JP4713688B1 - Bioethanol production method - Google Patents

Bioethanol production method Download PDF

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JP4713688B1
JP4713688B1 JP2010252747A JP2010252747A JP4713688B1 JP 4713688 B1 JP4713688 B1 JP 4713688B1 JP 2010252747 A JP2010252747 A JP 2010252747A JP 2010252747 A JP2010252747 A JP 2010252747A JP 4713688 B1 JP4713688 B1 JP 4713688B1
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泰雄 福谷
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    • C12PFERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
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Abstract

【課題】植物体であるバイオマスを簡単な方法で効率よくエタノール化する方法を提供する。
【解決手段】セルロースを含有する植物体をpH12以上のカセイカリまたはカセイソーダの水溶液に浸漬するアルカリ処理工程、前記アルカリ処理工程で処理された植物体をpH1〜5のクエン酸水溶液に浸漬し該クエン酸水溶液とともに90〜140℃に加熱し、植物体を浸漬した状態の前記クエン酸水溶液にカセイカリまたはカセイソーダを加えて該クエン酸水溶液のpHを5を越えて7.5以下になるように調整し、調整された水溶液を発酵させる、発酵した水溶液からエタノールを抽出するバイオエタノールの製造方法である。
【選択図】なし
The present invention provides a method for efficiently ethanolizing biomass which is a plant body by a simple method.
An alkaline treatment step of immersing a plant body containing cellulose in an aqueous solution of caustic or caustic soda having a pH of 12 or more, and immersing the plant body treated in the alkaline treatment step in an aqueous citric acid solution of pH 1 to 5 Heat to 90-140 ° C. with an aqueous solution, add caustic potash or caustic soda to the citric acid aqueous solution in a state where the plant body is immersed, and adjust the pH of the citric acid aqueous solution to more than 5 to 7.5 or less, It is the manufacturing method of the bioethanol which extracts the ethanol from the fermented aqueous solution which ferments the adjusted aqueous solution.
[Selection figure] None

Description

本発明は、バイオエタノールを得る製造方法に関する。   The present invention relates to a production method for obtaining bioethanol.

バイオエタノールの製造方法としては、例えば、バイオマスの水スラリーを圧力4〜40MPaに加圧し、加圧された水スラリーを火力発電装置のボイラから供給される蒸気と反応器内で熱交換させることにより前記圧力での飽和温度以下かつ250〜400℃の範囲の温度に加熱して前記バイオマスに含有されるヘミセルロースおよびセルロースを加水分解して糖を生成し、生成された糖を発酵させるバイオエタノールの製造方法が知られている。(例えば、特許文献1参照)また、セルロースを酵素糖化させて得た糖を発酵させてエタノールを得る方法が知られている。(例えば、特許文献2参照)   As a method for producing bioethanol, for example, a biomass water slurry is pressurized to a pressure of 4 to 40 MPa, and the pressurized water slurry is subjected to heat exchange in a reactor with steam supplied from a boiler of a thermal power generator. Production of bioethanol that is heated to a temperature equal to or lower than the saturation temperature at the pressure and in the range of 250 to 400 ° C. to hydrolyze hemicellulose and cellulose contained in the biomass to produce sugar, and to ferment the produced sugar The method is known. (For example, refer patent document 1) Moreover, the method of fermenting the saccharide | sugar obtained by carrying out the enzymatic saccharification of a cellulose and obtaining ethanol is known. (For example, see Patent Document 2)

これらは大規模な高圧装置あるいは高価なセルロース糖化酵素を使用することが工業化のうえでネックとなっている。   The use of a large-scale high-pressure apparatus or an expensive cellulose saccharifying enzyme has become a bottleneck in industrialization.

特開2008−182925号公報JP 2008-182925 A 特開2008−161125号公報JP 2008-161125 A

本発明の目的は、植物体であるバイオマスを簡単な方法で効率よくエタノール化する方法を提供しようとすることである。   An object of the present invention is to provide a method for efficiently ethanolizing biomass that is a plant body by a simple method.

本発明の要旨とするところは、セルロースを含有する植物体をpH12以上のカセイカリまたはカセイソーダの水溶液に浸漬するアルカリ処理工程、
前記アルカリ処理工程で処理された植物体をpH1〜5のクエン酸水溶液に浸漬し該クエン酸水溶液とともに90〜140℃に加熱する加熱工程、
前記植物体を浸漬した状態の前記クエン酸水溶液にカセイカリまたはカセイソーダを加えて該クエン酸水溶液のpHを5を越えて7.5以下になるように調整するpH調整工程、
調整された水溶液を発酵させる発酵工程、
発酵した水溶液からエタノールを抽出する抽出工程
を含むバイオエタノールの製造方法であることにある。
The gist of the present invention is that an alkali treatment step of immersing a plant containing cellulose in an aqueous solution of caustic potash or caustic soda having a pH of 12 or more,
A heating step of immersing the plant treated in the alkali treatment step in a citric acid aqueous solution having a pH of 1 to 5 and heating the plant to 90 to 140 ° C. with the citric acid aqueous solution;
PH adjusting step of adjusting caustic acid or caustic soda to the citric acid aqueous solution in a state in which the plant body is immersed to adjust the pH of the citric acid aqueous solution to more than 5 and not more than 7.5,
A fermentation process for fermenting the adjusted aqueous solution,
It exists in the manufacturing method of bioethanol including the extraction process which extracts ethanol from fermented aqueous solution.

前記バイオエタノールの製造方法においては、前記発酵工程が、前記pH調整工程で調整された水溶液にさらに大根を加えた液を発酵させる工程であり得る。   In the bioethanol production method, the fermentation step may be a step of fermenting a solution obtained by adding radish to the aqueous solution adjusted in the pH adjustment step.

本発明によると、植物体であるバイオマスから簡単な方法で効率よくバイオエタノールを得る製造方法が提供される。   ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method which obtains bioethanol efficiently by the simple method from the biomass which is a plant body is provided.

本発明のバイオエタノールの製造方法は、
セルロースを含有する植物体をpH12以上のカセイカリまたはカセイソーダの水溶液に浸漬するアルカリ処理工程、
前記アルカリ処理工程で処理された植物体をpH1〜5のクエン酸水溶液に浸漬し該クエン酸水溶液とともに90〜140℃に加熱する加熱工程、
前記植物体を浸漬した状態の前記クエン酸水溶液にカセイカリまたはカセイソーダを加えて該クエン酸水溶液のpHを5を越えて7.5以下になるように調整するpH調整工程、
調整された水溶液を発酵させる発酵工程、
発酵した水溶液からエタノールを抽出する抽出工程
を含んで構成される。
The method for producing bioethanol of the present invention comprises:
An alkali treatment step of immersing a plant containing cellulose in an aqueous solution of caustic potash or caustic soda having a pH of 12 or more;
A heating step of immersing the plant treated in the alkali treatment step in a citric acid aqueous solution having a pH of 1 to 5 and heating the plant to 90 to 140 ° C. with the citric acid aqueous solution;
PH adjusting step of adjusting caustic acid or caustic soda to the citric acid aqueous solution in a state in which the plant body is immersed to adjust the pH of the citric acid aqueous solution to more than 5 and not more than 7.5,
A fermentation process for fermenting the adjusted aqueous solution,
It includes an extraction process for extracting ethanol from the fermented aqueous solution.

本発明に用いられる植物体はセルロースを含有するものであり、ほかにリグノセルロースが含有されていてもよい。本発明に用いられる植物体としては、松、杉、檜、その他の樹木などの山野に生息する樹木や山野に生息する草木類や湖沼などの水系環境に生息する藻類、水草類が例示される。   The plant used in the present invention contains cellulose and may contain lignocellulose in addition. Examples of plants used in the present invention include trees that inhabit mountains such as pine, cedar, cypress, and other trees, plants and trees that inhabit the mountains, and algae and aquatic plants that inhabit aquatic environments such as lakes. .

上記アルカリ処理工程にあっては、カセイカリまたはカセイソーダの水溶液100重量部に対して植物体が5〜15重量部(乾燥重量)用いられることが好ましい。アルカリ処理工程における処理液の温度は室温〜100℃が好ましい。処理時間は、処理液の温度が室温の場合は20〜40時間が好ましい。適した処理時間は処理液の温度が高いほど短くなり、処理液の温度が100℃の場合は1〜2分が好ましい。処理時間が長くなりすぎると液が黒ずんできて、上記加熱工程におけるセルロースの糖化が阻害される。   In the alkali treatment step, it is preferable to use 5 to 15 parts by weight (dry weight) of the plant body with respect to 100 parts by weight of the caustic potash or caustic soda aqueous solution. The temperature of the treatment liquid in the alkali treatment step is preferably room temperature to 100 ° C. The treatment time is preferably 20 to 40 hours when the temperature of the treatment liquid is room temperature. A suitable treatment time is shorter as the temperature of the treatment liquid is higher. When the temperature of the treatment liquid is 100 ° C., 1 to 2 minutes is preferable. If the treatment time is too long, the liquid will darken and saccharification of cellulose in the heating step will be inhibited.

カセイカリまたはカセイソーダの水溶液には植物体の処理によりリグニン等の非セルロースの多糖類を含む不純物が溶出するので、アルカリ処理によりこれら不純物が植物体から除去され後工程での発酵が効率よく行われる。上記加熱工程にあっては、アルカリ処理工程で処理された植物体を水洗したのちpH1〜5のクエン酸水溶液に浸漬し該クエン酸水溶液とともに90〜140℃に加熱することが好ましい。加熱時間は10〜50時間が好ましい。上記加熱工程により、植物体のセルロースが糖化される。この加熱工程においてはクエン酸水溶液100重量部に対して植物体がもとの乾燥重量換算で5〜15重量部投入されていることが好ましい。   Impurities containing non-cellulose polysaccharides such as lignin are eluted in the aqueous solution of caustic potash or caustic soda by the treatment of the plant body, so that these impurities are removed from the plant body by the alkali treatment, and fermentation in the subsequent process is efficiently performed. In the heating step, it is preferable that the plant treated in the alkali treatment step is washed with water and then immersed in an aqueous citric acid solution having a pH of 1 to 5 and heated to 90 to 140 ° C. together with the aqueous citric acid solution. The heating time is preferably 10 to 50 hours. The cellulose of a plant body is saccharified by the said heating process. In this heating step, it is preferable that 5 to 15 parts by weight of the plant body in terms of the original dry weight is added to 100 parts by weight of the citric acid aqueous solution.

上記pH調整工程においては、処理された植物体を含む加熱工程後の処理液を室温あるいは室温に近い温度に冷却した後カセイカリまたはカセイソーダを加えることが好ましい。また、この冷却の前または後に処理された植物体を含む加熱工程後の処理液をミキサーで攪拌することが好ましい。   In the pH adjustment step, it is preferable to add caustic potash or caustic soda after cooling the treatment liquid after the heating step containing the treated plant body to room temperature or a temperature close to room temperature. Moreover, it is preferable to stir the process liquid after the heating process containing the plant body processed before or after this cooling with a mixer.

上記発酵工程にあっては、pH調整工程で処理された植物体を含む加熱工程後の処理液に酵素、酵母、または微生物を添加して発酵を行わせる。pH調整工程で処理された植物体を含む加熱工程後の処理液を5時間以上、特に10〜100時間発酵可能温度に保つことが好ましい。この発酵可能温度としては酵素や酵母の種類にもよるが20〜37℃が好ましい。この発酵過程において、発酵にかかわる酵素がクエン酸塩に作用し、この作用が発酵の促進に寄与する。   In the said fermentation process, an enzyme, yeast, or microorganisms are added to the processing liquid after the heating process containing the plant body processed at the pH adjustment process, and fermentation is performed. It is preferable to keep the treatment solution after the heating step including the plant body treated in the pH adjustment step at a temperature allowing fermentation for 5 hours or more, particularly 10 to 100 hours. The fermentable temperature is preferably 20 to 37 ° C, although it depends on the type of enzyme or yeast. In this fermentation process, enzymes involved in fermentation act on citrate, and this action contributes to the promotion of fermentation.

また、上記発酵工程にあっては、pH調整工程で処理された植物体を含む加熱工程後の処理液に酵素、酵母、または微生物と大根を添加して発酵を行わせることがさらに好ましい。大根は当初投入された植物体100重量部に対して3〜5重量部添加されることが好ましい。これにより、エタノールの収率が2〜3割程度向上する。   Moreover, in the said fermentation process, it is still more preferable to add an enzyme, yeast, or microorganisms, and a radish to the processing liquid after the heating process containing the plant body processed at the pH adjustment process, and to perform fermentation. The radish is preferably added in an amount of 3 to 5 parts by weight with respect to 100 parts by weight of the plant body initially charged. Thereby, the yield of ethanol improves about 20-30%.

上記発酵工程において、処理液中の糖がエタノールに転化する。   In the fermentation process, the sugar in the treatment liquid is converted to ethanol.

上記抽出工程における、液中のエタノールを抽出する方法は特に限定されず、例えば、蒸留により多段濃縮する常法を用いることができる。   The method for extracting ethanol in the liquid in the extraction step is not particularly limited, and for example, a conventional method of multi-stage concentration by distillation can be used.

本発明により、乾燥した植物体に対して15重量%以上のエタノールを得ることができる。   According to the present invention, 15% by weight or more of ethanol can be obtained based on the dried plant body.

本発明の植物体糖化方法にあっては、草木類を用いる場合、カセイカリまたはカセイソーダの水溶液に浸漬する前に草木類を加圧盤で挟んで加圧して形態をほぐすことが糖化の効率上好ましい。   In the plant saccharification method of the present invention, when using vegetation, it is preferable from the viewpoint of the efficiency of saccharification that the plant is squeezed with a pressure plate before being dipped in an aqueous solution of caustic or caustic soda to press the plant.

本発明により植物体に含まれるセルロースを効率よく糖化することができる。また、本発明は高圧装置や高価なセルロース糖化酵素を購入して使用することがないので経済的である。   According to the present invention, cellulose contained in a plant can be efficiently saccharified. Further, the present invention is economical because it does not purchase and use a high-pressure apparatus or an expensive cellulose saccharifying enzyme.

実施例1
試料として琵琶湖に生息している水草(オオカナダモ)(乾燥重量300g)を用い、pH13のカセイカリ水溶液3Lに24時間浸漬したのち水洗し、pH2のクエン酸水溶液4Lに投入した。この試料を投入状態のクエン酸水溶液を121℃に昇温し、10時間この温度にキープした。次いでこの試料を投入状態のクエン酸水溶液を室温に自然冷却後カセイカリを加えて中和し、ミキサーで攪拌した。次いでこの液に酵母(白神コダマ酵母 ドライ)を2g加えて室温で24時間発酵させた。発酵液を2段蒸留して濃度80重量%のエタノール水溶液50mLを得た。
Example 1
As a sample, aquatic plants (Ocana mosquito) inhabiting Lake Biwa (dry weight 300 g) were immersed in 3 L of caustic solution of pH 13 for 24 hours, washed with water, and put into 4 L of citric acid solution of pH 2. The aqueous citric acid solution in which this sample was charged was heated to 121 ° C. and kept at this temperature for 10 hours. Then, the citric acid aqueous solution in which this sample was charged was naturally cooled to room temperature, neutralized by adding caustic, and stirred with a mixer. Next, 2 g of yeast (Shirakami Kodama Yeast Dry) was added to this solution and fermented at room temperature for 24 hours. The fermentation broth was distilled in two stages to obtain 50 mL of an aqueous ethanol solution having a concentration of 80% by weight.

実施例2
試料として琵琶湖に生息している水草(オオカナダモ)(乾燥重量300g)を用い、pH13のカセイカリ水溶液3Lに24時間浸漬したのち水洗し、pH2のクエン酸水溶液4Lに投入した。この試料を投入状態のクエン酸水溶液を121℃に昇温し、10時間この温度にキープした。次いでこの試料を投入状態のクエン酸水溶液を室温に自然冷却後カセイカリを加えて中和し、次いでこの液に大根15gを加えてミキサーで攪拌した。次にこの液に酵母(白神コダマ酵母 ドライ)を2gと室温で24時間発酵させた。発酵液を2段蒸留して濃度80重量%のエタノール水溶液67mLを得た。
Example 2
As a sample, aquatic plants (Ocana mosquito) inhabiting Lake Biwa (dry weight 300 g) were immersed in 3 L of caustic solution of pH 13 for 24 hours, washed with water, and put into 4 L of citric acid solution of pH 2. The aqueous citric acid solution in which this sample was charged was heated to 121 ° C. and kept at this temperature for 10 hours. Next, the citric acid aqueous solution in which the sample was charged was naturally cooled to room temperature, neutralized by adding caustic, and then 15 g of radish was added to this solution and stirred with a mixer. Next, 2 g of yeast (Shirakami Kodama yeast dry) was fermented to this solution at room temperature for 24 hours. The fermentation broth was distilled in two stages to obtain 67 mL of an aqueous ethanol solution having a concentration of 80% by weight.

比較例1
試料として琵琶湖に生息している水草(オオカナダモ)(乾燥重量300g)を用い、pH2のクエン酸水溶液4Lに投入した。この試料を投入状態のクエン酸水溶液を121℃に昇温し、10時間この温度にキープした。次いでこの試料を投入状態のクエン酸水溶液を室温に自然冷却後カセイカリを加えて中和し、ミキサーで攪拌した。次いでこの液に酵母(白神コダマ酵母 ドライ)を2g加えて室温で24時間発酵させた。発酵液を2段蒸留したがエタノールの生成は認められなかった。
Comparative Example 1
As a sample, aquatic plants (Ocana mocha) inhabiting Lake Biwa (dry weight 300 g) were used and introduced into 4 L of citric acid aqueous solution at pH 2. The aqueous citric acid solution in which this sample was charged was heated to 121 ° C. and kept at this temperature for 10 hours. Then, the citric acid aqueous solution in which this sample was charged was naturally cooled to room temperature, neutralized by adding caustic, and stirred with a mixer. Next, 2 g of yeast (Shirakami Kodama Yeast Dry) was added to this solution and fermented at room temperature for 24 hours. The fermentation broth was distilled in two stages, but no ethanol was observed.

本発明により得られるエタノールは石油系の燃料の代替として好適に使用できる。 Ethanol obtained by the present invention can be suitably used as an alternative to petroleum-based fuels.

Claims (1)

セルロースを含有する植物体をpH12以上のカセイカリまたはカセイソーダの水溶液に浸漬するアルカリ処理工程、
前記アルカリ処理工程で処理された植物体をpH1〜5のクエン酸水溶液に浸漬し該クエン酸水溶液とともに90〜140℃に加熱する加熱工程、
前記植物体を浸漬した状態の前記クエン酸水溶液にカセイカリまたはカセイソーダを加えて該クエン酸水溶液のpHを5を越えて7.5以下になるように調整するpH調整工程、
調整された水溶液にさらに大根を加えた液を発酵させる発酵工程、
発酵した水溶液からエタノールを抽出する抽出工程
を含むバイオエタノールの製造方法
An alkali treatment step of immersing a plant containing cellulose in an aqueous solution of caustic potash or caustic soda having a pH of 12 or more;
A heating step of immersing the plant treated in the alkali treatment step in a citric acid aqueous solution having a pH of 1 to 5 and heating the plant to 90 to 140 ° C. with the citric acid aqueous solution;
PH adjusting step of adjusting caustic acid or caustic soda to the citric acid aqueous solution in a state in which the plant body is immersed to adjust the pH of the citric acid aqueous solution to more than 5 and not more than 7.5,
A fermentation process for fermenting a solution obtained by adding radish to the prepared aqueous solution;
A method for producing bioethanol comprising an extraction step of extracting ethanol from a fermented aqueous solution .
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