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JP2005270056A - Method for removing fermentation inhibitory material in hydrolysate - Google Patents

Method for removing fermentation inhibitory material in hydrolysate Download PDF

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JP2005270056A
JP2005270056A JP2004091706A JP2004091706A JP2005270056A JP 2005270056 A JP2005270056 A JP 2005270056A JP 2004091706 A JP2004091706 A JP 2004091706A JP 2004091706 A JP2004091706 A JP 2004091706A JP 2005270056 A JP2005270056 A JP 2005270056A
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Shiro Saka
志朗 坂
Hisashi Miyato
久士 宮藤
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Hitachi Zosen Corp
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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
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Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for removing a fermentation inhibitory material contained in a treated material without reducing the yield of sugars in hydrolyzing a polysaccharide biomass and subjecting the obtained hydrolysate to ethanol fermentation. <P>SOLUTION: This method for removing the fermentation inhibitory material in hydrolyzing the polysaccharide biomass and subjecting the obtained hydrolysate to the ethanol fermentation is provided by treating the hydrolysate with a wood-based carbonized material. Thereby, it is possible to remove the fermentation inhibitory material or materials supposed to inhibit the fermentation contained in the hydrolysate to a concentration at which the fermentation is not affected. Preferable polysaccharide biomass is a lignocellulose, e.g. wood powder of Japanese cedar. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

本発明は、地球上に大量に存在する多糖類系バイオマスをエタノール発酵に適する状態に処理した後エタノール発酵に供する際に、糖類の収率を損なうことなく発酵阻害物あるいは発酵を阻害するであろう物質を発酵に影響を与えない濃度まで選択的に除去し高効率の発酵を可能ならしめる、加水分解物中の発酵阻害物の除去方法に関する。   The present invention inhibits fermentation inhibitors or fermentation without impairing the yield of sugars when the polysaccharide biomass present in large quantities on the earth is treated to a state suitable for ethanol fermentation and then subjected to ethanol fermentation. The present invention relates to a method for removing a fermentation inhibitor in a hydrolyzate, which selectively removes a wax substance to a concentration that does not affect fermentation and enables highly efficient fermentation.

化石資源の枯渇や地球温暖化によるエネルギー・環境問題は２１世紀における最も重大な問題である。これらの問題を解決するためには、環境負荷を最小限にし且つ石油のように豊富な資源を見つけることが重要である。その中で最も期待されているものの一つにバイオマス資源がある。バイオマス資源を構成し地球上で最大量を誇る構成成分はセルロースであり、セルロースの大部分はリグノセルロース（木質系資源）の構成物として存在する。しかしながら、その大部分は未利用の状態として存在し、リグノセルロースに対してこれまで以上に大きな期待が寄せられている。すなわち、リグノセルロースの化学工業原料としての利用に加えて、エネルギー資源としての利用を目的とした様々な技術開発が注目されている。近年未利用のリグノセルロース構成物、すなわちセルロースおよびヘミセルロースから単糖もしくはオリゴ糖を製造し、エタノール発酵や乳酸への発酵、さらにポリ乳酸などの生分解性高分子への変換が注目されている。しかし、自然界に存在するリグノセルロースはセルロース、ヘミセルロース、リグニンが複雑に構成されたものであり、その構成比率は原料によって様々であるため、有用な成分を得ることは容易でない。   Energy and environmental problems due to fossil resource depletion and global warming are the most serious problems in the 21st century. In order to solve these problems, it is important to find abundant resources such as oil with minimal environmental impact. One of the most promising of these is biomass resources. The constituent component that constitutes biomass resources and boasts the largest amount on the earth is cellulose, and most of the cellulose exists as a constituent of lignocellulose (woody resource). However, most of them exist in an unused state, and there are higher expectations than ever for lignocellulose. That is, in addition to the use of lignocellulose as a chemical industrial raw material, various technological developments aimed at use as an energy resource have attracted attention. In recent years, monosaccharides or oligosaccharides are produced from unused lignocellulose components, ie, cellulose and hemicellulose, and ethanol fermentation, fermentation to lactic acid, and conversion to biodegradable polymers such as polylactic acid have attracted attention. However, lignocellulose existing in nature is a complex composition of cellulose, hemicellulose, and lignin, and the composition ratio varies depending on the raw materials, so it is not easy to obtain useful components.

近年、この未利用リグノセルロースの利用法として、リグノセルロース構成物、すなわちセルロースおよびヘミセルロースから単糖もしくはオリゴ糖を製造し、これをさらには発酵に供することによりエタノールを製造する方法が注目されている。単糖もしくはオリゴ糖の製造方法としては、基本的には、酸加水分解法、酵素糖化法、および亜臨界もしくは超臨界水による加水分解法の三つの方法が知られている。中でも亜臨界水もしくは超臨界水による加水分解法は、秒単位あるいは分単位と処理に係る時間が短く、硫酸などの強酸を外部から添加する必要がないため石膏などの副産物が発生しないことから注目を浴びている。しかしながら、その反応性の高さから糖の過分解物であるフルフラール、５−ヒドロキシメチルフルフラール等のフラン化合物およびグアヤコール、バリニン等のリグニン由来の種々のフェノール性化合物等の種々の発酵阻害物も同時に発生するため、加水分解物をそのまま発酵に供することができない。この問題に対して活性炭による発酵阻害物の除去法等の検討が試みられているが、活性炭による除去に顕著な選択性を確認できず、発酵阻害物だけではなく同時に糖類の吸着が起きると報告されており、結果的にエタノールの収率が低下してしまう（非特許文献１）。
［Biotechnology Letters Vol.5, No.3, 175-178 (1983)］ In recent years, as a method of using this unused lignocellulose, a method for producing ethanol by producing a monosaccharide or oligosaccharide from a lignocellulose component, that is, cellulose and hemicellulose, and further subjecting it to fermentation has attracted attention. . There are basically known three methods for producing monosaccharides or oligosaccharides: acid hydrolysis, enzymatic saccharification, and hydrolysis using subcritical or supercritical water. Among them, the hydrolysis method using subcritical water or supercritical water is notable because byproducts such as gypsum are not generated because the processing time is short in seconds or minutes and there is no need to add a strong acid such as sulfuric acid from the outside. Have been bathed. However, because of its high reactivity, various fermentation inhibitors such as furl compounds, such as furfural and 5-hydroxymethylfurfural, which are hyperdegradable sugars, and various phenolic compounds derived from lignin such as guaiacol and valinine are also present. As a result, the hydrolyzate cannot be used for fermentation as it is. Attempts have been made to remove fermentation inhibitors using activated carbon to solve this problem, but it was not possible to confirm remarkable selectivity for removal using activated carbon, and it was reported that adsorption of saccharides occurred simultaneously with not only fermentation inhibitors. As a result, the yield of ethanol is reduced (Non-Patent Document 1).
[Biotechnology Letters Vol.5, No.3, 175-178 (1983)]

本発明は、こうした状況のもとになされたものであって、多糖類系バイオマスを加水分解し、得られた加水分解物をエタノール発酵に供するに当たり、糖類の収率を損なうことなく処理物に含まれる発酵阻害物または発酵を阻害するであろう物質を発酵に影響を与えない濃度まで除去する方法を提供することを目的とする。   The present invention has been made under such circumstances, in which polysaccharide biomass is hydrolyzed, and when the obtained hydrolyzate is subjected to ethanol fermentation, it is processed into a processed product without impairing the yield of saccharides. It is an object of the present invention to provide a method for removing contained fermentation inhibitors or substances that will inhibit fermentation to a concentration that does not affect fermentation.

本発明は上記目的を達成すべくなされたもので、多糖類系バイオマスを加水分解し、得られた加水分解物をエタノール発酵に供するに当たり、加水分解物を木質系炭化物で処理し、加水分解物に含まれる発酵阻害物または発酵を阻害するであろう物質を発酵に影響を与えない濃度まで除去することを特徴とする、加水分解物中の発酵阻害物の除去方法である。ここで木質系炭化物とはリグノセルロース資源の炭化処理で得られる炭化物を示しており、木質資源のみならず草本類などのリグノセルロース資源をも含むものである。   The present invention has been made to achieve the above-mentioned object. In hydrolyzing polysaccharide-based biomass and subjecting the obtained hydrolyzate to ethanol fermentation, the hydrolyzate is treated with a wood-based charcoal. Is a method for removing a fermentation inhibitor in a hydrolyzate, wherein the fermentation inhibitor or a substance that would inhibit fermentation is removed to a concentration that does not affect the fermentation. Here, the wood-based carbide refers to a carbide obtained by carbonizing lignocellulose resources, and includes not only wood resources but also lignocellulose resources such as herbs.

本発明方法の対象となる多糖類系バイオマスは、セルロースおよび／またはヘミセルロースからなる多糖類がリグニンにより木化したものであり、針葉樹、広葉樹、ササ、タケ、稲わら、もみ殻、麦わら、その他農林産物資源およびそれらの廃棄物、これらに由来する木材繊維、木材チップ、単板くず、パルプ類、古紙類等であり、さらにはさとうきび、てんさいなどの糖質資源、ばれいしょ、かんしょ、さといもなどのでんぷん資源などリグニン含量が少ないもしくは含まないバイオマスであってもよく、キチン・キトサン等の多糖類を含むバイオマスおよびそれらの廃棄物をも含む。これらのバイオマス資源は２以上の組み合わせであってもよい。   The polysaccharide-based biomass to be subjected to the method of the present invention is obtained by converting a polysaccharide composed of cellulose and / or hemicellulose into a tree by lignin, and conifer, broadleaf, bamboo grass, bamboo, rice straw, rice husk, wheat straw, and other agricultural forests. Product resources and their wastes, wood fibers, wood chips, veneer scraps, pulps, waste paper, etc. derived from them, as well as sugar resources such as sugar cane and sugar beet, starches such as potato, sugar cane and sugar cane It may be a biomass with low or no lignin content such as resources, and also includes biomass containing polysaccharides such as chitin and chitosan and wastes thereof. These biomass resources may be a combination of two or more.

好ましい多糖類系バイオマスはリグノセルロース、例えばスギ木粉である。   A preferred polysaccharide biomass is lignocellulose, such as cedar wood flour.

代表的な発酵阻害物は、糖の過分解物、リグニン由来の種々のフェノール性化合物である。例えばスギ木粉を加水分解して得られた加水分解物にはフルフラール、５−ヒドロキシメチルフルフラール等のフラン化合物およびグアヤコール、バリニン等のリグニン由来の種々のフェノール性化合物等の種々の発酵阻害物が存在し、加水分解物を１０時間の発酵に供したが発酵は進行しなかった。発酵を阻害するであろう針葉樹からのリグニン由来物質は、メチルグアヤコール、エチルグアヤコール、ビニルグアヤコール、オイゲノール、プロピルグアヤコール、イソオイゲノール、アセトグアイアコン、プロピオグアイアコン、グアイアシルアセトン、ジヒドロコニフェリルアルコールなどである。広葉樹を用いる場合には、これら以外に広葉樹リグニンを構成するシナピルアルコール類に由来する種々のフェノール性化合物（シナピルアルコール、エチルシリンゴール、ビニルシリンゴール、プロピルシリンゴール、アリルシリンゴール、プロペニルシリンゴール）などが含まれる。   Typical fermentation inhibitors are various phenolic compounds derived from sugar hyperdegradation, lignin. For example, the hydrolyzate obtained by hydrolyzing cedar wood flour contains various fermentation inhibitors such as furan compounds such as furfural and 5-hydroxymethylfurfural and various phenolic compounds derived from lignin such as guaiacol and valinine. Present and subjecting the hydrolyzate to fermentation for 10 hours, the fermentation did not proceed. Lignin-derived substances from conifers that will inhibit fermentation include methyl guaiacol, ethyl guaiacol, vinyl guaiacol, eugenol, propyl guaiacol, isoeugenol, acetoguaiacon, propioguaiacon, guaiacylacetone, dihydroconiferyl alcohol, etc. It is. When using broad-leaved trees, in addition to these, various phenolic compounds derived from the synapyl alcohols that make up broad-leaved tree lignin (sinapyrcohol, ethylsyringol, vinylsyringol, propylsyringol, allylsyringol, propenylsyring Goal).

多糖類系バイオマスの加水分解は、亜臨界状態の水による加水分解処理、超臨界状態の水による加水分解処理、酸による加水分解処理、および酵素糖化法のうちの１つであってもよいし、これらの２以上の組み合わせであってもよい。   Hydrolysis of the polysaccharide biomass may be one of subcritical water hydrolysis, supercritical water hydrolysis, acid hydrolysis, and enzymatic saccharification. A combination of two or more of these may be used.

本発明の加水分解物中の発酵阻害物の除去方法に用いる木質系炭化物は、針葉樹、広葉樹、ササ、タケ、稲わら、もみ殻、麦わら、その他農林産物資源およびそれらの廃棄物並びにこれらに由来する木材繊維、木材チップや単板くず、パルプ類、古紙類などのリグノセルロース資源、さらにはキチン・キトサンなどの資源を所定条件下に熱処理して得られた炭化物であるが、好ましくは木材などの木質バイオマス資源由来炭化物である。   The wood-based carbide used in the method for removing a fermentation inhibitor in the hydrolyzate of the present invention is derived from conifers, hardwoods, sasa, bamboo, rice straw, rice husk, wheat straw, other agricultural and forestry product resources and wastes thereof, and the like. Wood fiber, wood chips and veneer scraps, lignocellulose resources such as pulp and waste paper, and carbides obtained by heat-treating resources such as chitin and chitosan under specified conditions, preferably wood It is a carbide derived from woody biomass resources.

木質系炭化物製造時の処理条件については、Ａｒ、Ｈｅ、Ｎ２などの不活性雰囲気下、好ましくはＮ２雰囲気下にて、処理温度は好ましくは５００〜１，３００℃、より好ましくは７００〜９００℃の範囲であり、製造時の処理時間は好ましくは３０分〜１０時間、より好ましくは１時間〜３時間の範囲である。 The processing conditions at the time of wood-based carbide production, Ar, the He, under an inert atmosphere such as N 2, preferably under N 2 atmosphere, the treatment temperature is preferably 500～1,300 ° C., more preferably 700 to The processing time at the time of manufacture is preferably 30 minutes to 10 hours, more preferably 1 hour to 3 hours.

加水分解物を木質系炭化物で処理するには、通常、加水分解物を含む水溶液に木質系炭化物を添加し、全体を攪拌し、発酵阻害物が木質系炭化物に吸着されるようにする。   In order to treat the hydrolyzate with the wood-based carbide, the wood-based carbide is usually added to the aqueous solution containing the hydrolyzate, and the whole is stirred so that the fermentation inhibitor is adsorbed by the wood-based carbide.

本発明によると、例えばスギ木粉の加水分解物を木質系炭化物で処理することにより、処理前後で糖類の濃度変化をほぼゼロに保ったまま、発酵阻害物の濃度を検出限界レベルまで除去可能である。木質系炭化物処理を施したスギ木粉加水分解物は発酵阻害を受けない。   According to the present invention, for example, by treating a hydrolyzate of cedar wood flour with a wood-based carbide, it is possible to remove the concentration of fermentation inhibitors to a detection limit level while maintaining a change in the concentration of sugars before and after the treatment. It is. The cedar wood flour hydrolyzate subjected to the wood-based carbide treatment is not subject to fermentation inhibition.

本発明のエタノール発酵阻害物の除去方法によれば、多糖類系バイオマスを加水分解し、その加水分解物をエタノール発酵に供するに当たり、適切な条件にて調製を行った木質系炭化物で処理を行うことにより、加水分解で得られた糖類の収率を損なうことなく処理物中に含まれる発酵阻害物あるいは発酵を阻害するであろう物質を発酵に影響を与えない濃度まで選択的に除去し、発酵を効率よく行うことができる。木質系炭化物の処理で糖の濃度変化がほとんど無いため、バイオマスからエタノールを効率よく製造することができる。   According to the method for removing an ethanol fermentation inhibitor of the present invention, when a polysaccharide biomass is hydrolyzed and the hydrolyzate is subjected to ethanol fermentation, it is treated with a woody carbide prepared under appropriate conditions. By selectively removing the fermentation inhibitor contained in the processed product without impairing the yield of the saccharide obtained by hydrolysis or a substance that would inhibit the fermentation to a concentration that does not affect the fermentation, Fermentation can be performed efficiently. Since there is almost no change in sugar concentration due to the treatment of the wood-based carbide, ethanol can be efficiently produced from biomass.

本発明において、多糖類系バイオマスを加水分解し、単糖もしくはオリゴ糖、場合によっては多糖類を生成するに当たり、その方法および装置は特に制限は無く、公知の方法や装置が適応できる。多糖類系バイオマスの加水分解法には、酸加水分解法、酵素糖化法、亜臨界水による加水分解法、および超臨界水による加水分解法が適用でき、これらの１つであってもよいし、これらの２以上の組み合わせであってもよい。加水分解装置は、バッチ式、固定床反応式、連続式などであってよい。   In the present invention, when hydrolyzing polysaccharide biomass to produce monosaccharides or oligosaccharides, and in some cases, polysaccharides, there are no particular limitations on the method and apparatus, and known methods and apparatuses can be applied. For hydrolysis of polysaccharide biomass, acid hydrolysis, enzymatic saccharification, hydrolysis with subcritical water, and hydrolysis with supercritical water can be applied, and one of these may be used. A combination of two or more of these may be used. The hydrolysis apparatus may be a batch type, a fixed bed reaction type, a continuous type, or the like.

図１は本発明を実施するに当たっての実験フローである。バッチ型反応管内にスギ木粉および水を充填し、所定の温度まで加熱した後急冷し、水可溶部と水不溶部に分離する。エタノール発酵に必要な単糖およびオリゴ糖、場合によっては多糖類は水可溶部に含まれるため、この部分を発酵試験に供する。また、超臨界水による加水分解後、木質系炭化物による処理後の液、および発酵試験後の液については高速液体クロマトグラフー（ＨＰＬＣ）によって生成物を同定し定量分析する。これによって各生成物の収率を求める。   FIG. 1 is an experimental flow for carrying out the present invention. A batch type reaction tube is filled with cedar wood flour and water, heated to a predetermined temperature, then rapidly cooled, and separated into a water-soluble part and a water-insoluble part. Since monosaccharides and oligosaccharides necessary for ethanol fermentation, and in some cases polysaccharides, are contained in the water-soluble part, this part is subjected to a fermentation test. In addition, the product after hydrolysis with supercritical water, the solution after the treatment with the wood-based carbide, and the solution after the fermentation test are identified and quantitatively analyzed by high performance liquid chromatography (HPLC). This determines the yield of each product.

図２はスギ木粉を超臨界水で処理した加水分解物の組成の一部を示すクロマトグラムである。一般的にリグノセルロースを加水分解するとフルフラール、５−ヒドロキシメチルフルフラール等のフラン化合物およびグアヤコール、バリニン等のリグニン由来の種々のフェノール性化合物等の種々の化合物が生成する。リグノセルロースからエタノール発酵を行う際は、リグノセルロースから単糖もしくはオリゴ糖、場合によっては多糖類を製造し、さらにエタノール発酵を行う手順をとるが、上記化合物の存在下では単糖もしくはオリゴ糖、多糖類の発酵が阻害され、エタノール発酵が進行しない（図３参照）。   FIG. 2 is a chromatogram showing a part of the composition of a hydrolyzate obtained by treating cedar wood flour with supercritical water. In general, hydrolysis of lignocellulose produces furan compounds such as furfural and 5-hydroxymethylfurfural and various compounds such as various phenolic compounds derived from lignin such as guaiacol and valinine. When performing ethanol fermentation from lignocellulose, monosaccharides or oligosaccharides are produced from lignocellulose, and polysaccharides are produced in some cases, and the procedure for performing ethanol fermentation is further taken, but in the presence of the above compounds, monosaccharides or oligosaccharides, Polysaccharide fermentation is inhibited and ethanol fermentation does not proceed (see FIG. 3).

本発明において、リグノセルロース加水分解物を木質系炭化物で処理することにより単糖およびオリゴ糖の収率を低下させること無く発酵阻害物および発酵を阻害するであろう物質を発酵に影響を与えない濃度まで除去できる。具体的には、リグノセルロース加水分解物に含まれる化合物として、まずセルロース由来物質としてエリトロース、レボグルコサン、グリコールアルデヒド、グリセルアルデヒド、ジヒドロキシアセトン、メチルグリオキザール、フルフラール、５−ヒドロキシメチルフルフラール、リグニン由来物質としてバリニン、グアヤコール、フェルラ酸、コニフェリルアルデヒド、ホモバニリン酸、イソオイゲノールのそれぞれのエタノール発酵阻害性を調査した（図４参照）。これら以外に、発酵を阻害するであろう針葉樹からのリグニン由来物質には、メチルグアヤコール、エチルグアヤコール、ビニルグアヤコール、オイゲノール、プロピルグアヤコール、イソオイゲノール、アセトグアイアコン、プロピオグアイアコン、グアイアシルアセトン、ジヒドロコニフェリルアルコールなどがある。広葉樹を用いる場合には、これら以外に広葉樹リグニンを構成するシナピルアルコール類に由来する種々のフェノール性化合物として、シナピルアルコール、エチルシリンゴール、ビニルシリンゴール、プロピルシリンゴール、アリルシリンゴール、プロペニルシリンゴールなどがある。本発明により、木質系炭化物処理を行うことにより、例えばスギ木粉加水分解物に含まれるフルフラール、５−ヒドロキシメチルフルフラール、バリニン、アセトバリニン、グアヤコール、コニフェリルアルデヒド等の発酵阻害物、および、発酵を阻害するであろう上記化合物全てに対して、発酵に影響を与えない濃度までこれらを除去可能である。木質系炭化物の処理の前後で単糖およびオリゴ糖の量は変化しない。   In the present invention, the lignocellulosic hydrolyzate is treated with a wood-based carbide so as not to affect fermentation without inhibiting fermentation and substances that will inhibit fermentation without reducing the yield of monosaccharides and oligosaccharides. Can be removed up to concentration. Specifically, as a compound contained in the lignocellulose hydrolyzate, first as erythrose, levoglucosan, glycolaldehyde, glyceraldehyde, dihydroxyacetone, methylglyoxal, furfural, 5-hydroxymethylfurfural, lignin-derived substance as cellulose-derived substance The ethanol fermentation inhibitory properties of valinine, guaiacol, ferulic acid, coniferyl aldehyde, homovanillic acid, and isoeugenol were investigated (see FIG. 4). In addition to these, lignin-derived substances from conifers that would inhibit fermentation include methyl guaiacol, ethyl guaiacol, vinyl guaiacol, eugenol, propyl guaiacol, isoeugenol, acetoguaiacon, propioguaiacon, guaiacylacetone, Dihydroconiferyl alcohol. In the case of using broad-leaved trees, in addition to these, as various phenolic compounds derived from the synapyl alcohols constituting the broad-leaved tree lignin, synapyl alcohol, ethyl syringol, vinyl syringol, propyl syringol, allyl syringol, propenyl There is syringol. According to the present invention, by performing a wood-based carbide treatment, for example, furfural, 5-hydroxymethylfurfural, valinine, acetovalinin, guaiacol, coniferyl aldehyde, and other fermentation inhibitors contained in the cedar wood flour hydrolyzate, and fermentation For all of the above compounds that would inhibit, they can be removed to concentrations that do not affect the fermentation. The amount of monosaccharides and oligosaccharides does not change before and after the treatment of the wood-based carbide.

スギ木粉はリグノセルロースを含む代表的な材料であるが、本発明はスギ木粉に限定されるものではなくリグノセルロースに代表されるバイオマス資源全般に応用できる。すなわち、本発明で対象となる多糖類系バイオマス資源とはセルロースおよびヘミセルロースからなる多糖類がリグニンにより木化した資源である、針葉樹、広葉樹、ササ、タケ、稲わら、もみ殻、麦わら、その他農林産物資源およびそれらの廃棄物、さらにはこれらから由来する木材繊維、木材チップや単板くず、パルプ類、古紙類などである。さとうきびやてんさいなどの糖質資源、ばれいしょ、かんしょ、さといもなどのでんぷん資源などリグニン含量が少ないもしくは含まないバイオマス資源も含まれ、キチン・キトサン等の多糖類を含むバイオマス資源およびそれらの廃棄物も含まれる。これらのバイオマス資源は２以上の組み合わせであっても構わない。   Although cedar wood flour is a representative material containing lignocellulose, the present invention is not limited to cedar wood flour, and can be applied to all biomass resources represented by lignocellulose. That is, the polysaccharide-based biomass resource that is the subject of the present invention is a resource obtained by converting a polysaccharide consisting of cellulose and hemicellulose into a tree by lignin, conifer, broadleaf, bamboo grass, bamboo, rice straw, rice husk, wheat straw, and other agricultural forests Product resources and their wastes, as well as wood fibers, wood chips and veneer scraps, pulps, and waste papers derived from these. Includes biomass resources with low or no lignin content, such as sugar resources such as sugarcane and sugar beet, starch resources such as potato, sugarcane, and sweet potato, biomass resources containing polysaccharides such as chitin and chitosan, and wastes thereof It is. These biomass resources may be a combination of two or more.

木質系炭化物は、リグノセルロース加水分解物中に含まれる糖類の濃度をほとんど変化させること無く、発酵阻害物および発酵を阻害するであろう物質の除去を可能とするものである。木質系炭化物を製造するには、木質材料を不活性雰囲気下、好ましくは窒素雰囲気下にて、好ましくは５００〜１，３００℃、より好ましくは７００〜９００℃程度で熱処理する。製造時の処理時間は好ましくは３０分〜５時間、より好ましくは１時間〜３時間の範囲である。   The wood-based carbide enables the removal of fermentation inhibitors and substances that will inhibit fermentation with little change in the concentration of sugars contained in the lignocellulose hydrolyzate. In order to produce a wood-based carbide, the wood material is heat-treated in an inert atmosphere, preferably in a nitrogen atmosphere, preferably at 500 to 1,300 ° C, more preferably at about 700 to 900 ° C. The treatment time during production is preferably in the range of 30 minutes to 5 hours, more preferably 1 hour to 3 hours.

次に、本発明を実施例により、さらに詳細に説明するが、本発明はこれらの例によって何ら限定されるものではない。   EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

実施例１
図１の実験フローに基づき、試料としてスギ木粉を用い、バッチ型超臨界流体バイオマス変換装置により亜臨界および超臨界水処理を行った。処理後、残渣を分離し、水可溶部を得た。 Example 1
Based on the experimental flow of FIG. 1, cedar wood flour was used as a sample, and subcritical and supercritical water treatment was performed using a batch type supercritical fluid biomass converter. After the treatment, the residue was separated to obtain a water-soluble part.

スギ木粉を窒素雰囲気下で４００〜９００℃の温度にて１時間熱処理することで調製した木質系炭化物を水可溶部に添加し、１０分攪拌を行い、発酵阻害物の吸着・除去を試みた。木質系炭化物による処理後、高速液体クロマトグラフィー（ＨＰＬＣ）およびガスクロマトグラフー質量分析計（ＧＣ−ＭＳ）により分析をし、発酵阻害物の定性・定量を行った。   The wood-based carbide prepared by heat-treating cedar wood flour at a temperature of 400 to 900 ° C. for 1 hour in a nitrogen atmosphere is added to the water-soluble part, and stirred for 10 minutes to adsorb and remove fermentation inhibitors. Tried. After the treatment with the wood-based carbide, analysis was performed by high performance liquid chromatography (HPLC) and gas chromatograph mass spectrometer (GC-MS), and qualitative and quantitative determination of the fermentation inhibitor was performed.

図５は上記調製法により調製した木質系炭化物で処理した水可溶部の高速液体クロマトグラムを木質系炭化物調製温度別に示している。このクロマトグラムからは５−ヒドロキシメチルフルフラール、フルフラール、バニリン、コニフェリルアルデヒドが同定でき、これら化合物は図４に示す通り発酵阻害物であることが確認できた。   FIG. 5 shows the high-performance liquid chromatogram of the water-soluble part treated with the wood-based carbide prepared by the above preparation method according to the wood-based carbide preparation temperature. From this chromatogram, 5-hydroxymethylfurfural, furfural, vanillin, coniferyl aldehyde could be identified, and it was confirmed that these compounds were fermentation inhibitors as shown in FIG.

さらに、フルフラール、５−ヒドロキシメチルフルフラール、バニリン、アセトバニロン、グアヤコールおよびコニフェリルアルデヒドについて、様々な調製温度で上記調製法により調製した木質系炭化物で処理を施した水可溶部中の濃度を表１にまとめた。同表から、木質系炭化物処理によりこれらの発酵阻害物を除去することが可能であることが確認でき、木質系炭化物の調製温度が高くなるほどその除去効果が高いことが分かる。   Further, for furfural, 5-hydroxymethylfurfural, vanillin, acetovanillone, guaiacol, and coniferyl aldehyde, the concentrations in the water-soluble part treated with the wood-based carbide prepared by the above preparation method at various preparation temperatures are shown in Table 1. Summarized in From the table, it can be confirmed that these fermentation inhibitors can be removed by the wood-based carbide treatment, and it can be seen that the higher the preparation temperature of the wood-based carbide, the higher the removal effect.

加えて上記調製法により調製した木質系炭化物で処理した水可溶部中の糖類濃度を表２にまとめた。同表から木質系炭化物の調製温度に関係なく糖類は木質系炭化物によって除去されないことが確認できた。

Figure 2005270056
In addition, the saccharide concentrations in the water-soluble part treated with the wood-based carbide prepared by the above preparation method are summarized in Table 2. From the table, it was confirmed that the saccharide was not removed by the wood-based carbide regardless of the preparation temperature of the wood-based carbide.
Figure 2005270056

Figure 2005270056
Figure 2005270056

次に水可溶部に木質系炭化物を添加し、１０分攪拌を行い、発酵阻害物を除去した液について発酵試験を行った。栄養液として、ペプトン、イースト抽出物およびモルト抽出物の混合液を使用し、発酵温度は２８℃とした。発酵試験開始後１時間ごとにサンプリングを行った。図６〜図１１に木質系炭化物の調製温度別に発酵試験の結果をまとめた。これらの図によると、６００℃以下の温度で調製した木質系炭化物で処理を行ったものについては発酵阻害が認められたが、７００℃以上で調製した木質系炭化物で処理を行ったものについては発酵が滞りなく進行していることが認められた。調製温度７００℃〜９００℃ではエタノール発酵速度に差は見られず、７００℃で調製した木質系炭化物で十分にエタノール発酵阻害物の除去が可能であることがわかる。   Next, the wood-based carbide was added to the water-soluble part, and the mixture was stirred for 10 minutes, and a fermentation test was performed on the liquid from which the fermentation inhibitor was removed. As a nutrient solution, a mixed solution of peptone, yeast extract and malt extract was used, and the fermentation temperature was 28 ° C. Sampling was performed every hour after the start of the fermentation test. The result of the fermentation test according to the preparation temperature of the wood-based carbide is summarized in FIGS. According to these figures, fermentation inhibition was observed for those treated with wood-based carbide prepared at a temperature of 600 ° C. or lower, but those treated with wood-based carbide prepared at 700 ° C. or higher were observed. It was observed that the fermentation was progressing without delay. When the preparation temperature is 700 ° C. to 900 ° C., there is no difference in the ethanol fermentation rate, and it can be seen that the wood fermentation carbide prepared at 700 ° C. can sufficiently remove the ethanol fermentation inhibitor.

比較例１
木質系炭化物による処理を行わない以外は実施例１と全く同じ条件で発酵試験を行った。図３に発酵試験の結果を示した。同図から木質系炭化物による処理を行わない場合は発酵が進行せず発酵阻害を受けていることが確認できた。この結果は、上述の４００℃〜６００℃で調製した木質系炭化物で処理を施した液の発酵試験結果と同等の物であった。 Comparative Example 1
A fermentation test was performed under exactly the same conditions as in Example 1 except that the treatment with the wood-based carbide was not performed. FIG. 3 shows the results of the fermentation test. From the figure, it was confirmed that when the treatment with the wood-based carbide was not performed, the fermentation did not proceed and the fermentation was inhibited. This result was the same as the fermentation test result of the liquid treated with the wood-based carbide prepared at 400 ° C. to 600 ° C. described above.

本発明を示す実験フローである。It is an experimental flow which shows this invention. スギ木粉を超臨界水で処理した加水分解物の組成の一部を示すクロマトグラムである。It is a chromatogram which shows a part of composition of the hydrolyzate which processed cedar wood flour with supercritical water. 単糖類およびエタノールの濃度変化を示すグラフである。It is a graph which shows the density | concentration change of a monosaccharide and ethanol. 各化合物の発酵阻害濃度領域の比較である。It is the comparison of the fermentation inhibitory concentration area | region of each compound. 水可溶部のクロマトグラムである。It is a chromatogram of a water-soluble part. 単糖類およびエタノールの濃度変化を示すグラフである。It is a graph which shows the density | concentration change of a monosaccharide and ethanol. 単糖類およびエタノールの濃度変化を示すグラフである。It is a graph which shows the density | concentration change of a monosaccharide and ethanol. 単糖類およびエタノールの濃度変化を示すグラフである。It is a graph which shows the density | concentration change of a monosaccharide and ethanol. 単糖類およびエタノールの濃度変化を示すグラフである。It is a graph which shows the density | concentration change of a monosaccharide and ethanol. 単糖類およびエタノールの濃度変化を示すグラフである。It is a graph which shows the density | concentration change of a monosaccharide and ethanol. 単糖類およびエタノールの濃度変化を示すグラフである。It is a graph which shows the density | concentration change of a monosaccharide and ethanol.

Claims (6)

多糖類系バイオマスを加水分解し、得られた加水分解物をエタノール発酵に供するに当たり、加水分解物を木質系炭化物で処理し、加水分解物に含まれる発酵阻害物または発酵を阻害するであろう物質を発酵に影響を与えない濃度まで除去することを特徴とする、加水分解物中の発酵阻害物の除去方法。 In hydrolyzing polysaccharide biomass and subjecting the resulting hydrolyzate to ethanol fermentation, the hydrolyzate will be treated with woody charcoal to inhibit fermentation inhibitors or fermentation contained in the hydrolyzate A method for removing a fermentation inhibitor in a hydrolyzate, which comprises removing a substance to a concentration that does not affect fermentation. 多糖類系バイオマスがリグノセルロースである、請求項１に記載の加水分解物中の発酵阻害物の除去方法。 The removal method of the fermentation inhibitor in the hydrolyzate of Claim 1 whose polysaccharide biomass is lignocellulose. 発酵阻害物が、フルフラール、５−ヒドロキシメチルフルフラール等のフラン化合物、グアヤコール、バリニン等のリグニン由来のフェノール性化合物である、請求項１に記載の加水分解物中の発酵阻害物の除去方法。 The method for removing a fermentation inhibitor in a hydrolyzate according to claim 1, wherein the fermentation inhibitor is a furan compound such as furfural and 5-hydroxymethylfurfural, and a phenolic compound derived from lignin such as guaiacol and valinine. バイオマスの加水分解が、亜臨界状態の水による処理、超臨界状態の水による処理、酸による処理、および酵素糖化法のうちの少なくとも１つである、請求項１に記載の加水分解物中の発酵阻害物の除去方法。 The hydrolyzate in the hydrolyzate according to claim 1, wherein hydrolysis of the biomass is at least one of treatment with subcritical water, treatment with supercritical water, treatment with acid, and enzymatic saccharification. A method for removing fermentation inhibitors. 木質系炭化物が木質バイオマス由来の炭化物である、請求項１に記載の加水分解物中の発酵阻害物の除去方法。 The method for removing a fermentation inhibitor in a hydrolyzate according to claim 1, wherein the wood-based carbide is a carbide derived from woody biomass. 木質系炭化物が、木質バイオマスを不活性雰囲気下または高温水蒸気雰囲気下にて５００〜１，３００℃で３０分〜１０時間、熱処理して製造したものである、請求項１に記載の加水分解物中の発酵阻害物の除去方法。
The hydrolyzate according to claim 1, wherein the wood-based carbide is produced by heat-treating woody biomass at 500 to 1,300 ° C. for 30 minutes to 10 hours in an inert atmosphere or a high-temperature steam atmosphere. Method for removing fermentation inhibition substances inside.
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