CN102517403A - Method for preparing hemicellulose oligosaccharide by high-temperature liquid water - Google Patents
Method for preparing hemicellulose oligosaccharide by high-temperature liquid water Download PDFInfo
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Abstract
The invention provides a method for preparing hemicellulose oligosaccharide by high-temperature liquid water, in which agricultural and forestry wastes are used as raw materials. The method comprises the steps of: crushing raw materials, performing preliminary discoloring and desalting treatment, directly performing high-temperature liquid water hydrolysis on wet materials in an intermittent pressure reactor or a continuous reactor, obtaining hemicellulose oligosaccharide solutions with different distributions of polymerization degree and different yields by controlling the reaction temperature, reaction time and substrate concentration, and the like, performing multiple discoloring and desalting treatments on the hydrolysate by active carbon and ion exchange resin, removing macromolecular substances by an ultrafiltration membrane, and removing monosaccharide and micro-molecular sugar degradation products by a nanofiltration membrane, and vacuum concentrating or spray drying to prepare syrup or powdered sugar with oligosaccharide purity larger than 90%. The hydrolysis residues can be used for preparing cellulose oligosaccharide or producing energy sources or chemicals with high additional values by fermentation. Compared with the traditional biological enzyme method, the method provided by the invention has the advantages of simple technique, lower cost, shorter production period, and better suitability for large scale industrial production.
Description
Technical field
The invention belongs to chemical technology field, being specifically related to a kind of is raw material with the agriculture and forestry organic waste material, utilizes the high temperature liquid water legal system to be equipped with the technology of semicellulose oligose.
Technical background
Oligose is meant the low polymerization degree carbohydrate of the straight or branched that is formed by connecting through glycosidic link 2-10 monose, comprises functional oligose and ordinary oligosaccharide.Wherein oligofructose, xylooligosaccharides, oligomeric galactose, oligomeric isomaltose, cottonseed sugar etc. belong to functional oligose; Directly get into because their are difficult for being digested and assimilated and to be preferably bifidus bacillus in the large intestine and to utilize; So have propagation human body probiotics; And suppress the function that other harmful bacterium grows, breeds; But long-term edible delaying senility, defaecation, antibacterial, anti-cancer, anticancer, alleviate burden of liver, improve the dietetic alimentation rate, be widely used in fields such as food, healthcare products, beverage, medicine, fodder additives.
The semicellulose oligose mainly is meant the low polymerization degree polysaccharide that derives from lignocellulose-like biomass (agricultural crop straw and the forest products waste etc.) semicellulose, comprises xylooligosaccharides, glucose oligosaccharide, low araban, oligomeric Portugal wood sugar and a spot of oligomeric grape seminose, oligomeric Arabic semi-lactosi and oligomeric gala grape seminose etc.Usually, in the lignocellulose-like biomass xylooligosaccharides account for the semicellulose oligose 60% or more than, other functional oligoses relatively, it has, and physicochemical property is more stable, the better characteristics of physiologic properties; And raw material sources is more extensively more cheap, comprises wheat bran, rice husk, cotton seed hulls, straw, rice straw, bagasse, wood chip etc.
The functional low polyxylose development research with Japan the earliest in the world; Mention among the patent CN1646523A " Xylooligosaccharide composition with high purity "; Japan Suntory Ltd is a raw material with corn cob, cotton seed hulls, bagasse and straw etc.; At first use alkaline process extracting xylan, produce raw sugar liquid through xylanase hydrolysis then, with its carry out repeatedly concentrating, after desalination and decolouring handle; Concentration can reach 74.5%, and wherein wood sugar 23.4%, glucose 4.5%, xylo-bioses 34.4%, cellobiose 3.0%, xylotriose 8.51%, the polymerization degree are equal to or greater than the oligose 25.7% of Xylotetrose.Domestic since the nineties in 20th century, xylooligosaccharides production and research and development have had very fast progress.The one Chinese patent application that wherein relevant agricultural wastes prepare xylooligosaccharides has: CN1266633 " enzyme process prepares the production technique of functional low polyxylose "; CN101182559 " a kind of method of utilizing the extruding assisted enzymolysis wheat bran to be equipped with xylooligosaccharides "; CN101012466 " a kind of method of preparing low-polyxylose by microwave treatment corn core enzymatical process "; CN101597628 " method of preparing xylo-oligosaccharide by corn husk enzymatic hydrolysis "; CN101914589A " utilizing the novel method of microorganisms producing xylooligosaccharides "; CN101597629 " a kind of method of utilizing the ultrasonication agricultural wastes to prepare xylooligosaccharides "; CN102080116A " a kind of employing steam explosion-directional enzymatic is produced the method for xylooligosaccharides "; CN1364911 " a plant fiber raw material enzyme liberating prepares the method for xylooligosaccharides " etc.It is thus clear that biological enzyme is mostly adopted in the preparation of xylooligosaccharides both at home and abroad at present; This method at first with the xylan in the lignocellulose-like biomass through soda acid or other physico-chemical processeses extract and then carry out the zytase enzymolysis, or with directly carrying out the zytase enzymolysis after the pre-treatment of raw material physico-chemical processes.In the actual industrial application, enzyme process is produced xylooligosaccharides and is had following problem:
1) complicated process of preparation need be carried out pre-treatment or extracts its xylan and carry out enzymolysis again raw material
2) preparation cost is higher, and using zytase is one of high reason of xylooligosaccharides cost
3) production cycle long, this is the total shortcoming of biological process, also can cause the increase of production cost
High temperature liquid water is meant temperature between 150-250 ℃, and pressure is higher than the compressed liquid water of its saturation vapour pressure.High temperature liquid water is compared with normal-temperature water, and big 3 one magnitude of ionic product are 10
-11, i.e. [H] in the high temperature liquid water
+[OH]
-Exceed about 10 under the concentration ratio normal condition
1.5Doubly.Like this, high temperature liquid water self will have the function of acid catalysis and base catalysis.In addition, it and supercritical water (temperature is greater than 374 ℃, and pressure is higher than 22Mpa) equally have the characteristics of mass-transfer performance good (low-viscosity and high spread coefficient), and organism and inorganics are had solvability preferably.The high temperature liquid water technical application mainly concentrates on the preprocessing technical field of lignocellulose-like biomass at present, and is applied to the report that the related patent U.S. Patent No. technology is not also seen in oligose production aspect.
Summary of the invention
The object of the present invention is to provide a kind of is raw material with the agriculture and forestry organic waste material; Utilize high temperature liquid water to prepare the method for semicellulose oligose, be intended to simplify the oligose production technique, reduce production costs; Enhance productivity, realize maximum resource utilization agriculture and forestry organic waste material.
The lignocellulose raw material contains complicated semicellulose-Mierocrystalline cellulose-lignin structure, and its semicellulose closely links together through α-O-4 alkylaryl ehter bond and xylogen.In grass; Be generally known as lignin phenol-carbohydrate complexes (Lignin/phenolics-carbohydrate complexes; LPCC); This is that it is connected with xylogen through ehter bond on the one hand owing between xylogen and carbohydrate, contain a FLA unit, is connected with the semicellulose polysaccharide through ester bond on the other hand.Obtain the semicellulose oligose and must interrupt semicellulose on the one hand and be connected, be cut into the oligose of forming with 2-10 sugar unit to the semicellulose polysaccharide chain on the other hand with chemical bond between the xylogen.
For reaching above purpose, the technical scheme below the present invention has adopted:
The present invention with green, cheap high temperature liquid water as catalyzer and solvent, through [OH] wherein
-Ester linkage breaking between catalysis FLA and the polysaccharide discharges the semicellulose polysaccharide, through [H] wherein
+Interrupt semicellulose intramolecular β-1, thereby 4 glycosidic links discharge free semicellulose oligose, different according to the composition of semicellulose in the raw material, xylooligosaccharides and low araban etc. are arranged.
Concrete steps of the present invention are:
1) agriculture and forestry organic waste material is crushed to granularity less than 1cm, nonsugar is removed in pre-treatment;
Material choice contains the agriculture and forestry organic waste material kind of abundant wood sugar and pectinose, contains abundant wood sugar like the crust of corn cob, stalk, cotton boll, contains abundant pectinose in coniferale pith material, maize peel, the corn cob etc.
The pre-treatment of this step is a known technology, comprises that clear water soaks or high temperature steaming, or adds other chemical agents such as CaCO
3Or NaOH etc., remove the easy nonsugars such as pigment, salt or xylogen that dissolve, to reduce them to follow-up oligose preparation and isolating influence.
2) wet stock is directly put in the disclosed intermittent pressure reactor drum of patent CN201077823 " cellulose series biomass hydrolysis device " or patent CN101343292 " method of cellulose series biomass continuous hydrolysis and device thereof " and CN101818217A " pretreated method of a kind of high-temperature liquid water of cellulosic biomass and device " disclosed flow reactor or the similar reactor drum carried out the high temperature liquid water hydrolysis; Hydrolysising reacting temperature is 150-200 ℃; Reaction times is 10-50min; Material concentration is 5-20%, and reacting system pressure is higher than saturation vapour pressure under the temperature of reaction.
In this step, can comprise that temperature of reaction, reaction times and concentration of substrate (or reaction solution flow) wait the oligomeric liquid glucose of semicellulose that obtains different polymerization degree distribution and different yields through the control reaction conditions.
3) product liquid collection step 2), the centrifuging and taking supernatant adds CaCO
3Deposition sugared degradation product of part and lignin degradation thing carry out the decolouring first time and desalting treatment subsequently.
Decolouring and desalting treatment also are known technology, and available gac, ion exchange resin, electroosmose process etc. carry out.
4) product liquid in the step 3) being used molecular weight cut-off is the material that 1500 ultrafiltration membrance filter is removed macromolecule; Using molecular weight cut-off again is that 200 nf membrane is removed molecular weight and is lower than the nonsugar that 200 monose and organic acid, furfural, 5 hydroxymethyl furfural etc. not have removal, and it is concentrated simultaneously semicellulose oligose liquid to be carried out the first time.
5) product liquid in the collection step 4), the processing of further decolouring, available gac and ion exchange resin etc. carry out.
6) product liquid in the collection step 5) adopts vacuum concentration or spraying drying to prepare oligose purity and is higher than 90% syrup or Icing Sugar.
Preparation semicellulose oligose remaining solid residue contains abundant cellulose polysaccharide composition; Through selecting suitable cellulase can produce the Mierocrystalline cellulose oligose, or enzymolysis is produced the chemical of glucose and fermentative production of ethanol, butanols, bio-oil, lactic acid, Hydrocerol A equal energy source and high added value.
The waste water that produces in the whole technological process after treatment can the reuse hydrolysis material.
Characteristics of the present invention and technical superiority are:
1. adopt high-temperature liquid state water law direct hydrolysis agriculture and forestry organic waste material to produce oligose, technology is simpler, realizes heavy industrialization more easily.
2. replace zytase with green, cheap high temperature liquid water, greatly reduce production cost.
3. relative traditional biological enzyme method technique, the production cycle shortens greatly, has improved the efficient of producing.
4. adopting high temperature liquid water is reaction medium, need not add any chemical reagent, but and the waste water that generates in the production process after treatment direct reuse produce oligose, be the technology of an environmental protection.
5. remaining solid residue of the present invention contains and enriches cellulose components, can be used for papermaking, produce the chemical that the energy or high added value are produced in cellooligosaccharide or fermentation.
6. raw material adopts agriculture and forestry organic waste material cheap, difficult utilization to comprise agricultural by-products and forestry by products such as wood chip, branch such as corn cob, wheat bran, rice husk, straw, rice straw and bagasse, can realize the changing waste into resources utilization.
Description of drawings
Fig. 1 is the inventive method schema.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment technological method of the present invention is further described.
As shown in Figure 1, agriculture and forestry organic waste material is crushed to granularity less than 1cm, clear water soaks or high temperature steaming, or adds other chemical agents such as CaCO
3Or NaOH etc.; Remove and be prone to molten nonsugars such as pigment, salt or xylogen; Wet stock directly put into carry out the high temperature liquid water hydrolysis in intermittent pressure reactor drum or the flow reactor, hydrolysising reacting temperature is 150-200 ℃, and the reaction times is 10-50min; Material concentration is 5-20%, and reacting system pressure is higher than saturation vapour pressure under the temperature of reaction.Through controlling the thick liquid of semicellulose oligose that above reaction parameter obtains different polymerization degree distribution and different yields.In thick liquid, add CaCO
3The sugared degradation product of deposition part; Adopt gac, ion exchange resin etc. that it is decoloured and desalting treatment first afterwards; Adopt ultrafiltration membrance filter macromole lignin degradation thing; Adopt nf membrane to remove monose and small molecular sugar degradation product, further decolouring is handled afterwards, obtains oligose purity through vacuum concentration or spraying drying at last and is higher than 90% syrup or Icing Sugar.Preparation semicellulose oligose remaining solid residue contains abundant cellulose polysaccharide composition; Through selecting suitable cellulase can produce the Mierocrystalline cellulose oligose, or enzymolysis is produced the chemical of glucose and fermentative production of ethanol, butanols, bio-oil, lactic acid, Hydrocerol A equal energy source and high added value.The waste water that produces in the whole technological process after treatment can the reuse hydrolysis material.
Embodiment 1:
With the remaining bagasse of refining sugar is raw material, and it is crushed to granularity less than 1cm, boiling 1h in 80 ℃ of left and right sides water; Taking out wet stock and also calculate water ratio, it is rendered in the intermittent pressure reactor drum that patent CN201077823 " cellulose series biomass hydrolysis device " mentions, is 5% to add entry according to concentration of substrate; The confined reaction system is heated to 150 ± 5 ℃, and mixing speed is 500rpm; Keeping reactor assembly pressure is 4MPa, and hydrolysis 50min is after reaction finishes; Collect reaction solution and material residue, can know that through stratographic analysis raw material hydrolysis of hemicellulose rate is 90%; The cellulose hydrolysis rate is 10%, and the xylogen percent hydrolysis is 20%, and wherein total reducing sugar (comprising wood sugar and xylooligosaccharides) yield is 72% (accounting for the content of total wood sugar in the hydrolysis material not) in the hydrolyzed solution; And xylooligosaccharides accounts for 91.7% of total wood sugar of receiving, mainly comprises xylo-bioses, xylotriose, Xylotetrose, wooden pentasaccharides and other oligose, accounts for 4%, 16%, 21%, 24%, 35% of whole xylooligosaccharides respectively.Subsequently hydrolyzed solution centrifugal 10min under 10000rpm is removed solid sediment, get supernatant and add CaCO
3Deposition sugared degradation product of part and lignin degradation thing then adopt gac and ion exchange resin to carry out the decolouring first time and desalting treatment.The use molecular weight cut-off is 1500 ultrafiltration membrance filter removal macromolecule material; Using molecular weight cut-off again is that 200 nf membrane is removed molecular weight and is lower than the not nonsugar of removal such as 200 monose and organic acid, furfural, 5 hydroxymethyl furfural etc., simultaneously semicellulose oligose liquid is concentrated.The liquid concentrator that nanofiltration is generated adopts activated carbon treatment further to decolour, and can obtain oligose purity to its spraying drying afterwards and be higher than 90% Icing Sugar.The waste water that produces in the whole technological process is after conventional method is handled, but direct reuse carries out the raw material hydrolysis, has reduced production cost and to the pollution of environment.Preparation semicellulose oligose remaining solid residue contains abundant cellulose polysaccharide composition; Through selecting suitable cellulase can produce the Mierocrystalline cellulose oligose, or enzymolysis is produced the chemical of glucose and fermentative production of ethanol, butanols, bio-oil, lactic acid, Hydrocerol A equal energy source and high added value.
Embodiment 2:
With the remaining sorgo stalk of solid state fermentation is raw material; It is crushed to granularity less than 1cm; Water vapor steams 20min; Calculate the wet stock water ratio, it is rendered in the flow reactor that patent CN101818217A " pretreated method of a kind of high-temperature liquid water of cellulosic biomass and device " mentions, high temperature liquid water constantly flows into reactor catalysis sweet sorghum slag and generates oligose in entire reaction course; The reaction solution that contains product simultaneously pours reactor drum and gets in the splice jug, has avoided product overstand and gallon cone bottom tank in reactor drum like this.Control reaction process temperature is that 184 ± 5 ℃, pressure are 5MPa, and immobilized substrate concentration is 10% (promptly with hydrolysis material 30min under the 10ml/min flow), after reaction finishes; Cooling reactor; Take out residual residue, to the residue chemical composition analysis, the hydrolysis of hemicellulose rate is 95%; The cellulose hydrolysis rate is 5%; The xylogen percent hydrolysis is 7%, and wherein total wood sugar (comprising wood sugar and xylooligosaccharides) yield is 85% (accounting for the content of total wood sugar in the hydrolysis material not) in the hydrolyzed solution, and xylooligosaccharides accounts for and receives 93% of total wood sugar; Mainly comprise xylo-bioses, xylotriose, Xylotetrose, wooden pentasaccharides and other oligose, account for 12%, 18%, 29%, 35%, 6% of whole xylooligosaccharides respectively.Subsequently hydrolyzed solution is filtered on the plain filter membrane of 0.45 micrometer fibers and remove solid substance and part coloring matter, get filtrating and add CaCO
3Deposition sugared degradation product of part and lignin degradation thing then adopt gac and ion exchange resin to carry out the decolouring first time and desalting treatment.The use molecular weight cut-off is 1500 ultrafiltration membrance filter removal macromolecule material; Using molecular weight cut-off again is that 200 nf membrane is removed molecular weight and is lower than the not nonsugar of removal such as 200 monose and organic acid, furfural, 5 hydroxymethyl furfural etc., simultaneously semicellulose oligose liquid is concentrated.The liquid concentrator that nanofiltration is generated adopts activated carbon treatment further to decolour, and can obtain purity to its spraying drying afterwards and be higher than 90% oligomeric Icing Sugar.The waste water that produces in the whole technological process is after conventional method is handled, but direct reuse carries out the raw material hydrolysis, has reduced production cost and to the pollution of environment.Preparation semicellulose oligose remaining solid residue contains abundant cellulose polysaccharide composition; Through selecting suitable cellulase can produce the Mierocrystalline cellulose oligose, or enzymolysis is produced the chemical of glucose and fermentative production of ethanol, butanols, bio-oil, lactic acid, Hydrocerol A equal energy source and high added value.
Embodiment 3:
With the remaining sorgo stalk of solid state fermentation is raw material, and it is crushed to granularity less than 1cm, and water vapor steams 20min; Calculate the wet stock water ratio, it is rendered in the flow reactor that patent CN101818217A " pretreated method of a kind of high-temperature liquid water of cellulosic biomass and device " mentions, control reaction process temperature is that 200 ± 5 ℃, pressure are 5MPa; Immobilized substrate concentration is 20% (promptly with hydrolysis material 10min under the 20ml/min flow), after reaction finishes, and cooling reactor; Take out residual residue, to the residue chemical composition analysis, the hydrolysis of hemicellulose rate reaches 100%; The cellulose hydrolysis rate is 15%; The xylogen percent hydrolysis is 10%, and wherein total wood sugar (comprising wood sugar and xylooligosaccharides) yield is 89% (accounting for the content of total wood sugar in the hydrolysis material not) in the hydrolyzed solution, and xylooligosaccharides accounts for and receives 88% of total wood sugar; Mainly comprise xylo-bioses, xylotriose, Xylotetrose and other oligose, account for 35%, 38%, 15% and 12% of whole xylooligosaccharides respectively.Subsequently hydrolyzed solution is filtered on the plain filter membrane of 0.45 micrometer fibers and remove solid substance and part coloring matter, get filtrating and add CaCO
3Deposition sugared degradation product of part and lignin degradation thing then adopt gac and ion exchange resin to carry out the decolouring first time and desalting treatment.The use molecular weight cut-off is 1500 ultrafiltration membrance filter removal macromolecule material; Using molecular weight cut-off again is that 200 nf membrane is removed molecular weight and is lower than the not nonsugar of removal such as 200 monose and organic acid, furfural, 5 hydroxymethyl furfural etc., simultaneously semicellulose oligose liquid is concentrated.The liquid concentrator that nanofiltration is generated adopts activated carbon treatment further to decolour, and can obtain purity to its vacuum concentration afterwards and be higher than 90% oligosaccharide syrup.The waste water that produces in the whole technological process is after conventional method is handled, but direct reuse carries out the raw material hydrolysis, has reduced production cost and to the pollution of environment.Preparation semicellulose oligose remaining solid residue contains abundant cellulose polysaccharide composition; Through selecting suitable cellulase can produce the Mierocrystalline cellulose oligose, or enzymolysis is produced the chemical of glucose and fermentative production of ethanol, butanols, bio-oil, lactic acid, Hydrocerol A equal energy source and high added value.
Above embodiment proves; Utilize the above high-temperature liquid state water law semicellulose in the hydrolysis agriculture and forestry organic waste material well; Wherein the yield of xylooligosaccharides all accounts for about 90% of total reducing sugar yield; Can obtain highly purified oligose after the purification process such as hydrolyzed solution process decolouring desalination, visible this process method relatively is fit to preparation semicellulose oligose.
Should be understood that application of the present invention is not limited to above-mentioned giving an example, concerning those of ordinary skills, can improve or conversion that all these improvement and conversion all should belong to the protection domain of accompanying claims of the present invention according to above-mentioned explanation.
Claims (2)
1. method of utilizing high temperature liquid water to prepare the semicellulose oligose is characterized in that may further comprise the steps:
1) agriculture and forestry organic waste material is crushed to granularity less than 1cm, nonsugar is removed in pre-treatment;
2) wet stock is directly carried out the high temperature liquid water hydrolysis in intermittent pressure reactor drum or flow reactor;
3) centrifugal to semicellulose oligose liquid, get supernatant, add CaCO
3Deposition sugared degradation product of part and lignin degradation thing carry out the decolouring first time and desalting treatment subsequently;
4) adopt ultra-filtration membrane to remove molecular weight greater than 1500 material, adopt nanofiltration to remove molecular weight and be lower than 200 monose, organic acid and sugared degradation product, it is concentrated simultaneously semicellulose oligose liquid to be carried out first time;
5) product liquid in the collection step 4), the processing of further decolouring;
6) adopt vacuum concentration or spraying drying to prepare oligose purity and be higher than 90% syrup or Icing Sugar.
2. the method for utilizing high temperature liquid water to prepare the semicellulose oligose as claimed in claim 1; It is characterized in that: hydrolysising reacting temperature is 150-200 ℃ in the said step (2); Reaction times is 10-50min; Material concentration is 5-20%, and reacting system pressure is higher than water saturation vapour pressure under the temperature of reaction.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105483182A (en) * | 2015-12-29 | 2016-04-13 | 鹤壁市泰新科技有限公司 | Production technique of fiber oligosaccharide |
| CN105696396A (en) * | 2016-03-24 | 2016-06-22 | 广西壮族自治区中国科学院广西植物研究所 | Method for recovering hemicellulose, lignin and alkaline liquor from hemicellulose extraction liquid by separating flow |
| CN106755615A (en) * | 2016-12-07 | 2017-05-31 | 南京工业大学 | A kind of method that hydro-thermal method prepares xylo-oligosaccharide with acetic acid,diluted Hydrolyze method combined degradation lignocellulose biomass |
| CN108338984A (en) * | 2018-02-26 | 2018-07-31 | 量子高科(中国)生物股份有限公司 | Composition with gut purge effect and preparation method thereof and the application in carbohydrate-binding module spy cures formula food |
| CN108486285A (en) * | 2018-02-09 | 2018-09-04 | 北京林业大学 | A kind of method of acetyl group auxiliary xylooligosaccharides production |
| CN109181699A (en) * | 2018-09-07 | 2019-01-11 | 天津科技大学 | A method of antioxidant is prepared using agricultural crop straw |
| CN110256601A (en) * | 2019-06-12 | 2019-09-20 | 中国科学院广州能源研究所 | A method of levoglucosan is prepared using lignocellulose-like biomass |
| CN112301074A (en) * | 2020-10-23 | 2021-02-02 | 中国林业科学研究院林产化学工业研究所 | Method for preparing xylooligosaccharide and cellooligosaccharide by using forest biomass |
| CN112425732A (en) * | 2020-11-30 | 2021-03-02 | 丽江三川实业集团有限公司 | Dietary fiber ham and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105483182A (en) * | 2015-12-29 | 2016-04-13 | 鹤壁市泰新科技有限公司 | Production technique of fiber oligosaccharide |
| CN105696396A (en) * | 2016-03-24 | 2016-06-22 | 广西壮族自治区中国科学院广西植物研究所 | Method for recovering hemicellulose, lignin and alkaline liquor from hemicellulose extraction liquid by separating flow |
| CN106755615A (en) * | 2016-12-07 | 2017-05-31 | 南京工业大学 | A kind of method that hydro-thermal method prepares xylo-oligosaccharide with acetic acid,diluted Hydrolyze method combined degradation lignocellulose biomass |
| CN108486285A (en) * | 2018-02-09 | 2018-09-04 | 北京林业大学 | A kind of method of acetyl group auxiliary xylooligosaccharides production |
| CN108338984A (en) * | 2018-02-26 | 2018-07-31 | 量子高科(中国)生物股份有限公司 | Composition with gut purge effect and preparation method thereof and the application in carbohydrate-binding module spy cures formula food |
| CN109181699A (en) * | 2018-09-07 | 2019-01-11 | 天津科技大学 | A method of antioxidant is prepared using agricultural crop straw |
| CN109181699B (en) * | 2018-09-07 | 2020-11-27 | 天津科技大学 | Method for preparing antioxidant by using crop straws |
| CN110256601A (en) * | 2019-06-12 | 2019-09-20 | 中国科学院广州能源研究所 | A method of levoglucosan is prepared using lignocellulose-like biomass |
| CN112301074A (en) * | 2020-10-23 | 2021-02-02 | 中国林业科学研究院林产化学工业研究所 | Method for preparing xylooligosaccharide and cellooligosaccharide by using forest biomass |
| CN112301074B (en) * | 2020-10-23 | 2023-09-01 | 中国林业科学研究院林产化学工业研究所 | Method for preparing xylo-oligosaccharide and fiber oligosaccharide by using forest biomass |
| CN112425732A (en) * | 2020-11-30 | 2021-03-02 | 丽江三川实业集团有限公司 | Dietary fiber ham and preparation method thereof |
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| CN102517403B (en) | 2013-12-25 |
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