JP6666509B1 - Agglomeration inhibitor and aggregation suppression method - Google Patents
Agglomeration inhibitor and aggregation suppression method Download PDFInfo
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- JP6666509B1 JP6666509B1 JP2019143339A JP2019143339A JP6666509B1 JP 6666509 B1 JP6666509 B1 JP 6666509B1 JP 2019143339 A JP2019143339 A JP 2019143339A JP 2019143339 A JP2019143339 A JP 2019143339A JP 6666509 B1 JP6666509 B1 JP 6666509B1
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- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
- C08H6/00—Macromolecular compounds derived from lignin, e.g. tannins, humic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L97/00—Compositions of lignin-containing materials
- C08L97/005—Lignin
Abstract
【課題】リグノセルロース物質を原料とする酸加水分解物の凝集を抑制するための凝集抑制剤および該凝集抑制剤を用いたリグノセルロース物質を原料とする酸加水分解物の凝集抑制方法を提供する。【解決手段】本発明の凝集抑制剤は、芳香族スルホン酸基を有するポリマーを含む。【選択図】なしPROBLEM TO BE SOLVED: To provide a coagulation inhibitor for suppressing coagulation of an acid hydrolyzate made from a lignocellulosic material, and a method for suppressing coagulation of an acid hydrolyzate made from a lignocellulosic material using the coagulation inhibitor. . The aggregation inhibitor of the present invention contains a polymer having an aromatic sulfonic acid group. [Selection diagram] None
Description
本発明は、リグノセルロース物質を原料とする酸加水分解物の凝集抑制剤および該凝集抑制剤を用いる凝集抑制方法に関する。 The present invention relates to an aggregation inhibitor of an acid hydrolyzate using a lignocellulose substance as a raw material and an aggregation inhibition method using the aggregation inhibitor.
リグノセルロース物質は、水と炭酸ガスと太陽エネルギーから光合成により生産される再生可能な有機資源であり、エネルギー源または化学原料として利用可能である。リグノセルロース物質は、セルロース、ヘミセルロース、リグニン、その他成分（有機酸等）等により構成されており、成分比はリグノセルロース物質の種類によって異なる。例えば、木質系のリグノセルロース物質は、セルロースが約５０％、ヘミセルロースが２０〜２５％、リグニンが２０〜２５％、その他成分が約５％である。 Lignocellulosic substances are renewable organic resources produced by photosynthesis from water, carbon dioxide and solar energy, and can be used as energy sources or chemical raw materials. The lignocellulosic substance is composed of cellulose, hemicellulose, lignin, other components (such as organic acids) and the like, and the component ratio varies depending on the type of lignocellulosic substance. For example, a woody lignocellulosic material is about 50% cellulose, 20-25% hemicellulose, 20-25% lignin, and about 5% other components.
リグノセルロース物質を化学原料として利用する場合には、主成分であるセルロース、ヘミセルロース、リグニンを分離する必要があり、特にヘミセルロースを分離する手段として、酸加水分解処理が古くから知られている。酸加水分解処理によって生成される生成物として、例えば、酸加水分解処理の温度が１００〜１４０℃においては、有機酸や水溶性リグニンが報告されている。また、１４０〜２３０℃においては、ヘミセルロースに由来するオリゴ糖や、キシロース、アラビノース、マンノース、ガラクトース等の単糖類が報告されている（特許文献１、特許文献２参照）。 When a lignocellulose substance is used as a chemical raw material, it is necessary to separate cellulose, hemicellulose and lignin, which are main components, and an acid hydrolysis treatment has long been known as a means for separating hemicellulose. As a product generated by the acid hydrolysis treatment, for example, organic acids and water-soluble lignin are reported when the temperature of the acid hydrolysis treatment is 100 to 140 ° C. At 140 to 230 ° C., oligosaccharides derived from hemicellulose and monosaccharides such as xylose, arabinose, mannose, and galactose have been reported (see Patent Documents 1 and 2).
リグノセルロース物質の酸加水分解処理において、酸加水分解物の一部が凝集を起こしてしまうことがある。その結果、酸加水分解物の回収量が減少するだけでなく、凝集物が反応装置等に付着したり、液経路を閉塞する問題がある。凝集物を除去するためには、リグノセルロース物質の酸加水分解処理を一旦中断する等の対応が必要となり、生産効率を下げる一因となる。 In the acid hydrolysis treatment of a lignocellulosic substance, a part of the acid hydrolyzate may aggregate. As a result, not only does the recovery amount of the acid hydrolyzate decrease, but also there is a problem that the aggregates adhere to the reaction device or the like and block the liquid path. In order to remove the aggregates, it is necessary to take measures such as temporarily suspending the acid hydrolysis treatment of the lignocellulosic substance, which is one of the causes of lowering the production efficiency.
本発明は、上記に鑑みてなされたものであり、リグノセルロース物質を原料とする酸加水分解物の凝集を抑制するための凝集抑制剤および該凝集抑制剤を用いたリグノセルロース物質を原料とする酸加水分解物の凝集抑制方法を提供することを目的とする。 The present invention has been made in view of the above, and uses a lignocellulosic substance as a raw material and a coagulation inhibitor for suppressing coagulation of an acid hydrolyzate using a lignocellulose substance as a raw material. An object of the present invention is to provide a method for suppressing aggregation of an acid hydrolyzate.
本発明者らは、鋭意研究の結果、リグノセルロース物質を原料とする酸加水分解物の凝集を抑制するための凝集抑制剤として、芳香族スルホン酸基を有するポリマー（成分Ａ）が有効であることを見出した。 The present inventors have conducted intensive studies and found that a polymer having an aromatic sulfonic acid group (component A) is effective as an aggregation inhibitor for suppressing aggregation of an acid hydrolyzate using a lignocellulose substance as a raw material. I found that.
すなわち、本発明は以下の（１）〜（６）を提供するものである。
（１） 芳香族スルホン酸基を有するポリマー（成分Ａ）を含む、リグノセルロース物質を原料とする酸加水分解物の凝集抑制剤。
（２） 前記リグノセルロース物質が、広葉樹、針葉樹、バガス、稲わら、とうもろこし茎、とうもろこし葉、パーム空果房（ＥＦＢ）、籾殻、パーム殻、ココナッツ殻、カシューナッツ殻、紙類、および藻類よりなる群から選択される１種以上である、（１）に記載の凝集抑制剤。
（３） 前記酸加水分解物が、リグニン分解物を含む、（１）または（２）に記載の凝集抑制剤。
（４） 成分Ａの重量平均分子量が２０００以上３００００以下である、（１）〜（３）のいずれかに記載の凝集抑制剤。
（５） 成分Ａがナフタレンスルホン酸ホルマリン縮合物の塩およびリグニンスルホン酸の塩よりなる群から選択される少なくとも１つである、（１）〜（４）のいずれかに記載の凝集抑制剤。
（６） （１）〜（５）のいずれかに記載の凝集抑制剤を用いる、リグノセルロース物質を原料とする酸加水分解物の凝集抑制方法。
That is, the present invention provides the following (1) to (6).
(1) An aggregation inhibitor for an acid hydrolyzate containing a polymer having an aromatic sulfonic acid group (component A) and made from a lignocellulose substance.
(2) The lignocellulosic substance comprises hardwood, conifer, bagasse, rice straw, corn stalk, corn leaf, palm empty fruit cluster (EFB), rice hull, palm husk, coconut husk, cashew nut husk, paper, and algae. The aggregation inhibitor according to (1), which is at least one member selected from the group.
(3) The aggregation inhibitor according to (1) or (2), wherein the acid hydrolyzate contains a lignin decomposition product.
(4) The aggregation inhibitor according to any one of (1) to (3), wherein the component A has a weight average molecular weight of 2,000 to 30,000.
(5) The aggregation inhibitor according to any one of (1) to (4), wherein the component A is at least one selected from the group consisting of a salt of a naphthalenesulfonic acid formalin condensate and a salt of ligninsulfonic acid.
(6) A method for suppressing aggregation of an acid hydrolyzate using a lignocellulose substance as a raw material, using the aggregation inhibitor according to any one of (1) to (5).
本発明によれば、リグノセルロース物質を原料とする酸加水分解物の凝集を抑制できる凝集抑制剤および該凝集抑制剤を用いたリグノセルロース物質を原料とする酸加水分解物の凝集抑制方法が提供される。また、本発明の凝集抑制剤を用いることにより、酸加水分解物の有効利用が可能となる。 ADVANTAGE OF THE INVENTION According to this invention, the aggregation inhibitor which can suppress aggregation of the acid hydrolyzate which uses a lignocellulose substance as a raw material, and the aggregation suppression method of the acid hydrolyzate which uses a lignocellulose substance as a raw material using this aggregation inhibitor are provided. Is done. Further, by using the aggregation inhibitor of the present invention, the acid hydrolyzate can be effectively used.
［凝集抑制剤および凝集抑制方法］
本発明の凝集抑制剤は、リグノセルロース物質を原料とする酸加水分解物の凝集を抑制するための凝集抑制剤であって、芳香族スルホン酸基を有するポリマー（成分Ａ）を有効成分として含む。本発明において、「有効成分として含む」とは、主要な活性成分として含むという意味であり、効果を奏する程度に含有するという意味である。
また、本発明の凝集抑制方法は、前記本発明の凝集抑制剤を用いて、リグノセルロース物質を原料とする酸加水分解物の凝集を抑制する方法である。
[Aggregation inhibitor and aggregation suppression method]
The aggregation inhibitor of the present invention is an aggregation inhibitor for suppressing aggregation of an acid hydrolyzate using a lignocellulose substance as a raw material, and contains a polymer having an aromatic sulfonic acid group (component A) as an active ingredient. . In the present invention, “comprising as an active ingredient” means containing as a main active ingredient, and means containing to such an extent that an effect is exhibited.
Further, the aggregation suppressing method of the present invention is a method of suppressing the aggregation of an acid hydrolyzate using a lignocellulosic substance as a raw material by using the above-mentioned aggregation suppressing agent of the present invention.
＜芳香族スルホン酸基を有するポリマー（成分Ａ）＞
本発明の凝集抑制剤は、芳香族スルホン酸基を有するポリマー（成分Ａ）を含有する。
芳香族スルホン酸基を有するポリマーは、芳香族スルホン酸基を有するモノマーを構成単位に有するポリマーであってもよく、また、スルホン酸基を有さない芳香族モノマーを構成単位に有するポリマーをスルホン化したポリマーであってもよい。
<Polymer having aromatic sulfonic acid group (component A)>
The aggregation inhibitor of the present invention contains a polymer having an aromatic sulfonic acid group (component A).
The polymer having an aromatic sulfonic acid group may be a polymer having a monomer having an aromatic sulfonic acid group in a structural unit, or a polymer having an aromatic monomer having no aromatic sulfonic acid group in a structural unit. Polymer may be used.
芳香族スルホン酸基を有するモノマーは、少なくとも一つのスルホン酸基またはその塩を有する芳香族モノマーであればいずれのものであってもよく、具体的には、ベンゼンスルホン酸、ｐ−トルエンスルホン酸、ヒドロキシメチルベンゼンスルホン酸、ナフタレンスルホン酸、メチルナフタレンスルホン酸、スチレンスルホン酸、およびこれらの塩等が挙げられる。ポリマーを構成する他のモノマーは、スルホン酸基またはその塩を有する芳香族モノマーと反応しポリマーを形成できるモノマーであればいずれのものであってもよく、ホルムアルデヒドやビニル基を有するモノマー等が挙げられる。 The monomer having an aromatic sulfonic acid group may be any monomer as long as it is an aromatic monomer having at least one sulfonic acid group or a salt thereof. Specifically, benzenesulfonic acid, p-toluenesulfonic acid , Hydroxymethylbenzenesulfonic acid, naphthalenesulfonic acid, methylnaphthalenesulfonic acid, styrenesulfonic acid, and salts thereof. The other monomer constituting the polymer may be any monomer that can form a polymer by reacting with an aromatic monomer having a sulfonic acid group or a salt thereof, such as a monomer having formaldehyde or a vinyl group. Can be
成分Ａは、リグノセルロース物質を原料とする酸加水分解物の凝集抑制向上の観点から、ベンゼンスルホン酸またはナフタレンスルホン酸のホルマリン縮合物またはその塩が好ましく、ナフタレンスルホン酸のホルマリン縮合物（「ナフタレンスルホン酸ホルマリン縮合物」ともいう）またはその塩がより好ましい。 The component A is preferably a formalin condensate of benzenesulfonic acid or naphthalenesulfonic acid or a salt thereof from the viewpoint of suppressing aggregation of an acid hydrolyzate using a lignocellulose material as a raw material, and a formalin condensate of naphthalenesulfonic acid (“naphthalene condensate”). Sulfonic acid formalin condensate) or a salt thereof is more preferred.
また、スルホン酸基を有さない芳香族モノマーを構成単位に有するポリマーをスルホン化したポリマーとしては、例えば、リグニンをスルホン化したリグニンスルホン酸またはその塩が例示される。 Examples of the polymer obtained by sulfonating a polymer having an aromatic monomer having no sulfonic acid group as a constituent unit include ligninsulfonic acid obtained by sulfonating lignin or a salt thereof.
成分Ａとしては、ナフタレンスルホン酸ホルマリン縮合物の塩およびリグニンスルホン酸の塩よりなる群から選択される少なくとも１つであることが好ましく、ナフタレンスルホン酸ホルマリン縮合物の塩であることがより好ましい。 Component A is preferably at least one selected from the group consisting of a salt of a naphthalene sulfonic acid formalin condensate and a salt of a lignin sulfonic acid, and more preferably a salt of a naphthalene sulfonic acid formalin condensate.
成分Ａは、酸またはその塩として用いることができる。塩としては、具体的には、ナトリウム、カリウムといったアルカリ金属の塩、カルシウム、マグネシウムといったアルカリ土類金属の塩、アンモニウム塩、炭素数１〜４のアルキル基を１〜４個有するアミンの塩、モノエタノールアミン、ジエタノールアミン、トリエタノールアミンといったアミノアルコールの塩が挙げられ、酸またはナトリウム塩が好ましい。 Component A can be used as an acid or a salt thereof. As the salt, specifically, salts of alkali metals such as sodium and potassium, salts of alkaline earth metals such as calcium and magnesium, ammonium salts, salts of amines having 1 to 4 alkyl groups having 1 to 4 carbon atoms, Examples thereof include salts of amino alcohols such as monoethanolamine, diethanolamine and triethanolamine, and preferred are acids or sodium salts.
成分Ａは、リグノセルロース物質を原料とする酸加水分解物の凝集抑制向上の観点から、重量平均分子量が２０００以上３００００以下であることが好ましく、５０００以上２５０００以下がより好ましく、８０００以上２２０００以下がさらに好ましく、１００００以上１５０００以下がよりさらに好ましく、１００００以上１４０００以下がよりさらに好ましい。成分Ａの重量平均分子量は、実施例に記載の方法により測定される。 Component A has a weight average molecular weight of preferably 2,000 or more and 30,000 or less, more preferably 5,000 or more and 25,000 or less, and 8,000 or more 22,000 or less, from the viewpoint of suppressing aggregation of an acid hydrolyzate using a lignocellulose substance as a raw material. More preferably, it is more preferably 10,000 or more and 15,000 or less, and still more preferably 10,000 or more and 14,000 or less. The weight average molecular weight of the component A is measured by the method described in the examples.
本発明の凝集抑制剤は、成分Ａの含有量が好ましくは０．１質量％以上１００質量％以下の、液体、粉末、フレーク、ペースト状など、添加方法に応じた最適な形態であればよく、保管および取扱い性の観点から、成分Ａを含有する水溶液であることが好ましい。水溶液の場合、保管および取扱い性の観点から、成分Ａの含有量は、１０質量％以上が好ましく、２０質量％以上がより好ましく、３０質量％以上がさらに好ましい。また、水溶液の場合、保管および取扱い性の観点から、成分Ａの含有量は、６０質量％以下が好ましく、５５質量％以下がより好ましく、５０質量％以下がさらに好ましい。 The aggregation inhibitor of the present invention may have a content of component A of preferably 0.1% by mass or more and 100% by mass or less, as long as it is an optimal form according to the addition method, such as a liquid, powder, flake, or paste. From the viewpoints of storage, handling and handling, an aqueous solution containing the component A is preferable. In the case of an aqueous solution, the content of the component A is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of storage and handling. In the case of an aqueous solution, the content of the component A is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less, from the viewpoint of storage and handling.
本発明の凝集抑制剤は、必要に応じて、リグノセルロース物質を原料に酸加水分解処理する従来からの工程において用いることができる。 The agglomeration inhibitor of the present invention can be used in a conventional step of subjecting a lignocellulosic substance as a raw material to an acid hydrolysis treatment, if necessary.
本発明の凝集抑制剤は、成分Ａ以外の成分を、本発明の性能に影響しない範囲内で含有することができる。例えば、ポリオキシアルキレンアルキルエーテル等の非イオン性界面活性剤、アルキル硫酸エステル塩、ポリオキシアルキレンアルキル硫酸エステル塩、アルキルベンゼンスルホン酸塩、高級脂肪酸およびその塩等のアニオン性界面活性剤；苛性ソーダや珪酸ソーダ等のアルカリ薬剤；過酸化水素、次亜塩素酸塩、次亜硫酸塩等の漂白剤；ピッチコントロール剤；消泡剤；スライムコントロール剤等である。 The aggregation inhibitor of the present invention may contain components other than the component A within a range that does not affect the performance of the present invention. For example, nonionic surfactants such as polyoxyalkylene alkyl ethers, anionic surfactants such as alkyl sulfates, polyoxyalkylene alkyl sulfates, alkylbenzene sulfonates, higher fatty acids and salts thereof; caustic soda and silicic acid Alkaline agents such as soda; bleaching agents such as hydrogen peroxide, hypochlorite and hyposulfite; pitch control agents; defoamers; slime control agents.
本発明の凝集抑制剤の添加量は、リグノセルロース物質を原料とする酸加水分解物の凝集抑制向上の観点から、酸加水分解物（酸加水分解処理液）の総量に対して、成分Ａに換算して０．０１質量％以上の添加が好ましく、０．１質量％以上がより好ましく、０．２質量％以上がさらに好ましく、１質量％以上がよりさらに好ましい。また本発明の凝集抑制剤の添加量は、効果の飽和による経済性の観点から、成分Ａに換算して１０質量％以下が好ましく、５質量％以下がより好ましく、３質量％以下がさらに好ましい。 The amount of the coagulation inhibitor of the present invention is determined based on the total amount of the acid hydrolyzate (acid hydrolyzate) from the viewpoint of improving the coagulation suppression of the acid hydrolyzate using the lignocellulose substance as a raw material. It is preferably added in an amount of 0.01% by mass or more in terms of conversion, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, and still more preferably 1% by mass or more. Further, the addition amount of the aggregation inhibitor of the present invention is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 3% by mass or less, in terms of component A, from the viewpoint of economy due to saturation of the effect. .
本発明の凝集抑制剤は、リグノセルロース物質を酸加水分解処理する前に添加することもできるし、酸加水分解処理後に添加することもできるし、これを添加するタイミングは特に限定されるものではない。また、凝集抑制剤は原体をそのまま添加することもできるし、水など水溶液で希釈して添加することもできる。 The aggregation inhibitor of the present invention can be added before the acid hydrolysis treatment of the lignocellulosic substance, or can be added after the acid hydrolysis treatment, and the timing of adding this is not particularly limited. Absent. In addition, the aggregation inhibitor can be added as it is, or as diluted with an aqueous solution such as water.
＜リグノセルロース物質＞
本発明に用いられる「リグノセルロース物質」は、特に制限されるものではなく、例えば、広葉樹、針葉樹に代表される木材、竹、サトウキビ（バガス含む）、稲わら、とうもろこし、バナナ、ケナフ、パーム、ココナッツ、カシューナッツ等の殻、紙類、および藻類、等を挙げることができる。好適には、非可食であるという観点から、広葉樹、針葉樹、バガス、稲わら、とうもろこしの茎、とうもろこしの葉、パーム空果房（ＥＦＢ）、籾殻、パーム殻、ココナッツ殻、カシューナッツ殻、紙類および藻類、等が使用される。これらは単独で用いてもよいし、２種類以上を組み合わせて用いてもよい。
<Lignocellulosic substance>
The "lignocellulosic substance" used in the present invention is not particularly limited, and examples thereof include hardwood, wood represented by conifer, bamboo, sugarcane (including bagasse), rice straw, corn, banana, kenaf, palm, Shells such as coconut and cashew nuts, papers, and algae can be mentioned. Preferably, from the viewpoint of being non-edible, hardwood, conifer, bagasse, rice straw, corn stalk, corn leaf, palm empty fruit cluster (EFB), rice hull, palm husk, coconut husk, cashew nut husk, paper And algae, etc. are used. These may be used alone or in combination of two or more.
広葉樹としては、例えば、ユーカリ属；具体的には、Ｅｕｃａｌｙｐｔｕｓ ｇｌｏｂｕｌｕｓ（ユーカリ・グロブラス）、Ｅｕｃａｌｙｐｔｕｓ ｇｒａｎｄｉｓ（ユーカリ・グランディス）、Ｅｕｃａｌｙｐｔｕｓ ｕｒｏｇｒａｎｄｉｓ（ユーカリ・ユーログランディス）、Ｅｕｃａｌｙｐｔｕｓ ｐｅｌｌｉｔａ（ユーカリ・ペリータ）、Ｅｕｃａｌｙｐｔｕｓ ｂｒａｓｓｉａｎａ（ユーカリ・ブラシアーナ）およびアカシア属；具体的には、Ａｃａｃｉａ ｍｅａｒｎｓｉｉ（アカシア・メランシ）、Ａｃａｃｉａ ｍａｎｇｉｕｍ（アカシア・マンギューム）、Ａｃａｃｉａ ａｕｒｉｃｕｌｉｆｏｒｍｉｓ（アカシア・アウリカリフォルミス）等が挙げられる。
針葉樹としては、例えば、マツ属；具体的には、Ｐｉｎｕｓ ｒａｄｉａｔａ（ラジアータパイン）、Ｐｉｎｕｓ ｃａｒｉｂａｅａ（カリビアンパイン）、Ｐｉｎｕｓ ｅｌｌｉｏｔｔｉｉ（スラッシュパイン）、Ｐｉｎｕｓ ｔｈｕｎｂｅｒｇｉｉ（クロマツ）等、トガサワラ属;具体的には、Ｐｓｅｕｄｏｔｓｕｇａ ｍｅｎｚｉｅｓｉｉ（ダグラスファー）、Ｔｓｕｇａ ｈｅｔｅｒｏｐｈｙｌｌａ（ベイツガ）等、トウヒ属;具体的には、Ｐｉｃｅａ ｓｉｔｃｈｅｎｓｉｓ（シトカススプルース）、Ｐｉｃｅａ ｅｎｇｅｌｍａｎｎｉ（エンゲルマンスプルース）等、カラマツ属；具体的には、Ｌａｒｉｘ ｌｅｐｔｏｌｅｐｉｓ（カラマツ）等、その他（ヒノキ属、スギ属等）が挙げられる。
Examples of the hardwood include Eucalyptus; specifically, Eucalyptus globulus (Eucalyptus globras), Eucalyptus grandis (Eucalyptus grandis), Eucalyptus urograndis (Eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus eucalyptus) Eucalyptus brassiana) and the genus Acacia; specifically, Acacia meansiii, Acacia mangium, Acacia auriculiformis, and the like.
Examples of conifers include the genus Pinus; specifically, Pinus radiata (radiata pine), Pinus caribaea (Caribbean pine), Pinus elliottii (slash pine), Pinus thunbergii (black pine), and the like; Pseudosuga menziesii (Douglas fir), Tsuga heterophylla (Bleeding moth) and the like, spruce; specifically, Picea sitchensis (Sitka spruce), Picea engelmanni (Engelman sple; Larch) and others (the genus Cypress, the genus Cedar, etc.).
本発明において、リグノセルロース物質として木材を使用する場合は、チップの形状に加工する等、より酸加水分解処理し易い形状に加工することが好ましい。 In the present invention, when wood is used as the lignocellulosic substance, it is preferable that the wood is processed into a shape that is more easily subjected to acid hydrolysis treatment, such as processing into a chip shape.
＜酸加水分解処理＞
本発明において、「酸加水分解物」とは、リグノセルロース物質を原料に酸加水分解処理することで生成される生成物を意味する。従って、加水を行って酸加水分解を行う場合には、酸加水分解を行った処理液全体を酸加水分解物とする。
<Acid hydrolysis treatment>
In the present invention, “acid hydrolyzate” means a product produced by subjecting a lignocellulosic substance to acid hydrolysis treatment. Therefore, when acid hydrolysis is performed by adding water, the entire treatment solution subjected to acid hydrolysis is used as an acid hydrolyzate.
本発明において、酸加水分解処理としては、リグノセルロース物質を酸加水分解できる処理であればよく、特に制限されるものではない。例えば、リグノセルロース物質を硫酸、塩酸、硝酸等の無機酸を使って酸加水分解処理することもできるし、酢酸、蟻酸等の有機酸を使って酸加水分解処理することもできるし、あるいは、無機酸と有機酸を混合して処理することもできる。また、無機酸、有機酸については、外部よりリグノセルロース物質に添加することもできるし、リグノセルロース物質の分解物として生成するものをそのまま利用し、酸加水分解処理すること（「自己酸加水分解処理」ともいう）も可能である。 In the present invention, the acid hydrolysis treatment is not particularly limited as long as it is a treatment capable of acid hydrolysis of a lignocellulose substance. For example, a lignocellulose substance can be subjected to an acid hydrolysis treatment using an inorganic acid such as sulfuric acid, hydrochloric acid, and nitric acid, or can be subjected to an acid hydrolysis treatment using an organic acid such as acetic acid and formic acid, or It is also possible to mix and treat an inorganic acid and an organic acid. In addition, inorganic acids and organic acids can be added to the lignocellulose substance from the outside, or those produced as decomposed products of the lignocellulose substance can be used as they are and subjected to acid hydrolysis treatment ("auto-acid hydrolysis"). Processing).
本発明において、酸加水分解処理で用いる装置は、特に限定されるものではないが、腐食防止の観点から耐酸性の材質のものが好ましく、加えて反応条件の許容性を広げる観点から耐圧性のものが好適である。 In the present invention, the apparatus used in the acid hydrolysis treatment is not particularly limited, but is preferably an acid-resistant material from the viewpoint of corrosion prevention, and in addition, has a pressure resistance from the viewpoint of expanding the tolerance of reaction conditions. Those are preferred.
本発明において、酸加水分解処理では、必要に応じて加熱することができる。加熱方法は、蒸気等による直接加熱、ジャケット式ヒーター、コイルチューブ式ヒーター等による間接加熱でもよく、特に制限されるものではない。エネルギーを効率的に用いる観点からは、酸加水分解処理工程または前後の工程で回収した熱を用いて、加熱する方法が好ましい実施形態である。 In the present invention, in the acid hydrolysis treatment, heating can be performed if necessary. The heating method may be direct heating with steam or the like, indirect heating with a jacket type heater, a coil tube type heater, or the like, and is not particularly limited. From the viewpoint of efficient use of energy, a preferred embodiment is a method of heating using the heat recovered in the acid hydrolysis treatment step or the preceding and following steps.
本発明において、酸加水分解処理の方式は、バッチ式でも連続式でもよく、これらを組み合わせた反応形式でもよく、特に限定されるものではないが、生産性の観点からは、連続式が好ましい。 In the present invention, the method of the acid hydrolysis treatment may be a batch type or a continuous type, or may be a reaction type in which these are combined, and are not particularly limited. However, from the viewpoint of productivity, the continuous type is preferable.
本発明において、酸加水分解処理時の反応条件は、特に限定されるのもではないが、水等の溶媒の存在下で酸加水分解処理を行うことが好ましく、リグノセルロース物質に対する液比（溶媒／リグノセルロース物質、質量比）は、好ましくは０．５〜８．０、より好ましくは１．０〜４．０である。処理温度は好ましくは５〜２００℃、より好ましくは１００〜１８０℃である。処理時間は、処理温度により適宜変更でき、例えば、好ましくは１分〜８時間、より好ましくは３０分〜５時間である。 In the present invention, the reaction conditions during the acid hydrolysis treatment are not particularly limited, but the acid hydrolysis treatment is preferably performed in the presence of a solvent such as water, and the liquid ratio to the lignocellulose substance (solvent / Lignocellulose substance, mass ratio) is preferably 0.5 to 8.0, more preferably 1.0 to 4.0. The processing temperature is preferably from 5 to 200C, more preferably from 100 to 180C. The processing time can be appropriately changed depending on the processing temperature, and is, for example, preferably 1 minute to 8 hours, more preferably 30 minutes to 5 hours.
本発明において、酸加水分解物としては、例えば、リグニン分解物、セルロース分解物、ヘミセルロース分解物、およびこれらの複合体、等が挙げられる。また、本発明における酸加水分解物として、前述の分解物から派生した、有機酸やアルコール類、ジケトン類なども挙げることができる。本発明において、酸加水分解物が、リグニン分解物を含有することが好ましい。 In the present invention, examples of the acid hydrolyzate include a lignin decomposition product, a cellulose decomposition product, a hemicellulose decomposition product, and a complex thereof. Further, examples of the acid hydrolyzate in the present invention include organic acids, alcohols, and diketones derived from the above-mentioned hydrolyzate. In the present invention, the acid hydrolyzate preferably contains a lignin hydrolyzate.
リグニン分解物としては、例えば、バニリン、バニリン酸、シリンガアルデヒド、シリンガ酸、シリンガレジノール、等が挙げられる。また、リグニンの分解過程で発生する中間体や、リグニン分解物の縮合体も含まれる。
セルロース分解物およびヘミセルロース分解物としては、例えば、キシロース、アラビノース、グルコース、ガラクトース、マンノース等の単糖や、キシロオリゴ糖、セロオリゴ糖、ガラクトオリゴ糖、等のオリゴ糖が挙げられる。前記オリゴ糖にはアラビノース、マンノース、グルコース、キシロース、グルクロン酸、４−Ｏ−メチルグルクロン酸等が側鎖として付加したオリゴ糖も含まれる。例えば、キシロオリゴ糖に４−Ｏ−メチルグルクロン酸が側鎖として付加した場合には、酸性キシロオリゴ糖と呼ばれる。
Examples of the lignin decomposition product include vanillin, vanillic acid, syringaldehyde, syringic acid, and syringaresinol. In addition, it also includes intermediates generated in the process of lignin decomposition and condensates of lignin decomposition products.
Examples of the cellulose decomposition product and the hemicellulose decomposition product include monosaccharides such as xylose, arabinose, glucose, galactose, and mannose, and oligosaccharides such as xylo-oligosaccharide, cellooligosaccharide, and galacto-oligosaccharide. The oligosaccharides include oligosaccharides to which arabinose, mannose, glucose, xylose, glucuronic acid, 4-O-methylglucuronic acid, etc. are added as side chains. For example, when 4-O-methylglucuronic acid is added as a side chain to xylo-oligosaccharide, it is called acidic xylo-oligosaccharide.
［凝集抑制剤の用途］
本発明の一つの態様によれば、本発明の凝集抑制剤はリグノセルロース物質を原料とする酸加水分解物の凝集を抑制できることから、酸加水分解処理液から酸加水分解物を効率的に取り出し、有効利用するのに適している。また、酸加水分解物を原料とした有価物の製造にも適しており、有価物の製造収率が上がるという利点がある。具体的には、酸加水分解物であるリグニン分解物、セルロース分解物およびヘミセルロース分解物が凝集せずに分散されたままの状態で維持でき、取り出すことが可能であるばかりでなく、このような分解物の混合状態のまま、酸性キシロオリゴ糖を効率的に製造できるという利点がある。同様に、リグノセルロース物質からの糖類および糖化発酵物（例えば、エタノールや有機酸）の製造、リグニン分解物からのフェノール化合物等の芳香族系工業原料の製造、製紙用パルプおよび溶解パルプの製造、フルフラールおよびフルフラール誘導体の製造等も効率的に行うことができる。
[Use of aggregation inhibitor]
According to one embodiment of the present invention, since the aggregation inhibitor of the present invention can suppress aggregation of an acid hydrolyzate using a lignocellulose substance as a raw material, an acid hydrolyzate is efficiently removed from an acid hydrolysis treatment liquid. , Suitable for effective use. It is also suitable for the production of valuables using an acid hydrolyzate as a raw material, and has the advantage of increasing the production yield of valuables. Specifically, the lignin hydrolyzate, which is an acid hydrolyzate, the cellulose hydrolyzate and the hemicellulose hydrolyzate can be maintained in a state of being dispersed without agglomeration and can be taken out. There is an advantage that acidic xylo-oligosaccharides can be efficiently produced in a mixed state of the decomposition products. Similarly, production of saccharides and saccharified fermented products (eg, ethanol and organic acids) from lignocellulosic substances, production of aromatic industrial raw materials such as phenolic compounds from lignin decomposition products, production of paper pulp and dissolved pulp, Production of furfural and furfural derivatives can also be performed efficiently.
以下、本発明の方法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。 Hereinafter, the method of the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
［凝集抑制剤］
ポリマー１〜５は常法に従って合成し、有効成分量が４０質量％になるように水で希釈した。
ポリマー１（成分Ａ）：ナフタレンスルホン酸ホルマリン縮合物ナトリウム塩（重量平均分子量：１１５００）
ポリマー２（成分Ａ）：ナフタレンスルホン酸ホルマリン縮合物ナトリウム塩（重量平均分子量：２８００）
ポリマー３（成分Ａ）：ナフタレンスルホン酸ホルマリン縮合物ナトリウム塩（重量平均分子量：２２０００）
ポリマー４（成分Ａ）：ナフタレンスルホン酸ホルマリン縮合物ナトリウム塩（重量平均分子量：５２００）
ポリマー５（非成分Ａ）：ポリアクリル酸ナトリウム（重量平均分子量：２００００）
界面活性剤１（非成分Ａ）：ドデシルベンゼンスルホン酸ナトリウム（分子量：３４８）（花王株式会社製「ネオペレックスＧ−２５（有効成分量２５質量％）」）
モノマー１（非成分Ａ）：ナフタレンスルホン酸ナトリウム（分子量：２３０）（東京化成工業株式会社製「１−ナフタレンスルホン酸ナトリウム」）
[Aggregation inhibitor]
Polymers 1 to 5 were synthesized according to a conventional method, and diluted with water so that the amount of the active ingredient became 40% by mass.
Polymer 1 (component A): sodium salt of naphthalenesulfonic acid formalin condensate (weight average molecular weight: 11500)
Polymer 2 (component A): sodium salt of formalin condensate of naphthalenesulfonic acid (weight average molecular weight: 2800)
Polymer 3 (Component A): Naphthalenesulfonic acid formalin condensate sodium salt (weight average molecular weight: 22000)
Polymer 4 (Component A): sodium salt of formalin condensate of naphthalenesulfonic acid (weight average molecular weight: 5200)
Polymer 5 (non-component A): sodium polyacrylate (weight average molecular weight: 20,000)
Surfactant 1 (non-component A): sodium dodecylbenzenesulfonate (molecular weight: 348) ("Neoperex G-25 (active ingredient content: 25% by mass)" manufactured by Kao Corporation)
Monomer 1 (non-component A): sodium naphthalene sulfonate (molecular weight: 230) ("1-sodium naphthalene sulfonate" manufactured by Tokyo Chemical Industry Co., Ltd.)
［重量平均分子量の測定］
ポリマー１〜５の重量平均分子量は、ゲルパーミエーションクロマトグラフィー（以下「ＧＰＣ」ともいう）法を用いて下記条件で測定した。
＜ＧＰＣ条件＞
カラム：Ｇ４０００ＰＷＸＬ＋Ｇ２５００ＰＷＸＬ（東ソー株式会社製）
溶離液：０．２Ｍリン酸バッファー／ＣＨ３ＣＮ＝９／１（体積比）
流量：１．０ｍＬ／ｍｉｎ
カラム温度：４０℃
検出：ＲＩ
サンプルサイズ：０．５ｍｇ／ｍＬ
標準物質：ポリエチレングリコール換算
[Measurement of weight average molecular weight]
The weight average molecular weights of Polymers 1 to 5 were measured using gel permeation chromatography (hereinafter also referred to as “GPC”) under the following conditions.
<GPC conditions>
Column: G4000PWXL + G2500PWXL (Tosoh Corporation)
Eluent: 0.2 M phosphate buffer / CH 3 CN = 9/1 (volume ratio)
Flow rate: 1.0 mL / min
Column temperature: 40 ° C
Detection: RI
Sample size: 0.5mg / mL
Standard substance: polyethylene glycol equivalent
［実施例１〜７および比較例１〜３：酸加水分解物の分散性試験］
＜実施例１＞
リグノセルロース物質として広葉樹である２〜８ｍｍ厚のユーカリ材を用い、ユーカリ材に対して液比（質量比）３になるように加水し、処理温度１５５℃、処理時間３時間で自己酸加水分解処理した。得られた酸加水分解物（酸加水分解処理液）に含まれる成分として、リグニン分解物、糖類、フルフラール類、その他成分（水、有機酸類、アルコール類、ジケトン類等）を測定した。酸加水分解物成分は、それぞれ、リグニン分解物が１．００質量％、糖類が１．６３質量％、フルフラール類が０．２０質量％、その他が９７．１７質量％であった。次に、得られた酸加水分解物（酸加水分解処理液）の総量に対して、ポリマー１を有効成分量が０．１質量％となるように添加し、撹拌棒を用いて１分間撹拌を行なった後に、分散性評価を行った。表１に分散性評価の結果を示す。
[Examples 1 to 7 and Comparative Examples 1 to 3: Dispersibility test of acid hydrolyzate]
<Example 1>
Eucalyptus wood, a hardwood, having a thickness of 2 to 8 mm is used as a lignocellulose substance, and water is added to the eucalyptus wood so as to have a liquid ratio (mass ratio) of 3, and a self-acid hydrolysis is performed at a processing temperature of 155 ° C. and a processing time of 3 hours. Processed. As components contained in the obtained acid hydrolyzate (acid hydrolyzed liquid), lignin hydrolyzate, saccharides, furfurals, and other components (water, organic acids, alcohols, diketones, etc.) were measured. The acid hydrolyzate component contained 1.00% by mass of lignin hydrolyzate, 1.63% by mass of saccharides, 0.20% by mass of furfural, and 97.17% by mass of others. Next, Polymer 1 was added to the total amount of the obtained acid hydrolyzate (acid hydrolysis treatment liquid) so that the amount of the active ingredient was 0.1% by mass, and the mixture was stirred for 1 minute using a stirring rod. , And then the dispersibility was evaluated. Table 1 shows the results of the dispersibility evaluation.
（成分測定方法）
リグニン分解物は、ＯＰＴＩＭＡ社製分光光度計（ＳＰ−３０００ｎａｎｏ）を用い、波長２８０ｎｍの吸光度で測定し定量した。なお、吸光係数は、１１０Ｌ／ｇ／ｃｍを用いた。
糖類は、ＤＩＯＮＥＸ社製糖分析システム（ＩＣＳ５０００）を用いて、定量した。カラムはＣａｒｂｏ Ｐａｃ ＰＡ−１ （Ｔｈｅｒｍｏ製）を用い、移動層には２０ｍＭ ＮａＯＨ溶液を用い、パルスドアンペロメトリック検出器で検出した。各単糖の標品を用い、検量線を作成して含有量を求めた。また、オリゴ糖を算出する場合には、酸加水分解物を含んだ溶液の最終濃度が４質量％となるように硫酸を添加し、１２０℃で１時間の条件で酸加水分解を行った後、単糖の定量を行ない、酸加水分解前の単糖の含有量を差し引いた値をオリゴ糖の含有量として算出した。
フルフラール類は、Ｗａｔｅｒｓ社製ＨＰＬＣシステムを用いて定量した。カラムは、Ａｍｉｎｅｘ ＨＰＸ８７−Ｈ（Ｂｉｏ−Ｒａｄ社製）を用い、移動層には５ｍＭ硫酸を用い、ＰＤＡ検出器で検出した。フルフラール類の標品を用い、検量線を作成して、フルフラール類の含有量を求めた。
(Method of measuring components)
The lignin decomposition product was measured and quantified using a spectrophotometer (SP-3000nano) manufactured by OPTIMA at an absorbance at a wavelength of 280 nm. The absorption coefficient used was 110 L / g / cm.
The saccharides were quantified using a sugar analysis system (ICS5000) manufactured by DIONEX. The column used was Carbo Pac PA-1 (manufactured by Thermo), the mobile phase was a 20 mM NaOH solution, and detection was performed with a pulsed amperometric detector. Using a standard of each monosaccharide, a calibration curve was prepared to determine the content. When calculating the oligosaccharide, sulfuric acid was added so that the final concentration of the solution containing the acid hydrolyzate was 4% by mass, and the acid hydrolysis was performed at 120 ° C. for 1 hour. Then, the monosaccharide was quantified, and the value obtained by subtracting the monosaccharide content before acid hydrolysis was calculated as the oligosaccharide content.
Furfurals were quantified using a Waters HPLC system. Aminex HPX87-H (manufactured by Bio-Rad) was used for the column, and 5 mM sulfuric acid was used for the mobile phase, and detection was performed using a PDA detector. Using a sample of furfural, a calibration curve was prepared to determine the content of furfural.
（分散性評価）
分散性については、酸加水分解物が凝集せずに分散している場合には液の透明性が向上することから、目視にて透明度を評価すると共に、粒径を株式会社堀場製作所製レーザ回折／散乱式粒度分布測定装置ＬＡ−９２０によって測定し、算術平均径で評価した。
(Dispersibility evaluation)
Regarding the dispersibility, when the acid hydrolyzate is dispersed without agglomeration, the transparency of the liquid is improved. Therefore, the transparency is visually evaluated, and the particle size is determined by laser diffraction manufactured by Horiba, Ltd. / Measured by a scattering particle size distribution analyzer LA-920, and evaluated by the arithmetic mean diameter.
＜実施例２＞
実施例１において、ポリマー１の添加量を有効成分量として１．０質量％に変更すること以外は実施例１と同様の操作を行なった。表１に結果を示す。
<Example 2>
In the same manner as in Example 1, except that the amount of the polymer 1 added was changed to 1.0% by mass as the amount of the active ingredient, the same operation as in Example 1 was performed. Table 1 shows the results.
＜実施例３＞
実施例１において、ポリマー１の添加量を有効成分量として３．０質量％に変更すること以外は実施例１と同様の操作を行なった。表１に結果を示す。
<Example 3>
The same operation as in Example 1 was performed, except that the amount of Polymer 1 was changed to 3.0% by mass as the amount of the active ingredient. Table 1 shows the results.
＜実施例４＞
実施例１において、酸加水分解処理前に、ユーカリ材に対し酢酸を１．０質量％添加すること以外は実施例１と同様の操作を行なった。酸加水分解物成分は、それぞれ、リグニン分解物が１．０９質量％、糖類が１．９３質量％、フルフラール類が０．３０質量％、その他が９６．６８質量％であった。表１に結果を示す。
<Example 4>
The same operation as in Example 1 was performed, except that acetic acid was added to the eucalyptus wood in an amount of 1.0% by mass before the acid hydrolysis treatment. The acid hydrolyzate component contained 1.09% by mass of the lignin hydrolyzate, 1.93% by mass of the saccharide, 0.30% by mass of the furfural, and 96.68% by mass of the others. Table 1 shows the results.
＜実施例５＞
実施例１において、酸加水分解処理前に、ユーカリ材に対し硫酸を１．０質量％添加すること以外は実施例１と同様の操作を行なった。酸加水分解物成分は、それぞれ、リグニン分解物が１．１８質量％、糖類が２．０１質量％、フルフラール類が０．４７質量％、その他が９６．３４質量％であった。表１に結果を示す。
<Example 5>
In the same manner as in Example 1, except that sulfuric acid was added to the eucalyptus wood in an amount of 1.0% by mass before the acid hydrolysis treatment. The acid hydrolyzate component contained 1.18% by mass of a lignin hydrolyzate, 2.01% by mass of saccharides, 0.47% by mass of furfural, and 96.34% by mass of others. Table 1 shows the results.
＜実施例６＞
実施例１において、凝集抑制剤を添加する操作を、酸加水分解処理前（具体的には、ユーカリ材に添加する）に変更すること以外は実施例１と同様の操作を行なった。酸加水分解物成分は、それぞれ、リグニン分解物が１．０４質量％、糖類が１．９０質量％、フルフラール類が０．２４質量％、その他が９６．８２質量％であった。表１に結果を示す。
<Example 6>
In Example 1, the same operation as in Example 1 was performed except that the operation of adding the aggregation inhibitor was changed before the acid hydrolysis treatment (specifically, added to the eucalyptus material). The acid hydrolyzate component contained 1.04% by mass of the lignin hydrolyzate, 1.90% by mass of the saccharide, 0.24% by mass of the furfural, and 96.82% by mass of the others. Table 1 shows the results.
＜実施例７＞
実施例１において、リグノセルロース物質として、ユーカリ材の代わりに針葉樹であるラジアータパイン材を使用すること以外は実施例１と同様の操作を行なった。酸加水分解物成分は、それぞれ、リグニン分解物が０．４２質量％、糖類が３．７０質量％、フルフラール類が０．０７質量％、その他が９５．８１質量％であった。表１に結果を示す。
<Example 7>
In Example 1, the same operation as in Example 1 was performed except that radiata pine, which is softwood, was used instead of eucalyptus as the lignocellulosic material. The acid hydrolyzate component contained 0.42% by mass of a lignin hydrolyzate, 3.70% by mass of saccharides, 0.07% by mass of furfural, and 95.81% by mass of others. Table 1 shows the results.
＜比較例１＞
実施例１において、ポリマー１を添加しないこと以外は、実施例１と同様の操作を行なった。表１に結果を示す。
<Comparative Example 1>
The same operation as in Example 1 was performed except that Polymer 1 was not added. Table 1 shows the results.
＜比較例２＞
実施例１において、ポリマー１をポリマー５に変更すること以外は、実施例１と同様の操作を行なった。表１に結果を示す。
<Comparative Example 2>
The same operation as in Example 1 was performed, except that Polymer 1 was changed to Polymer 5 in Example 1. Table 1 shows the results.
＜比較例３＞
実施例１において、リグノセルロース物質として、ユーカリ材の代わりにラジアータパイン材を使用すること、およびポリマー１を添加しないこと以外は、実施例１と同様の操作を行なった。表１に結果を示す。
<Comparative Example 3>
In Example 1, the same operation as in Example 1 was performed, except that a radiator pine material was used instead of the eucalyptus material as the lignocellulose material, and no polymer 1 was added. Table 1 shows the results.
表１に示すように、有効成分として、芳香族スルホン酸基を有するポリマーを含む凝集抑制剤を添加することにより、酸加水分解物の液の透明性が上がり、かつ、液中の粒子が小径化し、酸加水分解物の凝集が抑制されたことがわかる。 As shown in Table 1, by adding a coagulation inhibitor containing a polymer having an aromatic sulfonic acid group as an active ingredient, the transparency of the acid hydrolyzate is increased, and the particles in the liquid have a small diameter. It turns out that aggregation of the acid hydrolyzate was suppressed.
［実施例８および比較例４：酸性キシロオリゴ糖の製造］
実施例２で示した凝集抑制剤を添加した酸加水分解物（酸加水分解処理液）を用い、特許６２２５３２１号公報の実施例１に記載の方法に従って酸性キシロオリゴ糖（実施例８）を製造した。同様にして、比較例１の凝集抑制剤を添加していない酸加水分解物を用いて酸性キシロオリゴ糖（比較例４）を製造した。
[Example 8 and Comparative Example 4: Production of acidic xylo-oligosaccharide]
An acidic xylo-oligosaccharide (Example 8) was produced according to the method described in Example 1 of Japanese Patent No. 6225321 using the acid hydrolyzate (acid hydrolysis treatment liquid) to which the aggregation inhibitor shown in Example 2 was added. . Similarly, acidic xylo-oligosaccharides (Comparative Example 4) were produced using the acid hydrolyzate of Comparative Example 1 to which the aggregation inhibitor was not added.
実施例８の凝集抑制剤を添加した酸加水分解物からの酸性キシロオリゴ糖の収率は、比較例４の凝集抑制剤を添加しなかった酸加水分解物からの酸性キシロオリゴ糖の収率より１０％以上有意に高かった。このように、凝集抑制剤を添加することで凝集が抑制されることにより、酸加水分解物を原料とした有価物の生産効率が向上することを確認できた。 The yield of acidic xylo-oligosaccharides from the acid hydrolyzate to which the aggregation inhibitor of Example 8 was added was 10 times higher than the yield of acidic xylo-oligosaccharides from the acid hydrolyzate of Comparative Example 4 to which the aggregation inhibitor was not added. % Or more. As described above, it was confirmed that the suppression of aggregation by adding the aggregation inhibitor improves the production efficiency of valuable resources using an acid hydrolyzate as a raw material.
［実施例９〜１４および比較例５〜８：濾過性］
＜実施例９＞
実施例１に示す方法で得た酸加水分解物を１か月間常温で静置し、処理液を得た。ラボランスクリュー管瓶（アズワン株式会社製、Ｎｏ．７、５０ｍＬ）に、よく撹拌した処理液１６ｇ、処理液に対してポリマー１を有効成分量で０．１質量％添加し、水を加えて総量１６．５ｇとした。蓋を閉め、上下に３０分間浸透し、メンブレンフィルター（東洋濾紙株式会社製、セルロース混合エステルタイプ、孔径５．０μｍ、寸法４７φｍｍ）をフィルターに用いて吸引濾過し、フィルター表面を水洗した後、乾燥し、フィルターの質量を測定した。濾過前後の質量差からフィルターを通過しなかった酸加水分解物（濾過残）の質量を算出した。
[Examples 9 to 14 and Comparative Examples 5 to 8: Filterability]
<Example 9>
The acid hydrolyzate obtained by the method shown in Example 1 was allowed to stand at room temperature for one month to obtain a treatment liquid. To a Lablan screw tube bottle (manufactured by AS ONE Corporation, No. 7, 50 mL), 16 g of a well-stirred treatment liquid, 0.1% by mass of Polymer 1 in an amount of an active ingredient based on the treatment liquid, and water were added. The total amount was 16.5 g. Close the lid, infiltrate up and down for 30 minutes, filter by suction using a membrane filter (manufactured by Toyo Roshi Kaisha, cellulose mixed ester type, pore size: 5.0 μm, size: 47 mm), wash the filter surface with water, and then dry. Then, the mass of the filter was measured. The mass of the acid hydrolyzate that did not pass through the filter (filtration residue) was calculated from the difference in mass before and after filtration.
＜実施例１０〜１４および比較例５〜８＞
実施例１０〜１４および比較例５〜８として、実施例９と同じ処理液を用い、表２に示す各凝集抑制剤および添加量（有効成分量換算）にて、実施例９と同様の方法で濾過性を確認した。なお、凝集抑制剤を用いない比較例５の結果に基づき、下記式にて通過率を算出した。
通過率（％）＝（Ａ−Ｓ）÷Ａ×１００
Ａ：比較例５の濾過残（ｇ）
Ｓ：各凝集抑制剤の濾過残（ｇ）
<Examples 10 to 14 and Comparative Examples 5 to 8>
As Examples 10 to 14 and Comparative Examples 5 to 8, the same treatment solution as in Example 9 was used, and the same method as in Example 9 was performed using the respective coagulation inhibitors and the added amounts (in terms of the amount of active ingredient) shown in Table 2. Was used to confirm the filterability. In addition, based on the result of the comparative example 5 which does not use an aggregation inhibitor, the passing rate was calculated by the following formula.
Passage rate (%) = (A−S) ÷ A × 100
A: Filtration residue (g) of Comparative Example 5
S: Filtration residue (g) of each aggregation inhibitor
表２に示すように、有効成分として、芳香族スルホン酸基を有するポリマーを含む凝集抑制剤を添加することにより、酸加水分解物の凝集が抑制され、濾過残が顕著に低下し、高い濾過性が得られた。 As shown in Table 2, by adding an aggregation inhibitor containing a polymer having an aromatic sulfonic acid group as an active ingredient, aggregation of an acid hydrolyzate is suppressed, filtration residue is significantly reduced, and high filtration is achieved. Sex was obtained.
本発明の凝集抑制剤によれば、リグノセルロース物質を原料とする酸加水分解物の凝集が顕著に抑制される。本発明の凝集抑制剤を使用することにより、リグノセルロース物質を原料とする酸加水分解物や、これを原料とする各種の反応において、収率の向上等に寄与することが期待される。 ADVANTAGE OF THE INVENTION According to the aggregation inhibitor of this invention, aggregation of the acid hydrolyzate which uses a lignocellulose substance as a raw material is suppressed remarkably. The use of the aggregation inhibitor of the present invention is expected to contribute to an improvement in yield and the like in an acid hydrolyzate using a lignocellulose substance as a raw material and various reactions using the same as a raw material.
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