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JP4309196B2 - Simulated moving bed chromatographic separation method - Google Patents

Simulated moving bed chromatographic separation method Download PDF

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JP4309196B2
JP4309196B2 JP2003279997A JP2003279997A JP4309196B2 JP 4309196 B2 JP4309196 B2 JP 4309196B2 JP 2003279997 A JP2003279997 A JP 2003279997A JP 2003279997 A JP2003279997 A JP 2003279997A JP 4309196 B2 JP4309196 B2 JP 4309196B2
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大介 種田
敏樹 宮崎
義基 上野
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    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13B—PRODUCTION OF SUCROSE; APPARATUS SPECIALLY ADAPTED THEREFOR
    • C13B20/00—Purification of sugar juices
    • C13B20/14—Purification of sugar juices using ion-exchange materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
    • B01D15/08—Selective adsorption, e.g. chromatography
    • B01D15/10—Selective adsorption, e.g. chromatography characterised by constructional or operational features
    • B01D15/18—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns
    • B01D15/1814—Selective adsorption, e.g. chromatography characterised by constructional or operational features relating to flow patterns recycling of the fraction to be distributed
    • B01D15/1821—Simulated moving beds
    • B01D15/185—Simulated moving beds characterized by the components to be separated
    • C—CHEMISTRY; METALLURGY
    • C13—SUGAR INDUSTRY
    • C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
    • C13K1/00—Glucose; Glucose-containing syrups
    • C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
    • C13K1/04—Purifying

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Description

この発明は、擬似移動層クロマト分離によって分離されるエクストラクトの再利用により、資源の効率的な利用、プロセス全体のエネルギーの低減を計るものである。例えば、木材、紙、繊維、食品などのセルロースまたはヘミセルロースを含む物質（以下、バイオマスと言う。）を硫酸などの酸によって糖化し、グルコースなどの糖を回収する方法において、糖化工程に用いられる硫酸などの酸の回収のためのエネルギーコストの低減を図ったものである。   The present invention aims to efficiently use resources and reduce the energy of the entire process by reusing extracts separated by simulated moving bed chromatographic separation. For example, sulfuric acid used in the saccharification step in a method of saccharifying a substance containing cellulose or hemicellulose (hereinafter referred to as biomass) such as wood, paper, fiber, food, etc. with an acid such as sulfuric acid and recovering sugar such as glucose. This is intended to reduce the energy cost for recovering the acid.

バイオマスを硫酸などの強酸で加水分解して、糖と酸を含む加水分解液とし、この加水分解液からグルコース、キシロースなどの糖を回収する技術は、周知である。
特表平１１−５０６９３４号公報や特表２００１−５１１４１８号公報には、上記加水分解液を擬似移動層クロマト分離装置に送り、ここで糖を主体とする流出液と酸を主体とする流出液とに分離することが開示されている。 A technique for hydrolyzing biomass with a strong acid such as sulfuric acid to obtain a hydrolyzed solution containing sugar and acid, and recovering sugars such as glucose and xylose from this hydrolyzed solution is well known.
In Japanese Patent Publication No. 11-506934 and Japanese Patent Publication No. 2001-511418, the above hydrolyzate is sent to a simulated moving bed chromatographic separation apparatus, where an effluent mainly composed of sugar and an effluent mainly composed of acid. It is disclosed that they are separated.

ここで使用される擬似移動層クロマト分離装置とは、例えば図６に示されるように、陰イオン交換樹脂などの充填材を充填した複数のカラムＣ１、Ｃ２・・・Ｃ８を、直列に、かつ閉回路として管路で接続したものである。この擬似移動層クロマト分離装置の初段のカラムＣ１に加水分解液を注入して、移動速度の速い糖を主体とする流出液（以下、ラフィネートと言う）を２段目のカラムＣ２から導出し、移動速度の遅い硫酸を主体とする流出液（以下、エクストラクトと言う）を溶離水の注入によって６段目のカラムＣ６から導出するもので、この移動速度の差によってラフィネートとエクストラクトとに分離するものである。   The simulated moving bed chromatographic separation apparatus used here is, for example, as shown in FIG. 6, a plurality of columns C1, C2,... C8 filled with a filler such as an anion exchange resin, It is connected by a pipeline as a closed circuit. The hydrolyzed liquid is injected into the first column C1 of the simulated moving bed chromatographic separation apparatus, and an effluent mainly composed of sugar having a high moving speed (hereinafter referred to as raffinate) is derived from the second column C2. An effluent mainly composed of sulfuric acid with a slow moving speed (hereinafter referred to as “extract”) is derived from the sixth column C6 by injection of elution water, and is separated into raffinate and extract by the difference in moving speed. To do.

そして、上記先行発明では、擬似移動層クロマト分離装置で分離されたエクストラクトを全量硫酸濃縮装置９に送って、エクストラクト中の硫酸濃度を高めたのち、これをバイオマスの糖化工程用の硫酸として再利用している。
しかしながら、エクストラクトには、擬似移動層クロマト分離装置での溶離水が含まれるので、エクストラクト中の硫酸濃度は糖化工程で使用される硫酸濃度に比べて大幅に低下しており、硫酸濃縮工程での濃縮に膨大な熱エネルギーが必要となる欠点がある。
特表平１１−５０６９３４号公報 特表２００１−５１１４１８号公報 And in the said prior invention, after sending the extract isolate | separated with the pseudo | simulation moving bed chromatographic separation apparatus to the sulfuric acid concentration apparatus 9 whole quantity, and raising the sulfuric acid concentration in an extract, this is made into sulfuric acid for the saccharification process of biomass. It is reused.
However, the extract contains the elution water from the simulated moving bed chromatographic separation device, so the sulfuric acid concentration in the extract is significantly lower than the sulfuric acid concentration used in the saccharification step, and the sulfuric acid concentration step There is a disadvantage that enormous amount of heat energy is required for concentration.
Japanese National Patent Publication No. 11-506934 Special table 2001-511418 gazette

本発明における課題は、擬似移動層クロマト分離方法において、資源を効率的に利用し、さらにはプロセス全体のエネルギーの低減、エネルギーコストを低減化することにある。   An object of the present invention is to efficiently use resources in the simulated moving bed chromatographic separation method, and further to reduce energy of the entire process and energy cost.

かかる課題を解決するため、
請求項１にかかる発明は、流入液が、セルロースおよび／またはヘミセルロースを含む原料を酸により糖化する糖化工程から排出される酸と糖を含み、
この流入液を、糖を分画とする成分と酸を分画とする成分とに分離する擬似移動層クロマト分離方法であって、
酸を分画とする成分を高濃度分画液Ａと低濃度分画液Ｂとに分画することを特徴とする擬似移動層クロマト分離方法である。 To solve this problem,
The invention according to claim 1 includes an acid and a sugar discharged from a saccharification process in which the inflow liquid saccharifies the raw material containing cellulose and / or hemicellulose with an acid,
A simulated moving bed chromatographic separation method for separating the influent into a component containing a sugar fraction and a component containing an acid fraction,
A pseudo moving bed chromatographic separation method comprising fractionating an acid fraction into a high concentration fraction A and a low concentration fraction B.

請求項２にかかる発明は、分画された酸のうち高濃度分画液Ａが、原料の糖化工程で再利用されることを特徴とする請求項１記載の擬似移動層クロマト分離方法である。
請求項３にかかる発明は、分画された酸のうち低濃度分画液Ｂが、擬似移動層クロマト分離装置の溶離水および／または原料の糖化工程で再利用されることを特徴とする請求項１または２記載の擬似移動層クロマト分離方法である。 The invention according to claim 2 is the simulated moving bed chromatographic separation method according to claim 1, wherein the high-concentration fraction A of the fractionated acid is reused in the raw material saccharification step. .
The invention according to claim 3 is characterized in that the low-concentration fraction B of the fractionated acid is reused in the elution water and / or raw material saccharification step of the simulated moving bed chromatographic separation device. Item 3. The simulated moving bed chromatographic separation method according to Item 1 or 2.

請求項４にかかる発明は、酸が硫酸であることを特徴とする請求項１ないし３のいずれかに記載の擬似移動層クロマト分離方法である。
請求項５にかかる発明は、高濃度分画液Ａの硫酸濃度が２０〜３５ｗｔ％であり、低濃度分画液Ｂの硫酸濃度が１〜６ｗｔ％であることを特徴とする請求項４記載の擬似移動層クロマト分離方法である。 The invention according to claim 4 is the simulated moving bed chromatographic separation method according to any one of claims 1 to 3, wherein the acid is sulfuric acid.
The invention according to claim 5 is characterized in that the high concentration fraction A has a sulfuric acid concentration of 20 to 35 wt%, and the low concentration fraction B has a sulfuric acid concentration of 1 to 6 wt%. This is a pseudo moving bed chromatographic separation method.

請求項６にかかる発明は、セルロースおよび／またはヘミセルロースを含む原料を酸により糖化する糖化装置と、
この糖化装置からの酸と糖を含む液を流入し、糖を分画とする成分と酸を分画とする成分とに分離する擬似移動層クロマト分離装置本体と、
この擬似移動層クロマト分離装置本体から分離された酸を分画とする成分を、酸濃度によって高濃度分画液Ａと低濃度分画液Ｂとに分画する分画装置を備えたことを特徴とする糖化処理装置である。 The invention according to claim 6 is a saccharification apparatus for saccharifying a raw material containing cellulose and / or hemicellulose with an acid;
A simulated moving bed chromatographic separation apparatus main body that flows into the liquid containing acid and sugar from the saccharification apparatus and separates into a component that separates sugar and a component that separates acid.
A fractionation device for fractionating the component separated from the pseudo moving bed chromatographic separation apparatus into a high concentration fraction A and a low concentration fraction B according to the acid concentration; A saccharification treatment apparatus is characterized.

請求項７にかかる発明は、高濃度分画液Ａを濃縮する濃縮装置が設けられ、この濃縮装置で濃縮された酸が糖化装置に送られ、再利用されるようになっていることを特徴とする請求項６記載の糖化処理装置である。   The invention according to claim 7 is provided with a concentrating device for concentrating the high-concentration fraction A, and the acid concentrated by the concentrating device is sent to the saccharification device and reused. It is a saccharification processing apparatus of Claim 6.

請求項８にかかる発明は、低濃度分画液Ｂが擬似移動層クロマト分離装置に送られ、その溶離水として再利用されるようになっていることを特徴とする請求項６記載の糖化処理装置である。
請求項９にかかる発明は、低濃度分画液Ｂが糖化装置に送られ、再利用されるようになっていることを特徴とする請求項６記載の糖化処理装置である。 The invention according to claim 8 is the saccharification treatment according to claim 6, wherein the low concentration fraction B is sent to the simulated moving bed chromatographic separation apparatus and reused as the elution water. Device.
The invention according to claim 9 is the saccharification apparatus according to claim 6, wherein the low-concentration fraction B is sent to the saccharification apparatus and reused.

本発明によれば、酸を分画とする成分を、酸濃度が高い分画液Ａと、酸濃度が低い分画液Ｂとに分画することで、酸濃度の高い分画液Ａを回収でき、これの酸を濃縮することで濃縮に要する熱エネルギーを少なくすることができる。また、酸濃度が低い分画液Ｂは、擬似移動層クロマト分離装置の溶離水や加水分解用水として再利用することができ、無駄になることがない。   According to the present invention, the fraction A having a high acid concentration is obtained by fractionating the component having an acid fraction into a fraction A having a high acid concentration and a fraction B having a low acid concentration. The heat energy required for concentration can be reduced by concentrating the acid. In addition, the fraction B having a low acid concentration can be reused as elution water or hydrolysis water for the simulated moving bed chromatographic separation apparatus, and is not wasted.

図１は、本発明の糖化処理装置の一例を示すもので、ここでは加水分解に硫酸を使用した例を示す。この例での糖化処理装置は、糖化装置と擬似移動層クロマト分離装置と硫酸濃縮装置から概略構成されている。
糖化装置は、バイオマス中のセルロース、ヘミセルロースを非晶質・可溶化する非晶質化装置１と、これを硫酸で加水分解する加水分解装置２と、加水分解された溶液から固形分を固液分離する固液分離装置３と、固液分離された固形分を洗浄処理する洗浄装置４とから構成され、糖化工程とは、これら装置による一連のプロセスを言う。
また、擬似移動層クロマト分離装置は、糖化工程で得られた酸と糖を含む流入液をラフィネートとエクストラクトに分離する擬似移動層クロマト分離装置本体５と、この装置本体５からのエクストラクトをエクストラクト濃度によって高濃度分画液Ａと低濃度分画液Ｂとに分画する分画装置２１から構成されている。 FIG. 1 shows an example of a saccharification treatment apparatus according to the present invention. Here, an example in which sulfuric acid is used for hydrolysis is shown. The saccharification treatment apparatus in this example is roughly composed of a saccharification apparatus, a simulated moving bed chromatographic separation apparatus, and a sulfuric acid concentration apparatus.
The saccharification apparatus comprises an amorphization apparatus 1 for amorphizing and solubilizing cellulose and hemicellulose in biomass, a hydrolysis apparatus 2 for hydrolyzing this with sulfuric acid, and solids from the hydrolyzed solution. The saccharification step refers to a series of processes by these devices. The saccharification step is composed of a solid-liquid separation device 3 for separation and a washing device 4 for washing the solid content separated by solid-liquid.
Further, the simulated moving bed chromatographic separation apparatus includes a simulated moving bed chromatographic separation apparatus main body 5 that separates the influent containing acid and sugar obtained in the saccharification step into raffinate and an extract, and extracts from the apparatus main body 5. It comprises a fractionation device 21 that fractionates a high-concentration fraction A and a low-concentration fraction B according to the extract concentration.

以下、この糖化処理装置による処理方法の一例について説明する。
まず、原料となるバイオマスを用意する。このバイオマスとしては、紙、木材、建材、草、わら、天然繊維、食品などのセルロースまたはヘミセルロースを含む物質が用いられ、これらは古紙、廃木材、廃建材、残飯などの産業廃棄物として排出されたものも使用できる。このバイオマスは、切断、粉砕されて適当な大きさとされ、必要に応じて水洗などによって異物を除去したものが好ましい。 Hereinafter, an example of the processing method by this saccharification processing apparatus will be described.
First, biomass as a raw material is prepared. As this biomass, substances containing cellulose or hemicellulose, such as paper, wood, building materials, grass, straw, natural fibers, foods, etc., are used, and these are discharged as industrial waste such as waste paper, waste wood, waste building materials, and leftover food. Can also be used. This biomass is preferably cut and pulverized to have an appropriate size, and foreign substances are removed by washing or the like as necessary.

このバイオマスは、まず非晶質化装置１に送られ、濃度５０〜８０ｗｔ％の硫酸と、温度２０〜７０℃の条件で接触せしめられ、セルロースまたはヘミセルロースの分子間結合が解離され、非晶質・可溶化される。この非晶質・可溶化により、次工程でのセルロースまたヘミセルロースの加水分解が容易に進行するようになされる。
この非晶質・可溶化工程を経た高粘度のゲル状の反応物は、加水分解装置２に送られ、別途供給される加水分解用水により濃度２０〜５０ｗｔ％の硫酸濃度の下で加水分解される。加水分解時の温度は、７０〜１００℃、時間は０．５〜８時間程度とされる。この加水分解により、セルロース、ヘミセルロースはグルコース、キシロースなどの糖に転化し、糖と硫酸とからなる溶液が得られる。 This biomass is first sent to the amorphizing device 1 and is brought into contact with sulfuric acid having a concentration of 50 to 80 wt% at a temperature of 20 to 70 ° C., so that the intermolecular bond of cellulose or hemicellulose is dissociated and becomes amorphous. -Solubilized. This amorphous / solubilization facilitates the hydrolysis of cellulose or hemicellulose in the next step.
The highly viscous gel-like reaction product that has undergone this amorphous / solubilization process is sent to the hydrolysis apparatus 2 and hydrolyzed under a sulfuric acid concentration of 20 to 50 wt% by separately supplied hydrolysis water. The The temperature during hydrolysis is 70 to 100 ° C., and the time is about 0.5 to 8 hours. By this hydrolysis, cellulose and hemicellulose are converted into sugars such as glucose and xylose, and a solution comprising sugar and sulfuric acid is obtained.

この溶液には、原料由来のシリカなどの無機物、リグニンなどの未加水分解物などの固形分が含まれているので、これを分離、除去するために、フィルタープレスなどの固液分離装置３に送り、固液分離を行う。
固液分離装置３において、分離されたケーキは、ついで洗浄装置４に送られ、水洗された後、系外に排出される。水洗後の水は回収されて加水分解用水の一部として加水分解装置２に送られる。
固液分離装置３において分離された濾液は、ついで擬似移動層クロマト分離装置本体５に、流入液として送られ、ここでラフィネートとエクストラクトとに分離される。 This solution contains solids such as silica derived from raw materials and non-hydrolyzed products such as lignin. In order to separate and remove this, a solid-liquid separation device 3 such as a filter press is used. Feed and perform solid-liquid separation.
In the solid-liquid separator 3, the separated cake is then sent to the washing device 4, washed with water, and then discharged out of the system. The water after washing is collected and sent to the hydrolysis apparatus 2 as part of the hydrolysis water.
The filtrate separated in the solid-liquid separation device 3 is then sent to the simulated moving bed chromatographic separation device main body 5 as an influent, where it is separated into raffinate and extract.

図２は、この擬似移動層クロマト分離装置本体５での分離の一例を示すもので、図中符号Ｃ１、Ｃ２・・・Ｃ８は、充填材として陽イオン交換樹脂または陰イオン交換樹脂のイオン交換樹脂を充填した８基のカラムを示す。この８基のカラムＣ１、Ｃ２・・・Ｃ８は、管路で直列に接続され、かつカラムＣ８の出口はカラムＣ１の入口に接続されて閉回路となっており、液がカラムＣ１から順次カラムＣ２、Ｃ３・・・カラムＣ８に流れ、さらにカラムＣ８からカラムＣ１に流れるようになって、この例の擬似移動層クロマト分離装置本体５が構成されている。   FIG. 2 shows an example of the separation in the simulated moving bed chromatographic separation apparatus main body 5. In the figure, reference numerals C1, C2,... C8 denote ion exchange of a cation exchange resin or an anion exchange resin as a filler. Eight columns packed with resin are shown. The eight columns C1, C2,... C8 are connected in series by a pipe line, and the outlet of the column C8 is connected to the inlet of the column C1 to form a closed circuit. C2, C3... Flows to column C8 and further flows from column C8 to column C1 to constitute the simulated moving bed chromatographic separation apparatus main body 5 of this example.

そして、この例では、陰イオン交換樹脂が充填されたカラムＣ１、Ｃ２、Ｃ３・・・Ｃ８が用いられ、そのうち、１番目のカラムＣ１の入口に、流入液が注入されるようになっている。流入液中の糖は、硫酸に比べて移動速度が速く、糖は２番目のカラムＣ２の出口からラフィネートの主成分として導出され、硫酸は、溶離水を５番目のカラムＣ５に注入することで、６番目のカラムＣ６の出口からエクストラクトの主成分として導出される。
ラフィネートは、次工程に送られる。 In this example, columns C1, C2, C3... C8 filled with an anion exchange resin are used, and the influent is injected into the inlet of the first column C1. . The sugar in the influent has a higher moving speed than sulfuric acid, the sugar is derived from the outlet of the second column C2 as the main component of raffinate, and sulfuric acid is injected into the fifth column C5 by eluting water. , Derived from the exit of the sixth column C6 as the main component of the extract.
The raffinate is sent to the next step.

擬似移動層クロマト分離装置本体５から導出されるエクストラクトは、その硫酸濃度が経時的に変化し、導出初期は硫酸濃度が高く、次第に硫酸濃度が低下する。そこで、エクストラクトの硫酸濃度に応じて、硫酸濃度が高い分画液Ａと硫酸濃度が低い分画液Ｂとに分画装置２１によって分画する。
具体的には、図１に示すように、擬似移動層クロマト分離装置本体５から導出されるエクストラクトを二分する管路６Ａ、６Ｂを設け、この管路６Ａ、６Ｂにそれぞれ自動弁７Ａ、７Ｂを設ける。また、タイマー８を設けて、このタイマー８からの開閉信号によりそれぞれの自動弁７Ａ、７Ｂの開閉操作を行うことで分画が行われる。この例での分画装置２１は、上記管路６Ａ、６Ｂ、自動弁７Ａ、７Ｂ、タイマー８から構成されている。 The extract derived from the simulated moving bed chromatographic separation apparatus main body 5 has a sulfuric acid concentration that changes with time, the sulfuric acid concentration is high at the initial stage of derivation, and the sulfuric acid concentration gradually decreases. Therefore, according to the sulfuric acid concentration of the extract, the fractionation device 21 performs fractionation into a fraction solution A having a high sulfuric acid concentration and a fraction solution B having a low sulfuric acid concentration.
Specifically, as shown in FIG. 1, pipes 6A and 6B that bisect the extract derived from the simulated moving bed chromatographic separation apparatus main body 5 are provided, and automatic valves 7A and 7B are provided in the pipes 6A and 6B, respectively. Is provided. In addition, a timer 8 is provided, and fractionation is performed by opening / closing the respective automatic valves 7A and 7B by an opening / closing signal from the timer 8. The fractionation device 21 in this example includes the pipe lines 6A and 6B, automatic valves 7A and 7B, and a timer 8.

擬似移動層クロマト分離装置本体５からのエクストラクト中の硫酸濃度は、分離条件等の条件が一定であれば、導出開始からの時間によってほぼ定まるので、分画時点での硫酸濃度を定めておけば、タイマー８の開閉設定時間を適切に設定することで、所望の硫酸濃度の分画液Ａと分画液Ｂとに分画できる。
タイマー８の開閉設定時間の設定は、ステップタイム（擬似移動層クロマト分離装置５への糖化液および溶離水の供給バルブと、ラフィネートおよびエクストラクトの導出バルブを流体移動と同じ方向に１カラム分移動させる切替時間間隔を言う。）に応じてなされ、例えばステップタイムが７分であれば、０〜４分の間では自動弁７Ａを開とし、自動弁７Ｂを閉とし、４〜７分の間では自動弁７Ａを閉とし、自動弁７Ｂを開とする。 The concentration of sulfuric acid in the extract from the simulated moving bed chromatographic separation apparatus main body 5 is substantially determined by the time from the start of derivation if conditions such as separation conditions are constant, so the sulfuric acid concentration at the time of fractionation can be determined. For example, it is possible to fractionate into a fraction solution A and a fraction solution B having a desired sulfuric acid concentration by appropriately setting the opening / closing set time of the timer 8.
The opening / closing set time of the timer 8 is set to the step time (the supply valve for the saccharified solution and the eluent water to the simulated moving bed chromatographic separation device 5 and the raffinate and extract derivation valve are moved by one column in the same direction as the fluid movement For example, if the step time is 7 minutes, the automatic valve 7A is opened and the automatic valve 7B is closed for 4 to 7 minutes. Then, the automatic valve 7A is closed and the automatic valve 7B is opened.

これにより、硫酸濃度が高い分画液Ａは、管路６Ａから硫酸濃縮装置９に送られ、一方硫酸濃度が低い分画液Ｂは、管路６Ｂから水洗水、加水分解用水あるいは溶離水として、洗浄装置４、加水分解装置２あるいは擬似移動層クロマト分離装置本体５に送られる。なお、管路６Ａ、６Ｂには、必要に応じて、ブリックス濃度計などの硫酸濃度を計測する酸濃度計を設けて、各分画液Ａ、Ｂの硫酸濃度を測定するようにしてもよい。   Thereby, the fraction A having a high sulfuric acid concentration is sent from the pipe 6A to the sulfuric acid concentrator 9, while the fraction B having a low sulfuric acid concentration is fed from the pipe 6B as washing water, hydrolyzing water or elution water. , Sent to the washing device 4, the hydrolysis device 2 or the simulated moving bed chromatographic separation device body 5. In addition, the pipe lines 6A and 6B may be provided with an acid concentration meter that measures the sulfuric acid concentration such as a Brix concentration meter, if necessary, so as to measure the sulfuric acid concentration of each of the fractions A and B. .

また、分画装置２１の他の形態として、擬似移動層クロマト分離装置本体５からのエクストラクトを導出する管路に硫酸濃度を測定する酸濃度計を設置し、この酸濃度計からの硫酸濃度信号を受け、この濃度信号によって自動弁７Ａ、７Ｂを開閉操作する制御装置を設けて、分画液Ａと分画液Ｂとを分画するようにしてもよい。   Further, as another form of the fractionation device 21, an acid concentration meter for measuring the sulfuric acid concentration is installed in a conduit for extracting the extract from the simulated moving bed chromatographic separation device main body 5, and the sulfuric acid concentration from the acid concentration meter is set. A control device that receives the signal and opens and closes the automatic valves 7A and 7B according to the concentration signal may be provided to fractionate the fraction A and the fraction B.

分画液Ａから分画液Ｂに分画する時点での硫酸濃度は、厳密に定められるものではなく、１〜１５ｗｔ％の範囲で、処理条件等に応じて決められ、分画液Ａ全体としての硫酸濃度が２０〜３５ｗｔ％に、分画液Ｂ全体としての硫酸濃度が１〜６ｗｔ％になるように分画することが望ましい。分画液Ａ全体の硫酸濃度を２０〜３５ｗｔ％とすることで、濃縮にかかる熱エネルギーを十分低減することが可能になる。   The concentration of sulfuric acid at the time of fractionation from fraction A to fraction B is not strictly determined and is determined in accordance with the processing conditions in the range of 1 to 15 wt%. It is desirable to fractionate so that the sulfuric acid concentration of 20 to 35 wt% as a whole and the sulfuric acid concentration of the entire fraction B as 1 to 6 wt%. By setting the sulfuric acid concentration of the entire fraction A to 20 to 35 wt%, it is possible to sufficiently reduce the heat energy required for concentration.

このように、分画液Ａ全体としての硫酸濃度が２０〜３５ｗｔ％に、分画液Ｂ全体としての硫酸濃度が１〜６ｗｔ％になるように分画することは、換言するとエクストラクトの全量のうち、前半の約５０〜８０ｗｔ％が分画液Ａとされ、後半の約２０〜５０ｗｔ％が分画液Ｂとされることになる。
硫酸濃縮装置９に送られた分画液Ａは、ここで硫酸が濃縮され、この濃縮硫酸は非晶質化装置１に送られ、再利用される。 In this way, fractionation so that the concentration of sulfuric acid as the whole of the fractionation liquid A is 20 to 35 wt% and the concentration of sulfuric acid as the whole of the fractionation liquid B is 1 to 6 wt% is, in other words, the total amount of extract. Among them, about 50 to 80 wt% in the first half is used as the fraction A, and about 20 to 50 wt% in the second half is used as the fraction B.
In the fraction A sent to the sulfuric acid concentrator 9, the sulfuric acid is concentrated here, and this concentrated sulfuric acid is sent to the amorphizing device 1 and reused.

図３は、本発明での擬似移動層クロマト分離装置５本体での分離方法の他の例を示すもので、この例では、１番目のカラムＣ１の入口に流入液を注入し、２番目のカラムＣ１の出口からラフィネートを導出し、４番目のカラムＣ４の出口に溶離水を注入し、６番目のカラムＣ６の出口からエクストラクトを導出するものである。ただし、分画液Ｂを擬似移動層クロマト分離装置本体５の溶離水として再利用する際、分画液Ｂと新たな溶離水とを混合して擬似移動層クロマト分離装置本体５に供給すると、分画液Ｂ中の硫酸がラフィネートに混入することがある。このため、擬似移動層クロマト分離装置５本体には、初めに分画液Ｂを供給し、ついで新たな溶離水を供給するようにする必要があり、分画液Ｂおよび新たな溶離水の管路に自動弁１０、１１を設け、タイマー（図示せず）により設定された開閉信号に基づいて所定の流量を維持するように開閉操作を行うようになっている。   FIG. 3 shows another example of the separation method in the simulated moving bed chromatographic separation apparatus 5 main body according to the present invention. In this example, the influent is injected into the inlet of the first column C1, and the second The raffinate is derived from the outlet of the column C1, the elution water is injected into the outlet of the fourth column C4, and the extract is derived from the outlet of the sixth column C6. However, when the fraction solution B is reused as the eluting water of the simulated moving bed chromatographic separation device main body 5, when the fraction solution B and new elution water are mixed and supplied to the simulated moving bed chromatography separation device main body 5, The sulfuric acid in the fraction B may be mixed into the raffinate. For this reason, it is necessary to supply the fractionated liquid B to the simulated moving bed chromatographic separation apparatus 5 first, and then supply new eluted water. Automatic valves 10 and 11 are provided on the road, and an opening / closing operation is performed so as to maintain a predetermined flow rate based on an opening / closing signal set by a timer (not shown).

図４は、擬似移動層クロマト分離装置５本体での分離方法の他の例を示すもので、この例では、１番目のカラムＣ１の入口に流入液を注入し、２番目のカラムＣ１の出口からラフィネートを導出し、４番目のカラムＣ４の出口に新たな溶離水を注入し、５番目のカラムＣ５の出口に低濃度分画液Ｂを注入し、６番目のカラムＣ６の出口からエクストラクトを導出するものである。   FIG. 4 shows another example of the separation method in the simulated moving bed chromatographic separation apparatus 5 main body. In this example, the influent is injected into the inlet of the first column C1, and the outlet of the second column C1. The raffinate is derived from the column, fresh eluent water is injected into the outlet of the fourth column C4, the low concentration fraction B is injected into the outlet of the fifth column C5, and the extract is extracted from the outlet of the sixth column C6. Is derived.

図５は、擬似移動層クロマト分離装置５本体での分離方法の他の例を示すもので、この例では、１番目のカラムＣ１の入口に流入液を注入し、２番目のカラムＣ１の出口からラフィネートを導出し、３番目のカラムＣ３の出口に新たな溶離水を注入し、４番目のカラムＣ４の出口に低濃度分画液Ｂを注入し、６番目のカラムＣ６の出口からエクストラクトを導出するものである。   FIG. 5 shows another example of the separation method in the simulated moving bed chromatographic separation apparatus 5 main body. In this example, the influent is injected into the inlet of the first column C1, and the outlet of the second column C1. The raffinate is derived from the column, fresh eluent water is injected into the outlet of the third column C3, low concentration fraction B is injected into the outlet of the fourth column C4, and the extract is extracted from the outlet of the sixth column C6. Is derived.

このような擬似移動層クロマト分離方法にあっては、擬似移動層クロマト分離装置本体５からのエクストラクトを硫酸濃度が高い分画液Ａと硫酸濃度が低い分画液Ｂとに分画し、硫酸濃度が高い分画液Ａのみを硫酸濃縮装置９に送って濃縮するようにしているので、硫酸濃縮に要する熱エネルギーが少なくて済み、エネルギーコストを低廉化でき、かつ硫酸濃縮装置９を小型化できる。   In such a simulated moving bed chromatographic separation method, the extract from the simulated moving bed chromatographic separation apparatus main body 5 is fractionated into a fraction solution A having a high sulfuric acid concentration and a fraction solution B having a low sulfuric acid concentration, Since only the fraction A having a high sulfuric acid concentration is sent to the sulfuric acid concentrator 9 for concentration, less heat energy is required for the sulfuric acid concentration, the energy cost can be reduced, and the sulfuric acid concentrator 9 can be made compact. Can be

また、硫酸濃度の低い分画液Ｂを洗浄装置４の水洗水、加水分解装置２の加水分解用水あるいは擬似移動層クロマト分離装置本体５の溶離水として再利用しているので、これらの用水として新たに系外から補給する水を節約できる。   Moreover, since the fraction solution B having a low sulfuric acid concentration is reused as washing water for the washing device 4, hydrolysis water for the hydrolysis device 2 or elution water for the simulated moving bed chromatographic separation device main body 5, It can save water newly supplied from outside the system.

以下、具体例を示すが、本発明はこれに限定されるものではない。
（１）糖化液（硫酸３０ｗｔ％、グルコース１０ｗｔ％、キシロース２ｗｔ％を含む）を、陰イオン交換樹脂を用いた擬似移動層クロマト分離装置本体により、ラフィネートとエクストラクトとに分離した。このエクストラクト１００ｋｇを分画１から分画１０まで各１０ｋｇづつに分画した。各分画での硫酸濃度は以下の通りである。 Hereinafter, although a specific example is shown, this invention is not limited to this.
(1) A saccharified solution (containing 30 wt% sulfuric acid, 10 wt% glucose, and 2 wt% xylose) was separated into raffinate and extract by a simulated moving bed chromatographic separation apparatus body using an anion exchange resin. 100 kg of this extract was fractionated into 10 kg from fraction 1 to fraction 10. The sulfuric acid concentration in each fraction is as follows.

分画 硫酸濃度（ｗｔ％）
１ ３１．１
２ ３１．１
３ ３１．１
４ ２９．４
５ ２２．６
６ １１．２
７ ６．０５
８ ３．８０
９ ３．２８
１０ ３．２８ Fractionation sulfuric acid concentration (wt%)
1 31.1
2 31.1
3 31.1
4 29.4
5 22.6
6 11.2
7 6.05
8 3.80
9 3.28
10 3.28

分画１〜１０までの全量をまとめて回収すると、その硫酸濃度は１７．３ｗｔ％となる。
分画１〜６までを硫酸濃度が高い分画液Ａとして回収すると、分画液Ａ（６０ｋｇ）の硫酸濃度は２６．１ｗｔ％となる。また、分画７〜１０までを硫酸濃度が低い分画液Ｂとして回収すると、分画液Ｂ（４０ｋｇ）の硫酸濃度は４．１ｗｔ％となる。 When all the fractions 1 to 10 are collected together, the sulfuric acid concentration becomes 17.3 wt%.
When fractions 1 to 6 are collected as a fraction A having a high sulfuric acid concentration, the sulfuric acid concentration of fraction A (60 kg) is 26.1 wt%. Further, when fractions 7 to 10 are collected as fraction solution B having a low sulfuric acid concentration, the concentration of sulfuric acid in fraction solution B (40 kg) is 4.1 wt%.

分画１〜１０までの全量１００ｋｇ（硫酸濃度１７．３ｗｔ％）を回収して硫酸濃度８０ｗｔ％まで濃縮しようとすると、７８．４ｋｇの水分を蒸発させる必要がある。
一方、分画１〜６までを回収して得られた分画液Ａ６０ｋｇ（硫酸濃度２６．１ｗｔ％）を硫酸濃度８０ｗｔ％まで濃縮しようとすると、４０．４ｋｇの水分を蒸発させればよく、濃縮に要する熱エネルギーを５１．６％節約できる。 When collecting 100 kg (sulfuric acid concentration: 17.3 wt%) of the fractions 1 to 10 and concentrating them to a sulfuric acid concentration of 80 wt%, it is necessary to evaporate 78.4 kg of water.
On the other hand, when the fraction A 60 kg (sulfuric acid concentration 26.1 wt%) obtained by collecting fractions 1 to 6 is concentrated to 80 wt% sulfuric acid, 40.4 kg of water may be evaporated, The heat energy required for concentration can be saved by 51.6%.

（２）糖化液を擬似移動層クロマト分離装置本体でラフィネートとエクストラクトとに分離する際に、流入液に対して重量基準で１．５倍の溶離水を供給し、ラフィネートとエクストラクトとの抜き出し比率を１：１．６とし、流入液を１００ｋｇとしたとき、ラフィネートが９５ｋｇ、エクストラクトが１５５ｋｇ回収される。エクストラクト１５５ｋｇのうち、硫酸濃度の低い分画液Ｂ６２ｋｇ（重量基準でエクストラクト全体の４０ｗｔ％）を擬似移動層クロマト分離装置本体の溶離水として再利用すると、溶離水として使用する水を４１．３％節約できる。 (2) When the saccharified solution is separated into raffinate and extract by the simulated moving bed chromatographic separation apparatus main body, the elution water is supplied 1.5 times by weight with respect to the influent, and the raffinate and extract are separated. When the extraction ratio is 1: 1.6 and the influent is 100 kg, 95 kg of raffinate and 155 kg of extract are recovered. Of the 155 kg extract, 62 kg of fraction B having a low sulfuric acid concentration (40 wt% of the entire extract on a weight basis) is reused as the eluting water of the simulated moving bed chromatographic separation apparatus, so that the water used as the eluting water is 41. Save 3%.

本発明の分離方法は、バイオマスから糖を回収し、この糖を発酵してエタノールを製造する新エネルギー開発などの分野に利用できる。   The separation method of the present invention can be used in fields such as new energy development in which sugar is recovered from biomass and this sugar is fermented to produce ethanol.

本発明の処理装置を示す概略構成図である。It is a schematic block diagram which shows the processing apparatus of this invention. 本発明の処理方法における擬似移動層クロマト分離装置本体での分離の一例を示す概略構成図である。It is a schematic block diagram which shows an example of the isolation | separation in the pseudo | simulation moving bed chromatographic separation apparatus main body in the processing method of this invention. 本発明の処理方法における擬似移動層クロマト分離装置本体での分離の他の例を示す概略構成図である。It is a schematic block diagram which shows the other example of the isolation | separation in the pseudo | simulation moving bed chromatographic separation apparatus main body in the processing method of this invention. 本発明の処理方法における擬似移動層クロマト分離装置本体での分離の他の例を示す概略構成図である。It is a schematic block diagram which shows the other example of the isolation | separation in the pseudo | simulation moving bed chromatographic separation apparatus main body in the processing method of this invention. 本発明の処理方法における擬似移動層クロマト分離装置本体での分離の他の例を示す概略構成図である。It is a schematic block diagram which shows the other example of the isolation | separation in the pseudo | simulation moving bed chromatographic separation apparatus main body in the processing method of this invention. 従来の処理方法における擬似移動層クロマト分離装置を示す概略構成図である。It is a schematic block diagram which shows the simulated moving bed chromatographic separation apparatus in the conventional processing method.

符号の説明Explanation of symbols

２・・・加水分解装置、５・・・擬似移動層クロマト分離装置本体、６Ａ、６Ｂ・・・管路、７Ａ、７Ｂ・・・自動弁、８・・・タイマー、９・・・硫酸濃縮装置、２１・・・分画装置
2 ... Hydrolysis unit, 5 ... Pseudo moving bed chromatographic separation unit, 6A, 6B ... Pipe, 7A, 7B ... Automatic valve, 8 ... Timer, 9 ... Sulfuric acid concentration Device, 21 ... fractionation device

Claims (9)

流入液が、セルロースおよび／またはヘミセルロースを含む原料を酸により糖化する糖化工程から排出される酸と糖を含み、
この流入液を、糖を分画とする成分と酸を分画とする成分とに分離する擬似移動層クロマト分離方法であって、
酸を分画とする成分を高濃度分画液Ａと低濃度分画液Ｂとに分画することを特徴とする擬似移動層クロマト分離方法。 The influent contains acid and sugar discharged from a saccharification process in which a raw material containing cellulose and / or hemicellulose is saccharified with an acid;
A simulated moving bed chromatographic separation method for separating the influent into a component containing a sugar fraction and a component containing an acid fraction,
A pseudo moving bed chromatographic separation method comprising fractionating an acid fraction into a high concentration fraction A and a low concentration fraction B. 分画された酸のうち高濃度分画液Ａが、原料の糖化工程で再利用されることを特徴とする請求項１記載の擬似移動層クロマト分離方法。 2. The simulated moving bed chromatographic separation method according to claim 1, wherein the high-concentration fraction A of the fractionated acid is reused in the raw material saccharification step. 分画された酸のうち低濃度分画液Ｂが、擬似移動層クロマト分離装置の溶離水および／または原料の糖化工程で再利用されることを特徴とする請求項１または２記載の擬似移動層クロマト分離方法。 The simulated transfer according to claim 1 or 2, wherein the fractionated acid B of the fractionated acid is reused in the elution water and / or raw material saccharification step of the simulated moving bed chromatographic separation apparatus. Layer chromatographic separation method. 酸が硫酸であることを特徴とする請求項１ないし３のいずれかに記載の擬似移動層クロマト分離方法。 The simulated moving bed chromatographic separation method according to any one of claims 1 to 3, wherein the acid is sulfuric acid. 高濃度分画液Ａの硫酸濃度が２０〜３５ｗｔ％であり、低濃度分画液Ｂの硫酸濃度が１〜６ｗｔ％であることを特徴とする請求項４記載の擬似移動層クロマト分離方法。 5. The simulated moving bed chromatographic separation method according to claim 4, wherein the high concentration fraction A has a sulfuric acid concentration of 20 to 35 wt%, and the low concentration fraction B has a sulfuric acid concentration of 1 to 6 wt%. セルロースおよび／またはヘミセルロースを含む原料を酸により糖化する糖化装置と、
この糖化装置からの酸と糖を含む液を流入し、糖を分画とする成分と酸を分画とする成分とに分離する擬似移動層クロマト分離装置本体と、
この擬似移動層クロマト分離装置本体から分離された酸を分画とする成分を、酸濃度によって高濃度分画液Ａと低濃度分画液Ｂとに分画する分画装置を備えたことを特徴とする糖化処理装置。 A saccharification apparatus for saccharifying a raw material containing cellulose and / or hemicellulose with an acid;
A simulated moving bed chromatographic separation apparatus main body that flows into the liquid containing acid and sugar from the saccharification apparatus and separates into a component that separates sugar and a component that separates acid.
A fractionation device for fractionating the component separated from the pseudo moving bed chromatographic separation apparatus into a high concentration fraction A and a low concentration fraction B according to the acid concentration; A saccharification processing apparatus. 高濃度分画液Ａを濃縮する濃縮装置が設けられ、この濃縮装置で濃縮された酸が糖化装置に送られ、再利用されるようになっていることを特徴とする請求項６記載の糖化処理装置。 The saccharification according to claim 6, wherein a concentrating device for concentrating the high-concentration fraction A is provided, and the acid concentrated by the concentrating device is sent to the saccharification device and reused. Processing equipment. 低濃度分画液Ｂが擬似移動層クロマト分離装置に送られ、その溶離水として再利用されるようになっていることを特徴とする請求項６記載の糖化処理装置。 The saccharification treatment apparatus according to claim 6, wherein the low-concentration fraction B is sent to the simulated moving bed chromatographic separation apparatus and reused as the elution water. 低濃度分画液Ｂが糖化装置に送られ、再利用されるようになっていることを特徴とする請求項６記載の糖化処理装置。
The saccharification treatment apparatus according to claim 6, wherein the low-concentration fraction B is sent to the saccharification apparatus and reused.
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