JP5720131B2 - Method for producing lignin and composition thereof - Google Patents
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- JP5720131B2 JP5720131B2 JP2010153741A JP2010153741A JP5720131B2 JP 5720131 B2 JP5720131 B2 JP 5720131B2 JP 2010153741 A JP2010153741 A JP 2010153741A JP 2010153741 A JP2010153741 A JP 2010153741A JP 5720131 B2 JP5720131 B2 JP 5720131B2
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- 229920005610 lignin Polymers 0.000 title claims description 63
- 238000004519 manufacturing process Methods 0.000 title claims description 23
- 239000000203 mixture Substances 0.000 title claims description 23
- 108090000790 Enzymes Proteins 0.000 claims description 25
- 102000004190 Enzymes Human genes 0.000 claims description 25
- 238000000034 method Methods 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 14
- 239000002994 raw material Substances 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 150000004676 glycans Chemical class 0.000 claims description 7
- 229920001282 polysaccharide Polymers 0.000 claims description 7
- 239000005017 polysaccharide Substances 0.000 claims description 7
- 230000000593 degrading effect Effects 0.000 claims description 6
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- 229940088598 enzyme Drugs 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 17
- 239000007787 solid Substances 0.000 description 17
- 239000002023 wood Substances 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000004744 fabric Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 108010059892 Cellulase Proteins 0.000 description 5
- 239000008351 acetate buffer Substances 0.000 description 5
- 229940106157 cellulase Drugs 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 244000166124 Eucalyptus globulus Species 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 230000002255 enzymatic effect Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000011343 solid material Substances 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- 101710121765 Endo-1,4-beta-xylanase Proteins 0.000 description 2
- 229920001131 Pulp (paper) Polymers 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007385 chemical modification Methods 0.000 description 2
- 238000012993 chemical processing Methods 0.000 description 2
- 229920005611 kraft lignin Polymers 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 241001019659 Acremonium <Plectosphaerellaceae> Species 0.000 description 1
- 108010065511 Amylases Proteins 0.000 description 1
- 102000013142 Amylases Human genes 0.000 description 1
- 241000228212 Aspergillus Species 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- 108010084185 Cellulases Proteins 0.000 description 1
- 102000005575 Cellulases Human genes 0.000 description 1
- 229920003043 Cellulose fiber Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 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 1
- 108010060309 Glucuronidase Proteins 0.000 description 1
- 102000053187 Glucuronidase Human genes 0.000 description 1
- 241000222385 Phanerochaete Species 0.000 description 1
- 241000222354 Trametes Species 0.000 description 1
- 241000223259 Trichoderma Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000019418 amylase Nutrition 0.000 description 1
- 229940025131 amylases Drugs 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 108010062085 ligninase Proteins 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000010893 paper waste Substances 0.000 description 1
- OQUKIQWCVTZJAF-UHFFFAOYSA-N phenol;sulfuric acid Chemical compound OS(O)(=O)=O.OC1=CC=CC=C1 OQUKIQWCVTZJAF-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229930015704 phenylpropanoid Natural products 0.000 description 1
- 150000002995 phenylpropanoid derivatives Chemical class 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 230000007928 solubilization Effects 0.000 description 1
- 238000005063 solubilization Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Description
本発明はリグニンの製造方法、特に天然リグニンに近く、反応性の高いリグニンの製造方法及びその組成物に関するものである。 The present invention relates to a method for producing lignin, and more particularly to a method for producing lignin that is close to natural lignin and has high reactivity, and a composition thereof.
植物バイオマス中に含まれる炭化水素化合物の主要な成分はセルロースとリグニンである。グルコースなどの糖を構成モノマーとするセルロースは紙パルプやセロハンをはじめとする素材産業で利用されているが、フェニルプロパノイドをモノマーとした三次元立体構造を有するリグニンは、構造が複雑であることから、燃焼によるエネルギー回収が主であり、化学的利用については現段階で採算性のあるものは少ない。特に紙パルプ工程から得られる黒液はリグノセルロース原料をアルカリによってリグニンのみを溶出した液であり、リグニン含有率が高いことで知られるが、リグニンポリマーがパルプ抽出工程において多大な化学変性を受けており、高度に縮重合しているという報告がある（文献１）。このため、黒液中に含まれるリグニンは化学反応性が低く、素材などへの利用は難しいとされている。
黒液以外のリグニンの製造方法としてはリグノセルロース原料を濃酸とフェノール誘導体によって分離方法（特許文献１）、金属イオンの存在下に破砕、圧搾等し、抽出する方法（特許文献２）、微粉砕して得られる粉末に高温高圧下に過酸化水素水を添加し、マイクロ波を照射することにより可溶化する方法（特許文献３）などが報告されている。しかし、いずれも製造法が困難であることやコストの問題などから実用化には至っていない。
The main components of hydrocarbon compounds contained in plant biomass are cellulose and lignin. Cellulose with sugar as a constituent monomer such as glucose is used in the material industry such as paper pulp and cellophane, but lignin having a three-dimensional structure with phenylpropanoid as a monomer has a complicated structure. Therefore, energy recovery by combustion is the main, and there are few profitable chemical uses at this stage. In particular, black liquor obtained from the paper pulp process is a lignocellulosic raw material that elutes only lignin with alkali and is known for its high lignin content, but the lignin polymer has undergone significant chemical modification in the pulp extraction process. There is a report that it is highly polycondensed (Reference 1). For this reason, lignin contained in black liquor has low chemical reactivity and is considered difficult to use as a raw material.
As a method for producing lignin other than black liquor, a method of separating lignocellulosic raw materials with concentrated acid and a phenol derivative (Patent Document 1), a method of extracting by crushing and pressing in the presence of metal ions (Patent Document 2), There has been reported a method of solubilization by adding hydrogen peroxide water to a powder obtained by pulverization under high temperature and high pressure and irradiating with microwaves (Patent Document 3). However, none of them have been put into practical use because of the difficulty of the production method and cost.
本発明は、上記のように従来有効な利用法が十分に検討されていないリグニンの有用な用途を開発するためになされたものであり、特に反応性の高い新規なリグニンとそれを好適に得ることができるリグノセルロースの新規な処理方法を提供することである。 The present invention has been made in order to develop a useful application of lignin for which effective utilization methods have not been sufficiently studied as described above, and in particular, a highly reactive novel lignin and suitably obtained thereof. It is to provide a novel method for treating lignocellulose.
本発明者らは、上記の課題を解決するために鋭意検討した結果、第一糖化工程から得られる残渣を摩砕処理を行った後、酵素糖化することで、反応性の高いリグニンが得られることを見出し、下記発明を完成した。
即ち、上記課題を解決するため、本発明は以下の(1)〜(9)の方法を採用する。
(1)粗破砕および又は磨砕処理を行ったリグノセルロースを多糖分解酵素により、糖を除去する第一糖化工程から得られる残渣に、磨砕処理を行った後、多糖分解酵素により糖を除去する第二糖化工程によって得られることを特徴とするリグニンの製造方法。
(2) 第二糖化工程によって得られるリグニン組成物に対し、更に磨砕処理を行った後、多糖分解酵素により糖を除去する措置を繰り返すことを特徴とするリグニンの製造方法。
(3)前記記載の磨砕処理がニーダー、レファイナーなどを用いることを特徴とする請求項１〜２のいずれかに記載のリグニンの製造方法。
(4)前記記載の少なくとも第一糖化工程、第二工程のいずれかもしくは両方の工程において、工程前に化学処理を行うことを特徴とする請求項1〜3のいずれかに記載のリグニンの製造方法。
(5)前記記載の化学処理が水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、炭酸ナトリウム、炭酸水素ナトリウムなどのアルカリ薬品もしくはそれらの混合物に接触させることを特徴とする請求項４記載のリグニンの製造方法。
(6)前記記載の化学処理におけるアルカリ濃度が対リグノセルロース原料25％以下、望ましくは15％以下であることを特徴とする請求項4〜5のいずれかに記載のリグニンの製造方法。
(7)前記記載の化学処理における処理温度が170℃以下、望ましくは90〜110℃であり、処理時間が3時間以下、望ましくは15〜60分であることを特徴とする請求項4〜６のいずれかに記載のリグニンの製造方法。
(8)得られるリグニンの糖含有率が30％以下であることを特徴とする請求項1〜7のいずれかに記載のリグニンの製造方法。
(9)得られるリグニンの水酸基価5mmol/g以上であることを特徴とする請求項1〜8のいずれかに記載のリグニンの製造方法。
As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a highly reactive lignin by performing enzymatic saccharification after grinding the residue obtained from the first saccharification step. As a result, the following invention was completed.
That is, in order to solve the above problems, the present invention employs the following methods (1) to (9).
(1) Crushed and / or ground lignocellulose is subjected to grinding with the polysaccharide-degrading enzyme, and then the residue obtained from the first saccharification step is removed, and then the sugar is removed with the polysaccharide-degrading enzyme. A process for producing lignin characterized by being obtained by a second saccharification step.
(2) A method for producing lignin, characterized in that the lignin composition obtained by the second saccharification step is further subjected to grinding treatment, and thereafter the step of removing the sugar with a polysaccharide-degrading enzyme is repeated.
(3) The method for producing lignin according to any one of claims 1 to 2, wherein the grinding treatment described above uses a kneader, a refiner or the like.
(4) The production of lignin according to any one of claims 1 to 3, wherein a chemical treatment is performed before the process in at least one or both of the first saccharification process and the second process. Method.
(5) The lignin according to claim 4, wherein the chemical treatment is brought into contact with an alkaline chemical such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium hydrogen carbonate or a mixture thereof. Production method.
(6) The method for producing lignin according to any one of claims 4 to 5, wherein the alkali concentration in the chemical treatment is 25% or less, preferably 15% or less, relative to the lignocellulose raw material.
(7) The treatment temperature in the chemical treatment described above is 170 ° C. or less, desirably 90 to 110 ° C., and the treatment time is 3 hours or less, desirably 15 to 60 minutes. The manufacturing method of the lignin in any one of.
(8) The method for producing lignin according to any one of claims 1 to 7, wherein the sugar content of the obtained lignin is 30% or less.
(9) The method for producing lignin according to any one of claims 1 to 8, wherein the obtained lignin has a hydroxyl value of 5 mmol / g or more.
本発明者は化学変性を受けることが比較的少なく、かつ、リグノセルロースに賦存するリグニンから天然リグニンの構造に近く、反応性の高いリグニンポリマーの製造方法について検討した結果、リグノセルロースから酵素によって効率よく糖を除去することによって、目的とする反応性の高いリグニンが製造可能である。 As a result of studying a method for producing a highly reactive lignin polymer having a relatively low chemical modification and having a structure similar to that of natural lignin from lignin existing in lignocellulose, the present inventors By efficiently removing sugar, the desired highly reactive lignin can be produced.
以下、本発明をさらに詳しく説明する。
本発明が対象とするリグノセルロースとしては、製紙原料樹木、樹木の伐採や造材のときに発生する林地残材、間伐材等のチップ、また製材工場等から発生する樹皮、のこ屑、木材チップ、おがくず、更に街路樹の剪定枝、建築廃材等である。なお、本発明においては、木材由来の紙、古紙、パルプ、パルプスラッジ等も木質バイオマスに含まれるものとする。
Hereinafter, the present invention will be described in more detail.
The lignocellulose targeted by the present invention is a papermaking raw material tree, woodland residual material generated when cutting or timbering trees, chips such as thinned wood, bark, sawdust, wood generated from a sawmill, etc. Chips, sawdust, pruned branches of street trees, construction waste, etc. In the present invention, wood-derived paper, waste paper, pulp, pulp sludge and the like are also included in the woody biomass.
前述のリグノセルロースの中でも、木材の樹皮は、現在ほとんど有効利用されておらず、製材工場やチップ工場で均一な品質のものが大量に入手可能であり、木材の木部部分より柔軟かつ可溶性成分が多く、本発明の原料として好適なリグノセルロースである。
リグノセルロースから効率的に糖を除去するためには、まず、第一糖化工程の前処理としてリグノセルロース原料を粗破砕処理し、さらに原料表面積を増大させ、酵素による糖化を促進させるために、微細化もしくは繊維化を行う。粗破砕処理には二軸破砕機、ハンマークラッシャーなどの機械によって行うことが可能であり、これらによって5〜50ｍｍ程度の木材チップを得る。その後、微一軸破砕機、カッターミル、ボールミル、ニーダー、レファイナーなどの機械によって２〜20ｍｍ程度の微細化もしくは繊維化を行う。第一糖化工程の前処理としては粗破砕処理だけでも良い。
Among the lignocelluloses mentioned above, the bark of wood is rarely used at present and is available in large quantities in a lumber mill and chip factory, which is more flexible and soluble than the wood part of the wood. Therefore, it is lignocellulose suitable as a raw material of the present invention.
In order to efficiently remove sugar from lignocellulose, first, the lignocellulose raw material is roughly crushed as a pretreatment in the first saccharification step, and the surface area of the raw material is further increased to promote saccharification by an enzyme. Or fiberizing. The rough crushing treatment can be performed by a machine such as a biaxial crusher or a hammer crusher, and a wood chip of about 5 to 50 mm is obtained by these. Then, refinement | miniaturization or fiberization of about 2-20 mm is performed with machines, such as a fine uniaxial crusher, a cutter mill, a ball mill, a kneader, and a refiner. As a pretreatment for the first saccharification step, only rough crushing treatment may be used.
糖を除去するために使用する多糖分解酵素は、使用するリグノセルロースに含まれるセルロース成分によって様々な酵素を選択することが可能である。酵素の種類としてはセルラーゼ、キシラナーゼ、リグニナーゼ、アミラーゼ、グルクロニダーゼなどが使用可能で、このうち主成分としてセルラーゼとキシラナーゼが含まれているものが、糖を除去する効率が高い。 As the polysaccharide degrading enzyme used for removing sugar, various enzymes can be selected depending on the cellulose component contained in the lignocellulose to be used. Cellulases, xylanases, ligninases, amylases, glucuronidases and the like can be used as the types of enzymes. Among them, those containing cellulase and xylanase as main components have high efficiency in removing sugar.
特に市販のセルラーゼ製剤としては、トリコデルマ（Ｔｒｉｃｈｏｄｅｒｍａ）属、アクレモニウム属（Ａｃｒｅｍｏｎｉｕｍ）属、アスペルギルス（Ａｓｐｅｒｇｉｌｌｕｓ）属、ファネロケエテ（Ｐｈａｎｅｒｏｃｈａｅｔｅ）属、トラメテス属（Ｔｒａｍｅｔｅｓ）、フーミコラ（Ｈｕｍｉｃｏｌａ）属、バチルス（Ｂａｃｉｌｌｕｓ）属などに由来するセルラーゼ製剤がある。このようなセルラーゼ製剤の市販品としては、全て商品名で、例えば、セルロイシンＴ２（エイチピィアイ社製）、メイセラーゼ（明治製菓社製）、ノボザイム１８８（ノボザイム社製）、マルティフェクトＣＸ１０Ｌ（ジェネンコア社製）、ＧＣ２２０（ジェネンコア社製）等が挙げられる。
原料固形分１００質量部に対するセルラーゼ製剤の使用量は、０．５〜１００質量部が好ましく、１〜５０質量部が特に好ましい。
In particular, commercially available cellulase preparations include the genus Trichoderma, the genus Acremonium, the genus Aspergillus, the genus Phanerochaete, the genus Trametes, the genus Bumil, There are cellulase preparations derived from genera and the like. Commercially available products of such cellulase preparations are all trade names, for example, cellulosin T2 (manufactured by HIPI), mecerase (manufactured by Meiji Seika Co., Ltd.), Novozyme 188 (manufactured by Novozyme), multifect CX10L (manufactured by Genencor) ), GC220 (manufactured by Genencor).
0.5-100 mass parts is preferable and, as for the usage-amount of the cellulase formulation with respect to 100 mass parts of raw material solid content, 1-50 mass parts is especially preferable.
反応条件はｐＨが４〜７が好ましい。温度は２５〜５０℃が好ましく、３０〜４０℃がさらに好ましい。酵素糖化反応は、連続式が好ましいが、バッチ方式でも良い。酵素糖化反応時間は、酵素濃度によっても異なるが、バッチ式の場合は１０〜２４０時間、さらに好ましくは１５〜１６０時間である。連続式の場合も、平均滞留時間が、１０〜１５０時間、さらに好ましくは１５〜１００時間である。 The reaction conditions are preferably pH 4-7. The temperature is preferably 25 to 50 ° C, more preferably 30 to 40 ° C. The enzyme saccharification reaction is preferably a continuous method, but may be a batch method. The enzyme saccharification reaction time varies depending on the enzyme concentration, but in the case of a batch system, it is 10 to 240 hours, more preferably 15 to 160 hours. Also in the case of a continuous type, the average residence time is 10 to 150 hours, more preferably 15 to 100 hours.
しかし、多糖分解酵素による一度の処理では糖を完全に除去することは難しい。そこで本発明では一度、酵素糖化処理を行って得られる残渣に対し、微細化もしくは繊維化処理を行うことにより、一度の処理では除去されなかったセルロースの結晶性を下げ、更に酵素糖化処理を行うことにより効率的に糖を除去することが可能であることを見出した。この微細化、繊維化処理は複数回行うことにより、糖の除去率を下げることは可能であるが、リグニン分子量の低下を招くため、2〜3回が経済的にも好ましいといえる。
さらに、酵素糖化工程前に、リグニンが変性しない程度の化学処理を行うことにより、セルロース繊維間の結合を緩めることが可能となる。これにより、酵素による糖の除去はさらに効率的となる。薬品としては水酸化ナトリウム、水酸化カリウム、水酸化カルシウム、炭酸ナトリウム、炭酸水素ナトリウムなどのアルカリ薬品もしくはそれらの混合物を使用した場合に効果が高く、特に、水酸化カルシウムや水酸化ナトリウムが望ましい。使用するアルカリ濃度は、対リグノセルロース原料25％以下、望ましくは15％以下で行うことにより、酵素による糖の除去効率を高め、かつリグニンの変成が少ない。処理温度についても、同様の理由から180℃以下、望ましくは90〜110℃であり、処理時間は3時間以下、望ましくは15〜60分が最適な条件である。
However, it is difficult to completely remove sugar by a single treatment with a polysaccharide-degrading enzyme. Therefore, in the present invention, the residue obtained by performing the enzymatic saccharification treatment once is refined or fiberized, thereby reducing the crystallinity of cellulose that was not removed by the single treatment, and further performing the enzymatic saccharification treatment. It was found that it is possible to remove sugar efficiently. It is possible to reduce the sugar removal rate by performing this micronization and fiberization treatment a plurality of times, but since it leads to a decrease in the lignin molecular weight, it can be said that 2 to 3 times is preferable economically.
Furthermore, it is possible to loosen the bonds between the cellulose fibers by performing chemical treatment to such an extent that lignin is not denatured before the enzymatic saccharification step. This makes the sugar removal by the enzyme more efficient. The chemical is highly effective when alkaline chemicals such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium hydrogen carbonate or a mixture thereof is used, and calcium hydroxide and sodium hydroxide are particularly desirable. The alkali concentration to be used is 25% or less, preferably 15% or less of the lignocellulose raw material, so that the sugar removal efficiency by the enzyme is increased and the lignin is not denatured. For the same reason, the treatment temperature is 180 ° C. or less, preferably 90 to 110 ° C., and the treatment time is 3 hours or less, preferably 15 to 60 minutes.
糖を除去して得られたリグニンは水で洗浄することにより、使用した酵素や薬品の除去を行うことが可能となる。得られたリグニンは高度に縮重合して暗紫色となったクラフトリグニンとは異なり、薄い茶色の粉末であり、ＦＴ−ＩＲ分析からもセルロース由来のスペクトルピークは観察されず、リグニン由来のスペクトルピークが主に観察される。リグニン残基と共有結合している糖一分子は多糖分解酵素での切断は困難であるため、糖の完全な除去は困難であるが、本発明によりリグニン中の糖含有率は30%以下にすることは可能である。 The lignin obtained by removing sugar can be washed with water to remove used enzymes and chemicals. The obtained lignin is a light brown powder, unlike kraft lignin which has become highly purple due to highly polycondensation, and the spectrum peak derived from cellulose is not observed even from FT-IR analysis, and the spectrum peak derived from lignin is Observed mainly. Since a single sugar molecule covalently bonded to a lignin residue is difficult to cleave with a polysaccharide-degrading enzyme, complete removal of the sugar is difficult, but according to the present invention, the sugar content in lignin is reduced to 30% or less. It is possible to do.
得られるリグニンには縮重合していないため、反応性の高いフリーの水酸基が多く含まれている。得られたリグニンにおける水酸基価はJIS法（K 0070、K 1557-1）で測定すると5mmol/g以上であり、製造条件によっては10mmol/g以上の水酸基価であるサンプルを得ることが可能であった。
以下、本発明のリグニンとそれを好適に得ることができるリグノセルロースの新規な処理方法について詳細に説明する。本発明はこれにより限定されるものではない。
Since the obtained lignin is not polycondensed, it contains a lot of free hydroxyl groups with high reactivity. The hydroxyl value of the obtained lignin is 5 mmol / g or more as measured by the JIS method (K 0070, K 1557-1), and it is possible to obtain a sample having a hydroxyl value of 10 mmol / g or more depending on the production conditions. It was.
Hereinafter, the novel processing method of the lignin of this invention and the lignocellulose which can obtain it suitably is demonstrated in detail. The present invention is not limited thereby.
＜比較例１＞
二軸破砕機（近畿工業製、ＲＲＣ−９３２Ｅ）によって50ｍｍ以下に破砕したユーカリチップを、一軸破砕機（西邦機工社製、ＳＣ-１５）で2~20mm程度に繊維化を行った。この試料300gに50mM酢酸緩衝液(pH5)を10L加え、多糖分解酵素（ジェネンコア製、GC220） 300mLを添加し、50℃、150rpmで攪拌し18時間反応させた。反応液を40メッシュのろ布でろ過した後、ろ布上に残った固形物をイオン交換水10Lで洗浄し、酢酸緩衝液、多糖分解酵素と酵素によって可溶化した糖の除去を行った。
得られた固形物はJIS法（P 8211）に従ってカッパー価を測定してリグニン量を算出した。固形物中の糖含有率は、絶乾４ｇの固形物に対し、７０％硫酸を50ml添加し、20℃、18時間の攪拌を行うことにより、糖を溶出し、反応後、反応液上清中の糖濃度をフェノール硫酸法で測定することによって算出した。固形物中の水酸基価はJIS法（K 0070、K 1557-1）に従って測定した。
<Comparative Example 1>
Eucalyptus chips crushed to 50 mm or less by a biaxial crusher (manufactured by Kinki Kogyo Co., Ltd., RRC-932E) were fiberized to about 2 to 20 mm using a uniaxial crusher (Seiho Kiko Co., Ltd., SC-15). To 300 g of this sample, 10 L of 50 mM acetate buffer (pH 5) was added, 300 mL of a polysaccharide-degrading enzyme (Genencor, GC220) was added, and the mixture was stirred at 50 ° C. and 150 rpm for 18 hours. After the reaction solution was filtered with a 40 mesh filter cloth, the solid matter remaining on the filter cloth was washed with 10 L of ion-exchanged water, and the sugar solubilized by the acetate buffer, the polysaccharide degrading enzyme and the enzyme was removed.
The solid matter obtained was measured for kappa number according to the JIS method (P 8211) to calculate the amount of lignin. The saccharide content in the solid was determined by adding 50 ml of 70% sulfuric acid to the absolutely dry 4 g of solid and stirring the mixture at 20 ° C for 18 hours to elute the sugar. The sugar concentration inside was calculated by measuring by the phenol sulfuric acid method. The hydroxyl value in the solid was measured according to the JIS method (K 0070, K 1557-1).
＜比較例２＞
比較例１と同様に繊維化、糖化工程を行って得られた固形物100ｇに対し、再度50mM酢酸緩衝液(pH5)を10L加え、多糖分解酵素（ジェネンコア製、GC220） 100mLを添加し、50℃、150rpmで攪拌し18時間反応させた。反応液を40メッシュのろ布でろ過した後、ろ布上に残った固形物をイオン交換水10Lで洗浄し、酢酸緩衝液、多糖分解酵素と酵素によって可溶化した糖の除去を行った。
得られた固形物は比較例１と同様にリグニン量、糖含有量、水酸基価の測定を行った。
<Comparative Example 2>
10 L of 50 mM acetate buffer (pH 5) is again added to 100 g of the solid material obtained by performing the fiberization and saccharification steps in the same manner as in Comparative Example 1, and 100 mL of polysaccharide degrading enzyme (Genencor, GC220) is added. The mixture was stirred at 150 ° C. and 150 rpm for 18 hours. After the reaction solution was filtered with a 40 mesh filter cloth, the solid matter remaining on the filter cloth was washed with 10 L of ion-exchanged water, and the sugar solubilized by the acetate buffer, the polysaccharide degrading enzyme and the enzyme was removed.
The obtained solid was measured for lignin amount, sugar content, and hydroxyl value in the same manner as in Comparative Example 1.
＜比較例３＞
ユーカリチップを比較例１と同様に繊維化工程を行って得られた固形物100gに対し、磨砕機（増幸産業社製 マスコーロイダー）にて磨砕処理を行った。磨砕処理におけるクリアランスは10nmで行い、処理後、50mM酢酸緩衝液(pH5)を10L加え、多糖分解酵素（ジェネンコア製、GC220） 100mLを添加し、50℃、150rpmで攪拌し18時間反応させた。反応液を5000rpm、10分間の遠心処理で沈殿させ、上清を取り除いた後、イオン交換水を添加して懸濁させた後、再度遠心処理を行った。上清の電気伝導度が100uS/cm以下になるまで懸濁、遠心処理を繰り返し、沈殿として固形物を回収した。
<Comparative Example 3>
The eucalyptus chip was subjected to a grinding process using a grinding machine (Massko Sangyo Co., Ltd., a mass colloider) on 100 g of the solid material obtained by subjecting the eucalyptus chip to the fiberizing step in the same manner as in Comparative Example 1. The clearance in the grinding process was 10 nm, and after the treatment, 10 L of 50 mM acetate buffer (pH 5) was added, 100 mL of polysaccharide degrading enzyme (Genencor, GC220) was added, and the mixture was stirred at 50 ° C. and 150 rpm for 18 hours. . The reaction solution was precipitated by centrifugation at 5000 rpm for 10 minutes, the supernatant was removed, ion-exchanged water was added and suspended, and then centrifuged again. Suspension and centrifugation were repeated until the electrical conductivity of the supernatant reached 100 uS / cm or less, and solid matter was collected as a precipitate.
＜比較例４＞
市販されているクラフトリグニン（アルドリッチ社製）について比較例１と同様にリグニン量、糖含有量、水酸基価の測定を行った。
<Comparative Example 4>
The lignin amount, sugar content, and hydroxyl value of the commercially available kraft lignin (manufactured by Aldrich) were measured in the same manner as in Comparative Example 1.
＜実施例１＞
ユーカリチップを比較例３と同様に繊維化、磨砕処理、糖化、遠心処理工程を行って得られた固形物100gに対し、再度、同じ条件で磨砕処理、糖化処理、遠心処理を行った。
得られた固形物は比較例１と同様にリグニン量、糖含有量、水酸基価の測定を行った。
<Example 1>
The eucalyptus chips were subjected to the same process as in Comparative Example 3, and the grinding, saccharification, and centrifugation processes were again performed under the same conditions on 100 g of the solid material obtained by performing the steps of fiberization, grinding, saccharification, and centrifugation. .
The obtained solid was measured for lignin amount, sugar content, and hydroxyl value in the same manner as in Comparative Example 1.
＜実施例２＞
比較例１と同様に繊維化工程を行った後、試料300gに2.7Lのイオン交換水と60gの水酸化ナトリウムを添加（対原料２０％）し、90℃、30分の化学処理を行った。処理後、反応液を40メッシュのろ布でろ過した後、ろ布上に残った固形物をイオン交換水10Lで洗浄した。得られた固形物に対し、比較例３と同様に磨砕処理、糖化処理、遠心処理を行い、再度、同じ条件で磨砕処理、糖化処理、遠心処理を行った。
得られた固形物は比較例１と同様にリグニン量、糖含有量、水酸基価の測定を行った。
<Example 2>
After performing the fiberization step in the same manner as in Comparative Example 1, 2.7 L of ion exchange water and 60 g of sodium hydroxide were added to 300 g of the sample (20% to the raw material), followed by chemical treatment at 90 ° C. for 30 minutes. . After the treatment, the reaction solution was filtered through a 40-mesh filter cloth, and the solid matter remaining on the filter cloth was washed with 10 L of ion-exchanged water. The obtained solid was ground, saccharified, and centrifuged in the same manner as in Comparative Example 3, and again ground, saccharified, and centrifuged under the same conditions.
The obtained solid was measured for lignin amount, sugar content, and hydroxyl value in the same manner as in Comparative Example 1.
＜実施例3＞
実施例２と同様に処理を行う際、化学処理における使用薬品が水酸化カリウム、水酸化カルシウム、炭酸ナトリウム、炭酸水素ナトリウムでそれぞれ行った。（実施例３−１〜３−４）
得られた固形物は比較例１と同様にリグニン量、糖含有量、水酸基価の測定を行った。
<Example 3>
When the treatment was performed in the same manner as in Example 2, chemicals used in the chemical treatment were respectively potassium hydroxide, calcium hydroxide, sodium carbonate, and sodium bicarbonate. (Examples 3-1 to 3-4)
The obtained solid was measured for lignin amount, sugar content, and hydroxyl value in the same manner as in Comparative Example 1.
＜実施例４＞
実施例２と同様に処理を行う際、化学処理における使用薬品（対原料％）が５，１０、２５，５０％でそれぞれ行った。（実施例４−１〜４−４）
得られた固形物は比較例１と同様にリグニン量、糖含有量、水酸基価の測定を行った。
<Example 4>
When the treatment was performed in the same manner as in Example 2, the chemicals used (% of raw material) in the chemical treatment were 5, 10, 25, and 50%, respectively. (Examples 4-1 to 4-4)
The obtained solid was measured for lignin amount, sugar content, and hydroxyl value in the same manner as in Comparative Example 1.
＜実施例５＞
実施例２と同様に処理を行う際、化学処理における処理温度が５０、１１０，１７０，１９０℃でそれぞれ行った。（実施例５−１〜５−４）
得られた固形物は比較例１と同様にリグニン量、糖含有量、水酸基価の測定を行った。
<Example 5>
When processing was performed in the same manner as in Example 2, the processing temperatures in chemical processing were 50, 110, 170, and 190 ° C., respectively. (Examples 5-1 to 5-4)
The obtained solid was measured for lignin amount, sugar content, and hydroxyl value in the same manner as in Comparative Example 1.
＜実施例６＞
実施例２と同様に処理を行う際、化学処理における処理時間が５，１５，６０，１８０，３６０分でそれぞれ行った。（実施例６−１〜６−５）
得られた固形物は比較例１と同様にリグニン量、糖含有量、水酸基価の測定を行った。
<Example 6>
When processing was performed in the same manner as in Example 2, the processing times in the chemical processing were 5, 15, 60, 180, and 360 minutes, respectively. (Examples 6-1 to 6-5)
The obtained solid was measured for lignin amount, sugar content, and hydroxyl value in the same manner as in Comparative Example 1.
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