JP6703562B2 - Method for producing polyphenol composition from bagasse - Google Patents
Method for producing polyphenol composition from bagasse Download PDFInfo
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- JP6703562B2 JP6703562B2 JP2018102472A JP2018102472A JP6703562B2 JP 6703562 B2 JP6703562 B2 JP 6703562B2 JP 2018102472 A JP2018102472 A JP 2018102472A JP 2018102472 A JP2018102472 A JP 2018102472A JP 6703562 B2 JP6703562 B2 JP 6703562B2
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- 150000008442 polyphenolic compounds Chemical class 0.000 title claims description 57
- 235000013824 polyphenols Nutrition 0.000 title claims description 56
- 239000000203 mixture Substances 0.000 title claims description 43
- 241000609240 Ambelania acida Species 0.000 title claims description 37
- 239000010905 bagasse Substances 0.000 title claims description 36
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 239000007788 liquid Substances 0.000 claims description 59
- 238000000034 method Methods 0.000 claims description 43
- 125000003118 aryl group Chemical group 0.000 claims description 38
- 239000003463 adsorbent Substances 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000012670 alkaline solution Substances 0.000 claims description 27
- 238000010828 elution Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 20
- 238000001914 filtration Methods 0.000 claims description 19
- 229920005989 resin Polymers 0.000 claims description 19
- 239000011347 resin Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000000706 filtrate Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 6
- CHRJZRDFSQHIFI-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;styrene Chemical compound C=CC1=CC=CC=C1.C=CC1=CC=CC=C1C=C CHRJZRDFSQHIFI-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- KSEBMYQBYZTDHS-HWKANZROSA-M (E)-Ferulic acid Natural products COC1=CC(\C=C\C([O-])=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-M 0.000 description 16
- KSEBMYQBYZTDHS-HWKANZROSA-N ferulic acid Chemical compound COC1=CC(\C=C\C(O)=O)=CC=C1O KSEBMYQBYZTDHS-HWKANZROSA-N 0.000 description 16
- 235000001785 ferulic acid Nutrition 0.000 description 16
- 229940114124 ferulic acid Drugs 0.000 description 16
- KSEBMYQBYZTDHS-UHFFFAOYSA-N ferulic acid Natural products COC1=CC(C=CC(O)=O)=CC=C1O KSEBMYQBYZTDHS-UHFFFAOYSA-N 0.000 description 16
- QURCVMIEKCOAJU-UHFFFAOYSA-N trans-isoferulic acid Natural products COC1=CC=C(C=CC(O)=O)C=C1O QURCVMIEKCOAJU-UHFFFAOYSA-N 0.000 description 16
- 230000002378 acidificating effect Effects 0.000 description 13
- 239000002253 acid Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 241000196324 Embryophyta Species 0.000 description 7
- NGSWKAQJJWESNS-UHFFFAOYSA-N 4-coumaric acid Chemical compound OC(=O)C=CC1=CC=C(O)C=C1 NGSWKAQJJWESNS-UHFFFAOYSA-N 0.000 description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 240000000111 Saccharum officinarum Species 0.000 description 6
- 235000007201 Saccharum officinarum Nutrition 0.000 description 6
- 150000004676 glycans Chemical class 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 229920001282 polysaccharide Polymers 0.000 description 6
- 239000005017 polysaccharide Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 229920002678 cellulose Polymers 0.000 description 5
- 239000001913 cellulose Substances 0.000 description 5
- 235000013305 food Nutrition 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 239000003480 eluent Substances 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 238000011085 pressure filtration Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- NGSWKAQJJWESNS-ZZXKWVIFSA-M 4-Hydroxycinnamate Natural products OC1=CC=C(\C=C\C([O-])=O)C=C1 NGSWKAQJJWESNS-ZZXKWVIFSA-M 0.000 description 3
- DFYRUELUNQRZTB-UHFFFAOYSA-N Acetovanillone Natural products COC1=CC(C(C)=O)=CC=C1O DFYRUELUNQRZTB-UHFFFAOYSA-N 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229920001429 chelating resin Polymers 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 229920002488 Hemicellulose Polymers 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004904 shortening Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- FYGDTMLNYKFZSV-URKRLVJHSA-N (2s,3r,4s,5s,6r)-2-[(2r,4r,5r,6s)-4,5-dihydroxy-2-(hydroxymethyl)-6-[(2r,4r,5r,6s)-4,5,6-trihydroxy-2-(hydroxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-6-(hydroxymethyl)oxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1OC1[C@@H](CO)O[C@@H](OC2[C@H](O[C@H](O)[C@H](O)[C@H]2O)CO)[C@H](O)[C@H]1O FYGDTMLNYKFZSV-URKRLVJHSA-N 0.000 description 1
- 229920002498 Beta-glucan Polymers 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- 108010059892 Cellulase Proteins 0.000 description 1
- 241000233866 Fungi Species 0.000 description 1
- 229930006000 Sucrose Natural products 0.000 description 1
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 229930002877 anthocyanin Natural products 0.000 description 1
- 235000010208 anthocyanin Nutrition 0.000 description 1
- 239000004410 anthocyanin Substances 0.000 description 1
- 150000004636 anthocyanins Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 150000001720 carbohydrates Chemical group 0.000 description 1
- 150000001765 catechin Chemical class 0.000 description 1
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 description 1
- 235000005487 catechin Nutrition 0.000 description 1
- 229940106157 cellulase Drugs 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229930003935 flavonoid Natural products 0.000 description 1
- 150000002215 flavonoids Chemical class 0.000 description 1
- 235000017173 flavonoids Nutrition 0.000 description 1
- 235000011389 fruit/vegetable juice Nutrition 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920005610 lignin Chemical group 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000010451 perlite Substances 0.000 description 1
- 235000019362 perlite Nutrition 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229930015704 phenylpropanoid Natural products 0.000 description 1
- 125000001474 phenylpropanoid group Chemical group 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229960004793 sucrose Drugs 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
Classifications
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L35/00—Food or foodstuffs not provided for in groups A23L5/00 – A23L33/00; Preparation or treatment thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
- C07G1/00—Lignin; Lignin derivatives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B63/00—Purification; Separation; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/42—Separation; Purification; Stabilisation; Use of additives
- C07C51/47—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/42—Unsaturated compounds containing hydroxy or O-metal groups
- C07C59/52—Unsaturated compounds containing hydroxy or O-metal groups a hydroxy or O-metal group being bound to a carbon atom of a six-membered aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C59/40—Unsaturated compounds
- C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
- C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
Description
本発明は、バガスからのポリフェノール組成物の製造方法に関する。 The present invention relates to a method for producing a polyphenol composition from bagasse.
近年、環境負荷軽減の観点から、バイオマスの活用が検討されている。その一例として、植物材料からポリフェノール組成物を得る方法がある。特許文献１には、植物材料、特に廃トウモロコシをアルカリ性煮出および／または酵素的処理にかけ、フェルラ酸および多糖類を含む水性液相を回収し、その後フェルラ酸を回収する方法が記載されている。 In recent years, utilization of biomass has been studied from the viewpoint of reducing environmental load. An example thereof is a method of obtaining a polyphenol composition from plant material. Patent Document 1 describes a method of recovering an aqueous liquid phase containing ferulic acid and a polysaccharide by subjecting a plant material, particularly waste corn, to alkaline boiling and/or enzymatic treatment, and then recovering ferulic acid. ..
非特許文献１〜３には、バガス等をアルカリ溶液で処理することによって、ポリフェノール類を得る方法が記載されている。非特許文献１には、サトウキビ外皮にアルカリ処理を行うと、多糖類とのエステル結合が加水分解を受け、フェルラ酸又はｐ−クマル酸が遊離することが開示されている。非特許文献２及び非特許文献３には、クマル酸及びフェルラ酸抽出のためのアルカリ処理として、バガスを水酸化ナトリウム水溶液で処理することにより、クマル酸が遊離することが開示されている。 Non-Patent Documents 1 to 3 describe methods for obtaining polyphenols by treating bagasse or the like with an alkaline solution. Non-Patent Document 1 discloses that when the sugarcane rind is subjected to an alkali treatment, the ester bond with the polysaccharide is hydrolyzed to release ferulic acid or p-coumaric acid. Non-Patent Documents 2 and 3 disclose that coumaric acid is released by treating bagasse with an aqueous sodium hydroxide solution as an alkali treatment for extracting coumaric acid and ferulic acid.
一方、バイオマスの活用に関する他の例として、主生産物として絶対量が多く回収率も高いことから、植物材料から糖を回収することも行われており、植物材料の加水分解方法が広く検討されている。例えば、特許文献２及び特許文献３には、バガス等のセルロース含有バイオマスについて糸状菌由来セルラーゼによる加水分解を行う工程を含む、糖液の製造方法が記載されている。 On the other hand, as another example of utilization of biomass, sugar is also recovered from plant material because of its large absolute amount and high recovery rate as a main product, and hydrolysis methods of plant material have been widely studied. ing. For example, Patent Documents 2 and 3 describe a method for producing a sugar solution, which includes a step of hydrolyzing a cellulose-containing biomass such as bagasse with a cellulase derived from a filamentous fungus.
植物材料から糖を得るためには、植物材料の細胞壁を、セルロース、マトリックス多糖類（ヘミセルロース及びβ-グルカン）、及びリグニンの各構造に分離する必要がある。細胞壁をある程度分離した後で、セルロース及びマトリックス多糖類を加水分解（酵素処理）することで、糖を得ることができる。 In order to obtain sugar from plant material, it is necessary to separate the cell wall of the plant material into cellulose, matrix polysaccharide (hemicellulose and β-glucan), and lignin structures. After separating the cell wall to some extent, the sugar can be obtained by hydrolyzing (enzymatically treating) the cellulose and the matrix polysaccharide.
特許文献２及び３に記載されている糖液の製造工程では、バガスを加水分解する前に、アルカリ溶液による前処理が行われる。前処理により得られる固形分にはセルロース及びヘミセルロースが含まれるため、これらを加水分解する糖化工程により糖液を得ることができる。しかし、前処理後の液分（前処理液）は糖液を得る上では不要であるために、これまで廃棄されていた。 In the sugar solution manufacturing process described in Patent Documents 2 and 3, a pretreatment with an alkaline solution is performed before hydrolyzing bagasse. Since the solid content obtained by the pretreatment contains cellulose and hemicellulose, a sugar solution can be obtained by a saccharification step of hydrolyzing these. However, the liquid component after the pretreatment (pretreatment liquid) is unnecessary for obtaining the sugar liquid, and thus has been discarded so far.
本発明は、バガスからポリフェノール組成物を製造するための新規な方法を提供することを目的とする。 The present invention aims to provide a novel method for producing a polyphenol composition from bagasse.
本発明者らは、糖液の製造工程で発生する前処理液にクマル酸、フェルラ酸等のポリフェノール類が含まれていることを見出し、更に、この前処理液を所定の方法で処理することにより、前処理液中のポリフェノール組成物を極めて効率的に製造できることを見出した。 The present inventors have found that the pretreatment liquid generated in the production process of the sugar liquid contains polyphenols such as coumaric acid and ferulic acid, and further treats this pretreatment liquid by a predetermined method. It was found that the polyphenol composition in the pretreatment liquid can be produced very efficiently.
すなわち本発明は、バガスからのポリフェノール組成物の製造方法であって、水酸化ナトリウム水溶液、水酸化カリウム水溶液、及びアンモニア水溶液からなる群より選ばれる少なくとも１種のアルカリ溶液を用いてバガスを前処理し、前処理液を得る工程と、前処理液のｐＨを塩酸で酸性に調整してからろ過し、ろ液を回収する工程と、ろ液を、芳香族系合成吸着剤が充填されたカラムに通液し、芳香族系合成吸着剤に吸着した成分をエタノール及び水の混合溶媒で溶出して溶出画分をポリフェノール組成物として得る工程と、を備える、製造方法を提供する。 That is, the present invention is a method for producing a polyphenol composition from bagasse, wherein bagasse is pretreated with at least one alkaline solution selected from the group consisting of an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution and an aqueous ammonia solution. Then, the step of obtaining the pretreatment liquid, the step of adjusting the pH of the pretreatment liquid to acidic with hydrochloric acid and then filtering, and collecting the filtrate, the filtrate is a column packed with an aromatic synthetic adsorbent. And elution of the component adsorbed on the aromatic synthetic adsorbent with a mixed solvent of ethanol and water to obtain an elution fraction as a polyphenol composition.
アルカリ溶液の温度は、好ましくは６０〜１００℃である。 The temperature of the alkaline solution is preferably 60 to 100°C.
アルカリ溶液は、好ましくは水酸化ナトリウム水溶液である。水酸化ナトリウム水溶液の濃度は、０．１〜１．０質量％であってよい。 The alkaline solution is preferably an aqueous sodium hydroxide solution. The concentration of the aqueous sodium hydroxide solution may be 0.1 to 1.0% by mass.
溶出工程における芳香族系合成吸着剤は、好ましくはスチレン−ジビニルベンゼン系合成吸着剤である。 The aromatic synthetic adsorbent in the elution step is preferably a styrene-divinylbenzene synthetic adsorbent.
本発明によれば、バガスからポリフェノール組成物を製造するための新規な方法を提供することができる。 According to the present invention, a novel method for producing a polyphenol composition from bagasse can be provided.
以下、本発明の実施形態について説明する。ただし、本発明は以下の実施形態に限定されるものではない。 Hereinafter, embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments.
本発明において製造されるポリフェノール組成物は、１種以上のポリフェノールを含む組成物である。本明細書におけるポリフェノールは、フォーリン−チオカルト法で測定できるフェノール性化合物である。ポリフェノールは、より具体的には、ｐ−クマル酸又はフェルラ酸のようなフェニルプロパノイド、カテキン又はアントシアニンのようなフラボノイド等であってよい。 The polyphenol composition produced in the present invention is a composition containing one or more polyphenols. Polyphenol in this specification is a phenolic compound that can be measured by the Folin-Ciocalteu method. The polyphenols may more specifically be phenylpropanoids such as p-coumaric acid or ferulic acid, flavonoids such as catechins or anthocyanins and the like.
本発明の一実施形態に係る製造方法では、まず、アルカリ溶液を用いてバガスを前処理し、前処理液を得る（前処理工程）。 In the manufacturing method according to one embodiment of the present invention, first, bagasse is pretreated with an alkaline solution to obtain a pretreatment liquid (pretreatment step).
本明細書において、バガスとは甘蔗の搾りかすであり、典型的には製糖工場における製糖過程で排出されるバガスをいう。なお、製糖工場における製糖過程で排出されるバガスには、最終圧搾機を出た最終バガスだけではなく、第１圧搾機を含む以降の圧搾機に食い込まれた細裂甘蔗も含まれる。好ましくは、製糖工場において圧搾工程により糖汁を圧搾した後に排出されるバガスを用いる。圧搾工程より排出されるバガスは、甘蔗の種類、収穫時期等により、その含まれる水分、糖分、及びその組成比が異なるが、これらのバガスを任意に用いることができる。バガスは、黒糖工場において排出される甘蔗圧搾後に残るバガスであってもよい。また、実験室レベルの小規模な実施では、甘蔗から糖液を圧搾した後のバガスを用いてもよい。 In the present specification, bagasse is squeezed sugarcane residue and typically refers to bagasse discharged in the sugar production process in a sugar factory. Note that the bagasse discharged in the sugar production process in the sugar factory includes not only the final bagasse that has left the final press machine, but also the shredded sugar cane that has been eaten by the subsequent press machines including the first press machine. Preferably, bagasse that is discharged after squeezing the sugar juice in the squeezing process in a sugar factory is used. The bagasse discharged from the squeezing step has different water content, sugar content, and composition ratio depending on the type of sugar cane, the harvest time, and the like, but these bagasses can be arbitrarily used. The bagasse may be bagasse remaining after squeezing sugar cane discharged in a brown sugar factory. Further, in a small-scale implementation at a laboratory level, bagasse after squeezing sugar solution from cane sugar may be used.
アルカリ溶液を用いた前処理は、一実施形態において、アルカリ溶液をバガスに接触させる処理であってよい。アルカリ溶液を接触させる方法としては、例えば、アルカリ溶液をバガスに振りかける方法、バガスをアルカリ溶液に浸漬させる方法等が挙げられる。バガスをアルカリ溶液に浸漬させる方法においては、バガス及びアルカリ溶液の混合物を撹拌しながら浸漬させてもよい。 The pretreatment with the alkaline solution may be a treatment of bringing the alkaline solution into contact with bagasse in one embodiment. Examples of the method of bringing the alkaline solution into contact include a method of sprinkling the alkaline solution on bagasse, a method of immersing the bagasse in the alkaline solution, and the like. In the method of immersing bagasse in the alkaline solution, the mixture of bagasse and the alkaline solution may be immersed while stirring.
アルカリ溶液は、水酸化ナトリウム水溶液、水酸化カリウム水溶液、及びアンモニア水溶液からなる群より選ばれる少なくとも１種であってよい。アルカリ溶液は、安価であり、食品製造工程で用いられる観点から、好ましくは水酸化ナトリウム水溶液である。 The alkaline solution may be at least one selected from the group consisting of an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous ammonia solution. The alkaline solution is preferably an aqueous sodium hydroxide solution because it is inexpensive and is used in the food manufacturing process.
アルカリ溶液の濃度は、使用するアルカリ溶液の種類によって適宜設定してよいが、前処理の処理時間を短縮する観点から、好ましくは０．１質量％以上であり、より好ましくは０．２質量％以上であり、更に好ましくは０．３質量％以上である。アルカリ溶液の濃度は、抽出効率を向上させる観点から、好ましくは１０質量％以下であり、より好ましくは５質量％以下であり、更に好ましくは１．０質量％以下である。 The concentration of the alkaline solution may be appropriately set depending on the type of the alkaline solution used, but from the viewpoint of shortening the treatment time of the pretreatment, it is preferably 0.1% by mass or more, more preferably 0.2% by mass. It is above, and more preferably 0.3% by mass or more. From the viewpoint of improving the extraction efficiency, the concentration of the alkaline solution is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1.0% by mass or less.
前処理工程時におけるアルカリ溶液は加熱されていることが好ましい。アルカリ溶液の温度（液温）は、前処理の処理時間を短縮する観点から、好ましくは５０℃以上であり、より好ましくは６０℃以上であり、更に好ましくは８０℃以上である。アルカリ溶液の温度は、前処理液に多糖類を残存させないようにする観点から、好ましくは１１０℃以下であり、より好ましくは１０５℃以下であり、更に好ましくは１００℃以下である。 The alkaline solution during the pretreatment step is preferably heated. The temperature of the alkaline solution (liquid temperature) is preferably 50° C. or higher, more preferably 60° C. or higher, and even more preferably 80° C. or higher, from the viewpoint of shortening the pretreatment time. The temperature of the alkaline solution is preferably 110° C. or lower, more preferably 105° C. or lower, still more preferably 100° C. or lower, from the viewpoint of preventing the polysaccharide from remaining in the pretreatment liquid.
アルカリ溶液の添加量は、バガス１００質量部に対して、５０質量部以上、１００質量部以上、又は１０００質量部以上であってよく、また、前処理工程における処理時間は、アルカリ溶液の種類、温度及び添加量によって適宜調整してよいが、例えば、１〜５時間であってよい。 The addition amount of the alkaline solution may be 50 parts by mass or more, 100 parts by mass or more, or 1000 parts by mass or more with respect to 100 parts by mass of bagasse, and the treatment time in the pretreatment step is the type of the alkaline solution, The time may be appropriately adjusted depending on the temperature and the addition amount, but may be, for example, 1 to 5 hours.
前処理液のｐＨは、８以上、又は９以上であってよく、１３以下、又は１２以下であってよい。 The pH of the pretreatment liquid may be 8 or higher, or 9 or higher, and 13 or lower, or 12 or lower.
本実施形態に係る前処理工程では、上述したアルカリ処理を行った後、不溶分と液分を分離してもよい。その場合、分離後の液分を前処理液とすることができる。不溶分と液分を分離する方法は、ストレーナー、ろ過、遠心分離、デカンテーション等による分離であってよい。 In the pretreatment step according to the present embodiment, the insoluble matter and the liquid matter may be separated after performing the above-mentioned alkali treatment. In that case, the separated liquid can be used as a pretreatment liquid. The method of separating the insoluble matter and the liquid matter may be separation by a strainer, filtration, centrifugation, decantation or the like.
前処理工程の後、得られた前処理液のｐＨを塩酸で酸性に調整してからろ過し、ろ液を回収する（ろ過工程）。 After the pretreatment step, the pH of the obtained pretreatment solution is adjusted to be acidic with hydrochloric acid and then filtered, and the filtrate is recovered (filtration step).
ろ過工程では、まず、前処理液に塩酸を添加して前処理液のｐＨを酸性に調整する。塩酸の濃度は、ｐＨが調整できれば適宜設定されてよく、例えば０．１〜３５質量％であってよい。ｐＨの調整のために塩酸を用いることにより、製造したポリフェノール組成物を食品工業分野において利用することができる。 In the filtration step, first, hydrochloric acid is added to the pretreatment liquid to adjust the pH of the pretreatment liquid to be acidic. The concentration of hydrochloric acid may be appropriately set as long as the pH can be adjusted, and may be, for example, 0.1 to 35% by mass. By using hydrochloric acid to adjust the pH, the produced polyphenol composition can be used in the food industry field.
塩酸添加後の前処理液（以下、「酸性前処理液」ともいう。）のｐＨは、ポリフェノールの凝集沈殿の抑制及び合成吸着剤の吸着を両立させる観点から、好ましくは１．５以上であり、より好ましくは２．０以上であり、更に好ましくは２．５以上であり、また、好ましくは４．５以下であり、より好ましくは４．０以下であり、更に好ましくは３．５以下である。酸性前処理液のｐＨが１．５以上であると、ポリフェノールが凝集沈殿しにくいため、ｐＨ調整後にろ過を実施してもポリフェノールがろ過により除去されにくくなる。一方、酸性前処理液のｐＨが４．５以下であると、後述する溶出工程において、芳香族系合成吸着剤へポリフェノールを吸着させやすくすることができる。すなわち、酸性前処理液のｐＨが上記の範囲内であると、ポリフェノールの凝集沈殿を抑制しつつ、芳香族系合成吸着剤への吸着を促進させることができる。 The pH of the pretreatment liquid after the addition of hydrochloric acid (hereinafter, also referred to as “acidic pretreatment liquid”) is preferably 1.5 or more from the viewpoint of simultaneously suppressing the aggregation and precipitation of polyphenol and the adsorption of the synthetic adsorbent. , More preferably 2.0 or more, further preferably 2.5 or more, preferably 4.5 or less, more preferably 4.0 or less, further preferably 3.5 or less. is there. If the pH of the acidic pretreatment liquid is 1.5 or more, the polyphenols are less likely to aggregate and precipitate, so that even if filtration is performed after adjusting the pH, the polyphenols are difficult to remove by filtration. On the other hand, when the pH of the acidic pretreatment liquid is 4.5 or less, the polyphenol can be easily adsorbed to the aromatic synthetic adsorbent in the elution step described later. That is, when the pH of the acidic pretreatment liquid is within the above range, the adsorption of the polyphenol on the aromatic synthetic adsorbent can be promoted while suppressing the aggregation and precipitation of the polyphenol.
酸性前処理液のｐＨを上記の範囲に調整することにより、酸性前処理液に不溶な成分が析出する。ろ過工程では、析出した不溶性成分をろ過により除去する。ろ過は、自然ろ過、減圧ろ過、加圧ろ過、遠心ろ過等により行われてよく、好ましくは加圧ろ過により行われる。加圧ろ過は、加圧ろ過機（フィルタープレス）により行われてよい。 By adjusting the pH of the acidic pretreatment liquid to the above range, the components insoluble in the acidic pretreatment liquid are precipitated. In the filtration step, the precipitated insoluble component is removed by filtration. The filtration may be carried out by natural filtration, vacuum filtration, pressure filtration, centrifugal filtration, etc., preferably pressure filtration. The pressure filtration may be performed by a pressure filtration machine (filter press).
ろ過の際には、酸性前処理液にろ過助剤を添加してもよい。ろ過助剤としては、珪藻土、パーライト、及びセルロース等を挙げることができる。ろ過助剤を添加する場合、ろ過助剤の含有量は、酸性前処理液全量を基準として、０．２〜２．０質量％であってよい。 At the time of filtration, a filter aid may be added to the acidic pretreatment liquid. Examples of filter aids include diatomaceous earth, perlite, and cellulose. When the filter aid is added, the content of the filter aid may be 0.2 to 2.0 mass% based on the total amount of the acidic pretreatment liquid.
ろ過工程の後、得られたろ液を、芳香族系合成吸着剤が充填されたカラムに通液する。芳香族系合成吸着剤に吸着した成分を、エタノール及び水の混合溶媒で溶出して、溶出画分を得ることにより、ポリフェノール組成物を製造することができる（溶出工程）。 After the filtration step, the obtained filtrate is passed through a column filled with an aromatic synthetic adsorbent. The polyphenol composition can be produced by eluting the components adsorbed on the aromatic synthetic adsorbent with a mixed solvent of ethanol and water to obtain an elution fraction (elution step).
芳香族系合成吸着剤は、ろ液に含まれるポリフェノール組成物を効率よく吸着させる観点から、芳香族系樹脂からなる合成吸着剤である。芳香族系樹脂としては、スチレン−ジビニルベンゼン系の芳香族樹脂が好ましい。スチレン−ジビニルベンゼン系の芳香族樹脂としては、例えば、疎水性置換基を有する芳香族系樹脂、無置換基型の芳香族系樹脂、無置換基型に特殊処理を施した芳香族系樹脂等の多孔性樹脂等が挙げられる。スチレン−ジビニルベンゼン系の芳香族系樹脂としては、無置換基型の芳香族系樹脂、又は無置換基型に高比表面積化の特殊処理を施した芳香族系樹脂が好ましく、無置換基型に高比表面積化の特殊処理を施した芳香族系樹脂がより好ましい。 The aromatic synthetic adsorbent is a synthetic adsorbent composed of an aromatic resin from the viewpoint of efficiently adsorbing the polyphenol composition contained in the filtrate. As the aromatic resin, a styrene-divinylbenzene aromatic resin is preferable. Examples of the styrene-divinylbenzene-based aromatic resin include an aromatic-based resin having a hydrophobic substituent, an unsubstituted-group-type aromatic resin, and an unsubstituted-group-type aromatic resin. And the like. The styrene-divinylbenzene-based aromatic resin is preferably an unsubstituted aromatic resin or an unsubstituted aromatic resin which has been subjected to a special treatment for increasing the specific surface area. It is more preferable to use an aromatic resin that has been subjected to a special treatment for increasing the specific surface area.
芳香族系合成吸着剤の比表面積は、吸着率を向上させる観点から、乾燥質量として、好ましくは５００ｍ２/ｇ以上であり、より好ましくは７００ｍ２/ｇ以上である。芳香族系合成吸着剤の比表面積は、ガス吸着法の測定値をＢＥＴの式に当てはめることより算出することができる。芳香族系合成吸着剤の最頻度細孔直径（最頻細孔径）は、高分離性及び高吸着性の観点から、好ましくは６００Å以下であり、より好ましくは３００Å以下であり、更に好ましくは２００Å以下である。最頻度細孔直径は、ガス吸着法により測定することができる。 The specific surface area of the aromatic synthetic adsorbent is preferably 500 m 2 /g or more, more preferably 700 m 2 /g or more, as a dry mass, from the viewpoint of improving the adsorption rate. The specific surface area of the aromatic synthetic adsorbent can be calculated by applying the measured value of the gas adsorption method to the BET formula. The most frequent pore diameter (most frequent pore diameter) of the aromatic synthetic adsorbent is preferably 600 Å or less, more preferably 300 Å or less, and further preferably 200 Å, from the viewpoint of high separability and high adsorbability. It is below. The most frequent pore diameter can be measured by a gas adsorption method.
このような合成吸着剤は市販されており、例えばダイヤイオン（商標）ＨＰ−１０、ＨＰ−２０、ＨＰ−２１、ＨＰ−３０、ＨＰ−４０、ＨＰ−５０（以上、無置換基型の芳香族系樹脂、いずれも商品名、三菱ケミカル株式会社製）；ＳＰ−８２５、ＳＰ−８００、ＳＰ−８５０、ＳＰ−８７５、ＳＰ−７０、ＳＰ−７００（以上、無置換基型に特殊処理を施した芳香族系樹脂、いずれも商品名、三菱ケミカル株式会社製）；ＳＰ−９００（芳香族系樹脂、商品名、三菱ケミカル株式会社製）；アンバーライト（商標）ＸＡＤ−２、ＸＡＤ−４、ＸＡＤ−１６、ＸＡＤ−１８、ＸＡＤ−２０００（以上、芳香族系樹脂、いずれも商品名、株式会社オルガノ製）；ダイヤイオン（商標）ＳＰ−２０５、ＳＰ−２０６、ＳＰ−２０７（以上、疎水性置換基を有する芳香族系樹脂、いずれも商品名、三菱ケミカル株式会社製）；ＨＰ−２ＭＧ、ＥＸ−００２１（以上、疎水性置換基を有する芳香族系樹脂、いずれも商品名、三菱ケミカル株式会社製）などが挙げられる。その中でも、ダイヤイオン（商標）ＳＰ−８５０が好ましい。これらの合成吸着剤は、１種単独でも、２種以上を組み合わせて用いてもよい。 Such synthetic adsorbents are commercially available, and include, for example, Diaion (trademark) HP-10, HP-20, HP-21, HP-30, HP-40, HP-50 (above, non-substituted group type aroma). Group resins, all trade names, manufactured by Mitsubishi Chemical Co., Ltd.; SP-825, SP-800, SP-850, SP-875, SP-70, SP-700 (above, special treatment for non-substituted group type) Aromatic resin that has been applied, all trade names, manufactured by Mitsubishi Chemical Co., Ltd.; SP-900 (aromatic resin, trade name, manufactured by Mitsubishi Chemical Co., Ltd.); Amberlite (trademark) XAD-2, XAD-4 , XAD-16, XAD-18, XAD-2000 (above, aromatic resins, all are trade names, manufactured by Organo Corporation); Diaion (trademark) SP-205, SP-206, SP-207 (above, Aromatic resins having hydrophobic substituents, all trade names, manufactured by Mitsubishi Chemical Corporation; HP-2MG, EX-0021 (above, aromatic resins having hydrophobic substituents, all trade names, Mitsubishi Chemical Co., Ltd.) and the like. Among them, DIAION (trademark) SP-850 is preferable. These synthetic adsorbents may be used alone or in combination of two or more.
カラムに充填する芳香族系合成吸着剤の量は、カラムの大きさ、合成吸着剤の種類等によって適宜決定することができる。 The amount of the aromatic synthetic adsorbent packed in the column can be appropriately determined depending on the size of the column, the type of the synthetic adsorbent, and the like.
ろ液をカラムに通液する際、ろ液の温度は、２５〜４５℃であってよい。ろ液をカラムに通液する時の通液量及び通液速度は、芳香族系合成吸着剤の種類等によって適宜決定することができる。 When passing the filtrate through the column, the temperature of the filtrate may be 25 to 45°C. The flow rate and flow rate when the filtrate is passed through the column can be appropriately determined depending on the kind of the aromatic synthetic adsorbent and the like.
溶出工程においては、通液終了後、カラムに吸着された成分を、エタノール及び水の混合溶媒により溶出する。混合溶媒の混合体積比（エタノール／水）は、５０／５０〜９９／１であってよく、溶出効率を向上させる観点からは、好ましくは、５０／５０〜７０／３０の範囲内である。溶出速度は、カラムの大きさ、芳香族系合成吸着剤の種類等によって適宜決定することができる。なお、カラムに吸着された成分を効率的に溶出させるために、ろ液をカラムに通液する前に、カラム内を水洗することが好ましい。 In the elution step, the components adsorbed on the column are eluted with a mixed solvent of ethanol and water after the passage of the liquid. The mixed volume ratio (ethanol/water) of the mixed solvent may be 50/50 to 99/1, and from the viewpoint of improving the elution efficiency, it is preferably within the range of 50/50 to 70/30. The elution rate can be appropriately determined depending on the size of the column, the type of the aromatic synthetic adsorbent, and the like. In order to efficiently elute the components adsorbed on the column, it is preferable to wash the inside of the column with water before passing the filtrate through the column.
溶出工程において溶出画分を得ることにより、バガス由来のポリフェノール組成物を製造することができる。 By obtaining an elution fraction in the elution step, a bagasse-derived polyphenol composition can be produced.
溶出工程の後、必要に応じて溶出画分（ポリフェノール組成物）を濃縮する工程（濃縮工程）を更に設けてもよい。濃縮工程は、例えば、遠心式薄膜真空蒸発装置を用いて、５〜２０倍に濃縮すればよい。これにより、ポリフェノール組成物を含む濃縮液を得ることができる。 After the elution step, a step (concentration step) of concentrating the elution fraction (polyphenol composition) may be further provided if necessary. In the concentration step, for example, a centrifugal thin film vacuum evaporator may be used to concentrate the concentration 5 to 20 times. Thereby, a concentrated liquid containing the polyphenol composition can be obtained.
本実施形態の方法によって製造できるポリフェノール組成物は、主にクマル酸、フェルラ酸を含有してよい。ポリフェノール組成物がポリフェノールを含有することは、フォーリン−チオカルト法による測定によって確認することができる。また、ポリフェノール組成物の組成は、得られたポリフェノール組成物を高速液体クロマトグラフィー（ＨＰＬＣ）により定性定量分析することによって確認することができる。 The polyphenol composition that can be produced by the method of the present embodiment may mainly contain coumaric acid and ferulic acid. The fact that the polyphenol composition contains polyphenol can be confirmed by the measurement by the Folin-Ciocalteu method. The composition of the polyphenol composition can be confirmed by performing a qualitative and quantitative analysis on the obtained polyphenol composition by high performance liquid chromatography (HPLC).
本実施形態の方法によって得られたポリフェノール組成物は、特に、溶出工程において芳香族系合成吸着剤を用い、エタノール及び水の混合溶媒を使用して溶出することによって得られるため、食品素材として好適に利用することができる。 The polyphenol composition obtained by the method of the present embodiment is particularly suitable as a food material because it is obtained by eluting with a mixed solvent of ethanol and water using an aromatic synthetic adsorbent in the elution step. Can be used for.
本実施形態の方法は、バガスからポリフェノール組成物を製造する従来の方法とは異なる新たな方法であり、特に、バガスから糖液を製造する工程で発生する前処理液（廃液）からポリフェノール組成物を製造することができる点で、有用な方法である。 The method of the present embodiment is a new method different from the conventional method of producing a polyphenol composition from bagasse, and particularly, a polyphenol composition from a pretreatment liquid (waste liquid) generated in the step of producing a sugar solution from bagasse. Is a useful method in that it can be produced.
例えば、上述した特許文献１の方法は、フェルラ酸をバニリンの原料とするために、フェルラ酸の純度を高くし、結晶として回収する方法であるが、廃トウモロコシのアルカリ性煮出として、二軸スクリュー押し出し機及びグラインダー−ホモジナイザーを用い、フェルラ酸及び多糖類が混合された状態の処理液を得ている点で、本実施形態の方法とは異なる。 For example, the method of Patent Document 1 described above is a method of increasing the purity of ferulic acid and recovering it as crystals in order to use ferulic acid as a raw material for vanillin. The method differs from the method of the present embodiment in that a processing solution in which ferulic acid and a polysaccharide are mixed is obtained using an extruder and a grinder-homogenizer.
また、非特許文献１〜３に記載の方法は、比較的低温のアルカリ溶液で植物材料を長時間処理する方法であるが、これは、マイルドな条件でアルカリ処理を行った方が、マトリックス多糖類にエステル結合しているモノフェノール類が遊離しやすくなり、クマル酸、フェルラ酸の純度が高くなるためである。しかし、これらの方法を糖化工程で発生する廃液に利用しようとすると、処理時間が長時間になってしまい、バガスから糖液を得る糖化工程に要する時間と、廃液の処理に要する時間とのバランスがとれなくなるおそれがある。本実施形態の方法によれば、糖化工程を優先しつつ、糖化工程で生じる廃液から効率よくポリフェノール組成物を製造することができる。 Further, the method described in Non-Patent Documents 1 to 3 is a method of treating a plant material with an alkaline solution at a relatively low temperature for a long time, but this is because the alkali treatment under mild conditions results in more matrix. This is because the monophenols ester-bonded to the saccharides are easily released, and the purity of coumaric acid and ferulic acid is increased. However, if these methods are applied to the waste liquid generated in the saccharification step, the processing time becomes long, and the time required for the saccharification step to obtain the sugar solution from bagasse and the time required for the treatment of the waste solution are balanced. There is a risk that it will not be removed. According to the method of the present embodiment, the polyphenol composition can be efficiently produced from the waste liquid generated in the saccharification step while giving priority to the saccharification step.
さらに、本実施形態の方法によれば、バガスから糖液を製造する工程において、従来は廃棄されていた前処理液を廃棄することなく有効に活用できるため、糖液の製造工程で発生していた前処理液の廃棄コストを削減することもできる。 Further, according to the method of the present embodiment, in the step of producing a sugar solution from bagasse, it is possible to effectively utilize the pretreatment liquid that has been conventionally discarded without discarding it. It is also possible to reduce the disposal cost of the pretreatment liquid.
本実施形態の方法によって製造できるポリフェノール組成物は、ポリフェノール組成物に含まれるポリフェノール類を高い収率で単離、精製するための原料としても用いることができる。ポリフェノール組成物からポリフェノール類を単離、精製する方法は公知の方法であってよい。すなわち、本実施形態の方法は、フェルラ酸、ｐ−クマル酸等のポリフェノール類を単離、精製可能な原料を製造する方法ということもできる。ポリフェノール組成物から単離、精製されたポリフェノール類も、上述したポリフェノール組成物と同様に、食品素材として好適に利用することができる。 The polyphenol composition that can be produced by the method of the present embodiment can also be used as a raw material for isolating and purifying the polyphenols contained in the polyphenol composition in a high yield. The method of isolating and purifying the polyphenols from the polyphenol composition may be a known method. That is, the method of the present embodiment can also be said to be a method of producing a raw material capable of isolating and purifying polyphenols such as ferulic acid and p-coumaric acid. The polyphenols isolated and purified from the polyphenol composition can also be suitably used as a food material, like the above-mentioned polyphenol composition.
以下、実施例により本発明を具体的に説明するが、本発明はこれらの実施例に限定されるものではない。 Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
［試験例１：ポリフェノール組成物の製造試験］
＜実施例１＞
（前処理工程）
ステンレス製寸胴鍋に、サトウキビの搾りかすであるバガス３．２ｋｇ（含水率５０質量％）及び９０℃の０．５％（ｗ／ｗ）水酸化ナトリウム水溶液２０Ｌを添加し、２時間混合することによって、前処理を行った。前処理後の混合液を不溶分と液分に分離して、液分を約２０Ｌ得た。これを２回繰り返し、４０Ｌの液分（前処理液）を得た。
[Test Example 1: Production test of polyphenol composition]
<Example 1>
(Pretreatment process)
Add 3.2 kg of bagasse which is squeezed sugarcane residue (water content 50% by mass) and 20 L of 0.5% (w/w) sodium hydroxide aqueous solution at 90° C. to a stainless steel pot and mix for 2 hours. Pretreatment was carried out by. The mixed liquid after the pretreatment was separated into an insoluble component and a liquid component to obtain about 20 L of the liquid component. This was repeated twice to obtain 40 L of liquid component (pretreatment liquid).
（ろ過工程）
上記の前処理液全量に対して、３５％（ｗ/ｗ）塩酸を４７５ｍＬ添加し、ｐＨを３．０に調整した。これを酸性前処理液とした。酸性前処理液に、ろ過助剤として珪藻土を３９５ｇ（前処理液全量基準で１％（ｗ/ｗ）になるように）添加し、フィルタープレスでろ過することにより、不溶性成分を除去し、ろ液を３８ｋｇ得た。
(Filtration process)
To the total amount of the above pretreatment liquid, 475 mL of 35% (w/w) hydrochloric acid was added to adjust the pH to 3.0. This was used as an acidic pretreatment liquid. To the acidic pretreatment liquid, 395 g of diatomaceous earth was added as a filter aid (so that the total amount of pretreatment liquid was 1% (w/w)), and the mixture was filtered with a filter press to remove insoluble components, 38 kg of liquid was obtained.
（溶出工程）
ろ過工程により得られたろ液を、芳香族系合成吸着剤（ダイヤイオンＳＰ−８５０、三菱ケミカル株式会社製）３８３ｍＬを充填したカラム（カラム容量：１Ｌ）に、流速７．６Ｌ／ｈ（ＳＶ＝２０）の条件で通液した。その後、合成吸着剤の体積の１０倍量の水で洗浄し、６０％（ｖ／ｖ）エタノール水溶液をＳＶ＝２で７６６ｇ通液して溶出し、溶出画分を得た。溶出画分を、４８％（ｗ／ｗ）水酸化ナトリウム水溶液を用いてｐＨ６．７に調整し、ロータリーエバポレーターにより１０倍の濃度に濃縮して、ポリフェノール組成物を７７ｇ得た。
(Elution process)
The filtrate obtained by the filtration step was put into a column (column volume: 1 L) packed with 383 mL of an aromatic synthetic adsorbent (Diaion SP-850, manufactured by Mitsubishi Chemical Corporation) at a flow rate of 7.6 L/h (SV= The solution was passed under the condition of 20). Then, it was washed with 10 times the volume of water of the synthetic adsorbent, and 766 g of a 60% (v/v) ethanol aqueous solution was passed through at SV=2 to elute, and an elution fraction was obtained. The elution fraction was adjusted to pH 6.7 with a 48% (w/w) sodium hydroxide aqueous solution and concentrated to a 10-fold concentration by a rotary evaporator to obtain 77 g of a polyphenol composition.
（組成の確認）
得られたポリフェノール組成物について、高速液体クロマトグラフィー（ＨＰＬＣ、Ａｇｉｌｅｎｔ １２６０ Ｉｎｆｉｎｉｔｙ ＬＣ、アジレント・テクノロジー株式会社製）による分析を行い、組成を確認した。分析条件は次のとおりである。
サンプル注入量：３０μＬ
溶離液流速：０．６ｍＬ／ｍｉｎ
溶離液：水（６％酢酸）（溶離液Ａ）、メタノール（６％酢酸）（溶離液Ｂ）
カラム：ＬｉＣｈｒｏＣＡＲＴ（長さ１５０ｍｍ×内径４．６ｍｍ、粒子径５μｍ、メルク株式会社）
カラム温度：６０℃
ＵＶ−ＶＩＳ検出器設定波長：２６０ｎｍ
(Confirmation of composition)
The obtained polyphenol composition was analyzed by high performance liquid chromatography (HPLC, Agilent 1260 Infinity LC, manufactured by Agilent Technologies) to confirm the composition. The analysis conditions are as follows.
Sample injection volume: 30 μL
Eluent flow rate: 0.6 mL/min
Eluent: water (6% acetic acid) (eluent A), methanol (6% acetic acid) (eluent B)
Column: LiChroCART (length 150 mm x inner diameter 4.6 mm, particle diameter 5 μm, Merck Ltd.)
Column temperature: 60℃
UV-VIS detector setting wavelength: 260 nm
ＨＰＬＣによる分析において、濃度勾配（グラジエント）の条件は表１のとおりである。
得られたチャートを図１に示す。保持時間（Ｒｅｔｅｎｔｉｏｎ Ｔｉｍｅ：ＲＴ）１９分のピークとしてクマル酸が、ＲＴ２５分のピークとしてフェルラ酸の存在が確認された。 The obtained chart is shown in FIG. It was confirmed that coumaric acid was present as a peak at retention time (Retention Time: RT) of 19 minutes and ferulic acid was present at a peak of RT of 25 minutes.
［試験例２：芳香族系合成吸着剤の検討］
＜実施例２〜４＞
実施例１と同様の前処理工程及びろ過工程に従って、バガス約３ｋｇ（含水率５０質量％）からフィルタープレスによるろ液２０Ｌを得た。溶出工程においては、芳香族系合成吸着剤として、ダイヤイオンＳＰ−８５０（三菱ケミカル株式会社製、実施例２）、アンバーライトＸＡＤ−４（株式会社オルガノ製、実施例３）、及び、アンバーライトＸＡＤ−１８（株式会社オルガノ製、実施例４）をそれぞれ用いた。各吸着剤５０ｍＬをそれぞれ充填したカラム（カラム容量１００ｍＬ）を用意し、流速１０００ｍＬ／ｈ（ＳＶ＝２０）の条件でろ液を５Ｌずつ通液した。その後、各カラムにおいて、合成吸着剤の体積の１０倍量の水で洗浄し、６０％（ｖ／ｖ）エタノール水溶液をＳＶ＝２で１００ｍＬ通液して溶出し、溶出画分を得た。実施例２〜４に係る溶出画分の固形分濃度（質量％、溶出画分全量基準）及びポリフェノール濃度（質量％、溶出画分全量基準）を、表２に示す。
[Test Example 2: Examination of aromatic synthetic adsorbent]
<Examples 2 to 4>
According to the same pretreatment process and filtration process as in Example 1, 20 L of a filtrate by a filter press was obtained from about 3 kg of bagasse (water content 50% by mass). In the elution step, as a synthetic aromatic adsorbent, Diaion SP-850 (manufactured by Mitsubishi Chemical Co., Example 2), Amberlite XAD-4 (manufactured by Organo Corporation, Example 3), and Amberlite. XAD-18 (manufactured by Organo Corporation, Example 4) was used. A column (column volume 100 mL) filled with 50 mL of each adsorbent was prepared, and 5 L of the filtrate was passed under the condition of a flow rate of 1000 mL/h (SV=20). Thereafter, in each column, the column was washed with 10 times the volume of the synthetic adsorbent, and 100 mL of a 60% (v/v) ethanol aqueous solution was passed through at SV=2 to elute the column, to obtain an elution fraction. Table 2 shows the solid content concentration (mass %, elution fraction total amount basis) and the polyphenol concentration (mass %, elution fraction total amount basis) of the elution fractions according to Examples 2 to 4.
［試験例３：前処理液のｐＨの影響］
＜実施例５〜７、比較例１＞
（前処理工程、ろ過工程）
実施例１と同様の前処理工程に従って、バガス約３ｋｇ（含水率５０質量％）から前処理液２０Ｌを得た。この液分を４つに分け、そのうち３つを、３５％（ｗ/ｗ）塩酸により、ｐＨ６（実施例５）、ｐＨ５．５（実施例６）、ｐＨ３（実施例７）にそれぞれ調整した。また、４つに分けた前処理液のうち１つは、ｐＨを調整しなかった（比較例１）。ｐＨを調整していない比較例１の前処理液のｐＨは１０．８であった。これら４種類の前処理液を、実施例１と同様の方法によってろ過した。
[Test Example 3: Influence of pH of pretreatment liquid]
<Examples 5 to 7, Comparative Example 1>
(Pretreatment process, filtration process)
According to the same pretreatment process as in Example 1, 20 L of pretreatment liquid was obtained from about 3 kg of bagasse (water content 50% by mass). This liquid was divided into four, and three of them were adjusted to pH 6 (Example 5), pH 5.5 (Example 6) and pH 3 (Example 7) with 35% (w/w) hydrochloric acid. .. In addition, one of the four pretreatment liquids did not adjust the pH (Comparative Example 1). The pretreatment liquid of Comparative Example 1 in which the pH was not adjusted was 10.8. These four types of pretreatment liquids were filtered by the same method as in Example 1.
（溶出工程）
ろ過工程により得られたろ液を、芳香族系合成吸着剤（ダイヤイオンＳＰ−８５０、三菱ケミカル株式会社製）３８３ｍＬを充填したカラム（カラム容量：１Ｌ）に、流速ＳＶ＝１０、通液量ＢＶ＝５０の条件で通液した。その後、合成吸着剤の体積の１０倍量の水で洗浄し、６０％（ｖ／ｖ）エタノール水溶液をＳＶ＝２、ＢＶ＝２で通液して溶出した。カラム通液後の通過液（合成吸着剤に吸着しなかった液分）、及び、溶出画分（合成吸着剤に吸着した液分）に含まれる総ポリフェノール、クマル酸、及びフェルラ酸のそれぞれの回収量（ｇ）を測定し、溶出前のろ液中に含まれるポリフェノール量（ｇ）に対する、通過液又は溶出画分に含まれる総ポリフェノール（ポリフェノール組成物）、クマル酸、及びフェルラ酸の質量比（回収率）をそれぞれ求めた。なお、総ポリフェノールの回収量はフォーリン−チオカルト法により測定し、クマル酸及びフェルラ酸の回収量は、ＨＰＬＣにより測定した。結果を表３に示す。
(Elution process)
The filtrate obtained by the filtration step was put into a column (column volume: 1 L) packed with 383 mL of an aromatic synthetic adsorbent (Diaion SP-850, manufactured by Mitsubishi Chemical Corporation), flow rate SV=10, flow rate BV. The liquid was passed under the condition of =50. Then, it was washed with 10 times the volume of water of the synthetic adsorbent, and a 60% (v/v) ethanol aqueous solution was passed through at SV=2 and BV=2 to elute. Each of the total polyphenols, coumaric acid, and ferulic acid contained in the passing liquid after passing through the column (the liquid that did not adsorb to the synthetic adsorbent) and the elution fraction (the liquid that adsorbed to the synthetic adsorbent) Mass of total polyphenols (polyphenol composition), coumaric acid, and ferulic acid contained in the flow-through liquid or elution fraction with respect to the amount of polyphenols (g) contained in the filtrate before elution by measuring the recovered amount (g) The ratio (recovery rate) was obtained. The amount of total polyphenol recovered was measured by the Folin-Ciocalteu method, and the amount of coumaric acid and ferulic acid recovered was measured by HPLC. The results are shown in Table 3.
Claims (5)
水酸化ナトリウム水溶液、水酸化カリウム水溶液、及びアンモニア水溶液からなる群より選ばれる少なくとも１種のアルカリ溶液を用いてバガスを前処理し、前処理液を得る工程と、
前記前処理液のｐＨを塩酸で４．５以下に調整してからろ過し、ろ液を回収する工程と、
前記ろ液を、比表面積が７００ｍ ２ ／ｇ以上である、高比表面積化の特殊処理を施した無置換基型の芳香族系樹脂からなる芳香族系合成吸着剤が充填されたカラムに通液し、前記芳香族系合成吸着剤に吸着した成分をエタノール及び水の混合溶媒で溶出して溶出画分をポリフェノール組成物として得る工程と、を備える、製造方法。 A method for producing a polyphenol composition from bagasse,
Pretreatment of bagasse with at least one alkaline solution selected from the group consisting of an aqueous sodium hydroxide solution, an aqueous potassium hydroxide solution, and an aqueous ammonia solution to obtain a pretreatment liquid;
Adjusting the pH of the pretreatment liquid to 4.5 or less with hydrochloric acid and then filtering, and collecting the filtrate,
The filtrate is passed through a column packed with an aromatic synthetic adsorbent made of a non-substituted aromatic resin that has been subjected to a special treatment for increasing the specific surface area and has a specific surface area of 700 m 2 /g or more. A step of liquefying and eluting a component adsorbed on the aromatic synthetic adsorbent with a mixed solvent of ethanol and water to obtain an elution fraction as a polyphenol composition.
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