CN107034241B - Pretreatment process for saccharification and utilization of bagasse - Google Patents
Pretreatment process for saccharification and utilization of bagasse Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
- C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/16—Butanols
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
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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
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- Bioinformatics & Cheminformatics (AREA)
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Abstract
The invention discloses a pretreatment process for saccharification and utilization of bagasse, which comprises the following steps: (1) first pretreatment: adding a sodium hydroxide solution into bagasse, and carrying out constant-temperature water bath pretreatment for 0.5-1.5 h at the temperature of 48-52 ℃ to obtain a bagasse solid-liquid mixture subjected to primary pretreatment; (2) and (3) second pretreatment: and adding urea into the bagasse solid-liquid mixture subjected to the first pretreatment, quickly cooling to-14 to-10 ℃, carrying out constant-temperature pretreatment for 0.5 to 1.5 hours, filtering to remove filtrate, and drying filter residues to obtain a pretreated bagasse sample. The bagasse pretreated by the bagasse pretreatment process disclosed by the invention is high in enzymolysis efficiency, high in reducing sugar conversion rate and low in cost.
Description
Technical Field
The invention belongs to the technical field of solid waste resource utilization, and particularly relates to a pretreatment process for bagasse saccharification and utilization.
Background
The conflict between the increasing demand for energy from economic development and the gradual decrease of traditional fossil energy has caused concerns about energy safety, and the greenhouse effect caused by the use of traditional fossil energy has caused concerns about deterioration of living environment, which has prompted intensive research on different renewable energy sources for the past decades. Biomass has also attracted attention as the only renewable organic carbon source on earth, and sugarcane, which is a perennial plant, is the largest crop grown worldwide, widely grown in tropical and subtropical regions, and utilizes abundant sunlight and carbon dioxide to synthesize carbohydrates. The annual output of sugar cane in China is large, the sugar cane is basically used for producing sugar, after sugar extraction, the residual sugar cane bagasse is not effectively utilized in China, the residual sugar cane bagasse is burnt like other crop straws, not only is the resource waste caused, but also serious environmental pollution is caused, the sugar cane bagasse contains rich cellulose, cellulose raw materials can be hydrolyzed by cellulase and converted into saccharified liquid, then ethanol or butanol is produced by fermentation of microbial strains (saccharomyces cerevisiae and monospora mobilis), and then the ethanol or butanol is obtained by distillation and dehydration, and the production of energy substances such as fuel ethanol by using the sugar cane bagasse is more and more widely concerned at home and abroad at present.
The components of the dried bagasse mainly comprise cellulose, hemicellulose and lignin, and the content of protein, starch and soluble sugar is low. Cellulose is a high molecular polymer formed by connecting glucose through glycosidic bonds, contains a large number of crystalline regions, and has a large number of hydrogen bonds among molecules; the main components of the hemicellulose comprise xylose, mannose, glucose, arabinose, galactose and the like, and the hemicellulose surrounds the cellulose and extends into the cellulose; the lignin is a biopolymer compound with a three-dimensional network structure formed by connecting three phenylpropane units through ether bonds and carbon-carbon bonds, and is linked with hemicellulose through chemical bonds to surround and reinforce the cellulose and the hemicellulose, the structure makes the cellulose difficult to degrade, and the enzymatic hydrolysis efficiency is low, so bagasse needs to be properly pretreated to destroy the natural structure of the bagasse, increase the loose degree of raw materials, and increase the effective contact of cellulase or microorganisms to improve the enzymatic hydrolysis rate and the conversion rate of the cellulose, thereby realizing the effective conversion of the cellulose in the bagasse into energy products such as ethanol or butanol. At present, a plurality of pretreatment methods exist, but the problems of high cost and low pretreatment efficiency still exist, so that the biomass energy utilization is difficult to promote in a large scale, and further research is needed.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a pretreatment process for saccharification and utilization of bagasse, which has the advantages of high enzymolysis efficiency of pretreated products, high conversion rate of reducing sugar and low cost.
In order to achieve the aim, the pretreatment process for saccharification and utilization of bagasse comprises the following steps:
step (1): first pretreatment: adding a sodium hydroxide solution into bagasse, and pretreating in a constant-temperature water bath at 48-52 ℃ for 0.5-1.5 h to obtain a bagasse solid-liquid mixture subjected to first pretreatment;
step (2): and (3) second pretreatment: and adding urea into the bagasse solid-liquid mixture subjected to the first pretreatment, quickly cooling to-14 to-10 ℃, carrying out constant-temperature pretreatment for 0.5 to 1.5 hours, filtering to remove filtrate, and drying filter residues to obtain a pretreated bagasse sample.
The bagasse sample after the pretreatment can be converted into saccharified liquid through cellulase hydrolysis, then ethanol or butanol is produced through fermentation of microbial strains (saccharomyces cerevisiae, sports monascus and the like), and absolute ethanol or butanol is obtained through distillation and dehydration.
The alkaline pretreatment of biomass is researched more and is a mature process, and the alkaline pretreatment of biomass, especially strong alkali such as sodium hydroxide, has a good pretreatment effect on biomass and can remove lignin and partial hemicellulose, which is very helpful for saccharification and utilization of biomass; the combination of sodium hydroxide and urea can well dissolve low-polymerization-degree cellulose and swell high-polymerization-degree cellulose at low temperature, the effect of dissolving and swelling cellulose can reduce the polymerization degree (DP <800) of crystalline cellulose, and is favorable for improving the saccharification efficiency of biomass, but the pretreatment at low temperature is not favorable for exerting the effect of removing lignin and partial hemicellulose of sodium hydroxide, so that the sodium hydroxide and urea can not be added simultaneously for use, the good bagasse structure destruction effect can not be achieved, the urea can not be effectively contacted with crystalline cellulose, the dissolving and swelling effect can not be exerted, the improvement of the enzymolysis efficiency is not obvious, and the early addition of urea can possibly cause the hydrogen bonds to be formed by the urea, water and sodium hydroxide, the amount of hydroxide ions is reduced, and the amount of pretreated biomass of sodium hydroxide can be reduced, so the invention reasonably analyzes the conditions required by the action of two advantageous effects of sodium hydroxide and urea, the process of step-by-step pretreatment is carried out, different temperatures are adopted, so that two advantageous effects can be fully exerted, and the high-efficiency biomass saccharification pretreatment process is obtained, wherein the suitable temperature range of the first pretreatment of the sodium hydroxide obtained through tests is 48-52 ℃, and the suitable temperature range of the second pretreatment of the urea and the sodium hydroxide is-14 to-10 ℃.
The invention has the beneficial effects that: the bagasse is pretreated by sodium hydroxide for the first time, the sodium hydroxide can effectively remove lignin and destroy hemicellulose, the specific surface area of the bagasse surface is increased, more gaps are generated, the effective contact between cellulase and cellulose and hemicellulose is increased, the enzymolysis efficiency is improved, the cellulose and the hemicellulose are promoted to be hydrolyzed by the cellulase to generate reducing sugar, the bagasse after the first pretreatment by the sodium hydroxide is pretreated for the second time by urea in a low-temperature environment, crystalline cellulose can be effectively swelled, the crystallinity of the cellulose is reduced, the exposure degree of the cellulose is increased, the enzymolysis efficiency of the cellulose is further improved, the conversion rate of reducing sugar in the matrix is improved, the bagasse after being treated by the pretreatment process of the invention is subjected to enzymolysis by the cellulase for about 8 hours, the conversion rate of the reducing sugar (containing the cellulose and the hemicellulose) in the matrix reaches over 75 percent, the conversion rate of reducing sugar reaches more than 93 percent after enzymolysis for about 72 hours by cellulase, thereby realizing effective conversion of energy substances such as ethanol produced by cellulose in bagasse; meanwhile, the method has simple process, the used chemical reagents are common reagents in the market, the bagasse raw materials are easy to obtain, and the cost is low.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and the description in this section is only exemplary and explanatory and should not be construed as limiting the scope of the present invention in any way.
The invention relates to a pretreatment process for saccharification and utilization of bagasse, which comprises the following steps:
step (1): first pretreatment: adding a sodium hydroxide solution into bagasse, and carrying out pretreatment in a constant-temperature water bath at 48-52 ℃ for 0.5-1.5 h to obtain a bagasse solid-liquid mixture subjected to first pretreatment;
step (2): and (3) second pretreatment: and adding urea into the bagasse solid-liquid mixture subjected to the first pretreatment, quickly cooling to-14 to-10 ℃, carrying out constant-temperature pretreatment for 0.5 to 1.5 hours, filtering to remove filtrate, and drying filter residues to obtain a pretreated bagasse sample.
The first pretreatment temperature is 48-52 ℃, which is a reasonable temperature range within which a large amount of sodium hydroxide obtained by experiments can effectively react with groups such as acetyl groups of lignin and hemicellulose so as to destroy and remove the lignin and the hemicellulose; the temperature of the second pretreatment is-14 to-10 ℃, which is a reasonable temperature range for swelling the crystalline cellulose by using urea and sodium hydroxide obtained by a large amount of experiments and converting the crystalline cellulose into non-crystalline cellulose, thereby reducing the crystallinity of the cellulose and improving the cellulose hydrolysis rate.
Preferably, in the step (1), the temperature of the first pretreatment is 50 ℃, which is the most suitable temperature for removing lignin and destroying hemicellulose by sodium hydroxide; in the step (2), the temperature of the second pretreatment is-12 ℃, and the temperature is the optimum temperature for dissolving and swelling the crystalline cellulose by combining urea and sodium hydroxide, and converting the crystalline cellulose into the non-crystalline cellulose, thereby reducing the crystallinity and improving the enzymolysis rate of the cellulose.
Preferably, in the step (1), the mass concentration of the sodium hydroxide solution is 6-8 w%; in the step (2), the mass concentration of the urea in the bagasse solid-liquid mixture is 1-3 w%. The mass concentration of the sodium hydroxide solution is controlled to be 6-8 w%, and the mass concentration of the urea is controlled to be 1-3 w%, so that the sodium hydroxide and the urea obtained by a large number of orthogonal optimization experiments can well swell the mass concentration range of crystalline cellulose at-14 to-10 ℃.
More preferably, in the step (1), the mass concentration of the sodium hydroxide solution is 7 w%; in the step (2), the mass concentration of the urea in the bagasse solution is 2 w%.
Preferably, in the step (1), the volume-to-mass ratio of the added sodium hydroxide solution to the bagasse is 8-10: 1, the lignin and hemicellulose cannot be effectively removed when the amount of the sodium hydroxide is small, the sodium hydroxide is combined with urea to swell crystalline cellulose, and the raw material is wasted when the amount of the sodium hydroxide is large, so that the ratio is in an optimum ratio range.
Preferably, in the step (2), the temperature reduction rate is-6 ℃ to-12 ℃/min.
Example 1: pretreated bagasse samples
The pretreatment process of the embodiment comprises the following steps:
weighing 10.0000 +/-0.0010 g of bagasse, adding 100.0 +/-0.1 mL of sodium hydroxide solution with the mass concentration of 7 w%, uniformly stirring, transferring to a constant-temperature water bath oscillator, pretreating at 50 ℃ for 0.5h, adding 2g of urea, rapidly cooling to-12 ℃ at the speed of-6 to-12 ℃/min, pretreating at the constant temperature for 1.5h, filtering to remove filtrate, washing the filter residue with distilled water until the washing water is neutral, and drying the filter residue to obtain a pretreated bagasse sample.
Example 2: pretreated bagasse samples
The pretreatment process of the embodiment comprises the following steps:
weighing 10.0000 +/-0.0010 g of bagasse, adding 100.0 +/-0.1 mL of sodium hydroxide solution with the mass concentration of 7 w%, uniformly stirring, transferring to a constant-temperature water bath oscillator, pretreating at 50 ℃ for 1h, then adding 2g of urea, rapidly cooling to-12 ℃ at the speed of-6 to-12 ℃/min, pretreating at constant temperature for 1h, filtering to remove filtrate, washing filter residue with distilled water until the washing water is neutral, and drying the filter residue to obtain a pretreated bagasse sample.
Example 3: pretreated bagasse samples
The pretreatment process of the embodiment comprises the following steps:
weighing 10.0000 +/-0.0010 g of bagasse, adding 100.0 +/-0.1 mL of sodium hydroxide solution with the mass concentration of 7 w%, uniformly stirring, transferring to a constant-temperature water bath oscillator, pretreating at 50 ℃ for 1.5h, adding 2g of urea, rapidly cooling to-12 ℃ at the speed of-6 to-12 ℃/min, pretreating at the constant temperature for 0.5h, filtering to remove filtrate, washing the filter residue with distilled water until the washing water is neutral, and drying the filter residue to obtain a pretreated bagasse sample.
Example 4: pretreated bagasse samples
Weighing 10.0000 +/-0.0010 g of bagasse, adding 100.0 +/-0.1 mL of sodium hydroxide solution with the mass concentration of 6 w%, uniformly stirring, transferring to a constant-temperature water bath oscillator, pretreating at 48 ℃ for 0.5h, adding 1g of urea, rapidly cooling to-14 ℃ at the speed of-6 to-12 ℃/min, pretreating at the constant temperature for 1.5h, filtering to remove filtrate, washing the filter residue with distilled water until the washing water is neutral, and drying the filter residue to obtain a pretreated bagasse sample.
Example 5: pretreated bagasse samples
Weighing 10.0000 +/-0.0010 g of bagasse, adding 100.0 +/-0.1 mL of sodium hydroxide solution with the mass concentration of 8 w%, uniformly stirring, transferring to a constant-temperature water bath oscillator, pretreating at 52 ℃ for 0.5h, adding 3g of urea, rapidly cooling to-10 ℃ at the speed of-6 to-12 ℃/min, pretreating at the constant temperature for 1.5h, filtering to remove filtrate, washing the filter residue with distilled water until the washing water is neutral, and drying the filter residue to obtain a pretreated bagasse sample.
Example 6: pretreated bagasse samples
Weighing 10.0000 +/-0.0010 g of bagasse, adding 80.0 +/-0.1 mL of sodium hydroxide solution with the mass concentration of 7 w%, uniformly stirring, transferring to a constant-temperature water bath oscillator, pretreating at 50 ℃ for 0.5h, then adding 1.6g of urea, rapidly cooling to-12 ℃ at the speed of-6 to-12 ℃/min, pretreating at the constant temperature for 1.5h, filtering to remove filtrate, washing filter residue with distilled water until the washing water is neutral, and drying the filter residue to obtain a pretreated bagasse sample.
Comparative example 1: sugar cane bagasse without pretreatment.
The results of determining the cellulose, hemicellulose and lignin contents and the crystallinity index of the bagasse samples pretreated in examples 1 to 3 and the bagasse sample not pretreated in comparative example 1, respectively, and adding cellulase for an enzymatic hydrolysis sugar production test, and determining the reducing sugar conversion rates after 8 hours and 72 hours are shown in table 1 (the reducing sugar conversion rates of 8 hours and 72 hours in examples 4 to 6 are lower than those in examples 1 to 3, and the corresponding results are not shown).
TABLE 1
As can be seen from Table 1, lignin and hemicellulose in bagasse treated by the pretreatment process and bagasse not pretreated by the pretreatment process are both removed significantly, the content of cellulose is increased significantly, the crystallinity of cellulose is reduced significantly, the conversion rate of reducing sugar is increased greatly, the conversion rate of reducing sugar after 8 hours of enzymolysis by cellulase reaches more than 75%, and the conversion rate of reducing sugar after 72 hours of enzymolysis by cellulase reaches more than 93%.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the technical scope of the present invention, so that any minor modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the technical scope of the present invention.
Claims (2)
1. A pretreatment process for saccharification and utilization of bagasse is characterized by comprising the following steps: the method comprises the following steps:
step (1): first pretreatment: adding a sodium hydroxide solution into bagasse, and pretreating in a thermostatic water bath at 50 ℃ for 0.5-1.5 h to obtain a bagasse solid-liquid mixture subjected to first pretreatment; the mass concentration of the sodium hydroxide solution is 7 w%;
step (2): and (3) second pretreatment: adding urea into the bagasse solid-liquid mixture subjected to the first pretreatment, rapidly cooling to-12 ℃, carrying out constant-temperature pretreatment for 0.5-1.5 h at the cooling rate of-6 ℃ to-12 ℃/min, filtering to remove filtrate, and drying filter residues to obtain a pretreated bagasse sample; the mass concentration of the urea in the bagasse solid-liquid mixture is 2 w%.
2. A pretreatment process for bagasse saccharification as defined in claim 1, characterized by: in the step (1), the volume-to-mass ratio of the added sodium hydroxide solution to the bagasse is 8-10: 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710350965.7A CN107034241B (en) | 2017-05-17 | 2017-05-17 | Pretreatment process for saccharification and utilization of bagasse |
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| CN201710350965.7A CN107034241B (en) | 2017-05-17 | 2017-05-17 | Pretreatment process for saccharification and utilization of bagasse |
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| CN107034241A CN107034241A (en) | 2017-08-11 |
| CN107034241B true CN107034241B (en) | 2020-10-23 |
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| CN101160409A (en) * | 2005-04-12 | 2008-04-09 | 纳幕尔杜邦公司 | System and process for biomass treatment |
| CN101705267A (en) * | 2009-11-02 | 2010-05-12 | 安徽丰原发酵技术工程研究有限公司 | Method for efficiently saccharifying bagasse |
| CN103205473A (en) * | 2013-04-16 | 2013-07-17 | 昆明理工大学 | Bagasse pretreatment method |
| CN104498562A (en) * | 2014-12-17 | 2015-04-08 | 江苏大学 | Method for pretreating agricultural waste biomass by adopting sodium hydroxide/urea/water system |
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| CN101160409A (en) * | 2005-04-12 | 2008-04-09 | 纳幕尔杜邦公司 | System and process for biomass treatment |
| CN101705267A (en) * | 2009-11-02 | 2010-05-12 | 安徽丰原发酵技术工程研究有限公司 | Method for efficiently saccharifying bagasse |
| CN103205473A (en) * | 2013-04-16 | 2013-07-17 | 昆明理工大学 | Bagasse pretreatment method |
| CN104498562A (en) * | 2014-12-17 | 2015-04-08 | 江苏大学 | Method for pretreating agricultural waste biomass by adopting sodium hydroxide/urea/water system |
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| 化学处理提高甘蔗渣营养价值的研究;毛华明等;《动物营养学报》;20000430;第12卷(第2期);第62页摘要 * |
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