JP2010115171A - Method for producing saccharide from bark feedstock - Google Patents
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Abstract
Description
本発明は、樹皮を糖類製造用の原料として利用するための前処理方法及び該前処理樹皮を原料とする酵素糖化方法に関する。 The present invention relates to a pretreatment method for using bark as a raw material for saccharide production, and an enzymatic saccharification method using the pretreated bark as a raw material.
樹木は細胞分裂が活発な形成層を境界にその内側の木部と外側の樹皮に分けられる。樹皮は総樹木重量の約１０〜１５％を占め、若いユーカリでは、樹皮は木部と比べてリグニン含量が比較的に低く、可溶性成分を多く含み柔軟である。さらに、樹皮は死んだ組織の外樹皮と生きている組織の内樹皮に分けられる。 A tree is divided into an inner xylem and an outer bark with a formation layer where cell division is active as a boundary. The bark accounts for about 10-15% of the total tree weight, and in young eucalyptus, the bark has a relatively low lignin content compared to the xylem and is soft with many soluble components. In addition, the bark is divided into an outer bark of dead tissue and an inner bark of living tissue.
外樹皮は主に周皮あるいはコルク層からなり、木材組織を機械的損傷から守るとともに、温度と湿度の変動を小さくしている。
内樹皮は師要素、柔細胞および厚壁細胞からなり、師要素は液体と栄養素の運搬の機能を持ち、柔細胞はデンプン等の栄養素貯蔵の機能を持ち、内樹皮の師要素間に介在する。厚壁細胞は支持組織として機能し、木部の年輪と同じように層状に観察され、形によって靭皮繊維とスクレレイドとに区別される。
The outer bark mainly consists of pericytes or cork layers, which protects the wood tissue from mechanical damage and reduces fluctuations in temperature and humidity.
The inner bark consists of mentor elements, parenchyma cells and thick-walled cells. The mentor elements have the function of transporting liquids and nutrients. . Thick wall cells function as a supporting tissue, are observed in layers like the xylem rings, and are differentiated into bast fibers and scleroids by shape.
樹皮組織は、大きく分けて、繊維、コルク細胞及び柔細胞を含む微細物質からなる。樹皮の繊維は、木部の繊維と化学的に似ており、セルロース、ヘミセルロース及びリグニンからなる。コルク細胞及び柔細胞を含む微細物質には多量の抽出成分が存在し、コルク細胞の壁にはスベリン類が、微細物質画分にはポリフェノール類が多い。このように、樹皮は木部と異なり多くの有用な可溶性成分を含有し、その量は乾燥質量の２０から４０％に達し、しかも繊維画分には木部と同様な繊維質を有しているという優れた性質を有している。しかし、樹皮は、材木用途では使用されず、製紙工程のパルプ化の際には、わずかに混入してもパルプの品質を低下させるため、枝や根とともに植林地で肥料として土壌に戻されるか、製材工場又はチップ工場で剥皮され焼却されており、木質系バイオマスとして有効利用されていない。 Bark tissue is roughly divided into fine substances including fibers, cork cells, and parenchyma cells. Bark fibers are chemically similar to xylem fibers and are composed of cellulose, hemicellulose and lignin. A fine substance containing cork cells and parenchyma contains a large amount of extracted components, and the cork cell walls are rich in suberins and the fine substance fraction is rich in polyphenols. Thus, the bark, unlike the xylem, contains many useful soluble components, the amount of which reaches 20 to 40% of the dry mass, and the fiber fraction has fibers similar to the xylem. Has excellent properties. However, bark is not used in timber applications and can be returned to the soil as a fertilizer in the plantation along with branches and roots when pulping in the papermaking process to reduce pulp quality even if mixed slightly. They are peeled and incinerated at lumber mills or chip mills and are not effectively used as woody biomass.
現在、製紙用パルプ原料としてマツ、アカシア、ユーカリなどが植林されている。その中でユーカリは５００種類以上あり、生長が早く伐採期間が７年から１０年と短く、乾燥地帯でも生育するため、製紙用材以外にも緑化目的などでも世界中に広く植林されている。
一方、地球温暖化防止の観点から化石燃料由来のＣＯ２排出削減のため、バイオマスの有効利用が注目されている。しかし、近年、トウモロコシ等の食品系バイオマスからのバイオエタノールの製造は食品価格の上昇を引き起こし、発展途上国では食糧不足などの重大な問題を引き起こしている。そこで食料と競合しない木質系バイオマス、すなわちリグノセルロースからのバイオエタノールの製造が注目されている。
At present, pine, acacia, eucalyptus, etc. are planted as pulp materials for papermaking. Among them, there are more than 500 types of eucalyptus, fast growing, short logging period of 7 to 10 years and growing in dry areas, so it is widely planted all over the world not only for papermaking but also for greening purposes.
On the other hand, effective use of biomass has attracted attention from the viewpoint of preventing global warming in order to reduce CO2 emissions derived from fossil fuels. However, in recent years, the production of bioethanol from food-based biomass such as corn has caused an increase in food prices and has caused serious problems such as food shortages in developing countries. Therefore, production of bioethanol from woody biomass that does not compete with food, that is, lignocellulose, has attracted attention.
リグノセルロースを利用する際には、セルロースを単糖であるグルコース等に分解する糖化が重要な段階となる。
現在、リグノセルロースから単糖を生成する方法として基本的には、酸加水分解法、超臨界水による加水分解法、そして酵素糖化法の三つの方法がよく知られている。
酸加水分解法は酸の濃度によって、希酸法と濃酸法が提案されている（特許文献１、特許文献２）。希酸法では、温度、圧力がともに高く、添加した酸により装置が腐食してしまう。さらに生成した糖類と酸を分離するのが困難で経済的に有効な酸回収方法がない等の問題がある。また、濃酸法は、比較的に温度及び圧力が低いため、安価な反応装置材料が利用でき、グルコースの収率も高い。しかし、希酸法と同様に生成した糖類から経済的
に有効な酸の分離・回収法がないため、多量の廃酸が発生するという問題がある。
When using lignocellulose, saccharification that decomposes cellulose into monosaccharides such as glucose is an important step.
At present, three basic methods for producing monosaccharides from lignocellulose are well known: acid hydrolysis, hydrolysis with supercritical water, and enzymatic saccharification.
As the acid hydrolysis method, a dilute acid method and a concentrated acid method have been proposed depending on the acid concentration (Patent Document 1, Patent Document 2). In the dilute acid method, both the temperature and the pressure are high, and the device is corroded by the added acid. Furthermore, there is a problem that it is difficult to separate the produced saccharide and acid and there is no economically effective acid recovery method. Moreover, since the concentrated acid method has a relatively low temperature and pressure, an inexpensive reactor material can be used, and the yield of glucose is high. However, there is a problem that a large amount of waste acid is generated because there is no economically effective method for separating and recovering acid from saccharides produced in the same manner as the diluted acid method.
一方、亜臨界状態又は超臨界状態の水を用いてセルロースを加水分解処理し、オリゴ糖や単糖類のグルコースを生産する超臨界法が提案されている（特許文献３、特許文献４）。超臨界法では、超臨界水の特徴を利用し、短時間でセルロースを完全にオリゴ糖や単糖に分解することが可能であるが、高温、高圧下で反応を行うため、装置が高価になってしまうこと、発生する酸による装置の腐食等の問題がある。 On the other hand, a supercritical method has been proposed in which cellulose is hydrolyzed using subcritical or supercritical water to produce oligosaccharide or monosaccharide glucose (Patent Document 3 and Patent Document 4). In the supercritical method, it is possible to completely decompose cellulose into oligosaccharides and monosaccharides in a short time using the characteristics of supercritical water, but the reaction is performed at high temperature and high pressure, so the equipment is expensive. And there are problems such as corrosion of the apparatus due to the generated acid.
酵素糖化法においては、リグノセルロース中のリグニン及びヘミセルロースがセルロースと結合しており、酵素のセルロースへの接触を阻害しているため、グルコース収率が低くなってしまう。そこで、通常、酵素による分解性を促進するため、酵素糖化に先立って加圧熱水処理、蒸煮及び爆砕による物理的前処理、酸やアルカリによる化学的前処理が施される。 In the enzymatic saccharification method, lignin and hemicellulose in lignocellulose are bound to cellulose and inhibit the enzyme from contacting cellulose, resulting in a low glucose yield. Therefore, usually, in order to promote the degradability by the enzyme, prior to the enzymatic saccharification, a pressurized hot water treatment, a physical pretreatment by steaming and explosion, and a chemical pretreatment with acid or alkali are performed.
加圧熱水処理は１２８〜２０５℃、１〜２ＭＰａという高温高圧条件で処理する方法が提案されている（特許文献５）。
また、１００〜５００℃、飽和蒸気圧〜５０ＭＰａという高温高圧条件で処理する方法が提案されている（特許文献６）。
As the pressurized hot water treatment, a method of treating at a high temperature and a high pressure of 128 to 205 ° C. and 1 to 2 MPa has been proposed (Patent Document 5).
Moreover, the method of processing on the high temperature / high pressure conditions of 100-500 degreeC and saturated vapor pressure-50MPa is proposed (patent document 6).
蒸煮処理としては、１５８〜２２５℃、５〜３０ｋｇ／ｃｍ２という高温高圧条件で処理する方法が提案されている（特許文献７）。
また、爆砕処理としては、蒸煮処理と同程度の条件下でリグノセルロースを保持した後、瞬時に常圧に戻す方法が提案されている（特許文献８）。
上記した各方法は、いずれも高温高圧で処理することが必要であり、反応装置が高価であり、高温高圧にするための投入エネルギーが大きいという問題がある。
As the steaming treatment, a method of treating under high temperature and high pressure conditions of 158 to 225 ° C. and 5 to 30 kg / cm 2 has been proposed (Patent Document 7).
Moreover, as a blasting process, a method has been proposed in which lignocellulose is held under the same conditions as the steaming process and then instantaneously returned to normal pressure (Patent Document 8).
Each of the above methods requires treatment at high temperature and high pressure, and there is a problem that the reaction apparatus is expensive and the input energy for high temperature and high pressure is large.
酸処理法としては、０．１〜５％希硫酸で１４０〜２３０℃の高温で処理した後、湿式粉砕する方法が提案されている（特許文献９）。
アルカリ処理法としては、バイオマスを２〜３０％の水酸化カルシウムで処理する方法が提案されている（特許文献１０）
As an acid treatment method, a method of wet pulverization after treatment with 0.1 to 5% dilute sulfuric acid at a high temperature of 140 to 230 ° C. has been proposed (Patent Document 9).
As an alkali treatment method, a method of treating biomass with 2 to 30% calcium hydroxide has been proposed (Patent Document 10).
上記の各提案は、あらかじめリグノセルロースを数ｍｍから数百μｍまで粉砕する必要があり、さらに高温高圧下で処理するため、処理に要するエネルギーが大きく、かつ反応装置が高価となる問題がある。一般的に粒径を小さくすればする程、粉砕に多量のエネルギーを要する。しかしながらこれらの提案には粉砕工程に必要なエネルギー量についての記述がない。
現在、様々なバイオマスの前処理法が検討されているが、多くの前処理方法はバイオマスを数ｍｍ以下程度まで粉砕しなければ、続く糖化工程での糖化効率が大きく低下するという問題がある。しかし、バイオマスを数ｍｍ以下程度まで粉砕するとバイオエタノール製造に要するエネルギーがバイオマスから得られるエネルギーを上回ってしまい、バイオマスからバイオエタノールを製造しても、ＣＯ２の排出削減とはならないという大きな問題がある。
In each of the above proposals, lignocellulose needs to be pulverized from several mm to several hundred μm in advance, and further, since it is processed under high temperature and high pressure, there is a problem that the energy required for the processing is large and the reaction apparatus is expensive. Generally, the smaller the particle size, the more energy is required for grinding. However, these proposals do not describe the amount of energy required for the grinding process.
Currently, various pretreatment methods for biomass are being studied. However, many pretreatment methods have a problem that the saccharification efficiency in the subsequent saccharification step is greatly reduced unless the biomass is pulverized to about several millimeters or less. However, when biomass is pulverized to about several millimeters or less, the energy required for bioethanol production exceeds the energy obtained from biomass, and even if bioethanol is produced from biomass, it does not reduce CO 2 emissions. is there.
従来のリグノセルロースの前処理方法は、高温高圧条件下で行わなくてはならないために設備が高価となり、かつ、粉砕に大量のエネルギーを要するため、コスト面からも、またバイオマスからのエネルギー回収面においても問題点があった。
本発明は、バイオマスとして未利用資源である樹皮を原料し、比較的穏和な条件下で少ないエネルギーにて、リグノセルロースの酵素糖化を促進することを可能とする前処理方法を提供することを課題とする。
The conventional lignocellulose pretreatment method has to be performed under high-temperature and high-pressure conditions, so that the equipment is expensive and a large amount of energy is required for pulverization. Therefore, from the viewpoint of cost and energy recovery from biomass. There was also a problem.
It is an object of the present invention to provide a pretreatment method that makes it possible to promote enzymatic saccharification of lignocellulose using raw material of bark, which is an unused resource as biomass, and with less energy under relatively mild conditions. And
本発明は、前記課題を解決するため鋭意研究した結果、木部と比べてリグニン含量が低く、可溶性成分を多量に含む樹皮に注目し、以下の各技術手段を選択し採用することによって、少ないエネルギーで原料樹皮の糖化を促進せしめることができることを可能ならしめた「樹皮原料から糖類を製造する方法」の発明である。 As a result of diligent research to solve the above problems, the present invention has a low lignin content as compared with xylem, paying attention to bark containing a large amount of soluble components, and by selecting and employing the following respective technical means, It is an invention of a “method for producing a saccharide from a bark raw material” that makes it possible to promote the saccharification of the raw bark with energy.
（１）樹皮原料を、温水で湿潤処理する温水処理工程及び該温水処理工程からの温水処理樹皮を機械的に破砕処理する機械的破砕処理工程及び、該破砕処理樹皮を、アルカリ化合物水溶液を用いて浸漬処理するアルカリ処理工程に従って処理してアルカリ処理樹皮を調整し、該アルカリ処理樹皮を酵素で糖化処理する。 (1) A warm water treatment step in which the bark raw material is wet-treated with warm water, a mechanical crush treatment step in which the hot water treatment bark from the warm water treatment step is mechanically crushed, and the crushed bark using an alkaline compound aqueous solution. The alkali-treated bark is prepared by treatment according to the alkali treatment step of dipping treatment, and the alkali-treated bark is saccharified with an enzyme.
（２）前記（１）における温水処理工程が、温水を乾燥樹皮原料１質量部に対して２０質量部以下となる割合で使用する浸漬処理工程とする。 (2) The warm water treatment step in (1) is an immersion treatment step in which warm water is used at a ratio of 20 parts by mass or less with respect to 1 part by mass of the dry bark raw material.
（３） 前記（１）〜（２）における温水処理工程における浸漬処理温度が５０℃〜１３０℃、好ましくは８０〜１００℃とする。 (3) The immersion treatment temperature in the hot water treatment step in (1) to (2) is 50 ° C to 130 ° C, preferably 80 to 100 ° C.
（４）前記（１）〜（３）における温水処理工程を、温水による樹皮原料の浸漬処理時間が１分〜７２時間、さらに好ましくは５分〜３時間である処理工程とする。 (4) The warm water treatment step in the above (1) to (3) is a treatment step in which the bark raw material immersion treatment time with warm water is 1 minute to 72 hours, more preferably 5 minutes to 3 hours.
（５）前記（１）〜（４）におけるアルカリ処理工程を、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、酸化カルシウム、炭酸ナトリウム及びアンモニアからなる群から選ばれる少なくとも１種のアルカリ化合物の水溶液による浸漬処理工程とする。 (5) An aqueous solution of at least one alkali compound selected from the group consisting of sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate and ammonia in the alkali treatment step in the above (1) to (4) It is set as the immersion treatment process by.
（６）前記（１）〜（５）におけるアルカリ処理工程が、アルカリ化合物の添加量を、乾燥樹皮１００質量部に対して０．１〜５０質量部となる割合とする、アルカリ化合物水溶液を用いた浸漬処理工程とする。 (6) An alkaline compound aqueous solution in which the alkali treatment step in the above (1) to (5) sets the addition amount of the alkali compound to 0.1 to 50 parts by mass with respect to 100 parts by mass of the dried bark. The dipping process was performed.
（７）前記（１）〜（６）における樹皮原料を、グランディス（ｇｒａｎｄｉｓ）種、グロブラス（ｇｌｏｂｕｌｕｓ）種、ナイテンス（ｎｉｔｅｎｓ）種、カマルドレンシス（ｃａｍａｌｄｕｌｅｎｓｉｓ）種、デグラプタ（ｄｅｇｌｕｐｔａ）種、ビミナリス（ｖｉｍｉｎａｌｉｓ）種、ユーロフィラ（Ｕｒｏｐｈｙｌｌａ）種、ダニアイ（ｄｕｎｎｉｉ）種及びこれらの交雑種から選ばれるユーカリ（Ｅｕｃａｌｙｐｔｕｓ）属に属する樹木の樹皮の少なくとも１種とする。 (7) The bark raw material in the above (1) to (6) is a Grandis species, a globulous species, a nitens species, a camaldulensis species, a degrapta species, a biminaris ( At least one kind of bark of a tree belonging to the genus Eucalyptus selected from the species of Viminalis, Urophylla, Dunnii and a hybrid of these species.
（８）前記機械的破砕処理工程が、レファイナー、破砕機及び離解機のいずれかを用いて樹皮原料を破砕する処理工程である(１)〜(７)のいずれかにおける樹皮原料から糖類を製造する方法。 (8) The said mechanical crushing process is a processing process which crushes a bark raw material using either a refiner, a crusher, and a disaggregator, and manufactures saccharides from the bark raw material in any one of (1)-(7) how to.
本発明により、少ない投入エネルギーで、リグノセルロースを効率的に酵素糖化することができる状態に転化することができる前処理方法を含む「樹皮原料から糖類を製造する方法」が提供されるので、従来、木質系資源として未利用であった樹皮からバイオエタノールを製造する途を拓くものである。 According to the present invention, a “method for producing saccharides from bark raw materials” including a pretreatment method that can convert lignocellulose into a state in which enzymatic saccharification can be efficiently performed with less input energy is provided. This will open the way to produce bioethanol from bark that has not been used as a woody resource.
以下、本発明の「樹皮原料から糖類を製造する方法」について詳述する
本発明で対象となるリグノセルロースは、木本植物の樹皮である。用いる樹皮は、特に限定されないが、好ましくは、ユーカリ（Ｅｕｃａｌｙｐｔｕｓ）属、さらに好ましくはグランディス（ｇｒａｎｄｉｓ）種、グロブラス（ｇｌｏｂｕｌｕｓ）種、ナイテンス（ｎｉｔｅｎｓ）種、カマルドレンシス（ｃａｍａｌｄｕｌｅｎｓｉｓ）種、デグラプタ（ｄｅｇｌｕｐｔａ）種、ビミナリス（ｖｉｍｉｎａｌｉｓ）種、ユーロフィラ（Ｕｒｏｐｈｙｌｌａ）種、ダニアイ（ｄｕｎｎｉｉ）及びこれらの交雑種である。
Hereinafter, the “method for producing a saccharide from a bark raw material” of the present invention will be described in detail. The lignocellulose targeted by the present invention is a bark of a woody plant. The bark to be used is not particularly limited, but preferably, Eucalyptus genus, more preferably grandis, globulus, nitens, camaldulensis, degrapta ) Species, Viminalis species, Urophylla species, Dunnii and their hybrids.
本発明では、樹皮原料を酵素糖化原料とするために、樹皮原料を、温水で浸漬処理する温水処理工程、及び該温水処理工程からの温水処理樹皮を機械的に破砕処理する機械的破砕処理工程、及び該機械的破砕処理工程からの破砕処理樹皮をアルカリ化合物水溶液に浸漬してなるアルカリ処理工程に従って前処理する。 In the present invention, in order to use the bark raw material as the enzyme saccharification raw material, the bark raw material is subjected to a hot water treatment step in which the bark raw material is immersed in warm water, and the mechanical crushing treatment step in which the hot water treated bark from the hot water treatment step is mechanically crushed. And pretreatment according to an alkali treatment step in which the crushed bark from the mechanical crushing step is immersed in an aqueous alkali compound solution.
樹皮原料は、入手できる状態のままで原料とすることができる。通常、搬送時の取り扱い性等を考慮して数ｃｍ２に裁断乃至粉砕されている状態のものであればそのまま処理することが好ましい。樹皮原料のサイズは小さいほど処理しやすいが、本発明の方法では、温水処理工程において処理された樹皮は機械的破砕処理により少ないエネルギーコストで容易に微細化できるので、乾燥樹皮原料を過度に微細化処理することは避けることが好ましい。 The bark raw material can be used as a raw material in an available state. Usually, it is preferable to treat the material as it is if it is in a state of being cut or pulverized into several cm 2 in consideration of handling property at the time of conveyance. The smaller the size of the bark raw material, the easier it is to treat. However, in the method of the present invention, the bark treated in the hot water treatment process can be easily refined at a low energy cost by mechanical crushing treatment. It is preferable to avoid the chemical treatment.
温水処理工程とは、上記で得た樹皮原料を、温水で湿潤処理する工程である。湿潤処理とは、樹皮原料を温水中に浸漬した状態で一定時間保持するか、または水蒸気に暴露した状態で一定時間保持することにより行う。なお、本発明においては、手段を問わず、樹皮原料を加温された湿潤状態で保持することを、温水処理工程という。
乾燥樹皮原料１質量部に対して添加する温水の量は、適宜選択可能であるが、温水の量が多すぎると、加熱に必要なエネルギーコストが増大し、また、温水処理工程後の液分を廃液として処理する際のコストも増大する。従って、２０質量部以下が好適である。
浸漬処理温度は、樹皮を柔化せしめる温度であれば特に限定されないが、好ましくは５０℃〜１３０℃、さらに好ましくは８０〜１００℃である。温水処理は、オートグレーブ等を用いた加圧条件下で行ってもよく、常圧下で行うことも可能である。樹皮を柔化する効果と水の蒸発を考えると、８０〜１００℃が好適である。
また、浸漬処理時間は、樹皮を柔化せしめるに十分な時間であれば特に限定されないが、好ましくは１分〜７２時間、さらに好ましくは、５分〜３時間である。
A warm water treatment process is a process of wet-treating the bark raw material obtained above with warm water. The wet treatment is performed by holding the bark raw material for a certain period of time in a state of being immersed in warm water, or by maintaining the bark raw material for a certain period of time while being exposed to water vapor. In the present invention, holding the bark raw material in a heated and moist state regardless of the means is referred to as a warm water treatment step.
The amount of warm water added to 1 part by weight of the dry bark raw material can be selected as appropriate. However, if the amount of warm water is too large, the energy cost required for heating increases, and the liquid content after the warm water treatment step is increased. The cost for processing as a waste liquid also increases. Therefore, 20 parts by mass or less is preferable.
The immersion treatment temperature is not particularly limited as long as it is a temperature that softens the bark, but is preferably 50 ° C to 130 ° C, and more preferably 80 ° C to 100 ° C. The hot water treatment may be performed under a pressure condition using an auto grave or the like, and may be performed under normal pressure. Considering the effect of softening the bark and the evaporation of water, 80 to 100 ° C. is suitable.
In addition, the dipping treatment time is not particularly limited as long as it is sufficient to soften the bark, but is preferably 1 minute to 72 hours, and more preferably 5 minutes to 3 hours.
温水に浸漬して処理された樹皮は、そのまま機械的破砕処理に供しても良いが、固液分離により、固形分と液分に分けて固形分のみを機械的破砕処理に供しても良い。固液分離手段としては、フィルター等を用いた常圧下での濾過のほか、加圧濾過、吸引濾過や、遠心分離手段を用いることができる。 The bark treated by immersing in warm water may be subjected to a mechanical crushing process as it is, or may be subjected to a mechanical crushing process by separating the solid and liquid components by solid-liquid separation. As solid-liquid separation means, filtration under normal pressure using a filter or the like, pressure filtration, suction filtration, or centrifugal separation means can be used.
機械的破砕処理工程で用いる機械は、樹皮を破砕できれば特に限定されないが、レファイナー、破砕機、離解機などが使用できる。 The machine used in the mechanical crushing process is not particularly limited as long as it can crush bark, but a refiner, a crusher, a disaggregator, or the like can be used.
本発明においては、上記の機械的破際処理工程に続いてアルカリ処理工程を有する。
アルカリ処理工程で使用するアルカリ化合物としては、樹皮を柔化させ得るものであれば特に限定されない。例えば、水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、酸化カルシウム、炭酸ナトリウム、アンモニアを用いることができ、好ましくは水酸化ナトリウムを用いることができる。
In this invention, it has an alkali treatment process following said mechanical breakage treatment process.
The alkali compound used in the alkali treatment step is not particularly limited as long as it can soften the bark. For example, sodium hydroxide, potassium hydroxide, calcium hydroxide, calcium oxide, sodium carbonate, and ammonia can be used, and preferably sodium hydroxide can be used.
アルカリ化合物の樹皮原料に対する添加量は、樹皮を柔化せしめる量であれば特に限定されない。例えば、乾燥樹皮１００質量部に対して０．１質量部以上、好ましくは０．１〜５０質量部である。
アルカリ化合物水溶液への浸漬処理温度は、樹皮を柔化せしめる温度であれば特に限定されないが、好ましくは１０℃〜３００℃、さらに好ましくは２５℃〜９５℃である。また浸漬処理は、簡易な設備で実施することができ、投入エネルギーも削減できるという点で、常圧下で行うことが特に好ましい。
また、浸漬処理時間は、樹皮を柔化せしめるに十分な時間であれば特に限定されないが、好ましくは１０分〜７２時間、さらに好ましくは、１時間〜１７時間である。
アルカリ処理樹皮は、洗浄後もしくは洗浄せずに所望のｐＨに調整し、糖化工程で糖化酵素により処理される。
The amount of the alkali compound added to the bark raw material is not particularly limited as long as it is an amount that softens the bark. For example, it is 0.1 mass part or more with respect to 100 mass parts of dry bark, Preferably it is 0.1-50 mass parts.
The immersion treatment temperature in the aqueous alkali compound solution is not particularly limited as long as it is a temperature that softens the bark, but is preferably 10 ° C to 300 ° C, more preferably 25 ° C to 95 ° C. Further, the immersion treatment is particularly preferably performed under normal pressure in that it can be carried out with simple equipment and the input energy can be reduced.
In addition, the dipping treatment time is not particularly limited as long as it is sufficient to soften the bark, but is preferably 10 minutes to 72 hours, and more preferably 1 hour to 17 hours.
The alkali-treated bark is adjusted to a desired pH after washing or without washing and is treated with a saccharifying enzyme in a saccharification step.
酵素糖化処理工程では、機械的破砕処理工程で破砕乃至磨砕された樹皮中のセルロース
成分が糖化酵素に糖化される。
酵素糖化処理工程は、通常のリグノセルロース系バイオマスの糖化処理方法で採用されている酵素の種類や、反応時間、反応温度等の反応条件を採用して行われる。
In the enzymatic saccharification treatment step, the cellulose component in the bark crushed or ground in the mechanical crushing treatment step is saccharified into a saccharification enzyme.
The enzymatic saccharification treatment step is carried out by adopting reaction conditions such as the type of enzyme, reaction time, reaction temperature and the like employed in the usual lignocellulosic biomass saccharification treatment method.
［実施例１］
ユーカリ・グロブラスの樹皮を約４ｃｍ角に切断し、以下の試験に用いた。
絶乾６００ｇ相当の上記樹皮を、樹皮に含まれる水分も含め計３０００ｇとなるイオン交換水に浸漬し、この混合物をオートクレーブを用いて１２０℃にて１時間加熱することにより温水処理を施した。なお、温水処理後、篩を用いて樹皮と温水を分離した。
温水処理済み樹皮を、レファイナー（熊谷理機工業製）を用いて、クリアランス１ｍｍにて破砕処理を行った。樹皮の破砕に要したレファイナー動力は電力積算計を用いて計測した。所要動力は実際に樹皮を破砕するのに要した消費電力から空転に要した電力を差し引いた電力として求めた。空転は樹皮を破砕せずにレファイナーを動作させることと定義する。結果を表１に示す。
[Example 1]
Eucalyptus globulus bark was cut into approximately 4 cm square and used for the following tests.
The above-mentioned bark corresponding to 600 g of absolute dryness was immersed in a total of 3000 g of ion-exchanged water including the water contained in the bark, and this mixture was heated at 120 ° C. for 1 hour using an autoclave to perform hot water treatment. In addition, bark and warm water were isolate | separated using the sieve after the warm water process.
The warm-bark-treated bark was crushed with a clearance of 1 mm using a refiner (manufactured by Kumagai Riki Kogyo). The refiner power required for breaking the bark was measured using a power accumulator. The required power was calculated as the power consumed by actually cutting the bark minus the power required for idling. Idle rotation is defined as operating the refiner without breaking the bark. The results are shown in Table 1.
［比較例１］
温水処理を施さず、実施例１と同様にして処理を行った。結果を表１に示す。
表１より、温水処理を行うことにより、レファイナーを動作させるのに要する電力が大幅に減少することが示された。
[Comparative Example 1]
The treatment was performed in the same manner as in Example 1 without performing the hot water treatment. The results are shown in Table 1.
Table 1 shows that the power required to operate the refiner is significantly reduced by performing the hot water treatment.
［実施例２］
実施例１において温水処理及び破砕処理した樹皮絶乾６０ｇ相当を、前記樹皮が含有する水分も含めて全体の質量が６００ｇとなるように、所定量の水酸化ナトリウムを含有するアルカリ水溶液に浸漬し、この混合物を９５℃にて９０分処理することによりアルカリ処理を施した。
篩を用いて樹皮とアルカリ水溶液を分離し、以下の反応組成にて、３０℃、反応時間２０時間の酵素糖化を行った。
生成したグルコースをバイオセンサーＢＦ４（王子計測機器製）にて測定した。結果を表２及び図１に示す。
＜反応液組成＞
５％樹皮
５％セルラーゼ（「Ｍｕｌｔｉｆｅｃｔ ＣＸ１０Ｌ」 ジェネンコア協和社製）
５０ｍＭ酢酸緩衝液（ｐＨ４．５）
[Example 2]
60 g of bark absolutely dry treated with warm water and crushed in Example 1 is immersed in an aqueous alkaline solution containing a predetermined amount of sodium hydroxide so that the total mass including the water contained in the bark is 600 g. The mixture was treated with alkali by treating at 95 ° C. for 90 minutes.
The bark and the aqueous alkaline solution were separated using a sieve, and enzymatic saccharification was performed at 30 ° C. for 20 hours with the following reaction composition.
The produced glucose was measured with a biosensor BF4 (manufactured by Oji Scientific Instruments). The results are shown in Table 2 and FIG.
<Reaction solution composition>
5% bark 5% cellulase ("Multifect CX10L" manufactured by Genencor Kyowa)
50 mM acetate buffer (pH 4.5)
図１の結果より、アルカリ水溶液処理により樹皮の酵素糖化が促進されたことが示された。 From the result of FIG. 1, it was shown that enzymatic saccharification of the bark was promoted by the alkaline aqueous solution treatment.
本発明によれば、温水処理した樹皮を機械的破砕処理することにより、低い投入エネルギーで、酵素糖化を促進することが可能になり、バイオエタノールをはじめ様々な発酵産物の原料となる糖を供給することができる。 According to the present invention, it is possible to promote enzymatic saccharification with low input energy by mechanically crushing hot water-treated bark, and supply sugar as a raw material for various fermentation products including bioethanol can do.
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| JP2008092910A (en) * | 2006-10-16 | 2008-04-24 | Forestry & Forest Products Research Institute | Method for producing ethanol |
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