CN110747243A - Method for pretreating caragana microphylla in two steps - Google Patents
Method for pretreating caragana microphylla in two steps Download PDFInfo
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- CN110747243A CN110747243A CN201910934268.5A CN201910934268A CN110747243A CN 110747243 A CN110747243 A CN 110747243A CN 201910934268 A CN201910934268 A CN 201910934268A CN 110747243 A CN110747243 A CN 110747243A
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- caragana microphylla
- pretreatment
- ethylenediamine
- steam explosion
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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
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/14—Preparation of compounds containing saccharide radicals produced by the action of a carbohydrase (EC 3.2.x), e.g. by alpha-amylase, e.g. by cellulase, hemicellulase
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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
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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
- C12P19/00—Preparation of compounds containing saccharide radicals
- C12P19/02—Monosaccharides
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- 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
- D21B1/36—Explosive disintegration by sudden pressure reduction
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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
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
Abstract
The invention provides a method for pretreating caragana microphylla in two steps, which takes caragana microphylla as a raw material and adopts a two-step pretreatment technology of steam explosion-ethylenediamine. Firstly, performing steam explosion pretreatment on caragana microphylla to obtain a pretreatment raw material, then uniformly mixing the pretreatment raw material with ethylenediamine, placing the mixture in a closed reaction container, and reacting at a high temperature to obtain the caragana microphylla pretreated by two steps. The method adopts two-step pretreatment, can effectively remove hemicellulose and lignin in lignocellulose, retain cellulose, and effectively improve the enzymolysis efficiency of the cellulose and the hemicellulose. By adopting a two-step pretreatment technology, the strength of direct ethylene diamine pretreatment can be effectively reduced, and the dosage of ethylene diamine can be reduced.
Description
Technical Field
The invention belongs to the technical field of biomass refining, and particularly relates to a method for pretreating caragana microphylla in two steps.
Background
Fossil feedstock is a non-renewable resource and sustainability around the development of fossil feedstock is becoming an increasingly more challenging task. Meanwhile, the exploitation and utilization of fossil resources in large quantities also brings about serious environmental problems. Therefore, in recent years, the search for renewable alternative resources is facing increasing pressure. The lignocellulose raw material is a renewable biomass resource with wide distribution and rich yield. Lignocellulose can be used to produce a variety of chemical products (e.g., fuel ethanol, lactic acid, etc.). However, the strong cross-linked network structure of lignocellulose makes it very resistant to microbial degradation and physicochemical factors. This structure makes the utilization efficiency of cellulose, hemicellulose, lignin and other components extremely low. Therefore, pretreatment is usually required to change the structure of lignocellulose and promote the utilization of each component.
The existing pretreatment methods include physical methods such as mechanical pulverization, microwave pretreatment, freezing pretreatment, ultrasonic treatment, etc.; chemical methods such as acids, bases, organic solvents, ionic liquids, and the like; physical and chemical methods such as steam explosion pretreatment, ammonia fiber explosion pretreatment, high-temperature liquid water pretreatment and the like; biological methods such as biological enzyme pretreatment, white (brown) rot fungus pretreatment, etc. Although a single preprocessing method is highly targeted, the effect tends to be biased. Therefore, different pretreatment methods are combined in the application process, the pretreatment effect and the separation efficiency of components are expected to be improved, and the process is more economical.
The steam explosion method is a physical and chemical method, can effectively realize the separation of chemical components such as hemicellulose and the like, does not need to add chemicals, has no pollution to the environment and lower energy consumption, and is a lignocellulose high-efficiency pretreatment technology which is widely applied and has lower cost in recent years. Ethylenediamine pretreatment has been developed in recent years to provide good pretreatment of both herbaceous and woody plants. The ethylenediamine can open ether bonds connected between the lignin and the hemicellulose, so that the lignin is removed, the cellulose and the hemicellulose are retained to a greater extent, meanwhile, the crystal form of the cellulose can be effectively changed, and the enzymolysis accessibility of the lignocellulose is greatly improved. Meanwhile, the ethylenediamine is an organic base, the boiling point of which is 119 ℃, and can be recovered by heating and the like.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a two-step pretreatment method for caragana microphylla, which can significantly improve the conversion rate of cellulose and hemicellulose of caragana microphylla of woody plants and reduce the amount of ethylenediamine used.
The invention provides a method for pretreating caragana microphylla in two steps, which comprises the following steps:
(1) and (3) putting the pulverized caragana microphylla into a steam explosion reaction cylinder, introducing high-temperature steam to enable the pressure to reach a specified value, maintaining a certain reaction time, quickly opening an exhaust valve, collecting and washing the materials with water, and drying to obtain the caragana microphylla subjected to steam explosion pretreatment.
(2) Mixing the caragana microphylla subjected to steam explosion with ethylenediamine uniformly, placing the mixture in a closed reactor, heating for reaction, taking out the reactor after a certain period of time, quickly cooling, and taking out the material to obtain the caragana microphylla subjected to ethylenediamine pretreatment.
Preferably, the steam explosion reaction condition is 1.8-2.5Mpa, and the reaction time is 3-10 min.
Preferably, the temperature for heating the reaction is 120-210 ℃.
Preferably, the heating reaction time is 10 to 50 min.
Preferably, the mass volume ratio of the caragana microphylla to the ethylenediamine is 1 g: (1-4) mL.
Preferably, the caragana microphylla is subjected to steam explosion and ethylenediamine pretreatment, and then the caragana microphylla is washed with water, filtered or heated to recover ethylenediamine, so that a solid obtained after the two steps of pretreatment is obtained, and then the solid is dried.
Preferably, the size of the pulverized caragana microphylla is 20 mesh sieve, and the humidity is 1% -80%.
The steam explosion-ethylenediamine two-step pretreatment method provided by the invention can effectively improve the glucose yield of caragana microphylla. In the steam explosion process, hemicellulose and other components in the raw materials are removed, the solid recovery rate is 60-80%, so that compared with direct ethylenediamine pretreatment, the consumption of ethylenediamine in the second pretreatment is reduced by 20-40%, the results of the implementation example of the invention show that the yield of glucose obtained after the caragana microphylla ethylenediamine pretreatment enzymolysis is 89.71%, and compared with 70.62% of direct ethylenediamine pretreatment enzymolysis, the yield is obviously improved.
Detailed Description
Example 1: the invention relates to a method for pretreating caragana microphylla in two steps and carrying out enzymolysis
(1) Pretreatment method
Weighing 200g of caragana microphylla raw material, putting the caragana microphylla raw material into a reaction cylinder of steam explosion equipment, wherein the humidity of the caragana microphylla raw material is 5%, sieving the caragana microphylla raw material by a 20-mesh sieve, introducing high-pressure steam, raising the pressure in the reaction cylinder to 1.8MPa, and opening an exhaust valve to perform instantaneous explosion after the duration of 5 min. Collecting the materials, cleaning the materials by using deionized water, filtering and airing to obtain the steam explosion raw material, wherein the solid recovery rate of the raw material is as follows.
Weighing 20g of steam exploded material, putting the material into a 250mL stainless steel reaction kettle with a sealing cover, adding 40mL ethylenediamine, uniformly stirring, and screwing the sealing cover. The reaction kettle is put into an oil bath kettle at the temperature of 150 ℃ for reaction for 20 min. And (3) taking out the reaction kettle, quickly putting cold water into the reaction kettle, cooling, opening the reaction kettle, taking out the materials, washing the materials by using deionized water, filtering and airing the materials to obtain the pretreated caragana microphylla.
(2) Enzymolysis method
Adding a certain amount of pretreated materials into a 100mL conical flask with a small opening, adding cellulase, hemicellulase and water, carrying out enzymolysis reaction for 72h in a shaking table at 50 ℃ and 200rpm, sampling after the reaction is finished, centrifuging at 12000rpm for 5min, and taking supernatant and passing through a 0.22 mu m aqueous film. The monosaccharide content was determined using high performance liquid chromatography. The conversion rate of glucose obtained by calculation is 64.22%, and is obviously improved compared with the yield of 52.12% of caragana microphylla enzymatic hydrolysis which is directly pretreated by ethylenediamine under the same condition.
Example 2: the invention relates to a method for pretreating caragana microphylla in two steps and carrying out enzymolysis
(1) Pretreatment method
Weighing 200g of caragana microphylla raw material, putting the caragana microphylla raw material into a reaction cylinder of steam explosion equipment, wherein the humidity of the caragana microphylla raw material is 45%, sieving the caragana microphylla raw material with a 40-mesh sieve, introducing high-pressure steam, raising the pressure in the reaction cylinder to 2.2MPa, and opening an exhaust valve to perform instantaneous explosion after the duration of 7 min. Collecting the materials, cleaning the materials by using deionized water, filtering and airing to obtain the raw material for steam explosion.
Weighing 20g of steam exploded material, putting the material into a 250mL stainless steel reaction kettle with a sealing cover, adding 60mL ethylenediamine, uniformly stirring, and screwing the sealing cover. And (3) putting the reaction kettle into an oil bath kettle at 180 ℃ for reaction for 30 min. And (3) taking out the reaction kettle, quickly putting cold water into the reaction kettle, cooling, opening the reaction kettle, taking out the materials, washing the materials by using deionized water, filtering and airing the materials to obtain the pretreated caragana microphylla.
(2) Enzymolysis method
Adding a certain amount of material pretreated by ethylenediamine into a 100mL conical flask with a small opening, adding cellulase, hemicellulase and water, carrying out enzymolysis reaction for 72h in a shaking table at 50 ℃ and 200rpm, sampling after the reaction is finished, centrifuging at 12000rpm for 5min, and taking the supernatant and passing through a 0.22 mu m water system membrane. The monosaccharide content was determined using high performance liquid chromatography. The conversion rate of glucose obtained by calculation is 70.52%, and is obviously improved compared with the yield of 59.82% obtained by directly pretreating caragana microphylla by ethylenediamine under the same condition.
Example 3: the invention relates to a caragana microphylla pretreatment method and an enzymolysis method
(1) Pretreatment method
Weighing 200g of caragana microphylla raw material, placing into a reaction cylinder of steam explosion equipment, wherein the humidity of the caragana microphylla raw material is 80%, sieving with a 80-mesh sieve, introducing high-pressure steam to increase the pressure in the reaction cylinder to 2.5MPa, and opening an exhaust valve for instantaneous explosion after the duration of 9 min. Collecting the materials, cleaning the materials by using deionized water, filtering and airing to obtain the raw material for steam explosion.
Weighing 20g of steam exploded material, putting the material into a 250mL stainless steel reaction kettle with a sealing cover, adding 80mL ethylenediamine, uniformly stirring, and screwing the sealing cover. The reaction kettle is put into an oil bath kettle at 210 ℃ for reaction for 50 min. And (3) taking out the reaction kettle, quickly putting cold water into the reaction kettle, cooling, opening the reaction kettle, taking out the materials, washing the materials by using deionized water, filtering and airing the materials to obtain the pretreated caragana microphylla.
(2) Enzymolysis method
Adding a certain amount of material pretreated by ethylenediamine into a 100mL conical flask with a small opening, adding cellulase, hemicellulase and water, carrying out enzymolysis reaction for 72h in a shaking table at 50 ℃ and 200rpm, sampling after the reaction is finished, centrifuging at 12000rpm for 5min, and taking the supernatant and passing through a 0.22 mu m water system membrane. The monosaccharide content was determined using high performance liquid chromatography. The conversion rate of glucose obtained by calculation is 89.71%, and is obviously improved compared with the yield of 70.62% of caragana microphylla enzymatic hydrolysis which is directly pretreated by ethylenediamine under the same condition.
Claims (7)
1. A two-step pretreatment method of caragana microphylla comprises the following steps:
(1) putting the pulverized caragana microphylla into a steam explosion reaction cylinder, introducing high-temperature steam to enable the pressure to reach a specified value, maintaining a certain reaction time, quickly opening an exhaust valve, collecting and washing the materials with water, and drying to obtain caragana microphylla subjected to steam explosion pretreatment;
(2) mixing the caragana microphylla subjected to steam explosion with ethylenediamine uniformly, placing the mixture in a closed reactor, heating for reaction, taking out the reactor after a certain period of time, quickly cooling, and taking out the material to obtain the caragana microphylla subjected to ethylenediamine pretreatment.
2. The pretreatment method according to claim 1, wherein the steam explosion reaction is carried out under a pressure of 1.8 to 2.5MPa for 3 to 10 min.
3. The pretreatment method as claimed in claim 1, wherein the temperature of the heating reaction is 120-210 ℃.
4. The pretreatment method according to claim 1, wherein the heating reaction time is 10 to 50 min.
5. The pretreatment method according to claim 1, wherein the mass-to-volume ratio of caragana microphylla to ethylenediamine is 1 g: (1-4) mL.
6. The pretreatment method of claim 1, wherein the caragana microphylla is pretreated by steam explosion and ethylenediamine, and then washed with water, filtered or heated to recover ethylenediamine, so as to obtain a solid after the two steps of pretreatment, and then dried.
7. The pretreatment method of claim 1, wherein the size of the pulverized caragana microphylla is 20 mesh, and the humidity is 1-80%.
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| CN201910934268.5A CN110747243A (en) | 2019-09-29 | 2019-09-29 | Method for pretreating caragana microphylla in two steps |
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| CN201910934268.5A CN110747243A (en) | 2019-09-29 | 2019-09-29 | Method for pretreating caragana microphylla in two steps |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011002824A1 (en) * | 2009-06-29 | 2011-01-06 | Qteros, Inc. | Pretreatment of biomass |
| US20120180962A1 (en) * | 2010-11-21 | 2012-07-19 | Aicardo Roa-Espinosa | Apparatus and process for treatment of fibers |
| CN104611394A (en) * | 2015-03-04 | 2015-05-13 | 天津大学 | Method for pretreating lignocellulose raw material and application |
| CN104630286A (en) * | 2015-03-04 | 2015-05-20 | 天津大学 | Pretreatment method and application of lignocellulose raw material |
| CN109182396A (en) * | 2018-09-26 | 2019-01-11 | 天津科技大学 | A method of improving caragana microphylla steam blasting effect |
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2019
- 2019-09-29 CN CN201910934268.5A patent/CN110747243A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011002824A1 (en) * | 2009-06-29 | 2011-01-06 | Qteros, Inc. | Pretreatment of biomass |
| US20120180962A1 (en) * | 2010-11-21 | 2012-07-19 | Aicardo Roa-Espinosa | Apparatus and process for treatment of fibers |
| CN104611394A (en) * | 2015-03-04 | 2015-05-13 | 天津大学 | Method for pretreating lignocellulose raw material and application |
| CN104630286A (en) * | 2015-03-04 | 2015-05-20 | 天津大学 | Pretreatment method and application of lignocellulose raw material |
| CN109182396A (en) * | 2018-09-26 | 2019-01-11 | 天津科技大学 | A method of improving caragana microphylla steam blasting effect |
Non-Patent Citations (5)
| Title |
|---|
| LEI QIN ET AL.: "Ethylenediamine pretreatment changes cellulose allomorph and lignin structure of lignocellulose at ambient pressure", 《BIOTECHNOL BIOFUELS》 * |
| LEI QIN ET AL.: "Evaluation of soluble fraction and enzymatic residual fraction of dilute dry acid, ethylenediamine, and steam explosion pretreated corn stover on the enzymatic hydrolysis of cellulose", 《BIORESOURCE TECHNOLOGY》 * |
| 何士成 等: "蒸汽爆破与碱法协同预处理对小麦秸秆结构及酶解的影响", 《林产化学与工业》 * |
| 崔宗均主编: "《生物质能源与废弃物资源利用》", 30 June 2011, 中国农业大学出版 * |
| 李文超: "木质纤维素高固含量预处理与发酵过程研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》 * |
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