CN117737156A - Method for co-producing xylooligosaccharide, glucose and low-condensation lignin by using vanilla acid to catalyze gleditsia sinensis - Google Patents
Method for co-producing xylooligosaccharide, glucose and low-condensation lignin by using vanilla acid to catalyze gleditsia sinensis Download PDFInfo
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Abstract
The vanilloid catalyst adopted by the invention has the functions of antioxidation, anti-inflammatory, anticancer, antidiabetic, heart protection, liver protection and the like and good safety, and can be directly used as an additive of xylo-oligosaccharide products. The hot water leaching is carried out on the gleditsia sinensis, so that the degradation efficiency of hemicellulose is improved while the saponin is recovered. In addition, in the production process, the vanillic acid also serves as a lignin condensation inhibitor to eliminate active carbon positive ions generated by lignin depolymerization, so that the polycondensation reaction of lignin is effectively inhibited. The adsorption effect of the low-condensation lignin on the cellulose is reduced, so that the enzymolysis efficiency of the cellulose is improved. The residual low condensed lignin component has high beta-O-4 bond content, small molecular weight, high hydroxyl content and strong chemical reactivity, and is an excellent raw material for producing the PBAT/lignin composite membrane. The invention realizes the efficient conversion and utilization of three components of the gleditsia sinensis biomass cellulose, hemicellulose and lignin through hot water leaching, vanilla acid catalysis and cellulase enzymolysis operations.
Description
Technical Field
The invention relates to a method for producing xylooligosaccharide, glucose and low condensed lignin by using xylan-rich hemicellulose biomass (gleditsia sinensis lam shell) as a raw material through aromatic acid (vanillic acid) catalysis and cellulase enzymolysis, belonging to the field of biomass fine chemicals and application.
Background
Vanillic acid is an aromatic phenolic acid and is yellowish in appearance. It is an oxidized form of vanillin, giving off a pleasant smell. Vanillin is found in a variety of dietary sources and medicinal plants, which are formed by the secondary metabolism of plants, and its trace is found in olives, cereals, whole grains, fruits, green tea, fruit juices, beer and wine. In addition, vanillic acid can also be chemically synthesized. In the food industry, vanillic acid is used as a flavoring agent for various foods. In addition to being used as a food flavoring agent, vanilla acid also has excellent antioxidant, anti-inflammatory, anticancer, neuroprotective, antidiabetic, cardioprotective, liver protecting functions and good safety. It has been elucidated in various mechanistic pathways in the treatment of neurological and cardiovascular diseases, cancer, diabetes, and other diseases. These mechanisms include up-regulation of p53 expression by mitochondrial caspase activation and stimulation of apoptosis, disruption of protein expression levels in tumor cells involved in HIF-1 alpha activation, inhibition of biological targets involved in pathophysiology of disease, and the like. In forest chemistry, vanillic acid is considered as a lignin condensation reaction inhibitor, and can be used as an additive in acid-catalyzed pretreatment to improve the enzymatic saccharification rate of pretreated pulp, reduce the condensation degree of lignin and improve the quality of lignin by-products. Meanwhile, the weak acidity of the vanillic acid can be used as a catalyst for catalyzing and degrading xylan hemicellulose in biomass to be converted into xylooligosaccharide, and the xylooligosaccharide can be directly used as a functional additive in xylooligosaccharide products without an additional separation process.
Xylo-oligosaccharides are oligosaccharides consisting of 2 to 10 xylose groups linked by β - (1, 4) glycosidic bonds. Xylooligosaccharides are mainly produced by hydrolysis of xylan, which is the main component of hemicellulose polysaccharides in plant cell walls. Due to the different sources of xylan and different production processes, the xylo-oligosaccharide has great difference in polymerization degree, side group and substitution pattern thereof on xylose chain. Xylooligosaccharides with a degree of polymerization of 2-7 are generally considered as valuable prebiotics, as the lower the degree of polymerization, the greater the beneficial effect on human health. Xylo-oligosaccharides are classified as indigestible oligosaccharides which are not digested when passing through the upper digestive tract and thus reach the lower intestine where they are metabolized by probiotics. Therefore, the xylo-oligosaccharide has various characteristics and effects and is suitable for the production of health-care foods. In addition, xylo-oligosaccharide has been paid attention to its application in cosmetics because of its antioxidant and moisturizing ability and ability to recover microbial populations. The health benefits reported in numerous literature include lowering blood cholesterol, increasing calcium absorption, antioxidant effects, maintaining gastrointestinal health, reducing risk of colon cancer, and benefit to type ii diabetics. In view of these unique properties, xylooligosaccharides have been incorporated into a variety of functional foods and animal feeds, nutraceuticals and cosmetics.
During hydrothermal or organic acid pretreatment of biomass, lignin cannot be effectively removed, but rather undergoes depolymerization/polymerization reactions, ultimately producing highly condensed irreversible lignin. Lignin can pass through non-productive adsorption in cellulose hydrolysis, thereby remarkably reducing enzymolysis efficiency. Studies have shown that condensed lignin exhibits a stronger non-productive binding capacity with cellulases, i.e. lignin with a higher degree of condensation will more severely inhibit the enzymatic conversion of cellulose to glucose. In addition, condensed lignin has a large number of C-C bonds, which makes it chemically reactive, thereby negatively affecting the production of monomeric aromatic compounds by lignin depolymerization. Therefore, the inhibition of lignin condensation while producing xylo-oligosaccharides is very important for achieving efficient and full utilization of lignocellulosic biomass. The vanillic acid can eliminate active carbon positive ions generated by depolymerization of lignin, thereby preventing condensation reaction of lignin fragments. Polyadipic acid/butylene terephthalate (PBAT) is considered a good alternative to conventional non-degradable polymers due to its excellent mechanical properties and processability. It is often mixed with fillers or other polymers such as polylactic acid, starch and lignin in practice to reduce costs or to improve mechanical properties. And (3) melting, blending and hot-pressing the low-condensation lignin obtained by pretreatment of the vanillic acid with the PBAT according to a certain proportion, so as to obtain the PBAT/lignin composite film with excellent mechanical properties.
The gleditsia sinensis is a leguminous gleditsia plant and is widely distributed in China. The gleditsia sinensis has ecological significance due to the characteristics of drought resistance, water retention, heat resistance, cold resistance, pollution resistance and the like, and is widely applied to the forest land protection, water and soil conservation and road greening projects. The gleditsia sinensis seeds contain rich galactomannans, and have good water retention, thickening property, gelation property, emulsifying property and film forming property. The gleditsia sinensis thorns are traditional Chinese medicinal materials in China, and have the effects of detumescence, expelling pus, dispelling wind, killing parasites, opening and closing, promoting qi circulation, resolving hard mass and the like. The gleditsia sinensis shell is a lignocellulose biomass and mainly consists of saponin, cellulose, hemicellulose, lignin and a small amount of other substances. The saponin is a natural surfactant, is harmless to human body, has strong surface activity, and is widely used for the production of detergents and daily chemicals. The gleditsia sinensis shells after the extraction of the saponin are often discarded to cause environmental pollution and resource waste. The gleditsia sinensis shell contains 20-30% of xylan, and is an ideal raw material for preparing xylooligosaccharide.
Disclosure of Invention
The invention aims to efficiently produce xylooligosaccharide, glucose and low-condensation lignin by using vanillic acid as an acid catalyst, a lignin carbocation scavenger and various biological activities thereof and using gleditsia sinensis shells as raw materials through hydrothermal bath presoaking, vanillic acid catalysis and cellulose hydrolysis saccharification, so as to realize green conversion and high-value utilization of biomass resources.
According to the invention, vanillic acid is used as a catalyst, and the biomass raw material is treated by adopting hydrothermal presoaking, vanillic acid catalysis and cellulose enzymolysis, so that xylooligosaccharide, glucose and low-condensation lignin are efficiently produced. Vanillic acid can be used as a functional additive in oligosaccharide products without isolation. The clean separation and conversion of three components of biomass cellulose, hemicellulose and lignin can be realized only through acid catalysis and cellulase enzymolysis operation, and the production process is safe and efficient. The production method of the xylooligosaccharide, the glucose and the low-condensation lignin is characterized by comprising the following process steps of:
1) Gleditsia sinensis powder: the gleditsia sinensis shells are crushed by a dry method, sieved and sieved by a 40-mesh sieve, and the moisture is less than 10%.
2) Hot water extraction of gleditsia sinensis: mixing the gleditsia sinensis shell powder with deionized water in a certain proportion, heating and extracting, filtering and separating the mixture into gleditsia sinensis saponin water extract and solid filter residues after the reaction is finished, performing spray drying on the gleditsia sinensis saponin water extract to obtain gleditsia sinensis crude saponin, performing vacuum drying on the solid residues, crushing and sieving the crushed solid residues with a 40-mesh sieve to obtain the water-extracted gleditsia sinensis shell powder.
3) Vanilla acid catalyzed xylo-oligosaccharide production: adding a certain mass of vanilla acid into water extracted gleditsia sinensis shell powder, mixing with deionized water according to a certain proportion, and reacting for 15min at 180 ℃. And cooling after the reaction is finished, filtering, concentrating in vacuum, and spray-drying to obtain the xylo-oligosaccharide product.
4) Acid-catalyzed substrate enzymolysis: the solid residue is taken as an enzymolysis substrate, the concentration of the enzymolysis substrate is 10%, the dosage of cellulase is 18FPU/g cellulose, the enzymolysis temperature is 50 ℃, the enzymolysis system is acetate buffer solution with pH=4.8, and the enzymolysis time is 72 hours. Filtering after enzymolysis, vacuum concentrating, and spray drying to obtain glucose. The enzymatic hydrolysis residue is the low condensed lignin.
5) Preparation of a PBAT/lignin composite membrane: the mass ratio was 3 using a mini twin screw extruder: 7 and PBAT. The blending temperature was 140℃and the roll speed was 30Hz for 30min. And (3) pressing the uniformly blended composite material into a film by using a hot press, wherein the hot pressing temperature, the hot pressing pressure and the hot pressing time are 140 ℃, 5Mpa and 10min respectively.
The method for co-producing the xylo-oligosaccharide, the glucose and the low-condensation lignin is characterized in that the gleditsia sinensis shell in the step 2) is leached for 120-150min at 90 ℃ in a deionized water ratio of 1:10 (w/v).
The method for co-producing the xylooligosaccharide, the glucose and the low-condensation lignin is characterized in that the mass concentration of the vanilla acid in the step 3) is 8% relative to the gleditsia sinensis powder.
The method for co-producing the xylo-oligosaccharide, the glucose and the low-condensation lignin is characterized in that in the step 3), raw materials are deionized water=1:10 (w/v).
The method for co-producing the xylo-oligosaccharide, the glucose and the low-condensation lignin is characterized in that in the step 3), 8% of vanilla acid is added for reaction for 15min at 180 ℃.
The method for co-producing xylo-oligosaccharide, glucose and low-condensation lignin has the following advantages:
1. hemicellulose in the soapstock shell adopted by the invention mainly consists of xylan, and is an ideal raw material for producing xylooligosaccharide.
2. The catalyst vanillic acid adopted by the invention can be derived from natural plants or artificially synthesized, and is used as an additive of food flavoring for a long time, and is safe and nontoxic. The vanillic acid also has excellent antioxidant, anti-inflammatory, anticancer, neuroprotection, antidiabetic, cardioprotection and hepatoprotective functions, and can be used as an additive for health food and animal feed.
3. The invention uses the vanillic acid as a catalyst to catalyze and degrade hemicellulose to be converted into the xylooligosaccharide, and simultaneously uses the xylooligosaccharide as a functional additive in the xylooligosaccharide product, and the xylooligosaccharide product is separated from the xylooligosaccharide product without extra steps.
4. The vanilloid catalyst adopted in the invention has a carboxyl connected to benzene ring, has weak acidity, and can effectively prevent the generated xylose from being further oxidized into furfural.
5. The vanilloid adopted in the invention is lignin condensation inhibitor, which can catalyze xylan degradation and eliminate active carbon positive ions generated by lignin depolymerization, thereby preventing lignin polycondensation reaction.
6. The vanilloid adopted in the invention can prevent the polycondensation reaction of lignin, and the low-condensation lignin can effectively reduce the adsorption of cellulose and improve the cellulose enzymolysis efficiency.
7. The obtained low condensed lignin has high beta-O-4 bond content, small molecular weight, high hydroxyl content and strong chemical reaction activity, and is an excellent raw material for producing PBAT/lignin composite membranes.
8. According to the invention, the soapstock shell is subjected to hot water leaching pretreatment, so that the catalytic efficiency of the vanillic acid is improved while the effective components of the soap are recycled.
9. The product xylooligosaccharide, glucose and low-condensation lignin can realize the production of high-yield products only by carrying out vanilloid catalysis and cellulase enzymolysis operations on raw materials, and the process is safe and efficient.
10. The process can realize the efficient separation and utilization of biomass cellulose, hemicellulose and lignin components, and greatly improves the utilization efficiency of biomass resources compared with a single xylooligosaccharide production method.
Drawings
FIG. 1 is a process flow diagram of an embodiment combination.
Detailed Description
The process flow of the present invention is further illustrated in conjunction with the following examples. It should be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention.
Example 1
30g of gleditsia sinensis powder which is sieved by a 40-mesh sieve is taken, 300g of deionized water is added, leaching is carried out at 90 ℃ for 150min, filtering is carried out after leaching is finished, the solid filter residues of the gleditsia sinensis are transferred into a reaction kettle, 2.4g of vanillic acid and 300g of deionized water are added, and reaction is carried out at 180 ℃ for 15min. Cooling after the reaction is finished, filtering, concentrating in vacuum, and spray drying to obtain the xylo-oligosaccharide. The yield of xylooligosaccharide is 62.5%, and furfural and 5-hydroxymethylfurfural are not detected in the product. Then adding 300mL acetate buffer solution with pH value of 4.8 and 160FPU cellulase into the pretreated solid residue, carrying out enzymolysis for 72h at 50 ℃, filtering after the enzymolysis is finished, carrying out vacuum concentration, and carrying out spray drying to obtain the glucose with the glucose yield of 93.1%. The enzymatic hydrolysis residue is low condensed lignin, and the condensation degree is 0.39. The elongation at break of the PBAT/lignin composite membrane prepared by blending low-condensation lignin and PBAT is 536.3%, and the stretching light is 21.1Mpa.
Example 2
30g of gleditsia sinensis powder which is sieved by a 40-mesh sieve is taken, 300g of deionized water is added, leaching is carried out at 90 ℃ for 150min, filtering is carried out after leaching is finished, the solid filter residues of the gleditsia sinensis are transferred into a reaction kettle, 2.4g of vanillic acid and 300g of deionized water are added, and reaction is carried out at 180 ℃ for 15min. Cooling after the reaction is finished, filtering, concentrating in vacuum, and spray drying to obtain the xylo-oligosaccharide. The yield of xylooligosaccharide is 61.2%, and 0.01% of furfural is detected in the product. Then adding 300mL acetate buffer solution with pH value of 4.8 and 160FPU cellulase into the pretreated solid residue, carrying out enzymolysis for 72h at 50 ℃, filtering after the enzymolysis is finished, carrying out vacuum concentration, and carrying out spray drying to obtain the glucose, wherein the glucose yield is 91.8%. The enzymatic hydrolysis residue is low condensed lignin, and the condensation degree is 0.37. The elongation at break of the PBAT/lignin composite membrane prepared by blending low-condensation lignin and PBAT is 545.1%, and the stretching light is 20.5Mpa.
Example 3
30g of gleditsia sinensis powder which is sieved by a 40-mesh sieve is taken, 300g of deionized water is added, leaching is carried out at 90 ℃ for 150min, filtering is carried out after leaching is finished, the solid filter residues of the gleditsia sinensis are transferred into a reaction kettle, 2.4g of vanillic acid and 300g of deionized water are added, and reaction is carried out at 180 ℃ for 15min. Cooling after the reaction is finished, filtering, concentrating in vacuum, and spray drying to obtain the xylo-oligosaccharide. The yield of xylooligosaccharide is 63.7%, and 0.01% of furfural is detected in the product. Then adding 300mL acetate buffer solution with pH value of 4.8 and 160FPU cellulase into the pretreated solid residue, carrying out enzymolysis for 72h at 50 ℃, filtering after the enzymolysis is finished, carrying out vacuum concentration, and carrying out spray drying to obtain the glucose with the glucose yield of 93.8%. The enzymatic hydrolysis residue is low condensed lignin, and the condensation degree is 0.38. The elongation at break of the PBAT/lignin composite membrane prepared by blending low-condensation lignin and PBAT is 522.7%, and the stretching light is 20.8Mpa.
Comparative example 1
30g of gleditsia sinensis powder which is sieved by a 40-mesh sieve is taken, 300g of deionized water is added, leaching is carried out at 90 ℃ for 150min, filtering is carried out after leaching is finished, the solid filter residues of the gleditsia sinensis are moved into a reaction kettle, 300g of deionized water is added, and reaction is carried out at 180 ℃ for 15min. And cooling after the reaction is finished, filtering, concentrating in vacuum, and spray-drying to obtain the compound oligosaccharide. The yield of xylooligosaccharide is 23.5%, and 0.01% of furfural is detected in the product. Then adding 300mL acetate buffer solution with pH value of 4.8 and 160FPU cellulase into the pretreated solid residue, carrying out enzymolysis for 72h at 50 ℃, filtering after the enzymolysis is finished, carrying out vacuum concentration, and carrying out spray drying to obtain the glucose with the glucose yield of 82.7%. The lignin condensation degree in the enzymolysis residue is 0.57. The elongation at break of the PBAT/lignin composite membrane prepared by blending the condensed lignin and the PBAT is 225.8 percent, and the stretching light is 11.8Mpa.
Comparative example 2
30g of gleditsia sinensis powder which is sieved by a 40-mesh sieve is taken, 300g of deionized water is added, leaching is carried out at 90 ℃ for 150min, filtering is carried out after leaching is finished, the solid filter residues of the gleditsia sinensis are transferred into a reaction kettle, 2.4g of acetic acid and 300g of deionized water are added, and reaction is carried out at 180 ℃ for 15min. Cooling after the reaction is finished, filtering, concentrating in vacuum, and spray drying to obtain the xylo-oligosaccharide. The yield of xylooligosaccharide is 13.7%, and 0.10% of furfural is detected in the product. Then adding 300mL acetate buffer solution with pH value of 4.8 and 160FPU cellulase into the pretreated solid residue, carrying out enzymolysis for 72h at 50 ℃, filtering after the enzymolysis is finished, carrying out vacuum concentration, and carrying out spray drying to obtain the glucose, wherein the glucose yield is 78.8%. The lignin condensation degree in the enzymolysis residue is 0.66. The elongation at break of the PBAT/lignin composite membrane prepared by blending the condensed lignin and the PBAT is 203.4 percent, and the stretching light is 10.2Mpa.
Claims (5)
1. The invention takes vanillic acid as a catalyst, adopts hydrothermal presoaking, vanillic acid catalysis and cellulose enzymolysis to treat raw materials, and efficiently produces xylooligosaccharide, glucose and low-condensation lignin from gleditsia sinensis shells. Vanillic acid can be used as a functional additive in xylooligosaccharide products, and is separated without additional steps. The low condensed lignin improves the enzymolysis conversion efficiency of cellulose in the residual slag, and the obtained low condensed lignin has high beta-O-4 bond content, low molecular weight, high hydroxyl content and strong chemical reaction activity, and is an excellent raw material for producing PBAT/lignin composite membranes. The efficient preparation method of the xylooligosaccharide, glucose and low-condensation lignin is characterized by comprising the following process steps of:
1) Gleditsia sinensis powder: the gleditsia sinensis shells are crushed by a dry method, sieved and sieved by a 40-mesh sieve, and the moisture is less than 10%.
2) Hot water extraction of gleditsia sinensis: mixing the gleditsia sinensis shell powder with deionized water according to a certain proportion, heating and extracting, filtering and separating the mixture into a gleditsia sinensis saponin water extract and solid filter residues after the reaction is finished, and performing spray drying on the gleditsia sinensis saponin water extract to obtain gleditsia sinensis crude saponin, wherein the solid residues are transferred into a reaction kettle after vacuum drying, and xylooligosaccharide production is performed.
3) And (3) production of xylo-oligosaccharide: adding a certain mass of vanilla acid into water extracted gleditsia sinensis powder, mixing according to a certain proportion, and reacting for 15min at 180 ℃. Cooling after the reaction is finished, filtering, concentrating in vacuum, and spray drying to obtain the xylo-oligosaccharide.
4) Enzymolysis of solid residues: adding acetate buffer solution with pH of 4.8 and cellulase (18 FPU/g cellulose) into the solid residue, performing enzymolysis at 50deg.C for 72 hr, filtering after enzymolysis, vacuum concentrating, and spray drying to obtain glucose. The enzymatic hydrolysis residue is the low condensed lignin.
2. The method of claim 1, wherein the soapstock shell in step 2) is deionized water = 1:10 (w/v) and leached at 90 ℃ for 120-150min.
3. The method of claim 1, wherein the amount of added vanilloid in step 3) is 8% (w/w).
4. The process of claim 1, wherein in step 3) the raw materials, deionized water solution = 1:10 (w/v), are reacted at 180 ℃ for 15min.
5. The process of claim 1, wherein step 4) is solid residue acetate buffer = 1:10 (w/v).
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| CN202410164794.9A CN117737156A (en) | 2024-02-05 | 2024-02-05 | Method for co-producing xylooligosaccharide, glucose and low-condensation lignin by using vanilla acid to catalyze gleditsia sinensis |
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