JPH03224500A - Production of xylose - Google Patents
Production of xyloseInfo
- Publication number
- JPH03224500A JPH03224500A JP1896290A JP1896290A JPH03224500A JP H03224500 A JPH03224500 A JP H03224500A JP 1896290 A JP1896290 A JP 1896290A JP 1896290 A JP1896290 A JP 1896290A JP H03224500 A JPH03224500 A JP H03224500A
- Authority
- JP
- Japan
- Prior art keywords
- xylose
- core layer
- sulfuric acid
- raw material
- sugar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 title claims abstract description 75
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 title claims abstract description 41
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 239000012792 core layer Substances 0.000 claims abstract description 16
- 244000021150 Orbignya martiana Species 0.000 claims abstract description 14
- 235000014643 Orbignya martiana Nutrition 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 4
- 239000011707 mineral Substances 0.000 claims abstract description 4
- 244000060011 Cocos nucifera Species 0.000 claims description 15
- 235000013162 Cocos nucifera Nutrition 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000007791 liquid phase Substances 0.000 claims 2
- 239000002994 raw material Substances 0.000 abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 13
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000003456 ion exchange resin Substances 0.000 abstract description 7
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 7
- 230000007062 hydrolysis Effects 0.000 abstract description 6
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 6
- 239000007788 liquid Substances 0.000 abstract description 5
- 239000010410 layer Substances 0.000 abstract description 3
- 238000009835 boiling Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 2
- 238000005903 acid hydrolysis reaction Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 53
- 235000000346 sugar Nutrition 0.000 description 35
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 5
- 150000008163 sugars Chemical class 0.000 description 5
- 239000006188 syrup Substances 0.000 description 5
- 235000020357 syrup Nutrition 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- OIPPWFOQEKKFEE-UHFFFAOYSA-N orcinol Chemical compound CC1=CC(O)=CC(O)=C1 OIPPWFOQEKKFEE-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 229920001221 xylan Polymers 0.000 description 4
- 150000004823 xylans Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 3
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 235000012343 cottonseed oil Nutrition 0.000 description 3
- 239000008103 glucose Substances 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000002255 enzymatic effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000123 paper Substances 0.000 description 2
- -1 pentose sugars Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- PBUWCVBYMDVPCL-UHFFFAOYSA-N 3-anilinophthalic acid Chemical compound OC(=O)C1=CC=CC(NC=2C=CC=CC=2)=C1C(O)=O PBUWCVBYMDVPCL-UHFFFAOYSA-N 0.000 description 1
- 241000233788 Arecaceae Species 0.000 description 1
- 241000202772 Attalea Species 0.000 description 1
- 244000075850 Avena orientalis Species 0.000 description 1
- 235000007319 Avena orientalis Nutrition 0.000 description 1
- 235000007558 Avena sp Nutrition 0.000 description 1
- 235000018185 Betula X alpestris Nutrition 0.000 description 1
- 235000018212 Betula X uliginosa Nutrition 0.000 description 1
- WQZGKKKJIJFFOK-QTVWNMPRSA-N D-mannopyranose Chemical compound OC[C@H]1OC(O)[C@@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-QTVWNMPRSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 235000010099 Fagus sylvatica Nutrition 0.000 description 1
- 240000000731 Fagus sylvatica Species 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- IQZYFYFPIDNTKT-UHFFFAOYSA-N acetic acid;2-ethylpyridine Chemical compound CC(O)=O.CCC1=CC=CC=N1 IQZYFYFPIDNTKT-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000002385 cottonseed oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002402 hexoses Chemical class 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229920001542 oligosaccharide Polymers 0.000 description 1
- 150000002482 oligosaccharides Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 150000004804 polysaccharides Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012264 purified product Substances 0.000 description 1
- 229910052683 pyrite Inorganic materials 0.000 description 1
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 1
- 239000011028 pyrite Substances 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 125000000969 xylosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)CO1)* 0.000 description 1
Landscapes
- Saccharide Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明はババスヤシ殻の核層を原料として用い特定の加
水分解条件を適用することにより、高純度のキシロース
を工業的に安価か′つ効率良く製造する方法に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention uses the core layer of Babassu coconut shell as a raw material and applies specific hydrolysis conditions to produce high-purity xylose industrially at low cost and efficiently. Concerning how to manufacture well.
［従来の技術］
従来、キシロースはキシランの他にセルロース及び各種
のヘミセルロースを多量に含有する天然の植物原料（例
えば、からす麦、トウモロコシ又は綿実膜など単子葉植
物、及びブナ、ポプラ、カバなどの落葉樹のような双子
葉植物）やバルブ及び紙工業の廃棄有機原料（亜硫酸バ
ルブ、クラフトバルブ、セミケミカルバルブなどの廃棄
物）を出発原料として、鉱酸、有機酸又は酵素剤による
加水分解により得る方法が試みられきた。またこれら加
水分解物には多種類の糖類なと不純物を含むので、その
精製については酵母による不純物の発酵除去等の方法が
用いられてきた。[Prior Art] Conventionally, xylose has been produced from natural plant materials containing large amounts of cellulose and various hemicelluloses in addition to xylan (for example, monocotyledonous plants such as oat, corn, or cottonseed, and beech, poplar, and birch). Hydrolysis using mineral acids, organic acids, or enzymatic agents as starting materials from dicotyledonous plants such as deciduous trees (e.g., deciduous trees, etc.) and waste organic raw materials from the valve and paper industry (wastes such as sulfite valves, kraft valves, semi-chemical valves, etc.) Attempts have been made to obtain this method. Furthermore, since these hydrolysates contain many types of saccharides and other impurities, methods such as fermentation removal of impurities using yeast have been used to purify them.
［発明が解決しようとする課題］
一般にこれらの出発原料は各種の多糖類から構成されて
いるため、得られた加水分解糖液中には目的とするキシ
ロースの他にアラビノースなどの五炭糖やグルコース、
マンノース、ガラクトースなどの六炭糖及び酢酸等が生
じる。[Problems to be Solved by the Invention] Generally, these starting materials are composed of various polysaccharides, so in addition to the target xylose, the obtained hydrolyzed sugar solution also contains pentose sugars such as arabinose and glucose,
Hexoses such as mannose and galactose and acetic acid are produced.
従って、この混合物から各成分を分離してキシロースを
高純度で回収することは極めて困難てあリ、そのため多
くの費用と時間を要した。Therefore, it is extremely difficult to separate each component from this mixture and recover xylose with high purity, which requires a lot of cost and time.
一方、上述のような他の不純物の混入のないキシロース
の製造法としてババスヤシ殻の外皮層又は核層を原料と
し、酵素剤を用いる方法（特公昭５６−５０９６０）が
ある。しかし、この方法によると脱）ノグニンやキシラ
ンのアルカリ抽出等の前処理工程とともに酵素加水分解
液を中性成分であるキシロース及びウロン酸を含む酸性
成分であるポリアニオン性物質に分離する後処理があり
、キシロースのみを得るためにはプロセスが複雑で、ま
た費用と時間かかかるという問題点があった。On the other hand, as a method for producing xylose without contamination with other impurities as mentioned above, there is a method using the outer skin layer or core layer of the Babassu coconut shell as a raw material and using an enzyme agent (Japanese Patent Publication No. 56-50960). However, this method requires pretreatment steps such as de)nognonin and alkaline extraction of xylan, as well as post-treatment to separate the enzymatic hydrolyzate into xylose, a neutral component, and polyanionic substances, which are acidic components, including uronic acid. However, there were problems in that the process to obtain only xylose was complicated, and it was expensive and time consuming.
また−船釣に天然物を原料とすることは原料供給の安定
性が問題となるものであり、例えば綿実殻を原料とした
場合（特公昭４３−１２２３７１綿実油の利用価値の減
少に伴い将来的に原料の安定な供給に問題かある。なお
、原料とする植物においては、キシランの存在状態は、
その起源によって異なるもので、熱や薬品に対する挙動
についてもキシラン自体の分子量、リグニン質・セルロ
ース質との結合状態により各々異なっている。In addition, using natural products as raw materials for boat fishing poses problems regarding the stability of raw material supply. For example, if cottonseed husks are used as raw materials (Japanese Patent Publication No. 43-122371), due to the decrease in the utility value of cottonseed oil, there will be problems in the future. However, there is a problem with the stable supply of raw materials.In addition, in the plants used as raw materials, the state of existence of xylan is as follows.
They differ depending on their origin, and their behavior towards heat and chemicals also differs depending on the molecular weight of the xylan itself and the state of bonding with lignin and cellulose.
キシロースの製造原料として、ババスヤシ殻の核層は特
公昭５６−５０９６０に述べられているように他の原料
に比ベキシラン含量に冨み、また原木はブラジルなど南
米に大量に自生しているため原料供給安定性に優れてい
る。しかしながら、キシロースのみを製造する観点から
は先に述べた特許の製造方法ではプロセスが複雑であり
コスト面から必ずしも有利ではなかった。As a raw material for the production of xylose, the core layer of the Babasu coconut shell is rich in bexilan content compared to other raw materials, as stated in Japanese Patent Publication No. 56-50960, and the raw wood grows naturally in large quantities in South America such as Brazil, so it is used as a raw material. Excellent supply stability. However, from the viewpoint of producing only xylose, the above-mentioned patented production method requires a complicated process and is not necessarily advantageous in terms of cost.
そこで本発明では原料としてババスヤシ殻の核層を用い
、高純度のキシロースを工業的に安価で簡便に製造する
ことを目的とした。Therefore, the present invention aims to produce high-purity xylose industrially at low cost and simply by using the core layer of Babassu coconut shell as a raw material.
なおこの発明で言うババスヤシとは、ヤシ科植物に分類
されＢａｂａｓｓｕｐａｌｍ、Ｏｒｂｉｇｎｙａ ｍａ
ｒｔｉａｎａＢａｒｂ−Ｒｏｄｒ等の名称があり、核層
はその種子を包むＥｎｃｌｃａｒｐｏと呼ばれる部分を
指す。In addition, the Babassupalm referred to in this invention refers to Babassupalm, Orbignya palm, which is classified as a plant of the palm family.
There are names such as rtianaBarb-Rodr, and the nuclear layer refers to the part called Enclcarpo that envelops the seed.
［課題を解決するための手段］
本発明においては、原料供給性に優れているババスヤシ
殻の核層な用い、その加水分解の条件として０．１〜３
． ０Ｎの鉱酸を用い、１００１３０°Ｃ好ましくは１
２０°Ｃ前後、常圧又は加圧下で煮熟する。このことに
よってグルコース、アラビノース及び少糖類の生成を抑
えかつ高純度のキシロースを製造することができる。[Means for Solving the Problems] In the present invention, the core layer of Babassu coconut shell, which has excellent raw material supplyability, is used, and the hydrolysis conditions are 0.1 to 3.
．． using 0N mineral acid at 100130°C, preferably 1
Boil at around 20°C under normal pressure or pressure. This makes it possible to suppress the production of glucose, arabinose and oligosaccharides and to produce highly pure xylose.
更にババスヤシ殻の核層な原料とするについて、水又は
０．１Ｎ以下の希酸を加え煮熟し液に溶解した不純物を
流し去る前処理工程の後に、上記の加水分解を行うと、
さらに高純度のキシロースが得られることを見い出した
。Furthermore, in order to use Babasu coconut shell as a raw material for the core layer, if the above hydrolysis is performed after a pretreatment step of adding water or a dilute acid of 0.1N or less and boiling it to wash away impurities dissolved in the liquid,
It was also discovered that highly purified xylose could be obtained.
また得られた加水分解液からキシロースの分離精製は活
性炭処理、イオン交換樹脂処理及び結晶化等で達成され
る。Separation and purification of xylose from the obtained hydrolyzate is achieved by treatment with activated carbon, treatment with an ion exchange resin, crystallization, etc.
以下に実施例等により具体的に述べる。This will be described in detail below using examples and the like.
［実験例１コ
硫酸処理によるキシロース含有液製造（１）ババスヤシ
殻の核層部を取り出し、ウィレーミルにより粒径０，５
〜２．０ｍｍ程度に粉砕処理を行ってパウダーを得た。[Experimental Example 1 Production of xylose-containing liquid by co-sulfuric acid treatment (1) The core layer of the Babassu coconut shell was taken out and reduced to a particle size of 0.5 using a Willey mill.
A powder was obtained by pulverizing the powder to about 2.0 mm.
このパウダー（乾燥物）各８、ＯＯｇ（１０系列）を試
料とし栓付三角フラスコ中の０〜５０％（ｖ／ｖ）（約
Ｏ〜１８Ｎ）の硫酸１００ｍ１に加え、１２０℃加圧１
気圧６０分のオートクレーブ中でキシロースの溶出を試
みた。各系列の酸濃度は第１表に示した。A sample of 8 and 00 g (10 series) of this powder (dry product) was added to 100 ml of 0-50% (v/v) (approximately O-18 N) sulfuric acid in an Erlenmeyer flask with a stopper, and the mixture was heated at 120°C for 1 hour.
An attempt was made to elute xylose in an autoclave at atmospheric pressure for 60 minutes. The acid concentration of each series is shown in Table 1.
加熱処理後加水分解物はガラス繊維濾紙にて濾過し、固
形物と濾液に分離した。固形物は洗浄液が中性になるま
で水洗した後に１０５℃で５時間乾燥し秤量した。濾液
は水酸化バリウムでｐＨ６，５６，９に中和し、生じた
硫酸バリウムを濾過により除去し濾液を濃縮、凍結乾燥
を行い秤量した。ババスヤシ殻核層パウダーの各硫酸濃
度による溶出物と固形物の物質収支を第２表に示した。After the heat treatment, the hydrolyzate was filtered using glass fiber filter paper to separate solid matter and filtrate. The solid matter was washed with water until the washing solution became neutral, dried at 105° C. for 5 hours, and weighed. The filtrate was neutralized with barium hydroxide to pH 6,56,9, the resulting barium sulfate was removed by filtration, the filtrate was concentrated, freeze-dried, and weighed. Table 2 shows the mass balance of eluates and solids for each sulfuric acid concentration of the Babassu coconut shell core layer powder.
原料に対する溶出物の収率は実験系Ｄ−Ｆ（硫酸濃度１
．０〜５．０％（Ｖ／Ｖ）で４０％以上という最も効率
が良い結果となった。The yield of eluate relative to the raw material was determined using experimental system D-F (sulfuric acid concentration 1
．． The best efficiency of 40% or more was obtained at 0 to 5.0% (V/V).
溶出物の糖組成を調べるためにシリカゲルＴＬＣプレー
ト（ＭＥＲＣＫ Ａｒｔ、 ５５５４）で展開した結果
、驚くべきことに実験系Ｃ−Ｅ（硫酸濃度０．５〜２．
０％（Ｖ／Ｖ）の硫酸濃度で処理した物が唯一キシロー
スのみが生成していることが判明した（第１図）。また
実験系０−Ｂ（硫酸濃度Ｏ〜０．２％（Ｖ／Ｖ）ではバ
バスヤシ殻核層中に含まれる他のヘミセルロース由来の
アラビノース化の夾雑物が多く含まれ、実験系Ｆ〜工
（硫酸濃度５．０〜５０．０％（Ｖ ／ Ｖ ）ではセ
ルロース由来のグルコースの生成が伴うようになり、純
度の高いキシロースを得られるのはこの間の硫酸濃度で
のみ成立することが示された。In order to investigate the sugar composition of the eluate, it was developed on a silica gel TLC plate (MERCK Art, 5554), and surprisingly, experimental system C-E (sulfuric acid concentration 0.5-2.
It was found that only xylose was produced in the sample treated with 0% (V/V) sulfuric acid concentration (Figure 1). In addition, in experimental system 0-B (sulfuric acid concentration O ~ 0.2% (V/V)), a large amount of arabinose impurities derived from other hemicelluloses contained in the Babassu coconut shell core layer were contained, and in experimental system F~
(It has been shown that at sulfuric acid concentrations of 5.0 to 50.0% (V/V), glucose derived from cellulose is produced, and that highly pure xylose can only be obtained at sulfuric acid concentrations between this range. Ta.
次に各溶出物の全糖量をオルシノール硫酸法で還元糖量
をネルソンーソモギ法で定量した結果を第３表に示した
。全糖量の比率は実験系Ａ−Ｆ（硫酸濃度０．１〜５．
０％（ｖ／ｖ））で６０％前後の値か得られ、還元糖量
は実験系Ｃ−Ｆ（硫酸濃度０．５〜５．０％（ｖ／ｖ）
）で５５％前後の値か得られた。また全糖量／還元糖量
の値で溶出物に含まれる糖の重合度を換算すると、実験
系Ｃ−Ｇ（硫酸濃度１．０〜１０．０％（ｖ／ｖ））で
ほぼ１となり、溶出糖のほとんど全部が単糖まで分解し
ていることがわかる。またここで実験系Ｈ１■（硫酸濃
度２０．０〜５０．０％（ｖ／ｖ））では糖の過分解反
応が進行していることが明らかとなった。Next, the total sugar content of each eluate was determined by the orcinol sulfuric acid method, and the reducing sugar content was determined by the Nelson-Somogi method, and the results are shown in Table 3. The ratio of total sugar amount is experimental system A-F (sulfuric acid concentration 0.1-5.
0% (v/v)), a value of around 60% was obtained, and the amount of reducing sugar was determined by the experimental system C-F (sulfuric acid concentration 0.5-5.0% (v/v)).
), a value of around 55% was obtained. In addition, when converting the degree of polymerization of sugars contained in the eluate using the value of total sugar amount/reducing sugar amount, it is approximately 1 in experimental system C-G (sulfuric acid concentration 1.0 to 10.0% (v/v)). , it can be seen that almost all of the eluted sugars have been broken down to monosaccharides. Furthermore, it was revealed that in the experimental system H1 (sulfuric acid concentration 20.0 to 50.0% (v/v)), the excessive decomposition reaction of sugar was progressing.
溶出物中の糖分の対原料収率では、実験系Ｄ〜Ｆ（硫酸
濃度１．０〜５．０％（Ｖ／Ｖ））で２３％以上となっ
た（第４表）。The yield of sugar in the eluate relative to the raw material was 23% or more in experimental systems D to F (sulfuric acid concentration 1.0 to 5.0% (V/V)) (Table 4).
以上、溶出物の糖分の対原料収率、キシロースの純度、
糖含量、加水分制度のすべての実験結果を考慮した結果
、実験系り、 Ｅ （硫酸濃度１．０．２．０％（Ｖ／
Ｖ） ）で処理して得た溶出物が夾雑糖類を含まず、ま
た高い収率でキシロースか得られることが明らかとなっ
た。Above, the yield of sugar content in the eluate relative to the raw material, the purity of xylose,
As a result of considering all the experimental results regarding sugar content and hydrolysis system, the experimental system was as follows: E (sulfuric acid concentration 1.0.2.0% (V/
It was revealed that the eluate obtained by the treatment in (V)) did not contain any contaminant sugars and that xylose could be obtained in high yield.
第 １ 表
第
表
（重量は乾物換算値）
第
表
＼
第
表
［実験例２］キシロースシロツプのｍＭ実験例１の実験
系り、Ｅの濾液部分の凍結乾燥物（以下各県の濾液部分
の凍結乾燥物も単に溶出物と表現する。） １．ＯＯｇ
を水１０ｍ１に溶かし、ヤシ殻活性炭（和光純薬）５０
ｍｇを加え４’ Ｏ’Ｃで６０分間処理した。活性炭を
濾過して除去し、処理液を１０ｍ１に調整した。この５
．００ｍ１を強酸性イオン交換樹脂ＧＣ１２０（）ｌ”
）型１〜１．５ｍｌ及び強塩基性イオン交換樹脂ｌＲ４
１０Ｃ０）ｌ−）型１〜１．５ｍ１Ｏカラムに通過し精
製を行った。Table 1 Table 1 (Weight is calculated as dry weight) Table ＼ Table [Experiment Example 2] Xylose syrup in mM Experimental system of Experiment Example 1 The lyophilized product of a portion is also simply expressed as the eluate.) 1. OOg
Dissolve in 10ml of water, add 50ml of coconut shell activated carbon (Wako Pure Chemical Industries)
mg was added and treated at 4'O'C for 60 minutes. Activated carbon was removed by filtration, and the volume of the treated solution was adjusted to 10 ml. This 5
．． 00ml of strongly acidic ion exchange resin GC120()l”
) Type 1-1.5ml and strongly basic ion exchange resin lR4
Purification was performed by passing through a 10C0)l-) type 1-1.5mlO column.
各精製段階のシロップの糖純度をオルシノール硫酸法で
検定した結果、最終処理物は実験系りで９２．８％、Ｅ
で９０．２％となり（第５表）、またこれをＨＰＬＣで
糖組成を調べた結果、各々唯一キシロースのピークのみ
が検出された。As a result of testing the sugar purity of the syrup at each purification stage using the orcinol sulfuric acid method, the final treated product was 92.8% in the experimental system.
90.2% (Table 5), and when the sugar composition was examined by HPLC, only a xylose peak was detected in each case.
結果は第２図に示した。なおＨＰＬＣの条件は移動相ニ
アセトニトリル：水＝８０：２０流速 ： ０．５ｍｌ
／ｍｉｎ
カラム： ＴＯ３ＯＨＡｍ１ｄｅ ８０ （４，６ｍｍ
ＩＤｘ ２５ｃｍ）温度二８０°Ｃ
検出器： ＴＯ５Ｏ）Ｉ Ｒ１−８０１２装 置： Ｔ
Ｏ５ＯＨ５Ｃ−８０１０
試料注入量：２０μＩ
（アセトニトリル：試料水溶液＝８０：２０）また各精
製段階の糖分の対原料収率を第４表に示した。最終処理
物のキシロースの対原料収率は約２１％となった。The results are shown in Figure 2. Note that the HPLC conditions are mobile phase: niacetonitrile:water = 80:20 flow rate: 0.5ml
/min Column: TO3OHAm1de 80 (4.6mm
IDx 25cm) Temperature 280°C Detector: TO5O) I R1-8012 Device: T
O5OH5C-8010 Sample injection amount: 20 μI (acetonitrile: sample aqueous solution = 80:20) Table 4 also shows the yield of sugar to raw material in each purification step. The yield of xylose based on the raw material in the final treated product was approximately 21%.
第 ５ 表
［実験例３］前処理を含むキシロース含有液の製造（２
）
ババスヤシ核層パウダー（乾燥物）各８．ＯＯｇ（３系
列０−２、Ａ−２、Ｂ−２）を試料とし、栓付三角フラ
スコ中のＯ〜０，２％（ｖ ／ ｖ ） （約０〜０．
０７２Ｎ）の水又は希硫酸液１００ｍ１に加え、１２０
℃加圧１気圧６０分のオートクレーブ中で前処理し、溶
出物を濾過除去して得られた固形物の各４．００ｇ（乾
燥物換算）を以下のキシロース含有液の製造原料として
用いた。各実験系の前処理における硫酸濃度は、第１表
に示した同じアルファベット記号の実験系に準する。す
なわち○−２実験系では水を用い、Ａ−２実験系では０
．１％の、Ｂ−２実験系では０．２％の希硫酸を用いた
。Table 5 [Experimental Example 3] Production of xylose-containing liquid including pretreatment (2
) Babassu coconut core layer powder (dried) 8. OOg (3 series 0-2, A-2, B-2) was used as a sample, and O~0.2% (v/v) (approximately 0~0.0.
In addition to 100 ml of water or dilute sulfuric acid solution of 120
Pretreatment was carried out in an autoclave under pressure of 1 atm at 0.degree. C. for 60 minutes, and the eluate was removed by filtration. 4.00 g (in terms of dry matter) of each of the solids obtained was used as a raw material for producing the following xylose-containing liquid. The sulfuric acid concentration in the pretreatment of each experimental system is based on the experimental systems shown in Table 1 with the same alphabetical symbol. In other words, water was used in the ○-2 experimental system, and 0 was used in the A-2 experimental system.
．． 1% and 0.2% dilute sulfuric acid was used in the B-2 experimental system.
各前処理条件で処理した固形物４．００ｇ （乾燥物換
算）を栓付三角フラスコ中の１％（ｖ／ｖ）硫酸５０ｍ
１中に加え、１２０℃、加圧１気圧、６０分間のオート
クレーブ中でキシロースの溶出を試みた。溶出物と固形
物の物質収支を求めた結果を第６表に示した。4.00 g (dry weight) of the solids treated under each pretreatment condition was placed in a stoppered Erlenmeyer flask with 50 m of 1% (v/v) sulfuric acid.
1, and an attempt was made to elute xylose in an autoclave at 120° C. and a pressure of 1 atm for 60 minutes. Table 6 shows the results of determining the mass balance of eluate and solid matter.
溶出物の糖組成をＴＬＣで調べた結果、唯一キシロース
のみが生成していることが示された（第３図）。Examination of the sugar composition of the eluate by TLC revealed that only xylose was produced (Figure 3).
また全糖量及び還元糖量を実験例１と同様に測定した結
果、全糖量の比率は第７表に示した通り実験系０−２．
Ａ−２で８０％前後となり、実験例１で得られた前処理
を行わなかった実験系Ａ〜Ｆに比べ２０％程度向上した
。実験系Ｂ−２の前処理時の硫酸濃度（０，２％（Ｖ／
Ｖ）’）では、前処理段階でのキシロースのロスが多く
、かつ純度の向上が認められなかった。In addition, as a result of measuring the total sugar amount and reducing sugar amount in the same manner as in Experimental Example 1, the ratio of total sugar amount was as shown in Table 7 for experimental system 0-2.
In A-2, it was around 80%, which was an improvement of around 20% compared to experimental systems A to F obtained in Experimental Example 1 in which no pretreatment was performed. Sulfuric acid concentration (0.2% (V/
In V)'), there was a large loss of xylose in the pretreatment step, and no improvement in purity was observed.
この結果は、前処理がこの後の精製に用いる活性炭及び
イオン交換樹脂の消耗を低減する効果があることを示し
、また適切な条件の前処理では全糖量／還元糖量の値も
ほぼ１となり、生成糖のほとんど全部が単糖であること
を示している。This result shows that pretreatment has the effect of reducing the consumption of activated carbon and ion exchange resin used in subsequent purification, and that with appropriate pretreatment conditions, the value of total sugar content/reducing sugar content is approximately 1. This shows that almost all of the produced sugars are monosaccharides.
糖分の対原料収率は第４表に示したように実験系○−２
で約２４％と最も高く、前処理は水又は０．１％（Ｖ／
Ｖ）程度の硫酸を用いたものが良いことが明らかである
。As shown in Table 4, the sugar yield relative to the raw material was determined for experimental system ○-2.
is the highest at approximately 24%, and the pretreatment is with water or 0.1% (V/
It is clear that a method using sulfuric acid of grade V) is better.
第 ６ 表
第
表
［実験例４］キシロース製造（３）
これまでの実験例をもとにキシロース製造のスケールア
ップを試みた。パウダー３００．０ｇ（乾燥物換算）に
水道水を加え、全量１５００ｍｌとし、２Ｌ容ポリプロ
ピレン容器中で １２０℃、加圧（ゲージ圧１気圧）、
６０分間処理した。濾過により２８９．８ ｇ （乾燥
物換算）の残渣を得て、これに１％（Ｖ／Ｖ）硫酸（約
０．３６Ｎ）を加え全量１５００ｍｌとし、同様に１２
０℃で加圧６０分間処理した。濾過して残渣を除去し、
濾液に消石灰を加え中和し生じた硫酸カルシウムを濾過
除去した。濾液を濃縮し、再び濾過により沈殿物を除き
、活性炭、イオン交換樹脂処理を実験例２で述べた方法
に準じて行ってシロップを得、またこの一部をＨＰＬＣ
で糖組成の分析を行った。結果を第４図に示した。残る
シロップは濃縮、乾燥して糖純度９１．２％の固形分８
１．４ｇを得た。糖分の対原料収率な算出すると２４．
７％となった。Table 6 [Experimental Example 4] Xylose Production (3) Based on the previous experimental examples, an attempt was made to scale up xylose production. Add tap water to 300.0 g of powder (dry equivalent) to make a total volume of 1500 ml, and place in a 2 L polypropylene container at 120°C and pressurized (1 atm gauge pressure).
Processed for 60 minutes. A residue of 289.8 g (in terms of dry matter) was obtained by filtration, and 1% (V/V) sulfuric acid (approximately 0.36 N) was added to the residue to make a total volume of 1500 ml.
It was treated under pressure at 0°C for 60 minutes. Filter to remove residue;
Slaked lime was added to the filtrate to neutralize it, and the resulting calcium sulfate was removed by filtration. The filtrate was concentrated, the precipitate was removed by filtration again, and treated with activated carbon and ion exchange resin according to the method described in Experimental Example 2 to obtain syrup, and a portion of this was subjected to HPLC analysis.
The sugar composition was analyzed. The results are shown in Figure 4. The remaining syrup is concentrated and dried to a solid content of 8 with a sugar purity of 91.2%.
1.4g was obtained. Calculating the yield of sugar to raw materials is 24.
It was 7%.
［発明の効果］
従来植物原料からキシロースを製造する場合夾雑糖類の
生成及び高温処理（１３０℃以上）による酢酸の発生が
問題とされていた。本発明者等は酢酸の副生を１００〜
１３０°Ｃという低い温度に設定することで回避し、ま
たババスヤシ殻核屡を原料とし硫酸処理条件の選択だけ
で高純度のキシロースが製造出来ることを発見した。バ
バスヤシは南米に多量に自生し、また特に核層部はその
５８％をも占める一方用途に乏しく、未利用資源でもあ
り原料としての供給安定性に優れているものである。ま
た本性のプロセスの簡潔さは高純度のキシロースを低コ
ストで製造することを可能とし、工業的にも極めて有用
である。[Effects of the Invention] Conventionally, when producing xylose from plant materials, there were problems with the formation of contaminant sugars and the generation of acetic acid due to high temperature treatment (130° C. or higher). The present inventors have determined that the by-product of acetic acid is 100~
They discovered that this can be avoided by setting the temperature as low as 130°C, and that high-purity xylose can be produced by simply selecting the sulfuric acid treatment conditions using Babassu coconut shell kernels as a raw material. Babasu palm grows naturally in large quantities in South America, and the core layer in particular accounts for 58% of the palm, but it is of little use and is an untapped resource with excellent supply stability as a raw material. Moreover, the simplicity of the inherent process makes it possible to produce high purity xylose at low cost, making it extremely useful industrially.
第１図はババスヤシ殻の核層を各濃度の硫酸で処理して
得た溶出物のＴＬＣによる糖組成を示す。
第２図（Ａ）、（Ｂ）及び（Ｃ）はキシロース標準試料
、実験系り及びＥの活性炭・イオン交換樹脂による精製
物の）ＩＰＬＣによる糖組成を示す。
第３図は前処理を行った後に１％（Ｖ／Ｖ）硫酸処理に
よって得た溶出物のＴＬＣによる糖組成を示す。
第４図（Ａ）、（Ｂ）はキシロースの標準試料及び実験
例４の方法で得たシロップのＨＰＬＣによる糖組成を示
す。
展開溶媒：
酢酸エチル；ピリツノ： Ｑｔ酸： 水＝５ ： ５
； ｌ ：発色剤 ：
アニリノ−フタル酸発色剤
σ、Ｕロ
メ
ヌ
ン
第
図
展開溶媒：
酢酸エチル
ピリジン；酢酸；水＝：５ ；！ｉ ：１ ；
第
図
第４図FIG. 1 shows the sugar composition of the eluate obtained by treating the core layer of Babasu coconut shell with sulfuric acid at various concentrations, determined by TLC. Figures 2 (A), (B), and (C) show the sugar compositions determined by IPLC of the xylose standard sample, the experimental sample, and the purified product using activated carbon and ion exchange resin of E. FIG. 3 shows the sugar composition by TLC of the eluate obtained by treatment with 1% (V/V) sulfuric acid after pretreatment. FIGS. 4(A) and 4(B) show the sugar compositions of the xylose standard sample and the syrup obtained by the method of Experimental Example 4 by HPLC. Developing solvent: ethyl acetate; pyrite: Qt acid: water = 5: 5
; l: Color former: Anilino-phthalic acid color former σ, Uromenun diagram Developing solvent: Ethylpyridine acetate; Acetic acid; Water =: 5 ;! i:1; Figure 4
Claims (2)
１００１３０℃、常圧又は加圧下の条件で処理して液相
を得、この液相に含まれるキシロースを分離し精製する
ことを特徴とする高純度のキシロースの製造方法。(1) A liquid phase is obtained by treating the core layer of Babasu coconut shell in 0.1-3.0N mineral acid at 100,130°C under normal pressure or under pressure, and the xylose contained in this liquid phase is separated and purified. A method for producing high-purity xylose, characterized by:
液に溶解する不純物を分離する前処理を施されたもので
あることを特徴とする特許請求の範囲第１項に記載の方
法。(2) The core layer of the Babassu coconut shell is pretreated to separate impurities that dissolve in water or a dilute acid solution of 0.1N or less. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018962A JP2979125B2 (en) | 1990-01-31 | 1990-01-31 | Xylose production method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018962A JP2979125B2 (en) | 1990-01-31 | 1990-01-31 | Xylose production method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03224500A true JPH03224500A (en) | 1991-10-03 |
| JP2979125B2 JP2979125B2 (en) | 1999-11-15 |
Family
ID=11986275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2018962A Expired - Lifetime JP2979125B2 (en) | 1990-01-31 | 1990-01-31 | Xylose production method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2979125B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107475467A (en) * | 2017-09-14 | 2017-12-15 | 齐鲁工业大学 | A kind of highly effective extraction method of poplar xylose |
| NL2031203B1 (en) * | 2022-03-09 | 2023-09-18 | Univ Qilu Technology | Method for preparing reducing sugar by hydrolyzing coconut shell |
-
1990
- 1990-01-31 JP JP2018962A patent/JP2979125B2/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107475467A (en) * | 2017-09-14 | 2017-12-15 | 齐鲁工业大学 | A kind of highly effective extraction method of poplar xylose |
| NL2031203B1 (en) * | 2022-03-09 | 2023-09-18 | Univ Qilu Technology | Method for preparing reducing sugar by hydrolyzing coconut shell |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2979125B2 (en) | 1999-11-15 |
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