WO2021125515A1 - Procédé de préparation d'oligosaccharides à base de pentose à partir de biomasse - Google Patents

Procédé de préparation d'oligosaccharides à base de pentose à partir de biomasse Download PDF

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WO2021125515A1
WO2021125515A1 PCT/KR2020/013142 KR2020013142W WO2021125515A1 WO 2021125515 A1 WO2021125515 A1 WO 2021125515A1 KR 2020013142 W KR2020013142 W KR 2020013142W WO 2021125515 A1 WO2021125515 A1 WO 2021125515A1
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exchange resin
ion exchange
biomass
biomass extract
enzyme
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PCT/KR2020/013142
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English (en)
Korean (ko)
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한민
함충현
이애라
김선홍
이관형
김학준
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대상 주식회사
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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
    • C12P19/04—Polysaccharides, i.e. compounds containing more than five saccharide radicals attached to each other by glycosidic bonds
    • 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
    • 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
    • C08B37/0057—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Xylans, i.e. xylosaccharide, e.g. arabinoxylan, arabinofuronan, pentosans; (beta-1,3)(beta-1,4)-D-Xylans, e.g. rhodymenans; Hemicellulose; Derivatives thereof

Definitions

  • the present invention relates to a method for producing a pentose-based oligosaccharide, and more particularly, to a method for efficiently producing a pentose-based oligosaccharide such as xylooligosaccharide from biomass containing hemicellulose.
  • Xylo-oligosaccharides are formed from 2-8 D-xylose through ⁇ -1,4-xylose glycosidic bonds, which are important members of functional oligosaccharides.
  • Xylooligosaccharides are usually prepared from plant materials containing a large amount of xylan, for example, by hydrolyzing various biomass such as wood flour, corn core, cottonseed husk, rice husk, and rapeseed hull material using endo-type xylanase. Then, it is obtained by separation and purification.
  • Republic of Korea Patent Publication No. 10-0450563 discloses (a) immersing xylan-containing vegetable raw materials in water to swell, followed by explosion treatment, (b ) After adding water to the explosives obtained in (a) to form a slurry, solid-liquid separation using a solid-liquid separator to obtain a crude sugar solution, (c) centrifuging the crude sugar solution obtained in (b), and filtering the supernatant through a microfiltration membrane and (d) passing the filtrate obtained in (c) through an ion exchange resin to obtain a decolorized sugar solution and then concentrating it.
  • Korean Patent No. 10-0653748 discloses (1) mixing corncob powder and water in a ratio of 1:6 to 10, and using 0.1 to 1.5% of a weak acid catalyst based on the weight of the corn core, 155 decomposing at a high temperature for 30 minutes to 120 minutes under conditions of °C-180°C to extract xylan; (2) The pH of the xylan solution was adjusted to 5.0-6.0, xylanase was added at a ratio of 50-85 UI units of active xylanase per g, and enzymatic digestion was carried out under 45-60° C. conditions for 4-10 hours.
  • 10-2019-0024434 discloses a pre-treatment product manufacturing step of preparing a fibrous hydrate with a reduced average particle diameter and increased surface area through rapid hydration and frictional grinding of lignocellulosic biomass; a hot water pretreatment step of treating the pre-pretreatment product using hot water; A solid-liquid separation step of separating the biomass pretreated with hot water into a solid phase and a liquid phase; and an oligosaccharide separation step of separating xylose or xylooligosaccharide from the liquid phase separated through the solid-liquid separation step.
  • a method for producing xylo-oligosaccharide derived from lignocellulosic biomass by polymerization degree is disclosed.
  • the method for producing xylo-oligosaccharide disclosed in Korean Patent No. 10-0653748 is a technology developed by Shandong Longlive Bio-Technology Company Limited, a Chinese company, and the method for producing xylo-oligosaccharide from biomass is biomass.
  • a pre-treatment step of pre-heating to a temperature of 80°C in aqueous solution, adding acetic acid, and thermal decomposition at 160-170°C for 1.5-2 hr ⁇ pH of the pre-treated solution using hydrochloric acid solution or sodium hydroxide is 5.5
  • Step (pH Control) Add xylanase and perform enzymatic decomposition reaction, followed by filtration to obtain a sugar solution (Enzyme hydrolysis) ⁇ Add activated carbon powder to the sugar solution, carry out the decolorization reaction, and then filter Obtaining decolorizing sugar solution (1st Active carbon) ⁇ Concentrating the first decolorizing sugar solution to obtain xylo-oligosaccharide syrup (Evaporation) ⁇ Adding activated carbon powder to the xylo-oligosaccharide syrup, performing a decolorization reaction, and filtering 2 Obtaining secondary decolorization syrup (2nd Active carbon) ⁇ Ion exchange purification step of purifying the secondary decolorization syrup by passing it through an
  • a weak acid such as acetic acid is used in the pretreatment step and the pH is adjusted with hydrochloric acid or sodium hydroxide before the enzymatic decomposition reaction, so the 2 that flows into the ion exchange resin
  • the conductivity of the tea decolorization syrup is 5,000 ⁇ s or more, so the replacement or regeneration cycle of the ion exchange resin is very short, and it is difficult to obtain an ion purification product with a conductivity of 50 ⁇ s or less. As a result, the ion exchange purification process is overloaded and the process will cause cost increase.
  • the present invention was derived under the prior technical background, and an object of the present invention is to prevent overload of the ion exchange purification process to an appropriate level and improve the workability of the filtration step to stably produce pentose-based oligosaccharides from biomass. to provide a way.
  • the inventors of the present invention extract xylan from biomass using hot water, enzymatically hydrolyze the extracted xylan, and then purify it with an ion exchange resin to obtain a purified solution containing xylooligosaccharide, 1) enzymatic hydrolysis Before the step, the pH of the biomass extract is adjusted to the optimum pH for the enzymatic hydrolysis reaction using the ion exchange resin purification subtraction process instead of chemicals such as hydrochloric acid or sodium hydroxide, or 2) the biomass extract is decolorized before the enzymatic hydrolysis step.
  • the pH of the biomass extract is adjusted to the optimum pH for the enzymatic hydrolysis reaction using the ion exchange resin purification subtraction process instead of chemicals such as hydrochloric acid or sodium hydroxide, the filtration workability after enzymatic hydrolysis is greatly improved and the ion exchange purification process
  • the present invention was completed after confirming that high-quality xylo-oligosaccharides can be stably prepared by minimizing the overload of .
  • the term 'hemicellulose' used in the present invention is a polysaccharide of cellulose fibers constituting a plant cell wall, minus pectin, and contains xylan, glucan, glucuronoxylan, and arabinoxylan as main components. (arabinoxylan), xyloglucan, glucomannan, and the like.
  • the term 'solid/liquid separation' used in the present invention refers to a method of separating a mixture of a solid phase and a liquid phase into a solid phase and a liquid phase, and is a concept including various known methods. Examples of known solid/liquid separation methods include centrifugation, press filtration, filter cloth filtration, and membrane filtration.
  • the term 'biomass' used in the present invention refers to plant resources used as chemical raw materials or industrial raw materials.
  • an example of the present invention is (a) after heat-treating a biomass slurry consisting of a mixture of biomass and water containing hemicellulose at a temperature of 150 to 200 ° C. solid/liquid separation to obtain a biomass extract; (b) passing the biomass extract through an ion exchange resin to perform primary ion exchange purification to obtain a biomass extract whose pH is adjusted in the range of 4.8 to 6.5; (c) adding an enzyme capable of decomposing xylan to the pH-adjusted biomass extract, performing an enzymatic hydrolysis reaction, and then filtering to obtain an enzyme hydrolysis product solution; (d) concentrating the enzyme hydrolysis product solution to obtain an enzyme hydrolysis product concentrate; and (e) passing the enzymatic hydrolysis product concentrate through an ion exchange resin to perform secondary ion exchange purification and to obtain a purified solution containing xylooligosaccharide having a conductivity of 50 ⁇ s or less. to provide.
  • the biomass containing hemicellulose in step (a) is xylan, glucuronoxylan or arabinoxylan. If it is a plant resource or a specific part of a plant resource containing one or more selected species, the type is not significantly limited, and considering the xylan content and economic feasibility, it is one or more selected from elephant grass, corncob, or sugar cane bagasse. It is preferred to be constructed.
  • the biomass dry weight concentration in the biomass slurry of step (a) is not significantly limited, and 5 to 30% (w/w) based on the total weight of the biomass slurry in consideration of smooth workability and xylan extraction efficiency.
  • the heat treatment in step (a) is preferably performed at high pressure in order to efficiently extract xylan from biomass.
  • the heat treatment temperature of step (a) is preferably 160 ⁇ 200 °C, preferably 170 ⁇ 195 °C.
  • the heat treatment time of step (a) is not significantly limited in the range of extracting xylan to an appropriate level, and may be selected in the range of, for example, 5 minutes to 2 hr, and 5 minutes to 60 minutes in consideration of economic feasibility. It is preferably selected from the range of minutes, and more preferably from 5 minutes to 30 minutes.
  • the ion exchange resin used for the primary ion exchange purification in step (b) is preferably composed of a cation exchange resin and an anion exchange resin.
  • the ion exchange resin may be composed of a total of three stages of ion exchange resin in which a single-stage cation exchange resin, a two-stage anion exchange resin, and a three-stage mixed-phase ion exchange resin are sequentially disposed, It may be a single-stage mixed-phase ion exchange resin.
  • the mixed-phase ion exchange resin is a mixture of a bipolar exchange resin and an anion exchange resin, and the mixing volume ratio of the bipolar exchange resin to the anion exchange resin is preferably 1:1 to 1:4, and 1:1.5 to 1: 3 is more preferable.
  • the cation exchange resin and the anion exchange resin are preferably a strongly acidic cation exchange resin and a weakly basic anion exchange resin, respectively, in consideration of the impurities removal and pH control functions of the biomass extract.
  • the flow rate of the biomass extract passed through the ion exchange resin in step (b) may be selected from a variety of ranges depending on the biomass extraction raw material or extraction conditions, the characteristics and volume of the divorce exchange resin, for example, 2 ⁇ It can be selected from the range of 20 ml/min, it can be selected from the range of 4-15 ml/min, and it can be selected from the range of 5-10 ml/min.
  • the biomass extract that has passed through the ion exchange resin to adjust the pH of the biomass extract to a desired range is fractionated at a predetermined time interval and collected, and only a specific fraction is mixed, followed by (c) It can be used in step enzymatic hydrolysis reactions.
  • step (b) the primary ion exchange purification may be repeated several times to remove impurities in the biomass extract to an appropriate level and adjust the pH of the biomass extract to a desired range, for example, twice It can be carried out repeatedly to 10 times.
  • the pH range of the biomass extract obtained through the primary ion exchange purification in step (b) may be selected in consideration of the optimal pH of the enzyme used in the subsequent step (c), and can decompose xylan. In consideration of the general optimal pH of the enzyme, it is preferably 5.0 to 6.0, and more preferably 5.0 to 5.5.
  • the enzyme capable of decomposing xylan in step (c) is xylan, glucuronoxylan, which is a main component of hemicellulose, or It can be selected from a variety of known enzymes capable of degrading arabinoxylan, and considering the efficiency of xylooligosaccharide production, xylanase, xylosidase, or arabinofuranosidase (Arabinofuranosidase) is preferably composed of one or more selected from, xylanase (Xylanase), xylosidase (Xylosidase), and more preferably a mixed enzyme composition of arabinofuranosidase (Arabinofuranosidase).
  • the enzyme of step (c) is preferably added in an amount of 50 to 250 units per g of xylan contained in the biomass extract in consideration of enzymatic hydrolysis reaction efficiency and economic feasibility, and in the biomass extract. It is more preferably added in an amount of 150 to 220 units per g of xylan contained.
  • the enzymatic hydrolysis reaction temperature of step (c) may be selected in the optimum temperature range of the added enzyme, and is selected in the range of 45 to 60 ° C in consideration of the general optimum temperature of the enzyme capable of decomposing xylan. It is preferable and it is more preferable that it is selected in the range of 48-55 degreeC.
  • the method of filtering the reaction product after the enzymatic hydrolysis reaction in step (c) may be selected from various known filtration methods, and secondary ion exchange purification performed in step (e) after workability, etc.
  • a membrane filtration method is preferable in consideration.
  • the membrane filtration method includes micro-filtration (MF), ultra-filtration (UF), nano-filtration (NF), and the like.
  • Micro-filtration (MF) is a filtration method that separates substances using a membrane with a pore diameter of about 0.025-20 ⁇ m as a filter medium.
  • Ultra-filtration (UF) is a filtration method that separates substances using a membrane having a pore diameter of about 0.01 to 0.001 ⁇ m as a filter medium.
  • the filtration in step (c) may consist of one stage in which only micro-filtration (MF) is performed, and micro-filtration (MF) and ultra-filtration (UF) are sequentially performed. It may also be configured in two stages performed by
  • step (d) may be optionally omitted or added depending on the sugar concentration of the enzymatic hydrolysis product solution obtained in step (c).
  • the method for concentrating the enzyme hydrolysis product solution in step (d) may be selected from various known concentration methods, for example, room temperature evaporation, vacuum evaporation, and the like.
  • the sugar concentration of the enzymatic hydrolysis product concentrate obtained in step (d) is not significantly limited, considering the economic feasibility of the concentration process or the efficiency of the secondary ion exchange purification performed in step (e) after 20 ⁇ It is preferable that it is 35 Brix (Brix), and it is more preferable that it is 22-30 Brix.
  • the ion exchange resin used for the secondary ion exchange purification in step (e) is preferably composed of a cation exchange resin and an anion exchange resin.
  • the ion exchange resin may be composed of a total of three stages of ion exchange resin in which a single-stage cation exchange resin, a two-stage anion exchange resin, and a three-stage mixed-phase ion exchange resin are sequentially disposed, It may be a single-stage mixed-phase ion exchange resin, and in consideration of the efficiency of removing ionic substances and impurities contained in the concentrate of the enzymatic hydrolysis product, it is preferable to consist of a total of three stages of the ion exchange resin.
  • the mixed-phase ion exchange resin is a mixture of a bipolar exchange resin and an anion exchange resin, and the mixing volume ratio of the bipolar exchange resin to the anion exchange resin is preferably 1:1 to 1:4, and 1:1.5 to 1: 3 is more preferable.
  • the cation exchange resin and the anion exchange resin are preferably a strongly acidic cation exchange resin and a weakly basic anion exchange resin, respectively, in consideration of the efficiency of removing ionic substances and impurities contained in the enzyme hydrolysis product concentrate.
  • the concentrate of the enzyme hydrolysis product that has passed through the divorce exchange resin in step (e) is fractionated and collected at predetermined time intervals, and the fraction with conductivity exceeding 50 ⁇ s is managed out of specification, and only the fraction with conductivity of 50 ⁇ s or less It can be mixed to obtain a purified solution containing xylooligosaccharide.
  • the conductivity of the xylo-oligosaccharide-containing purified solution obtained in step (e) is not particularly limited as long as it satisfies 50 ⁇ s or less, and is preferably 25 ⁇ s or less in consideration of the aspect of securing a high-quality xylo-oligosaccharide product, It is more preferable that it is 10 microseconds or less.
  • step (f) in order to provide a xylooligosaccharide of high purity, preferably after step (e), (f) a purified solution containing xylooligosaccharide is separated by chromatography by chromatography. It may further comprise the step of obtaining a lo-oligosaccharide. Specifically, step (f) may consist of concentrating the purified solution containing xylooligosaccharide obtained in step (e), and passing the concentrate through a chromatography column to obtain a syrup containing xylooligosaccharide of high purity.
  • the high-purity xylooligosaccharide-containing syrup has a xylooligosaccharide content of about 70% (w/w) or more, preferably 80% (w/w) or more, and more preferably 90% (w/w) or more. Do.
  • the high-purity xylo-oligosaccharide-containing syrup may be solidified in powder form or the like through various drying methods such as spray drying and freeze drying.
  • another example of the present invention is (a') a biomass slurry consisting of a mixture of biomass and water containing hemicellulose at a temperature of 150 to 200 ° C. then solid/liquid separation to obtain a biomass extract; (b1') adding activated carbon to the biomass extract and performing a decolorization reaction, followed by solid/liquid separation to obtain a decolorized biomass extract; (b2') passing the decolorized biomass extract through an ion exchange resin to perform primary ion exchange purification to obtain a biomass extract whose pH is adjusted in the range of 4.8 to 6.5; (c') adding an enzyme capable of decomposing xylan or arabinoxylan to the pH-adjusted biomass extract, performing an enzymatic hydrolysis reaction, and then filtering to obtain an enzyme hydrolysis product solution; (d') concentrating the enzyme hydrolysis product solution to obtain an enzyme hydrolysis product concentrate; and (e') passing the enzymatic hydrolysis product concentrate through an ion exchange resin to perform secondary i
  • step (f') a purified solution containing xylooligosaccharide is separated by chromatography to obtain xylooligosaccharide It may include further steps.
  • the method for producing a pentose-based oligosaccharide according to another example of the present invention is compared with the above-described method for producing a pentose-based oligosaccharide according to an exemplary embodiment of the present invention, the steps of obtaining a biomass extract by heat treatment of a biomass slurry and primary ions A step of obtaining a decolorized biomass extract by treating the biomass extract with activated carbon is added between the steps of obtaining a biomass extract whose pH is adjusted by exchange purification.
  • step (a), (b2'), (c'), (d'), (e') and (f) constituting the method for producing a pentose-based oligosaccharide according to another example of the present invention ') is step (a), step (b), step (c), step (d), step (e) and step (f) constituting the method for producing a pentose-based oligosaccharide according to an embodiment of the present invention, respectively. Since it corresponds to , a detailed description of the technical characteristics of each step is omitted.
  • the activated carbon in step (b1') is 1 to 8% based on the total weight of sugars contained in the biomass extract in consideration of the decolorization efficiency and economic feasibility of the biomass extract. It is preferably added in an amount of (w/w) and more preferably in an amount of 2 to 6% (w/w).
  • the decolorization reaction temperature of step (b1') may be selected from a variety of ranges depending on the characteristics of the activated carbon to be added, and is preferably selected in the range of 50 to 90° C. in consideration of the general optimum temperature of activated carbon, 60 More preferably, it is selected in the range of ⁇ 80°C.
  • the decolorization reaction time of step (b1') can be selected from various ranges depending on the characteristics of the activated carbon, the amount of activated carbon added, the decolorization reaction temperature, etc., and is 20 minutes to 4 hr in consideration of ensuring an appropriate level of decolorization effect. It is preferably selected from the range, more preferably from 30 minutes to 2 hr.
  • a decolorization process using activated carbon and a primary purification process using an ion exchange resin are performed before the enzymatic decomposition step, and the pH adjustment and impurities of the biomass extract are removed by the primary purification process. It is possible to reduce the overload of the secondary purification process by the ion exchange resin after the enzymatic digestion step compared to the process of adjusting the pH suitable for the enzymatic digestion reaction using conventional chemicals.
  • the method of the present invention when used to prepare a pentose-based oligosaccharide from biomass, the overall process efficiency is improved and high-quality pentose-based oligosaccharides such as xylooligosaccharide can be stably produced from biomass.
  • Endo-xylanase Endo-xylanase
  • beta-xylosidase Beta-xylosidase
  • arabinofuranosidase Arabinofuranosidase
  • Cation exchange resin (Characteristic: Strong acidity; Product name: SCR-B; Manufacturer: Samyang Corporation), Anion exchange resin (Characteristic: Amphiphilic; Product name: S4286; Manufacturer: Lanxess)
  • Activated carbon product name: AP-2; manufacturer: Mitubishi, Japan
  • pH adjuster NaOH, CaCO 3
  • HPLC analysis conditions are as follows.
  • Phenolics represent lignin components derived from biomass, and were analyzed using the Folin-Denis method.
  • By-products are components generated by over-decomposition in the process of obtaining an extract by pretreating biomass with hot water. Specific examples include Acetic acid, Formic acid, 5-HydroxymethylfurfuralHMF), Furfural, and National Renewable Energy Laboratory (NREL, USA) was analyzed according to the 'Determination of Sugars, Byproducts, and Degradation Products in Liquid Fraction Process Samples' method.
  • the ion exchange purification capacity refers to the amount of discharge of a sample having a conductivity of 50 ⁇ s or less compared to the input amount of the ion exchange resin. For example, if the input amount of the ion exchange resin is 300 ml and the discharge amount of a sample having a conductivity of 50 ⁇ s or less after passing through the ion exchange resin is 2400 ml, the ion exchange purification capacity has a value of 8 Bv (bead volume).
  • biomass slurry After quantifying 500 g of biomass based on dry weight, it was uniformly mixed with 4500 ml of water to prepare a biomass slurry having a biomass content of 10% (w/w). After that, the biomass slurry was put into a high-pressure reaction tube with a capacity of 7L, and then heated for about 10 minutes at a temperature of 180 to 190° C., which is the optimum condition for each raw material, and cooled and filtered to obtain 4000 ml of a biomass extract.
  • the general physical properties of the biomass extract for each biomass raw material are shown in Table 1 below.
  • the sugar composition of the biomass extract for each biomass raw material is as shown in Table 2 below.
  • XOS xylo-oligosaccharide in the form of about 2-10 D-xylose bound to beta (1 ⁇ 4)
  • AOS arabino-oligosaccharide in the form of about 2-10 D-arabinose bound to beta (1 ⁇ 4)
  • biomass extract As described above, about 4,000 ml of biomass extract was prepared using elephant grass (Thailand) as a raw material.
  • the prepared biomass extract derived from elephant grass was named 'biomass extract pretreatment sample comparison 1', and xylan content and basic physical properties in the extract were analyzed through HPLC analysis.
  • the concentration process of the filtered enzymatic hydrolysis product solution was omitted because the conductivity (1117 ⁇ s) of the sample was too high, and thereafter, the first stage cation exchange resin 100 ml, the second stage anion exchange resin 100 ml, and the three stage mixed-phase ion exchange resin (cation The mixing volume ratio of the exchange resin to the anion exchange resin is 1:2)
  • the filtered enzyme hydrolysis product solution is passed through a total of 3 stages of ion exchange resin (total amount of ion exchange resin: 300 ml) composed of 100 ml to contain ionic substances and other substances. Impurities were removed, and fractions with a conductivity of 50 ⁇ s or more were managed out of specification.
  • biomass extract As described above, about 4,000 ml of biomass extract was prepared using elephant grass (Thailand) as a raw material, and then the pH of the biomass extract derived from elephant grass was adjusted to 5.2 using 3% (w/w) NaOH aqueous solution. .
  • the pH-controlled biomass extract derived from elephant grass was named 'biomass extract pretreatment sample comparison 2', and xylan content and basic physical properties in the extract were analyzed through HPLC analysis.
  • the sample was filtered using filter paper with a pore size of 1 ⁇ m, and workability during the filtration process was judged by the replacement cycle of the filter paper.
  • the sample subjected to the process was named 'Comparison of Enzyme Decomposition Products 2', and XOS DP composition, filtration process workability, basic physical properties, etc. were analyzed.
  • the concentration process of the filtered enzymatic hydrolysis product solution was omitted because the conductivity (4970 ⁇ s) of the sample was too high, and thereafter, the first stage cation exchange resin 100 ml, the second stage anion exchange resin 100 ml, and the three stage mixed-phase ion exchange resin (cation The mixing volume ratio of the exchange resin to the anion exchange resin is 1:2)
  • the filtered enzyme hydrolysis product solution is passed through a total of 3 stages of ion exchange resin (total amount of ion exchange resin: 300 ml) composed of 100 ml to contain ionic substances and other substances. Impurities were removed, and fractions with a conductivity of 50 ⁇ s or more were managed out of specification.
  • the sample was filtered using filter paper with a pore size of 1 ⁇ m, and workability during the filtration process was judged by the replacement cycle of the filter paper.
  • the sample subjected to the process was named 'Comparison of Enzyme Decomposition Products 3', and XOS DP composition, filtration process workability, basic physical properties, etc. were analyzed.
  • the concentration process of the filtered enzymatic hydrolysis product solution was omitted because the conductivity (4460 ⁇ s) of the sample was too high, and thereafter, the first stage cation exchange resin 100 ml, the second stage anion exchange resin 100 ml, and the three stage mixed-phase ion exchange resin (cation The mixing volume ratio of the exchange resin to the anion exchange resin is 1:2)
  • the filtered enzyme hydrolysis product solution is passed through a total of 3 stages of ion exchange resin (total amount of ion exchange resin: 300 ml) composed of 100 ml to contain ionic substances and other substances. Impurities were removed, and fractions with a conductivity of 50 ⁇ s or more were managed out of specification.
  • the mixed enzyme composition was added in an amount of 180 unit / g Xylan to the decolorized and filtered biomass extract, and 50 ° C.
  • the enzymatic hydrolysis reaction was carried out at a temperature of 24 hr.
  • the enzyme hydrolysis product solution was heated for 30 minutes under a temperature condition of 95°C to inactivate the residual enzyme, then cooled to 50°C, and the sample was filtered using a filter paper having a 1 ⁇ m pore size, and the filtration process The workability was judged by the replacement cycle of filter paper.
  • the sample subjected to the process was named 'Comparison of Enzyme Decomposition Products 4', and XOS DP composition, filtration process workability, basic physical properties, etc. were analyzed.
  • the concentration process of the filtered enzyme hydrolysis product solution was omitted because the conductivity (5191 ⁇ s) of the sample was too high, and thereafter, the first stage cation exchange resin 100 ml, the second stage anion exchange resin 100 ml, and the three stage mixed-phase ion exchange resin (cation The mixing volume ratio of the exchange resin to the anion exchange resin is 1:2)
  • the filtered enzyme hydrolysis product solution is passed through a total of 3 stages of 100 ml of ion exchange resin (total amount of ion exchange resin 300 ml) to contain ionic substances and other substances. Impurities were removed, and fractions with a conductivity of 50 ⁇ s or more were managed out of specification.
  • biomass extract As described above, about 16 L of biomass extract was prepared by using elephant grass (from Thailand) as a raw material and repeating the biomass extract preparation process a total of 4 times. Thereafter, the biomass extract derived from elephant grass was mixed with 100 ml of first-stage cation exchange resin, 100 ml of second-stage anion exchange resin, and three-stage mixed-phase ion exchange resin (the mixing volume ratio of cation exchange resin to anion exchange resin is 1:2) 100 ml
  • the primary ion exchange purification process was carried out by passing it through a total of three stages of ion exchange resin (total amount of ion exchange resin 300 ml) composed of Specifically, the sample was put into the ion exchange resin at a rate of 7.5 ml / min, using a fraction collector (fraction collector) to classify the purified sample at intervals of 5 minutes.
  • the average value of the ion exchange purification capacity was 13.4 Bv, and a sample with a pH of about 12 L was obtained.
  • the sugar concentration of 'biomass extract pretreatment sample preparation 1' was changed due to water generation by the exchange of ionic substances present in the biomass extract after passing through the ion exchange resin and the volume change by the ion exchange resin filling solution. The composition did not change significantly.
  • the filtered enzyme hydrolysis product solution was concentrated to a sugar concentration of about 25 Brix using a reduced pressure concentrator, and 25 ml of a first-stage cation exchange resin, 25 ml of a second-stage anion exchange resin, and a three-stage mixed phase
  • the enzymatic hydrolysis product concentrate is passed through a total of 3 stages of ion exchange resin (total amount of ion exchange resin: 75 ml) consisting of 25 ml of ion exchange resin (the mixing volume ratio of cation exchange resin to anion exchange resin is 1:2) to make the second
  • An ion exchange purification process was performed, through which ionic substances and other impurities were removed, and a fraction with a conductivity of 50 ⁇ s or more was managed out of specification.
  • the bleached and filtered biomass extract derived from elephant grass was mixed with 100 ml of a first-stage cation exchange resin, 100 ml of a second-stage anion exchange resin, and a three-stage mixed-phase ion exchange resin (the mixing volume ratio of cation exchange resin to anion exchange resin is 1:2
  • the first ion exchange purification process was carried out by passing it through a total of 3 stages of ion exchange resin (total amount of ion exchange resin 300 ml) composed of 100 ml, and the pH of the sample was adjusted to 5.0-5.5.
  • the sample was put into the ion exchange resin at a rate of 7.5 ml / min, using a fraction collector (fraction collector) to classify the purified sample at intervals of 5 minutes.
  • a fraction collector fraction collector
  • the mixing of the sample is stopped.
  • the sample whose pH was adjusted by the primary ion exchange purification process was named 'Preparation of biomass extract pretreatment sample 2', and the xylan content and basic physical properties in the extract were analyzed through HPLC analysis.
  • the average value of the ion exchange purification capacity was 20 Bv, and a sample with a pH of about 18 L was obtained.
  • the sugar concentration of 'biomass extract pretreatment sample preparation 2' was changed due to water generation by the exchange of ionic substances present in the biomass extract after passing through the ion exchange resin and the volume change by the ion exchange resin filling solution. The composition did not change significantly.
  • the filtered enzyme hydrolysis product solution was concentrated to a sugar concentration of about 25 Brix using a reduced pressure concentrator, and 25 ml of a first-stage cation exchange resin, 25 ml of a second-stage anion exchange resin, and a three-stage mixed phase
  • the enzymatic hydrolysis product concentrate is passed through a total of 3 stages of ion exchange resin (total amount of ion exchange resin: 75 ml) consisting of 25 ml of ion exchange resin (the mixing volume ratio of cation exchange resin to anion exchange resin is 1:2) to make the second
  • An ion exchange purification process was performed, through which ionic substances and other impurities were removed, and a fraction with a conductivity of 50 ⁇ s or more was managed out of specification.
  • the decolorized and filtered biomass extract derived from elephant grass was passed through 100 ml of a mixed-phase ion exchange resin (the mixing volume ratio of cation exchange resin to anion exchange resin is 1:2) in a total of one stage to perform the primary ion exchange purification process. and the pH of the sample was adjusted to 5.0-5.5. Specifically, the sample was put into the ion exchange resin at a rate of 7.5 ml/min, and the purified sample was sorted at 5 minute intervals using a fraction collector.
  • a mixed-phase ion exchange resin the mixing volume ratio of cation exchange resin to anion exchange resin is 1:2
  • the average value of the ion exchange purification capacity was 21.2 Bv, and a sample with a pH of about 12.7 L could be obtained. there was.
  • the sugar concentration of 'biomass extract pretreatment sample preparation 3' was changed due to water generation by the exchange of ionic substances present in the biomass extract after passing through the ion exchange resin and the volume change by the ion exchange resin filling solution. The composition did not change significantly.
  • the filtered enzyme hydrolysis product solution was concentrated to a sugar concentration of about 25 Brix using a reduced pressure concentrator, and 25 ml of a first-stage cation exchange resin, 25 ml of a second-stage anion exchange resin, and a three-stage mixed phase
  • the enzymatic hydrolysis product concentrate is passed through a total of 3 stages of ion exchange resin (total amount of ion exchange resin: 75 ml) consisting of 25 ml of ion exchange resin (the mixing volume ratio of cation exchange resin to anion exchange resin is 1:2) to make the second
  • An ion exchange purification process was performed, through which ionic substances and other impurities were removed, and a fraction with a conductivity of 50 ⁇ s or more was managed out of specification.
  • biomass extract As described above, about 16 L of biomass extract was prepared by using corncob (made in Indonesia) as a raw material and repeating the biomass extract preparation process a total of 4 times. Thereafter, activated carbon in an amount corresponding to 4% (w/w) of the total sugar weight was added to the biomass extract derived from corncob, and the mixture was stirred at a temperature of 70° C. for 1 hr to perform a decolorization process. After the type of decolorization process, the sample was filtered using a filter paper having a pore size of 1 ⁇ m.
  • the decolorized and filtered corncob-derived biomass extract was passed through 100 ml of a total of one stage of mixed-phase ion exchange resin (the mixing volume ratio of cation exchange resin to anion exchange resin is 1:2) to perform the primary ion exchange purification process. and the pH of the sample was adjusted to 5.0-5.5. Specifically, the sample was put into the ion exchange resin at a rate of 7.5 ml / min, using a fraction collector (fraction collector) to classify the purified sample at intervals of 5 minutes.
  • a fraction collector fraction collector
  • the average value of the ion exchange purification capacity was 20.3 Bv, and a sample with a pH of about 12.2 L could be obtained. there was.
  • the sugar concentration of 'biomass extract pretreatment sample preparation 4' was changed due to water generation by the exchange of ionic substances present in the biomass extract after passing through the ion exchange resin and the volume change by the ion exchange resin filling solution. The composition did not change significantly.
  • the filtered enzyme hydrolysis product solution was concentrated to a sugar concentration of about 25 Brix using a reduced pressure concentrator, and 25 ml of a first-stage cation exchange resin, 25 ml of a second-stage anion exchange resin, and a three-stage mixed phase
  • the enzymatic hydrolysis product concentrate is passed through a total of 3 stages of ion exchange resin (total amount of ion exchange resin: 75 ml) consisting of 25 ml of ion exchange resin (the mixing volume ratio of cation exchange resin to anion exchange resin is 1:2) to make the second
  • An ion exchange purification process was performed, through which ionic substances and other impurities were removed, and a fraction with a conductivity of 50 ⁇ s or more was managed out of specification.
  • biomass extract As described above, about 16 L of biomass extract was prepared by using sugarcane bagasse (from Indonesia) as a raw material and repeating the biomass extract preparation process a total of 4 times. Thereafter, activated carbon in an amount corresponding to 4% (w/w) of the total sugar weight was added to the biomass extract derived from sugar cane bagasse, and the decolorization process was performed by stirring at a temperature of 70° C. for 1 hr. After the type of decolorization process, the sample was filtered using a filter paper having a pore size of 1 ⁇ m.
  • the decolorized and filtered sugarcane bagasse-derived biomass extract is passed through 100 ml of a total of one stage of mixed-phase ion exchange resin (the mixing volume ratio of cation exchange resin to anion exchange resin is 1:2) for primary ion exchange purification.
  • the process was carried out and the pH of the sample was adjusted to 5.0-5.5. Specifically, the sample was put into the ion exchange resin at a rate of 7.5 ml / min, using a fraction collector (fraction collector) to classify the purified sample at intervals of 5 minutes.
  • the average value of the ion exchange purification capacity was 22.6 Bv, and a sample with a pH of about 13.6 L could be obtained. there was.
  • the sugar concentration of 'biomass extract pretreatment sample preparation 5' was changed due to water generation by the exchange of ionic substances present in the biomass extract after passing through the ion exchange resin and the volume change by the ion exchange resin filling solution. The composition did not change significantly.
  • the filtered enzyme hydrolysis product solution was concentrated to a sugar concentration of about 25 Brix using a reduced pressure concentrator, and 25 ml of a first-stage cation exchange resin, 25 ml of a second-stage anion exchange resin, and a three-stage mixed phase
  • the enzymatic hydrolysis product concentrate is passed through a total of 3 stages of ion exchange resin (total amount of ion exchange resin: 75 ml) consisting of 25 ml of ion exchange resin (the mixing volume ratio of cation exchange resin to anion exchange resin is 1:2) to make the second
  • An ion exchange purification process was performed, through which ionic substances and other impurities were removed, and a fraction with a conductivity of 50 ⁇ s or more was managed out of specification.
  • the biomass extract pretreatment sample is a sample that has undergone a decolorization process or a pH adjustment process starting from the left among the unit processes in Table 3 constituting the xylo-oligosaccharide manufacturing method.
  • the analysis results of the biomass extract pretreatment sample are shown in Tables 4 and 5 below.
  • Table 4 below shows the general physical properties and workability of the biomass extract pretreatment sample.
  • Table 5 below shows the sugar composition of the biomass extract pretreatment sample.
  • the enzymatic degradation product sample is a sample obtained by treating a biomass extract pre-treatment sample by the unit processes of Table 3 constituting the xylo-oligosaccharide manufacturing method, enzymatic degradation process or membrane filtration process.
  • Tables 6 and 7 show the general physical properties and workability of the enzyme degradation product sample.
  • Table 7 shows the sugar composition of the enzyme digestion product sample.
  • the enzymatic degradation product ion purification sample is a sample obtained by processing the enzyme degradation product sample by the ion exchange purification process, which is the concentration process or the last process among the unit processes of Table 3 constituting the xylo-oligosaccharide manufacturing method.
  • the analysis results of the enzyme-decomposed product ion purified sample are shown in Tables 8 and 9 below.
  • Table 8 below shows the general physical properties and workability of the ion purification sample of the enzymatic degradation product.
  • Table 9 below shows the sugar composition of the enzyme-decomposed product ion-purified sample.
  • the number of regeneration of the ion exchange resin is reduced to about 1/5 to 1/6 level when the same amount of the enzyme degradation product is treated with the ion exchange purification process compared to Comparative 1 to Comparative 4, and the same amount of Even when compared with the entire manufacturing process for producing xylooligosaccharide, the number of regenerations of the ion exchange resin is reduced to about 1/3, so the efficiency of the entire ion exchange purification process can be greatly improved.

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Abstract

La présente invention concerne un procédé de préparation efficace d'oligosaccharides à base de pentose tels que des xylo-oligosaccharides à partir de biomasse contenant de l'hémicellulose. L'invention concerne également un procédé de préparation d'oligosaccharides à base de pentose, selon la présente invention, un procédé de décoloration utilisant du charbon actif et un procédé de purification primaire utilisant une résine échangeuse d'ions sont effectués avant une étape de dégradation enzymatique, le processus de purification primaire ajustant le pH d'un extrait de biomasse et éliminant ses impuretés de telle sorte que la surcharge d'un processus de purification secondaire à l'aide d'une résine échangeuse d'ions après l'étape de dégradation enzymatique peut être inférieure à celle d'un procédé classique dans lequel un pH approprié pour une réaction de dégradation enzymatique est ajusté à l'aide d'un produit chimique. Par conséquent, lorsque des oligosaccharides à base de pentose sont préparés à partir de biomasse à l'aide du procédé de la présente invention, l'efficacité de traitement globale est améliorée, et des oligosaccharides à base de pentose de haute qualité tels que les xylooligosaccharides peuvent être produits de manière stable à partir de biomasse.
PCT/KR2020/013142 2019-12-20 2020-09-25 Procédé de préparation d'oligosaccharides à base de pentose à partir de biomasse WO2021125515A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040018323A (ko) * 2000-12-28 2004-03-03 다니스코 스위트너스 오와이 크실로스의 회수방법
KR20040038305A (ko) * 2002-10-31 2004-05-08 대한제당 주식회사 자일로올리고당의 생산 방법
KR20050097878A (ko) * 2004-04-05 2005-10-10 산동 롱라이브 바이오-테크놀로지 컴퍼니 리미티드 자일로올리고당의 제조 방법
US20110192560A1 (en) * 2008-10-21 2011-08-11 Danisco A/S Process of producing xylose and dissolving pulp
KR20190014407A (ko) * 2017-08-02 2019-02-12 대상 주식회사 올리고당 및 펄프를 제조하는 방법

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20040018323A (ko) * 2000-12-28 2004-03-03 다니스코 스위트너스 오와이 크실로스의 회수방법
KR20040038305A (ko) * 2002-10-31 2004-05-08 대한제당 주식회사 자일로올리고당의 생산 방법
KR20050097878A (ko) * 2004-04-05 2005-10-10 산동 롱라이브 바이오-테크놀로지 컴퍼니 리미티드 자일로올리고당의 제조 방법
US20110192560A1 (en) * 2008-10-21 2011-08-11 Danisco A/S Process of producing xylose and dissolving pulp
KR20190014407A (ko) * 2017-08-02 2019-02-12 대상 주식회사 올리고당 및 펄프를 제조하는 방법

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