CN110041446B - Comprehensive refining method for biomass - Google Patents

Comprehensive refining method for biomass Download PDF

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CN110041446B
CN110041446B CN201910214070.XA CN201910214070A CN110041446B CN 110041446 B CN110041446 B CN 110041446B CN 201910214070 A CN201910214070 A CN 201910214070A CN 110041446 B CN110041446 B CN 110041446B
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microwave
biomass
starting
refining method
liquid
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CN110041446A (en
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肖兵
董玉平
王仲钢
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Shandong Xiancao Biotechnology Co.,Ltd.
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肖兵
董玉平
王仲钢
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0003—General processes for their isolation or fractionation, e.g. purification or extraction from biomass
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
    • C08B37/0045—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid alpha-D-Galacturonans, e.g. methyl ester of (alpha-1,4)-linked D-galacturonic acid units, i.e. pectin, or hydrolysis product of methyl ester of alpha-1,4-linked D-galacturonic acid units, i.e. pectinic acid; Derivatives thereof
    • C08B37/0048—Processes of extraction from organic materials
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
    • D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
    • D21B1/30—Defibrating by other means
    • D21B1/303—Defibrating by other means using vibrating devices
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21B—FIBROUS RAW MATERIALS OR THEIR MECHANICAL TREATMENT
    • D21B1/00—Fibrous raw materials or their mechanical treatment
    • D21B1/04—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres
    • D21B1/12—Fibrous raw materials or their mechanical treatment by dividing raw materials into small particles, e.g. fibres by wet methods, by the use of steam
    • D21B1/30—Defibrating by other means
    • D21B1/306—Defibrating by other means using microwaves
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C3/00—Pulping cellulose-containing materials
    • D21C3/20—Pulping cellulose-containing materials with organic solvents or in solvent environment

Abstract

The invention discloses a comprehensive refining method of biomass, which comprises the following steps: 1) crushing and rinsing biomass raw materials, removing waste liquid, adding water into filter residues, adjusting the pH value, heating for reaction, starting microwave treatment, starting ultrasonic treatment after 10-20min, performing filter pressing after the ultrasonic treatment is finished, and performing evaporation concentration, standing for cold precipitation, drying and precipitation on filtrate to obtain pectin; 2) placing the filter residue prepared in the step 1) in a dilute alkali solution, heating to a set temperature, starting ultrasonic waves, performing ultrasonic treatment for a set time, heating for a set time, starting microwaves, performing solid-liquid separation after the microwave treatment for the set time, and evaporating and performing cold precipitation on the liquid to obtain a hemicellulose product; 3) adding a composite extracting agent of ethanol, 1, 4-butanediol and glycerol into the filter residue obtained in the step 2); then starting microwaves, stirring, standing, starting ultrasonic waves, squeezing and separating a solid phase and a liquid phase while the solid phase is hot, wherein the solid phase is cellulose, and drying the solid obtained after the liquid phase is centrifuged to obtain the lignin.

Description

Comprehensive refining method for biomass
Technical Field
The invention belongs to a new method for processing biomass materials, and particularly relates to a comprehensive refining method of biomass.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
As a big agricultural country in China, the annual yield of crop straws is higher than 7 hundred million tons, but the utilization rate is low. In recent years, the development and utilization of crop straws arouse extensive attention of people, but because the treatment cost of the straws is too high and the technological conversion is not enough, more than 70 percent of the straws are still used as fuel to be directly burnt every year, thus not only destroying the ecological balance, but also causing environmental pollution. The main components of crop straw are cellulose (25% -40%), followed by hemicellulose (20% -35%) and lignin (10% -25%). Pectin, a constituent of the cell wall, is present along with cellulose and forms a cohesive mass between adjacent cells, tightly binding the cells of the plant tissue together. These components have important application values in many fields.
At present, more processes are used for extracting substances such as cellulose, hemicellulose, lignin, pectin and the like from biomasses such as crop straws and the like, but the inventors find that the extraction efficiency of various substances is low. For example, the extraction of lignin is generally good when acid is used as a catalyst, but when sulfuric acid and hydrochloric acid are used for catalysis, cellulose and hemicellulose in biomass are hydrolyzed, and the lignin is hydrolyzed and subjected to high condensation reaction, so that the lignin removal rate is low, and is only about 30%. Under the catalytic action of acetic acid, hydronium ions capable of causing lignin hydrolysis are generated in the solvent, so that lignin is subjected to hydrolysis reaction to generate lignin fragments, and the lignin removal efficiency is about 65%. The nitric acid property is relatively mild, and the nitro cation NO generated in the reaction solvent2+And nitrite cation NO+The catalyst can generate electrophilic substitution reaction on benzene rings with phenolic and non-phenolic structural units in lignin, so that the molecular lyophilic property of the lignin is increased and the lignin is dissolved in a reaction solution, but when nitric acid is used as the catalyst, the removal efficiency of the lignin is about 75 percent, and the catalyst is not ideal.
In addition, the yield of hemicellulose extracted by the conventional method is about 66%, the yield of cellulose is about 60%, and the yields are low.
Disclosure of Invention
Aiming at overcoming the defects of the prior art, the invention aims to provide a comprehensive refining method of biomass. The comprehensive refining method can obtain higher yield of pectin, hemicellulose, lignin and cellulose. The method comprehensively utilizes the cellulosic raw materials, improves the production efficiency and the product quality, has strong practicability, and is suitable for large-scale industrial production.
In order to solve the problems, the technical scheme of the invention is as follows:
a comprehensive refining method of biomass comprises the following steps:
1) crushing and rinsing the biomass raw material, removing waste liquid, adding water into filter residue, adjusting the pH value to 3-5 with acetic acid, heating at 80-100 ℃ for 10-20min, starting microwave treatment with the microwave power of 550-2After 20-30min, starting ultrasonic treatment, after the ultrasonic treatment is finished, performing filter pressing, and performing evaporation concentration, standing for cold precipitation, drying and precipitation on the filtrate to obtain pectin;
2) placing the filter residue prepared in the step 1) in a dilute alkali solution, heating to a set temperature, starting ultrasonic waves, performing ultrasonic treatment for a set time, heating for a set time, starting microwaves, performing solid-liquid separation after the microwave treatment for the set time, and evaporating and performing cold precipitation on the liquid to obtain a hemicellulose product;
3) adding a composite extracting agent of ethanol, 1, 4-butanediol and glycerol into the filter residue obtained in the step 2), wherein the volume ratio of the ethanol to the 1, 4-butanediol to the glycerol is 1.2-1.5:3-3.5: 6; then starting the microwave and stirring, wherein the microwave power is 600-2Standing for 10-15min for 15-30min, and starting ultrasonic wave with intensity of 1-1.5w/cm3And working for 15-20min, squeezing and separating a solid phase and a liquid phase while the liquid phase is hot, wherein the solid phase is cellulose, and drying the solid obtained after the liquid phase is centrifuged to obtain the lignin.
And (3) drying the solid phase under reduced pressure in vacuum at the drying temperature of 80 ℃, condensing the gas phase substance to recover the extracting agent, cleaning the solid phase substance with clear water after the vacuum reduced pressure drying is finished, and drying to obtain the industrial cellulose raw material. Squeezing and separating to obtain liquid phase, centrifuging at 6000r/min, recovering supernatant as extractant, and vacuum drying the centrifuged solid at 80 deg.C under reduced pressure to obtain lignin.
Microwave high-frequency electromagnetic wave penetrates the extracting agent to reach the inside of the material, and the temperature inside the cell rises rapidly due to the absorption of microwave energy, so that the pressure inside the cell exceeds the force born by the expansion of the cell wall, the cell is broken, and the effective components in the cell flow out.
When the biomass material is heated in an acidic solution, pectic substances, hemicellulose and cellulose are hydrolyzed, part of lignin is dissolved out, the pectic substances are hydrolyzed to obtain pectin, the yield of the pectin is reduced due to the hydrolysis of the hemicellulose and the cellulose, the purity of the pectin is influenced, and the purity of the pectin is influenced due to the dissolution of the lignin. Therefore, if the acidic solution is used to extract pectin first, the extraction conditions of pectin need to be strictly controlled to ensure higher extraction rates of hemicellulose, lignin and cellulose.
By controlling the type, concentration, liquid pH value and reaction temperature and time of the selected acid, pectin can be preferentially extracted, and hemicellulose, lignin and cellulose are not hydrolyzed. After pectin extraction, hemicellulose is extracted again by using alkaline liquor, and lignin and cellulose are remained in a solid phase substance. After extracting hemicellulose, separating solid phase substances by using a glycerol extract to extract lignin, and obtaining residual residues which are cellulose.
The composite extractant obtained by mixing ethanol, 1, 4-butanediol and glycerol according to the volume ratio of 1.2-1.5:3-3.5:6 can quickly permeate into filter residues in a microwave field to completely and quickly extract hemicellulose flowing out after cell wall breakage, so that the extraction yield of the hemicellulose is effectively improved.
Lignin is relatively complex in composition, and has active groups such as aromatic group, phenolic hydroxyl group, alcoholic hydroxyl group, carbonyl group, methoxyl group, carboxyl group, conjugated double bond and the like in a molecular structure, so that chemical reactions such as oxidation, reduction, hydrolysis, alcoholysis, photolysis, acylation, sulfonation, alkylation, halogenation, nitration, condensation, graft copolymerization and the like easily occur. Originally degradation or condensation reactions. After the wood fiber is treated by acid-base solution and ultrasonic wave and microwave, the lignin structure and lignin are insoluble in any solvent, and in the solution environment, particularly under the acidic condition, the lignin is easy to denaturize and has changed chemical bonds and is degraded to different degrees, small molecular chains of the lignin also have the difference of polarity and non-polarity, and tests show that the mixed solution consisting of ethanol, 1, 4-butanediol and glycerol is used as an extracting agent, so that the extracting agent has a good effect on extracting the lignin in solid residues after pectin and hemicellulose are extracted. Actual measurement and detection prove that the lignin content in the treated cellulose is only 4-6% (mass percent) of the cellulose, and the cellulose meets the use requirement of industrial cellulose.
The nature and concentration of acid, the pH value of liquid and the reaction temperature and time are selected when pectin is extracted, and if the acidity is too strong or the temperature is too high and the time is too long, the hemicellulose and lignin are hydrolyzed. When extracting hemicellulose, cellulose is protected from being affected and destroyed. Only a chemical method is used for separating hemicellulose, lignin and cellulose, the substances are difficult to be not influenced, and the separation can be carried out under relatively mild chemical conditions through the intervention of a physical method (ultrasonic waves, microwaves and the like) so as to ensure the relative integrity of various substances and facilitate the extraction of single components after separation.
Preferably, in step 1), the biomass feedstock is pulverized to 2-5 mm.
Preferably, in the step 1), in the rinsing step, 1-3 times of the volume of water of the biomass raw material is added, and the biomass raw material is heated to 50-60 ℃ for rinsing for 1-2 hours. To thoroughly remove impurities from the biomass feedstock.
Preferably, in the step 1), the filtrate is concentrated by a water curtain film evaporation method, wherein the evaporation temperature is 60-80 ℃, and the concentration is carried out until the volume is 30-50% of the original volume.
Preferably, in the step 1), the standing and cold-precipitating step is to add 95% ethanol in the same volume as the concentrated solution, and to stand and cold-precipitate the pectin at 0-4 ℃ for 1-2 h.
Preferably, in step 1), the temperature for drying the precipitate is 80-90 ℃.
Preferably, in the step 2), the dilute alkali solution is a sodium hydroxide solution with a mass fraction of 2% -5%, and the volume of the sodium hydroxide solution is 2-3 times of the volume of the filter residue.
Preferably, in the step 2), after the filter residue is added to the dilute alkali solution to 50-80 ℃, ultrasonic waves are started, and the ultrasonic time is 10-20 min.
The ultrasonic waves are mainly cavitation effect, and the heat effect is not very obvious. The reaction liquid is heated by an external heat source, the external heat source is utilized to the maximum from the energy-saving angle, and after the temperature of the reaction liquid is increased, the molecular motion is accelerated, so that the reaction is convenient to carry out, and the ultrasonic wave can also play a role to the maximum.
Preferably, in the step 2), after ultrasonic treatment, heating to 80-100 ℃, preserving heat for 10-20min, and then starting microwave treatment, wherein the microwave density is 600-2The microwave treatment time is 20-30 min.
The temperature of the reaction system is not high after the ultrasonic treatment and is not more than 60 ℃, at the moment, the reaction liquid can be heated by using external heat, the reaction system can be uniformly heated, then the microwave is started, the reaction system is kept at the temperature by using the energy generated by the microwave, meanwhile, the plant cell membrane and the cell wall can be broken by using the microwave energy, water molecules easily permeate into tissues, and the separation of cellulose, hemicellulose and lignin is facilitated. If the system is heated only by the heat effect of the microwave, the reaction system is easily heated unevenly due to the excessive internal local temperature in the long-time heating state.
Preferably, in the step 2), the liquid is evaporated and concentrated by a water curtain film evaporation method to 25-45% of the original volume, then ethanol with the same volume and the mass fraction of 95% is added, and the mixture is placed in an environment with the temperature of 0-4 ℃ for standing and cold precipitation, wherein the cold precipitation time is 2-4 hours.
Preferably, in the step 3), the solid-to-liquid ratio of the filter residue to the composite extracting agent is 3-4: 10.
Preferably, in the step 3), before the separation of the solid phase and the liquid phase, the microwave is turned on twice, and the microwave power is 600-2The microwave time is 20-30min, after standing for 10-20min, the ultrasonic wave is started for the second time, the ultrasonic treatment is carried out for 10-20min, the standing is carried out for 10-20min, the microwave is started for the third time, and the microwave power is 600-2And the microwave time is 15-30 min.
The heat effect of the microwave is obvious, and the reaction system can keep higher temperature by the microwave for a long time. The microwave stops working after working for a period of time, energy accumulated by the system can be slowly digested and released, in addition, the reaction system is kept still for a period of time, the temperature of the reaction system is reduced, the reaction system is too high, the ultrasonic wave cannot work conveniently, the working temperature of the ultrasonic wave generator is not too high, therefore, from the angle of saving energy and protecting the ultrasonic wave generator, the microwave stops working after working for a period of time, and the ultrasonic wave starts working after being kept still.
Preferably, in step 3), the separated solid phase is washed with 2 volumes of 90-95% ethanol by mass fraction. Washing off the lignin attached to the solid phase.
The invention has the beneficial effects that:
microwave high-frequency electromagnetic wave penetrates the extracting agent to reach the inside of the material, and the temperature inside the cell rises rapidly due to the absorption of microwave energy, so that the pressure inside the cell exceeds the force born by the expansion of the cell wall, the cell is broken, and the effective components in the cell flow out.
When the biomass material is heated in an acidic solution, pectic substances, hemicellulose and cellulose are hydrolyzed, part of lignin is dissolved out, the pectic substances are hydrolyzed to obtain pectin, the yield of the pectin is reduced due to the hydrolysis of the hemicellulose and the cellulose, the purity of the pectin is influenced, and the purity of the pectin is influenced due to the dissolution of the lignin. Therefore, if the acidic solution is used to extract pectin first, the extraction conditions of pectin need to be strictly controlled to ensure higher extraction rates of hemicellulose, lignin and cellulose.
The composite extractant obtained by mixing ethanol, 1, 4-butanediol and glycerol according to the volume ratio of 1.2-1.5:3-3.5:6 can quickly permeate into filter residues in a microwave field to completely and quickly extract hemicellulose flowing out after cell wall breakage, so that the extraction yield of the hemicellulose is effectively improved.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
Example 1
A comprehensive refining method of biomass comprises the following steps:
first extraction of pectin
Drying 50g of corncob, crushing to 2-5mm, adding 3-fold water, rinsing for 1h at 50 ℃, and removing waste liquid by pressure filtration; adding 2-3 times of water into the filter residue, adjusting pH to 2 with acetic acid, heating to 80 deg.C, maintaining the temperature for 10min, stopping heating, starting microwave and stirring, wherein the microwave density is 550 μ W/cm2The microwave lasts for 20min, after the microwave stops working, the ultrasonic wave is started, and the intensity of the ultrasonic wave is 1w/cm3And the ultrasonic working time is 20 min. And after the ultrasonic treatment is finished, performing filter pressing, and making the filter residue into hemicellulose in the second step, wherein the filtrate is pectin solution. The pectin solution is evaporated to 30% of the original volume by a 60 ℃ water curtain film evaporation method (the water curtain film method is to spray the dilute solution on an evaporation panel heated by steam to form a liquid film, the evaporation efficiency is improved under the action of negative pressure and heating), equal volume of 95% ethanol is added, the pectin is placed in a 2 ℃ environment, the pectin is kept stand and is subjected to cold precipitation for 2 hours, the precipitate is filtered and collected, the precipitate is dried by normal pressure and 80 ℃ hot air, and the pectin product is crushed and sieved by a 100-mesh sieve to obtain the powdery pectin finished product.
Second hemicellulose extraction
Putting the filter residue obtained in the first step into a 5% NaOH solution with the volume being 3 times that of the filter residue, heating the filter residue to 70 ℃, starting ultrasonic waves with the ultrasonic intensity of 1w/cm3The ultrasonic wave working time is 15min, after the ultrasonic wave working is finished, the temperature is continuously increased to 80 ℃, the microwave is started, and the microwave intensity is 600 muW/cm2The microwave working time is 30min, and after the microwave working is finished, the hot material is heatedPerforming solid-liquid separation and filtration, allowing the solid phase substance to enter a third step, allowing the liquid phase substance to enter a water curtain film evaporator, allowing the liquid volume to evaporate to 25% of the original volume, adding equal volume of 95% ethanol, standing at 0 deg.C for cold precipitation for 4h, filtering, collecting precipitate, recovering ethanol from the filtrate, and recycling the alkali solution. And drying and crushing the collected precipitate to obtain the hemicellulose raw material.
The third step of lignin extraction
The ethanol-1, 4-butanediol-glycerol composite extractant has the following mixture ratio (V/V): 1.5:3.5: 6; extracting agent water (V/V) 9: 2.5; the solid-to-liquid ratio (M/V) is 3: 10.
Adding a composite extractant of ethanol-1, 4-butanediol-glycerol into the filter residue obtained in the second step according to the solid-to-liquid ratio (M/V) of 3:10, mixing and stirring after adding, wherein the stirring is to start microwaves, and the microwave intensity is 600-2The microwave works for 15min, the stirring and the microwave are stopped, the ultrasonic wave is started after the standing for 10min, and the intensity of the ultrasonic wave is 1w/cm3The working time is 20min, standing is carried out for 10min after the ultrasonic wave stops working, the microwave and stirring are started for the second time, the working time is 30min, standing is carried out for 20min, the ultrasonic wave is started for the second time, the working time is 15min, standing is carried out for 15min, the microwave is started for the third time, the working time is 30min, after the working is finished, the solid phase and the liquid phase are squeezed and filtered to separate while the liquid phase is hot, the liquid phase is a lignin solution, the solid phase is eluted once by using 95% ethanol with the volume being 2 times, the solid phase is used as a cellulose raw material, the ethanol and the liquid phase are mixed after the elution and then are centrifuged by a centrifuge, and the obtained solid is dried to obtain the lignin.
The corn cob in the example is detected by the existing method to have the pectin content of 4 g, the hemicellulose content of 10.6 g, the cellulose content of 11 g and the lignin content of 9 g.
The yield of pectin obtained by the method is 71%, the yield of hemicellulose is 90%, the yield of lignin is 81% and the yield of cellulose is 84%.
Example 2
A comprehensive refining method of biomass comprises the following steps:
first extraction of pectin
Drying and crushing 50g of wheat straw to 2-5mm, adding 2-fold water, rinsing for 2h at 55 ℃, and removing waste liquid by pressure filtration; adding 2-3 times of water into the filter residue, adjusting pH to 2.5 with acetic acid, heating to 100 deg.C, maintaining the temperature for 20min, stopping heating, starting microwave and stirring, and microwave density of 550 μ W/cm2The microwave lasts for 20min, after the microwave stops working, the ultrasonic wave is started, and the intensity of the ultrasonic wave is 1w/cm3And the ultrasonic working time is 20 min. And after the ultrasonic treatment is finished, performing filter pressing, and making the filter residue into hemicellulose in the second step, wherein the filtrate is pectin solution. Evaporating pectin solution to 40% of original volume by 80 deg.C water curtain film evaporation method, adding equal volume of 95% ethanol, placing in 0-4 deg.C environment, standing for cold precipitating pectin, cold precipitating for 2 hr, filtering, collecting precipitate, drying the precipitate with 90 deg.C hot air at normal pressure, pulverizing, and sieving with 100 mesh sieve to obtain powdered pectin product.
Second hemicellulose extraction
Putting the filter residue obtained in the first step into a 4% NaOH solution with the volume being 3 times that of the filter residue, heating the filter residue to 60 ℃, starting ultrasonic waves with the ultrasonic intensity of 1.5w/cm3The ultrasonic wave working time is 15min, after the ultrasonic wave working is finished, the temperature is continuously increased to 90 ℃, the microwave is started, and the microwave intensity is 700 mu W/cm2The microwave working time is 25min, after the microwave working is finished, solid-liquid separation and filtration are carried out while the liquid is hot, the solid phase substance enters the third step, the liquid phase substance enters a water curtain film evaporator, the liquid volume is evaporated to be 30% of the original volume, 95% ethanol with the same volume is added, the mixture is placed in an environment with the temperature of 3 ℃, standing and cold precipitation are carried out, the cold precipitation time is 4h, the precipitate is collected through filtration, the filtrate is subjected to ethanol recovery, and the alkali liquor is recycled. And drying and crushing the collected precipitate to obtain the hemicellulose raw material.
The third step of lignin extraction
The ethanol-1, 4-butanediol-glycerol composite extractant has the following mixture ratio (V/V): 1.5:3.5: 6; extracting agent water (V/V) 9: 2.5; the solid-to-liquid ratio (M/V) is 3: 10.
Adding a compound extractant of ethanol-1, 4-butanediol-glycerol into the filter residue obtained in the second step according to the solid-to-liquid ratio (M/V) of 3:10, mixing and stirring, wherein the microwave is turned on when the stirring is yes, and the microwave intensity is 700 muW/cm2The microwave works for 30min, the stirring and the microwave are stopped, the ultrasonic wave is started after the standing for 15min, and the intensity of the ultrasonic wave is 1.5w/cm3The working time is 20min, standing is carried out for 15min after the ultrasonic wave stops working, the microwave and stirring are started for the second time, the working time is 30min, standing is carried out for 15min, the ultrasonic wave is started for the second time, the working time is 15min, standing is carried out for 15min, the microwave is started for the third time, the working time is 20min, after the working is finished, the solid phase and the liquid phase are squeezed and filtered to separate while the liquid phase is hot, the liquid phase is a lignin solution, the solid phase is eluted once by using 95% ethanol with the volume being 2 times, the solid phase is used as a cellulose raw material, the ethanol and the liquid phase are mixed after the elution and then are centrifuged by a centrifuge, and the obtained solid is dried to obtain the lignin.
The content of pectin, the content of hemicellulose, the content of cellulose and the content of lignin in the wheat straw in the embodiment are detected to be 1-3%, 20%, 50% and 19% respectively by adopting the existing method.
The yield of pectin obtained by the method is 55%, the yield of hemicellulose is 82%, the yield of lignin is 90% and the yield of cellulose is 81%.
Example 3
A comprehensive refining method of biomass comprises the following steps:
first extraction of pectin
Drying and crushing 50g of wheat straw to 2-5mm, adding 3-fold water, rinsing for 2h at 60 ℃, and removing waste liquid by pressure filtration; adding 2 times volume of water into the filter residue, adjusting pH to 3 with acetic acid, heating to 100 deg.C, maintaining the temperature for 20min, stopping heating, starting microwave and stirring, wherein the microwave density is 650 μ W/cm2The microwave lasts for 20min, after the microwave stops working, the ultrasonic wave is started, and the intensity of the ultrasonic wave is 1w/cm3And the ultrasonic working time is 20 min. And after the ultrasonic treatment is finished, performing filter pressing, and making the filter residue into hemicellulose in the second step, wherein the filtrate is pectin solution. Evaporating pectin solution to 50% of original volume by 80 deg.C water curtain film evaporation method, adding equal volume of 95% ethanol, placing in 4 deg.C environment, standing for cold precipitating pectin, cold precipitating for 2 hr, filtering, collecting precipitate, drying the precipitate with normal pressure hot air at 90 deg.C, pulverizing, and sieving with 100 mesh sieve to obtain powdered pectin product.
Second hemicellulose extraction
Putting the filter residue obtained in the first step into 2-5% NaOH solution with 2 times volume, heating to 70 deg.C, and starting ultrasonic wave with intensity of 1.5w/cm3The ultrasonic wave working time is 15min, after the ultrasonic wave working is finished, the temperature is continuously increased to 90 ℃, the microwave is started, and the microwave intensity is 700 mu W/cm2And the microwave working time is 30min, after the microwave working is finished, solid-liquid separation and filtration are carried out while the liquid is hot, the solid phase substance enters the third step, the liquid phase substance enters a water curtain film evaporator, the liquid volume is evaporated to be 45% of the original volume, 95% ethanol with the same volume is added, the mixture is placed in an environment with the temperature of 3 ℃, standing and cold precipitation are carried out, the cold precipitation time is 4h, the precipitate is collected through filtration, the filtrate is subjected to ethanol recovery, and the alkali liquor is recycled. And drying and crushing the collected precipitate to obtain the hemicellulose raw material.
The third step of lignin extraction
The ethanol-1, 4-butanediol-glycerol composite extractant has the following mixture ratio (V/V): 1.5:3.5: 6; extracting agent water (V/V) 9: 2.5; the solid-to-liquid ratio (M/V) is 3: 10.
Adding a compound extractant of ethanol-1, 4-butanediol-glycerol into the filter residue obtained in the second step according to the solid-to-liquid ratio (M/V) of 3:10, mixing and stirring after adding, wherein the stirring is carried out by turning on microwaves, and the microwave intensity is 700 mu W/cm2The microwave works for 30min, the stirring and the microwave are stopped, the ultrasonic wave is started after the standing for 15min, and the intensity of the ultrasonic wave is 1.5w/cm3The working time is 20min, standing is carried out for 20min after the ultrasonic wave stops working, the microwave and stirring are started for the second time, the working time is 25min, standing is carried out for 15min, the ultrasonic wave is started for the second time, the working time is 15min, standing is carried out for 20min, the microwave is started for the third time, the working time is 15min, after the working is finished, the solid phase and the liquid phase are squeezed and filtered to separate while the liquid phase is hot, the liquid phase is a lignin solution, the solid phase is eluted once by 90% ethanol with the volume being 2 times, then the solid phase is used as a cellulose raw material, the ethanol and the liquid phase are mixed after the elution and then are centrifuged by a centrifuge, and the obtained solid is dried to obtain the lignin.
The content of pectin, the content of hemicellulose, the content of cellulose and the content of lignin in the wheat straw in the embodiment are detected to be 1-3%, 20%, 50% and 19% respectively by adopting the existing method.
The yield of pectin obtained by the method is 60%, the yield of hemicellulose is 83%, the yield of lignin is 92% and the yield of cellulose is 85%.
Comparative example 1
The differences from example 1 are: in the pectin extraction, acetic acid is used for adjusting the pH value to be 1, other parameters are not changed, the yield of pectin is 35%, the yield of hemicellulose is 64%, the yield of lignin is 75%, and the yield of cellulose is 66%.
Comparative example 2
The differences from example 1 are: in the pectin extraction, the microwave power is 500 muW/cm2The other parameters were unchanged, the yield of pectin was 40%, the yield of hemicellulose was 63%, the yield of lignin was 71%, and the yield of cellulose was 62%.
Comparative example 3
The differences from example 1 are: in the pectin extraction, the microwave power is 700 muW/cm2The other parameters were unchanged, the yield of pectin was 35%, the yield of hemicellulose was 65%, the yield of lignin was 64%, and the yield of cellulose was 61%.
Comparative example 4
The differences from example 1 are: in the lignin extraction, the extractant is a mixed solution of 1, 4-butanediol and glycerol, other parameters are unchanged, the yield of pectin is 51%, the yield of hemicellulose is 80%, the yield of lignin is 40%, and the yield of cellulose is 56%.
Comparative example 5
The differences from example 1 are: in the lignin extraction, the extractant is ethanol, other parameters are unchanged, the yield of pectin is 51%, the yield of hemicellulose is 80%, the yield of lignin is 38%, and the yield of cellulose is 58%.
Comparative example 6
The differences from example 1 are: in the lignin extraction, the extractant is a mixed solution of ethanol and 1, 4-butanediol, other parameters are unchanged, the yield of pectin is 51%, the yield of hemicellulose is 80%, the yield of lignin is 43%, and the yield of cellulose is 60%.
The above description is only a preferred embodiment of the present application and is not intended to limit the present application, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, improvement and the like made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims (13)

1. A comprehensive refining method of biomass is characterized in that: the method comprises the following steps:
1) crushing and rinsing the biomass raw material, removing waste liquid, adding water into filter residue, adjusting the pH value to 3-5 with acetic acid, heating at 80-100 ℃ for 10-20min, starting microwave treatment with the microwave power density of 550-2After 20-30min, starting ultrasonic treatment, after the ultrasonic treatment is finished, performing filter pressing, and performing evaporation concentration, standing for cold precipitation, drying and precipitation on the filtrate to obtain pectin;
2) placing the filter residue prepared in the step 1) in a dilute alkali solution, heating to a set temperature, starting ultrasonic waves, performing ultrasonic treatment for a set time, heating for a set time, starting microwaves, performing solid-liquid separation after the microwave treatment for the set time, and evaporating and performing cold precipitation on the liquid to obtain a hemicellulose product;
3) adding a composite extracting agent of ethanol, 1, 4-butanediol and glycerol into the filter residue obtained in the step 2), wherein the volume ratio of the ethanol to the 1, 4-butanediol to the glycerol is 1.2-1.5:3-3.5: 6; then starting the microwave and stirring, wherein the microwave power is 600-2Standing for 10-15min for 15-30min, and starting ultrasonic wave with intensity of 1-1.5w/cm3Working time is 15-20min, solid phase and liquid phase are squeezed and separated when the liquid phase is hot, the solid phase is cellulose, and the solid after the liquid phase is centrifuged is dried to obtain lignin;
the biomass is corncobs or wheat straws.
2. The integrated refining method of biomass according to claim 1, characterized in that: in the step 1), the biomass raw material is crushed to 2-5 mm.
3. The integrated refining method of biomass according to claim 1, characterized in that: in the step 1), in the rinsing step, water with the volume of 1-3 times that of the biomass raw material is added, and the biomass raw material is heated to 50-60 ℃ for rinsing for 1-2 hours.
4. The integrated refining method of biomass according to claim 1, characterized in that: in the step 1), the filtrate is concentrated by adopting a water curtain film evaporation method, wherein the evaporation temperature is 60-80 ℃, and the concentration is carried out until the volume is 30-50% of the original volume.
5. The integrated refining method of biomass according to claim 1, characterized in that: in the step 1), the step of standing and cold-precipitating is to add equal volume of 95 percent ethanol into the concentrated solution, and to stand and cold-precipitate the pectin in the environment of 0-4 ℃ for 1-2 h.
6. The integrated refining method of biomass according to claim 1, characterized in that: in step 1), the temperature for drying the precipitate is 80-90 ℃.
7. The integrated refining method of biomass according to claim 1, characterized in that: in the step 2), the dilute alkali solution is a sodium hydroxide solution with the mass fraction of 2% -5%, and the volume of the sodium hydroxide solution is 2-3 times of the volume of the filter residue.
8. The integrated refining method of biomass according to claim 1, characterized in that: in the step 2), after the filter residue is heated to 50-80 ℃ in a dilute alkali solution, ultrasonic waves are started, and the ultrasonic time is 10-20 min.
9. The integrated refining method of biomass according to claim 1, characterized in that: in the step 2), after ultrasonic treatment, heating to 80-100 ℃, preserving heat for 10-20min, and then starting microwave treatment, wherein the microwave power density is 600-2The microwave treatment time is 20-30 min.
10. The integrated refining method of biomass according to claim 1, characterized in that: in the step 2), the liquid is evaporated and concentrated to 25-45% of the original volume by a water curtain film evaporation method, then ethanol with the same volume and the mass fraction of 95% is added, and the mixture is placed in an environment with the temperature of 0-4 ℃ for standing and cold precipitation, wherein the cold precipitation time is 2-4 hours.
11. The integrated refining method of biomass according to claim 1, characterized in that: in the step 3), the solid-to-liquid ratio of the filter residue to the composite extracting agent is 3-4: 10.
12. The integrated refining method of biomass according to claim 1, characterized in that: in the step 3), before the separation of the solid phase and the liquid phase, the method also comprises the step of opening the microwave for two times, wherein the microwave power is 600-2The microwave time is 20-30min, after standing for 10-20min, the ultrasonic wave is started for the second time, the ultrasonic treatment is carried out for 10-20min, the standing is carried out for 10-20min, the microwave is started for the third time, and the microwave power is 600-2And the microwave time is 15-30 min.
13. The integrated refining method of biomass according to claim 1, characterized in that: in the step 3), the separated solid phase is washed by ethanol with the mass fraction of 90-95% in 2 times of volume.
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