JP5669171B2 - Method for producing alcohol or organic acid using biomass - Google Patents
Method for producing alcohol or organic acid using biomass Download PDFInfo
- Publication number
- JP5669171B2 JP5669171B2 JP2009238797A JP2009238797A JP5669171B2 JP 5669171 B2 JP5669171 B2 JP 5669171B2 JP 2009238797 A JP2009238797 A JP 2009238797A JP 2009238797 A JP2009238797 A JP 2009238797A JP 5669171 B2 JP5669171 B2 JP 5669171B2
- Authority
- JP
- Japan
- Prior art keywords
- cellulose
- water
- solid
- biomass
- polysaccharide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 150000007524 organic acids Chemical class 0.000 title description 11
- 239000002028 Biomass Substances 0.000 title description 8
- 229920002678 cellulose Polymers 0.000 claims description 21
- 239000001913 cellulose Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 14
- 229920001542 oligosaccharide Polymers 0.000 claims description 14
- 150000002482 oligosaccharides Chemical class 0.000 claims description 14
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims description 13
- 239000007788 liquid Substances 0.000 claims description 13
- 239000011973 solid acid Substances 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 229920002488 Hemicellulose Polymers 0.000 claims description 10
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 9
- 235000019743 Choline chloride Nutrition 0.000 claims description 9
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 9
- 229960003178 choline chloride Drugs 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 108010059892 Cellulase Proteins 0.000 claims description 6
- 229940106157 cellulase Drugs 0.000 claims description 4
- 239000002029 lignocellulosic biomass Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 description 18
- 150000004676 glycans Chemical class 0.000 description 12
- 229920001282 polysaccharide Polymers 0.000 description 12
- 239000005017 polysaccharide Substances 0.000 description 12
- 108090000790 Enzymes Proteins 0.000 description 9
- 102000004190 Enzymes Human genes 0.000 description 9
- 229940088598 enzyme Drugs 0.000 description 9
- -1 imidazolium compound Chemical class 0.000 description 9
- 231100000135 cytotoxicity Toxicity 0.000 description 8
- 230000003013 cytotoxicity Effects 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229920005610 lignin Polymers 0.000 description 6
- 229960001231 choline Drugs 0.000 description 5
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-O Imidazolium Chemical compound C1=C[NH+]=CN1 RAXXELZNTBOGNW-UHFFFAOYSA-O 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 240000000797 Hibiscus cannabinus Species 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 231100000433 cytotoxic Toxicity 0.000 description 2
- 230000001472 cytotoxic effect Effects 0.000 description 2
- 231100000263 cytotoxicity test Toxicity 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000855 fermentation Methods 0.000 description 2
- 230000004151 fermentation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000000855 fungicidal effect Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000000035 biogenic effect Effects 0.000 description 1
- 238000010170 biological method Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 150000002016 disaccharides Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 229930182478 glucoside Natural products 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 235000008216 herbs Nutrition 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 210000005253 yeast cell Anatomy 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Processing Of Solid Wastes (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
本発明は、ケナフ、稲ワラ等の草本類、木本類、及び建築廃材等の植物由来のバイオマスからアルコール又は有機酸を製造する方法に関し、特にリグノセルロース系バイオマスからアルコール又は有機酸を製造するのに適する。 The present invention relates to a method for producing alcohol or organic acid from plant-derived biomass such as kenaf, rice straw, and other herbs, woody, and building waste, and in particular, produces alcohol or organic acid from lignocellulosic biomass. Suitable for
化石資源を除いた生物由来の資源（バイオマス）はカーボンニュートラル資源として各種活用方法が検討されている。
その中で、リグノセルロース系バイオマスを用いたエタノール生産は、食料と競合しない大きなメリットがあるものの、リグノセルロースは、セルロースがヘミセルロース及びリグニンと結合して存在し、リグニンはフェノール性の高分子化合物であり、その分離、除去が低コスト化の障害になっていた。
例えば、リグニン分解菌、リグニン分解酵素による生物的手法は処理に極めて長期間がかかる問題がある。
希硫酸処理方法は、糖の過分解や廃硫酸処理に問題がある。
特許文献１にはマイクロ波、超音波処理方法を開示するが、リグニンの除去効果が未だ充分でない。
Various uses of biogenic resources (biomass) excluding fossil resources are being considered as carbon neutral resources.
Among them, ethanol production using lignocellulosic biomass has a great merit that it does not compete with food, but lignocellulose exists as cellulose binds to hemicellulose and lignin, and lignin is a phenolic polymer compound. The separation and removal were obstacles to cost reduction.
For example, biological methods using lignin-degrading bacteria and lignin-degrading enzymes have a problem that it takes a very long time for the treatment.
The dilute sulfuric acid treatment method has problems in excessive decomposition of sugar and waste sulfuric acid treatment.
また、セルロースのオリゴ糖あるいは単糖への分解プロセスにおいて、希硫酸等の液体酸触媒を用いた化学的手法は、その後の酸触媒の分離や廃液処理に問題があった。
そこで、近年はセルラーゼ酵素を用いた生物的加水分解処理の方法が広く研究されている。
しかし、セルロースは、β−グルコース分子が１，４グルコシド結合により重合した高分子同士が水素結合し、水に不溶性の結晶構造を有していることから、セルラーゼ酵素との接触面積が少なく、反応が遅い問題があった。
Further, in the process of decomposing cellulose into oligosaccharides or monosaccharides, the chemical method using a liquid acid catalyst such as dilute sulfuric acid has a problem in the subsequent separation of the acid catalyst and waste liquid treatment.
In recent years, therefore, methods for biological hydrolysis using cellulase enzymes have been widely studied.
However, cellulose has a crystal structure in which β-glucose molecules are polymerized by 1,4 glucoside bonds and hydrogen bonds with each other, and has a crystal structure that is insoluble in water. There was a slow problem.
近年、特許文献２に示すようにセルロースを選択的に可溶とするイミダゾリウム系化合物も報告されている。
しかし、本発明者らの調査によるとイミダゾリウム系化合物はセルロースを溶解するもののセルラーゼ酵素及び酵母菌を添加すると、この酵素活性が失活したり、酵母菌が死滅する問題があり、また、酵素等を添加するための最小限の水を加えることでもセルロースの溶解度が低下し、セルロースが析出、沈殿してしまう。
そこで、本発明者らは上記のイミダゾリウム系化合物を用いてセルロースを可溶化した後に固体酸触媒を加えて、セルロースを酸で予備的糖化しオリゴ糖類に分解させた後に水を加え、セルロースの析出、沈殿を抑えた。
しかし、それでも酵母菌の死滅を抑えることはできなかったことから、このイミダゾリウム系化合物は酵素や酵母菌に対する毒性が高いことが明らかになった。
また特許文献３によれば、従来より第４級イミダゾリウム化合物は防菌防カビ作用を有するものとも知られていた。
さらに、イミダゾリウム系化合物／水の混合溶液から分解したオリゴ糖類を抽出・回収することを検討したが、重合度の低いオリゴ糖は水に溶けているために、イミダゾリウム系化合物／水側に留まり多くのオリゴ糖類がロスになる問題があった。
このような予備的調査に基づいて本発明者らは、非水溶性の多糖類を可溶化する細胞毒性の低い溶媒を詳細に検討した結果、本発明に至った。
In recent years, as shown in Patent Document 2, an imidazolium-based compound that selectively dissolves cellulose has also been reported.
However, according to the investigation by the present inventors, the imidazolium-based compound dissolves cellulose, but if cellulase enzyme and yeast are added, there is a problem that this enzyme activity is inactivated or yeast is killed. Even if the minimum amount of water is added to add the solubility of cellulose, the solubility of cellulose is lowered, and cellulose is precipitated and precipitated.
Therefore, the present inventors solubilized cellulose using the imidazolium-based compound described above, added a solid acid catalyst, preliminarily saccharified the cellulose with an acid, decomposed into oligosaccharides, added water, Precipitation and precipitation were suppressed.
However, it was still impossible to suppress the death of yeast, and it was revealed that this imidazolium compound is highly toxic to enzymes and yeasts.
According to Patent Document 3, it has been known that a quaternary imidazolium compound has a fungicidal and fungicidal action.
Furthermore, extraction and recovery of decomposed oligosaccharides from a mixed solution of imidazolium compound / water was studied, but since oligosaccharides with a low degree of polymerization are dissolved in water, the imidazolium compound / water side There was a problem that many oligosaccharides remained and lost.
Based on such preliminary investigations, the present inventors have studied in detail a low cytotoxic solvent that solubilizes water-insoluble polysaccharides, and as a result, the present invention has been achieved.
本発明は、細胞毒性の低い多糖類可溶性溶媒を用いることで、植物由来のバイオマスを用いた副生成物が少なく、生産性の高いアルコール又は有機酸の製造方法の提供を目的とする。 An object of the present invention is to provide a method for producing an alcohol or organic acid with a high productivity by using a polysaccharide-soluble solvent having low cytotoxicity so that there are few by-products using plant-derived biomass.
本発明に係るエタノールの製造方法は、バイオマスを、植物由来の非水溶性多糖類を溶解でき、かつ細胞毒性の低い多糖類可溶性溶媒に溶解することで、溶解しない成分を分離除去するステップと、前記植物由来の非水溶性多糖類が溶解した溶液に固体酸触媒を加えることで前記多糖類をオリゴ糖類に分解するステップと、前記オリゴ糖類が含まれる溶液に水を加えるステップと、前記水を加えたオリゴ糖類溶液に糖化酵素及び酵母を加えるステップを有することを特徴とする。
植物由来の非水溶性多糖類としてはセルロース、ヘミセルロースが代表例であり、本発明にかかるアルコールの製造方法は、植物由来のバイオマスを原料として用いた点にあり、デンプン等の水溶性多糖類が混合している場合も含まれるが、水溶性の多糖類は水を溶媒として糖化及び発酵が可能であり、本発明が特に有効なのは、セルロースがヘミセルロース及びリグニンと結合したリグノセルロース等の植物細胞壁由来のバイオマスが原料に含まれる場合である。
多糖類が溶解した多糖類可溶性溶媒溶液に固体酸触媒を加えると多糖類のグリコシド結合を一部分解し、予備的に糖化する。
本発明にて、オリゴ糖類と表現したのは、二糖類から３０量体レベルの少糖類のみならず、一部単糖類にまで分解しているものを含む趣旨である。
In the method for producing ethanol according to the present invention, the biomass can be dissolved in a polysaccharide-soluble solvent that can dissolve plant-derived water-insoluble polysaccharides and has low cytotoxicity, thereby separating and removing components that do not dissolve, Decomposing the polysaccharide into oligosaccharides by adding a solid acid catalyst to the solution in which the plant-derived water-insoluble polysaccharide is dissolved; adding water to the solution containing the oligosaccharides; It has the step which adds a saccharification enzyme and yeast to the added oligosaccharide solution.
Cellulose and hemicellulose are typical examples of plant-derived water-insoluble polysaccharides, and the method for producing alcohol according to the present invention is in that plant-derived biomass is used as a raw material, and water-soluble polysaccharides such as starch are used. Although water-soluble polysaccharides are included, water-soluble polysaccharides can be saccharified and fermented using water as a solvent, and the present invention is particularly effective when derived from plant cell walls such as lignocellulose in which cellulose is combined with hemicellulose and lignin. This is a case where the biomass is contained in the raw material.
When a solid acid catalyst is added to a polysaccharide-soluble solvent solution in which the polysaccharide is dissolved, the glycosidic bond of the polysaccharide is partially broken and preliminarily saccharified.
In the present invention, the expression “oligosaccharide” is intended to include not only a disaccharide to a 30-mer level oligosaccharide but also a portion decomposed to a monosaccharide.
ここで細胞毒性の低い多糖類可溶性溶媒は、脂肪族第四級アンモニウム塩を主成分とするのがよく、特に細胞毒性の低い多糖類可溶性溶媒は、コリンに有機酸を混合したものであることが好ましい。
さらにコリンは塩化コリンがよい。
コリンは、図２に示した第四級アンモニウムの塩でＸ−がＣｌ−イオンの場合に塩化コリンとなる。
塩化コリンは融点が約２７０℃であることから、反応系を１００℃以下に抑えるには有機酸を混合して融点を下げるのがよい。
混合有機酸としてはクエン酸、マロン酸、フタル酸等の各種有機酸が例として挙げられるが、中でもクエン酸が好ましい。
本発明で細胞毒性の低いとは、セルロース可溶化化合物として公知のイミダゾリウム系化合物より酵素や酵母菌に対する毒性が低いものをいう。
オリゴ糖類のグリコシド結合を加水分解する糖化酵素としては、セルラーゼがよく、セルロースの他にヘミセルロースも糖化するものがよい。
Here, the polysaccharide-soluble solvent having low cytotoxicity should be mainly composed of an aliphatic quaternary ammonium salt. In particular, the polysaccharide-soluble solvent having low cytotoxicity should be a mixture of choline and an organic acid. Is preferred.
Furthermore, choline chloride is good for choline.
Choline is a salt of the quaternary ammonium shown in FIG. 2 and becomes choline chloride when X − is a Cl − ion.
Since choline chloride has a melting point of about 270 ° C., it is preferable to mix the organic acid to lower the melting point in order to keep the reaction system below 100 ° C.
Examples of the mixed organic acid include various organic acids such as citric acid, malonic acid, and phthalic acid. Among them, citric acid is preferable.
The term “low cytotoxicity” in the present invention means a substance having lower toxicity to enzymes and yeasts than a known imidazolium compound as a cellulose-solubilizing compound.
As a saccharifying enzyme that hydrolyzes a glycosidic bond of an oligosaccharide, cellulase is preferable, and one that saccharifies hemicellulose in addition to cellulose is preferable.
固体酸触媒とは、前記多糖類可溶性溶媒及びこれに水を加えた混合溶媒中に固体として存在し、酸触媒として機能するものをいい、固液分離により、系から容易に分離できる。
固体酸触媒としては、ゼオライト、アルミナ等の無機酸化物固体酸触媒、イオン交換樹脂等に用いられる高分子固体酸触媒、アモルファスカーボン等の炭素系固体酸触媒等が例として挙げられ、これらは単独又は混合して用いられる。
さらには、糖化酵素又は／及び酵母も担体に担持して生物的処理に使用すれば、反応後に担体を引き上げることで反応系から容易に分離でき、アルコール、有機酸と多糖類可溶性溶媒等とは蒸留等により容易に分離できるので多糖類可溶性溶媒を回収し再利用できる。
The solid acid catalyst refers to a solid acid catalyst that exists as a solid in the polysaccharide-soluble solvent and a mixed solvent obtained by adding water thereto and functions as an acid catalyst, and can be easily separated from the system by solid-liquid separation.
Examples of solid acid catalysts include inorganic oxide solid acid catalysts such as zeolite and alumina, polymer solid acid catalysts used for ion exchange resins, carbon solid acid catalysts such as amorphous carbon, and the like. Or it mixes and is used.
Furthermore, if saccharifying enzyme or / and yeast is also supported on a carrier and used for biological treatment, it can be easily separated from the reaction system by pulling up the carrier after the reaction, and alcohol, organic acid and polysaccharide-soluble solvent, etc. Since it can be easily separated by distillation or the like, the polysaccharide-soluble solvent can be recovered and reused.
本発明においては、細胞毒性の低い多糖類可溶性溶媒にバイオマスを加えることで、例えば、リグノセルロースからセルロース及びヘミセルロースを可溶化し、不溶性のリグニン等を容易に固液分離できる。
この固液分離した液体に固体酸触媒を添加することで、セルロース、ヘミセルロース等の非水溶性多糖類を予備的に、酸糖化し、水を添加してもセルロース、ヘミセルロース等の析出、沈殿を抑えることが可能になり、且つ、細胞毒性の低い多糖類可溶性溶媒を用いたので、その後にそのままセルラーゼ及び酵母菌を添加することで特異的糖化及び発酵ができるので、副生成物が少なく、従来に比較して短時間、高効率にアルコール又は有機酸を製造することができる。
また、固体酸触媒を用いたことで触媒を系から容易に分離、再利用ができる。
また、糖化酵素又は／及び酵母を担体に担持させることで、それを系から容易に分離でき、多糖類可溶性溶媒の回収再利用ができる。
In the present invention, by adding biomass to a polysaccharide-soluble solvent with low cytotoxicity, for example, cellulose and hemicellulose can be solubilized from lignocellulose, and insoluble lignin and the like can be easily solid-liquid separated.
By adding a solid acid catalyst to this solid-liquid separated liquid, water-insoluble polysaccharides such as cellulose and hemicellulose are preliminarily acidified, and even if water is added, precipitation and precipitation of cellulose, hemicellulose, etc. Since a polysaccharide-soluble solvent with low cytotoxicity can be suppressed, specific saccharification and fermentation can be performed by adding cellulase and yeast as it is, and there are few by-products. Compared to the above, alcohol or organic acid can be produced in a short time and with high efficiency.
Further, by using a solid acid catalyst, the catalyst can be easily separated from the system and reused.
Further, by supporting saccharifying enzyme or / and yeast on a carrier, it can be easily separated from the system, and the polysaccharide-soluble solvent can be recovered and reused.
まず始めに、多糖類可溶性溶媒の細胞毒性試験結果について説明する。
本発明に係る溶媒として塩化コリンに水を加え、容積で１０％濃度に調整したものと、比較例としてイミダゾリウム系化合物（1-butyl-3-methylimidazoliumchrolide）を容積で１０％濃度に水で薄めたものを用いて培地を作製し、発酵用酵母ＭＴ８−１株の培養をした。
その結果を図１のグラフに示す。
横軸が培養時間で、縦軸が酵母菌体の濃度を示す。
なお、コントロールとして水だけ加えたセルロース溶媒無添加のものの結果をあわせて示す。
培養時間に対して菌体量は増加し、２０時間で１０倍以上に増加した。
また、セルロース溶媒無添加のコントロールに対しても65％以上の菌体量増加率を示した。
一方、比較例のイミダゾリウム系化合物の場合は、菌体量は培養時間に対して減少した。
この結果から本発明に係る塩化コリンは、比較例のイミダゾリウム系化合物より細胞毒性が低いことを確認できた。
これは、コリンが細胞膜脂質の成分であり、塩化コリンは飼料添加物として使用されていることからも細胞毒性が低いと推定できる。
First, the cytotoxicity test results of the polysaccharide-soluble solvent will be described.
As a solvent according to the present invention, water is added to choline chloride and adjusted to a concentration of 10% by volume, and imidazolium compound (1-butyl-3-methylimidazolium chrolide) is diluted with water to a concentration of 10% by volume as a comparative example. A culture medium was prepared using the rice cake, and yeast for fermentation MT8-1 was cultured.
The result is shown in the graph of FIG.
The horizontal axis represents the culture time, and the vertical axis represents the yeast cell concentration.
In addition, as a control, the result of adding only water and adding no cellulose solvent is also shown.
The amount of bacterial cells increased with respect to the culture time, and increased to 10 times or more in 20 hours.
In addition, the cell mass increase rate was 65% or more compared to the control without addition of cellulose solvent.
On the other hand, in the case of the imidazolium compound of the comparative example, the amount of cells decreased with respect to the culture time.
From this result, it was confirmed that the choline chloride according to the present invention was less cytotoxic than the imidazolium compound of the comparative example.
This can be presumed that cytotoxicity is low because choline is a component of cell membrane lipid and choline chloride is used as a feed additive.
次に、アルコールの製造例について説明する。
塩化コリンに容積で約５０％のクエン酸を加え、約８０℃に加熱し液体状態にした。
これに、リグノセルロースとしてケナフパウダーを加え、２４時間反応させたところ、セルロース及びヘミセルロースが可溶化し、リグニンが不溶物として残った。
濾過により固液分離し、濾液に高分子系の固体酸触媒を加え、約１時間撹拌後に、濾過により固液分離した。
濾液に塩化コリン濃度が容積で１０％以下になるように水を加えた。
析出物が少し認められたが多くは、オリゴ糖類として混合溶媒に溶けていた。
さらに、セルラーゼと酵母菌を加え、約２４時間、糖化、発酵させ、定法に従い膜分離したところ、エタノールが得られた。
本実施例はアルコールの製造例であるが、酵素や酵母菌の種類を変えることで、各種有機酸を製造することも可能である。
Next, production examples of alcohol will be described.
About 50% by volume of citric acid was added to choline chloride and heated to about 80 ° C. to make it liquid.
When kenaf powder was added as lignocellulose and allowed to react for 24 hours, cellulose and hemicellulose were solubilized and lignin remained as an insoluble matter.
Solid-liquid separation was performed by filtration, a polymer-based solid acid catalyst was added to the filtrate, and after stirring for about 1 hour, solid-liquid separation was performed by filtration.
Water was added to the filtrate so that the choline chloride concentration was 10% or less by volume.
Although some precipitates were observed, many were dissolved in the mixed solvent as oligosaccharides.
Further, cellulase and yeast were added, saccharified and fermented for about 24 hours, and membrane separation was performed according to a conventional method, whereby ethanol was obtained.
This example is an example of alcohol production, but various organic acids can be produced by changing the type of enzyme or yeast.
Claims (1)
前記分離された液体に固体酸触媒を加えることで前記セルロース又は／及びヘミセルロースをオリゴ糖類に分解し固液分離するステップと、Decomposing the cellulose or / and hemicellulose into oligosaccharides by adding a solid acid catalyst to the separated liquid, and solid-liquid separation;
前記分離されたオリゴ糖類を含む液体に水を加え、さらにセルラーゼと酵母菌を加えることで糖化及び発酵させるステップを有することを特徴とするエタノールの製造方法。A method for producing ethanol, comprising the steps of adding water to the liquid containing the separated oligosaccharide, and further saccharifying and fermenting by adding cellulase and yeast.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009238797A JP5669171B2 (en) | 2009-10-16 | 2009-10-16 | Method for producing alcohol or organic acid using biomass |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009238797A JP5669171B2 (en) | 2009-10-16 | 2009-10-16 | Method for producing alcohol or organic acid using biomass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2011083231A JP2011083231A (en) | 2011-04-28 |
| JP5669171B2 true JP5669171B2 (en) | 2015-02-12 |
Family
ID=44076688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2009238797A Expired - Fee Related JP5669171B2 (en) | 2009-10-16 | 2009-10-16 | Method for producing alcohol or organic acid using biomass |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP5669171B2 (en) |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0806908A2 (en) * | 2007-01-23 | 2014-04-29 | Basf Se | PROCESSES FOR PREPARING A GLUCOSE PRODUCT FROM LIGNOCELLULOSTIC MATERIAL, AND FOR PREPARING A MICROBIAN METABOLISM PRODUCT, GLUCOSE PRODUCT, AND LIGNIN PRODUCT |
| AU2009210489A1 (en) * | 2008-01-31 | 2009-08-13 | Battelle Energy Alliance, Llc | Thermophilic and thermoacidophilic biopolymer- degrading genes and enzymes from Alicyclobacillus acidocaldarius and related organisms, methods |
| JP2009203454A (en) * | 2008-01-31 | 2009-09-10 | Toyota Central R&D Labs Inc | Method of producing cellulose decomposition product utilizing ionic liquid |
| JP2009189277A (en) * | 2008-02-13 | 2009-08-27 | Toyota Motor Corp | Method for treating woody biomass and method for producing organic acid or alcohol |
-
2009
- 2009-10-16 JP JP2009238797A patent/JP5669171B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JP2011083231A (en) | 2011-04-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8236536B2 (en) | Saccharifying cellulose | |
| JP5190858B2 (en) | Production method of low molecular weight carbohydrates from materials containing polysaccharides | |
| HUE035521T2 (en) | Conversion of biomass | |
| WO2012102175A1 (en) | Cellulosic biomass treatment method, method of producing sugar, alcohol or organic acid from cellulosic biomass | |
| CN105392793A (en) | Improved process for the organosolv treatment of lignocellulosic biomass | |
| JP2011205933A (en) | Method for producing high-concentration saccharified liquid | |
| CN102660882A (en) | Method for producing cellulose and fuel ethanol by dissolving plant straw with solvent | |
| CN106480128B (en) | Method for improving efficiency of cellulose in hydrolyzing rice straws by using lactic acid and guanidine hydrochloride | |
| Dai et al. | Multi-strategy in production of high titer gluconic acid by the fermentation of concentrated cellulosic hydrolysate with Gluconobacter oxydans | |
| CN111534556A (en) | Method for preparing high-concentration monosaccharide solution by using poplar enzyme method | |
| JP5669171B2 (en) | Method for producing alcohol or organic acid using biomass | |
| KR101543067B1 (en) | Biological pretreatment mehtods for sea algae using mixed microorganism | |
| KR101744817B1 (en) | Method for preparing galactose using agarese | |
| JP5544507B2 (en) | Method for producing degradation products from cellulose-containing materials | |
| JP2011050950A (en) | Method of producing decomposition product from cellulose-containing material | |
| JP2012055167A (en) | Method for treating cellulose-containing material and use thereof | |
| CN113289680A (en) | Two-phase catalyst, preparation method thereof and application thereof in lignocellulose biomass conversion | |
| CN102199641A (en) | Method for extracting sugar from enzymic hydrolysate of jerusalem artichoke residues | |
| JP2012139144A (en) | Method for producing sugar comprising glucose as main component | |
| CN110628832A (en) | Method for preparing straw ethanol with assistance of ionic liquid | |
| JP6474150B2 (en) | Saccharification method of biomass raw material | |
| WO2024058256A1 (en) | Method for producing monosaccharide or oligosaccharide from polysaccharide, solution used in said production method, and composition including monosaccharide or oligosaccharide | |
| JP2010083850A (en) | Saccharification of lignocellulose and ethanol fermentation method | |
| US8497097B2 (en) | Chlorine dioxide treatment of biomass feedstock | |
| WO2018042464A1 (en) | Rapid enzymatic hydrolysis of substrates for production of fermentable sugars |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20121015 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20140409 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20140522 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20141203 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20141211 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 5669171 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |