacterial classification in the reactor is kept 50mL as inoculum, in 72 hours, add hydrolyzed solution 400mL continuously.Leavening temperature is 30 ℃, and alcohol yied is 0.40g/g.
The used yeast bacterial classification is yeast saccharomyces cerevisiae (Saccharomyces cerevisiae Meyen et Hansen 2157) and shehatae candida (Candida shehatae) in the zymocyte liquid.
The acclimation method of used bacterial classification is as follows:
Substratum (g/L): peptone 3, yeast extract paste 2.5, MgSO
40.25, KH
2PO
42.5, CaCl
20.25, glucose 15.00,121 ℃ of sterilizations of pH5.0-5.5. substratum 20 minutes.
The enrichment culture of bacterial classification: in the 100mL liquid nutrient medium, 30 ℃, 80rpm activates 24h with the bacterial classification inoculation of preservation.Change fresh culture then into, breed 48h down in similarity condition.
Claims (6)
1, a kind of is the method that the hydrolysis of raw material organic acid prepares alcohol fuel with the bamboo wood, it is characterized in that, comprises the steps:
A, be starting material, it is blocked, dries, pulverizes, crosses 80 mesh sieves with mao bamboon tankage (also being applicable to other non-timber biomass).By 80 mesh sieves be the bamboo fine powder, what cross 80 mesh sieves is the bamboo meal.
B, boiling bamboo meal, hydrolyzed hemicellulose, removal lignin are isolated Mierocrystalline cellulose.
Mierocrystalline cellulose is isolated in c, organic acid hydrolysis.
D, organic acid hydrolysis bamboo fine powder.
E, with hydrolysis gained reducing sugar detoxification secondary fermentation.
2, according to the described method of claim 1 (b), it is characterized in that, use formic acid/acetic acid/water mixed solution in 100-105 ℃ of boiling 2h the bamboo meal.Remaining residue is a Mierocrystalline cellulose after the boiling, adds entry in the filtrate lignin precipitation is leached, and hydrolysis of hemicellulose is that pentose is dissolved in the acid solution, can obtain water-soluble piperylene after evaporation concentration.
According to the described method of claim 1 (c), it is characterized in that 3, the formic acid with 85% adds hydrochloric acid and makes catalyzer, the Mierocrystalline cellulose of hydrolysis claim 2 preparation.Liquid-solid ratio 25: 1, at 60 ℃ of hydrolysis 6h, underpressure distillation Separation and Recovery formic acid obtains reducing sugar.
4, according to the described method of claim 1 (d), it is characterized in that, the bamboo fine powder is added hydrochloric acid with 85% formic acid make catalyzer, liquid-solid ratio 25: 1, at 60 ℃ of hydrolysis 6h, underpressure distillation Separation and Recovery formic acid obtains reducing sugar.
5, the reducing sugar that obtains according to claim 2,3,4 described methods according to claim 1 (e) detoxification, is characterized in that, with excessive Ca (OH)
2Adjust pH is used H again to 9-10
2SO
4Recall to pH5.5.
6, according to claim 5, with hydrolysis sugar liquid 150ml after the detoxification treatment and the yeast saccharomyces cerevisiae bacterial classification concentrated solution 50mL mixed fermentation behind the multiplication culture, 30 ℃ the fermentation 48 hours after, fermented liquid is drawn off, bacterial classification in the reactor is kept 50mL as inoculum, in 72 hours, add hydrolyzed solution 400mL continuously, obtain tunning, carry out rectifying, collect ethanol wherein.
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Cited By (16)
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| CN101857885A (en) * | 2010-05-28 | 2010-10-13 | 农业部沼气科学研究所 | Process for producing fuel ethanol by utilizing bamboo biomass waste |
| WO2011082000A1 (en) * | 2009-12-31 | 2011-07-07 | Shell Oil Company | Direct aqueous phase reforming of bio-based feedstocks |
| CN101693905B (en) * | 2009-10-27 | 2011-09-07 | 哈尔滨工业大学 | Improved method of excess calcium hydrate detoxification during cellulose ethanol production |
| CN102660882A (en) * | 2012-05-17 | 2012-09-12 | 刘德江 | Method for producing cellulose and fuel ethanol by dissolving plant straw with solvent |
| CN103003435A (en) * | 2010-06-30 | 2013-03-27 | 欧内斯特·斯图尔特 | Universal biomass refinery |
| CN103061179A (en) * | 2012-12-25 | 2013-04-24 | 济南圣泉集团股份有限公司 | Comprehensive utilization process for lignocellulose biomass |
| CN103102334A (en) * | 2012-12-25 | 2013-05-15 | 济南圣泉集团股份有限公司 | Process for producing furfural from biomass raw material |
| CN103352057A (en) * | 2013-07-12 | 2013-10-16 | 浙江农林大学 | Method for preparing fuel ethanol by taking bamboo shoot processing residues as raw materials |
| CN103898787A (en) * | 2012-12-25 | 2014-07-02 | 济南圣泉集团股份有限公司 | Comprehensive utilization method of biomass raw material |
| CN103910766A (en) * | 2014-02-25 | 2014-07-09 | 北京林业大学 | Preparation method for poplar acetic acid lignin through separation and purification |
| CN104450830A (en) * | 2015-01-04 | 2015-03-25 | 南京林业大学 | Method for producing multiple kinds of monosaccharide through bamboo processing residues |
| US9150937B2 (en) | 2013-02-01 | 2015-10-06 | Industrial Technology Research Institute | Method for preparing sugars |
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| CN109337936A (en) * | 2018-10-30 | 2019-02-15 | 孙金良 | Association fibre element Ethanol Method |
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| CN101253276B (en) * | 2005-08-31 | 2012-10-10 | 国立大学法人三重大学 | Method of producing saccharide compositions starting with biomass |
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- 2008-02-21 CN CN200810080614XA patent/CN101514349B/en not_active Expired - Fee Related
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| CN101693905B (en) * | 2009-10-27 | 2011-09-07 | 哈尔滨工业大学 | Improved method of excess calcium hydrate detoxification during cellulose ethanol production |
| WO2011082000A1 (en) * | 2009-12-31 | 2011-07-07 | Shell Oil Company | Direct aqueous phase reforming of bio-based feedstocks |
| CN102712851A (en) * | 2009-12-31 | 2012-10-03 | 国际壳牌研究有限公司 | Direct aqueous phase reforming of bio-based feedstocks |
| CN102712851B (en) * | 2009-12-31 | 2015-02-25 | 国际壳牌研究有限公司 | Direct aqueous phase reforming of bio-based feedstocks |
| CN101857885A (en) * | 2010-05-28 | 2010-10-13 | 农业部沼气科学研究所 | Process for producing fuel ethanol by utilizing bamboo biomass waste |
| CN101857885B (en) * | 2010-05-28 | 2013-10-09 | 农业部沼气科学研究所 | Process for producing fuel ethanol by utilizing bamboo biomass waste |
| CN103003435A (en) * | 2010-06-30 | 2013-03-27 | 欧内斯特·斯图尔特 | Universal biomass refinery |
| CN102660882A (en) * | 2012-05-17 | 2012-09-12 | 刘德江 | Method for producing cellulose and fuel ethanol by dissolving plant straw with solvent |
| CN102660882B (en) * | 2012-05-17 | 2015-01-28 | 刘德江 | Method for producing cellulose and fuel ethanol by dissolving plant straw with solvent |
| US9695484B2 (en) | 2012-09-28 | 2017-07-04 | Industrial Technology Research Institute | Sugar products and fabrication method thereof |
| CN103898787A (en) * | 2012-12-25 | 2014-07-02 | 济南圣泉集团股份有限公司 | Comprehensive utilization method of biomass raw material |
| CN103102334B (en) * | 2012-12-25 | 2014-11-19 | 济南圣泉集团股份有限公司 | Process for producing furfural from biomass raw material |
| CN103102334A (en) * | 2012-12-25 | 2013-05-15 | 济南圣泉集团股份有限公司 | Process for producing furfural from biomass raw material |
| CN103061179B (en) * | 2012-12-25 | 2015-06-17 | 济南圣泉集团股份有限公司 | Comprehensive utilization process for lignocellulose biomass |
| CN103898787B (en) * | 2012-12-25 | 2016-06-15 | 济南圣泉集团股份有限公司 | A kind of comprehensive utilization process of biomass material |
| CN103061179A (en) * | 2012-12-25 | 2013-04-24 | 济南圣泉集团股份有限公司 | Comprehensive utilization process for lignocellulose biomass |
| US9150937B2 (en) | 2013-02-01 | 2015-10-06 | Industrial Technology Research Institute | Method for preparing sugars |
| CN103352057A (en) * | 2013-07-12 | 2013-10-16 | 浙江农林大学 | Method for preparing fuel ethanol by taking bamboo shoot processing residues as raw materials |
| CN103910766A (en) * | 2014-02-25 | 2014-07-09 | 北京林业大学 | Preparation method for poplar acetic acid lignin through separation and purification |
| CN104450830A (en) * | 2015-01-04 | 2015-03-25 | 南京林业大学 | Method for producing multiple kinds of monosaccharide through bamboo processing residues |
| CN109337936A (en) * | 2018-10-30 | 2019-02-15 | 孙金良 | Association fibre element Ethanol Method |
| CN111269947A (en) * | 2020-03-11 | 2020-06-12 | 吉林大学 | Method for detoxifying acid hydrolysis liquid and preparing cellulosic ethanol |
| WO2022116978A1 (en) * | 2020-12-04 | 2022-06-09 | 浙江华康药业股份有限公司 | Method for improving high-solid enzymolysis rate of biomass |
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