WO2013161935A1 - 糖液の製造方法 - Google Patents
糖液の製造方法 Download PDFInfo
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- WO2013161935A1 WO2013161935A1 PCT/JP2013/062195 JP2013062195W WO2013161935A1 WO 2013161935 A1 WO2013161935 A1 WO 2013161935A1 JP 2013062195 W JP2013062195 W JP 2013062195W WO 2013161935 A1 WO2013161935 A1 WO 2013161935A1
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- WIPO (PCT)
- Prior art keywords
- sugar
- nanofiltration membrane
- dielectric constant
- sugar solution
- liquid
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
- B01D61/026—Reverse osmosis; Hyperfiltration comprising multiple reverse osmosis steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/029—Multistep processes comprising different kinds of membrane processes selected from reverse osmosis, hyperfiltration or nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K1/00—Glucose; Glucose-containing syrups
- C13K1/02—Glucose; Glucose-containing syrups obtained by saccharification of cellulosic materials
-
- C—CHEMISTRY; METALLURGY
- C13—SUGAR INDUSTRY
- C13K—SACCHARIDES OBTAINED FROM NATURAL SOURCES OR BY HYDROLYSIS OF NATURALLY OCCURRING DISACCHARIDES, OLIGOSACCHARIDES OR POLYSACCHARIDES
- C13K13/00—Sugars not otherwise provided for in this class
- C13K13/002—Xylose
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
Definitions
- the present invention relates to a method for producing a sugar solution including a step of filtering through a nanofiltration membrane.
- sugars used as fermentation raw materials for example, those derived from edible raw materials such as sugar cane, starch, sugar beet are used industrially.
- sugars used as fermentation raw materials for example, those derived from edible raw materials such as sugar cane, starch, sugar beet are used industrially.
- the cellulose-containing biomass mainly contains lignin, which is an aromatic polymer, and cellulose and hemicellulose, which are monosaccharide polymers.
- a method for producing a sugar solution using cellulose-containing biomass as a raw material for example, a method of hydrolyzing cellulosic biomass that is a raw material directly using concentrated sulfuric acid or the like, or steaming treatment, pulverizing treatment, dilute sulfuric acid to cellulose-containing biomass
- a pretreatment-enzymatic saccharification method in which cellulose or hemicellulose is desorbed from lignin by pretreatment such as treatment, followed by hydrolysis with a saccharifying enzyme such as cellulase.
- an object of the present invention is to provide a method for reducing the loss of sugar to the permeation side of the nanofiltration membrane when the sugar solution is filtered through the nanofiltration membrane.
- the present inventor has found that when a sugar liquid containing an organic liquid compound having a relative dielectric constant of 17 or more at 25 ° C. is filtered through a nanofiltration membrane, the organic liquid The present inventors have found that the sugar permeation rate of sugar can be remarkably reduced as compared with the case where a sugar solution not containing a compound is filtered through a nanofiltration membrane.
- the present invention has the following configurations (1) to (5).
- a method for producing a sugar solution comprising a step of filtering a sugar solution through a nanofiltration membrane and recovering the sugar solution from the non-permeating side, and includes an organic liquid compound having a relative dielectric constant of 17 or more at 25 ° C.
- a method for producing a sugar liquid, comprising filtering the sugar liquid through a nanofiltration membrane.
- the organic liquid compound is ethanol, methanol, 1-propanol, 2-propanol, 1,2-propanediol, 1,3-propanediol, glycerin, 1-butanol, 2-butanol, isobutanol, 1,2 One or more selected from the group consisting of butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, ethylene glycol, acetone, acetonitrile, acrylonitrile, dimethylsulfoxide and dimethylformamide
- the manufacturing method of the sugar liquid as described in (1) characterized by the above-mentioned.
- the total concentration of organic liquid compounds having a relative dielectric constant of 17 or more at 25 ° C. in a sugar solution to be subjected to nanofiltration membrane treatment is 50 ppm or more, as described in (1) or (2) Method for producing a sugar solution.
- the sugar loss to the permeation side of the nanofiltration membrane is reduced, so that the yield of the sugar solution can be improved.
- embodiments of the present invention
- this invention is not limited by embodiment for implementing the following invention.
- constituent elements in the following embodiments include those that can be easily assumed by those skilled in the art, those that are substantially the same, and those in a so-called equivalent range.
- the constituent elements disclosed in the following embodiments may be appropriately combined or may be appropriately selected and used.
- Sugar solution is an aqueous solution in which sugar is dissolved.
- Sugars include monosaccharides such as glucose, xylose, galactose, fructose, mannose and arabinose, disaccharides such as maltose, cellobiose, sophorose, xylobiose, lactose and sucrose, water-soluble polysaccharides such as cellooligosaccharide and xylooligosaccharide, fucose and rhamnose Sugar alcohols such as deoxy sugars, xylitol, sorbitol and the like.
- the sugar liquid may contain an impurity component other than sugar, and the impurity component is not particularly limited.
- the raw material of the sugar solution used in the present invention is not particularly limited, and edible sugar or starch may be used as a raw material, and non-edible polysaccharides typified by cellulose may be used as a raw material.
- the step of filtering the sugar solution through the nanofiltration membrane is a step preferably employed in the method for producing a sugar solution using cellulose-containing biomass as a raw material (see WO2010 / 067875). In the present invention, it is preferable to use cellulose-containing biomass as a raw material.
- Cellulose-containing biomass refers to herbaceous biomass such as bagasse, switchgrass, napiergrass, eliansus, corn stover (corn stover), corn cob (corn core), rice straw, straw, etc., and wood such as trees and waste building materials Such as biomass.
- Cellulosic biomass contains polysaccharides such as cellulose or hemicellulose, and a sugar solution can be produced by hydrolyzing such polysaccharides.
- a sugar solution obtained by saccharifying cellulose-containing biomass is referred to as a cellulose-derived sugar solution.
- Cellulose-derived sugar liquid contains monosaccharides such as glucose, xylose, mannose and arabinose, disaccharides such as cellobiose and xylobiose, and water-soluble polysaccharides such as cellooligosaccharide and xylooligosaccharide. Source) and can be converted into various chemicals such as ethanol, lactic acid and amino acids by microorganisms.
- a manufacturing method of a cellulose origin sugar liquid For example, what is necessary is just to manufacture according to the method of WO2010 / 067785.
- the method for producing a sugar liquid according to the present invention includes a step of filtering the sugar liquid through a nanofiltration membrane and collecting the sugar liquid from the non-permeating side.
- the nanofiltration membrane is a separation membrane that is generally defined as “a membrane that transmits monovalent ions and blocks divalent ions”, and is also called a nanofilter, a nanofiltration membrane, or an NF membrane.
- the nanofiltration membrane is a membrane that is considered to have a minute void of about several nanometers, and is mainly used to block fine particles, molecules, ions, salts, and the like in water.
- the nanofiltration membrane can remove the fermentation inhibitor contained in the cellulose raw material-derived sugar liquid on the permeate side and block sugar on the non-permeate side. It is used in the concentration and purification process. What is necessary is just to implement the nanofiltration membrane processing process of the sugar liquid in this invention according to the method as described in WO2010 / 067785.
- the present invention is characterized by reducing the sugar permeability of the nanofiltration membrane by filtering a sugar solution containing an organic liquid compound having a relative dielectric constant of 17 or more at 25 ° C. through the nanofiltration membrane. .
- Organic liquid compound refers to an organic compound having a melting point of less than 30 ° C. at normal pressure (0.1 MPa).
- the relative dielectric constant is the ratio of the dielectric constant of vacuum to the dielectric constant of the dielectric.
- the dielectric constant represents the ease of polarization of the dielectric (insulator).
- a capacitor when nothing is interposed between the electrode plates, that is, when a constant voltage is applied between the electrode plates in a vacuum state, charges are stored on the electrode plate until a voltage equal to the applied voltage is generated.
- the dielectric When the dielectric is filled between the plates, the electric field is weakened by the polarization of the dielectric, so that more electric charge is stored in the capacitor. That is, the capacitance of the capacitor increases. Therefore, the more easily the dielectric interposed between the electrode plates is polarized, the more the capacitance increases.
- the dielectric constant ⁇ (F / m) is obtained when the capacitance of the capacitor is C (F), the distance between the plates is d (m), and the area of the plates is S (m 2 ). It is defined as the amount that satisfies ⁇ S / d.
- the relative dielectric constant is obtained from the ratio between the capacitance of the capacitor in which the gap between the plates is vacuum and the capacitance when the dielectric is filled between the plates. It is known that the relative dielectric constant of the organic liquid compound thus obtained has a value specific to the substance.
- the dielectric constant is also affected by the temperature of the dielectric, and it is generally known that the dielectric constant of the liquid decreases as the temperature increases.
- the change in the dielectric constant of the liquid with temperature tends to be larger as the dielectric constant is larger and smaller as the dielectric constant is smaller.
- the relative dielectric constant at 20 ° C. is 80.4, and the relative dielectric constant at 25 ° C. is 78.5.
- the relative dielectric constant at 20 ° C. is 10.65, and the relative dielectric constant at 25 ° C. is 10.36.
- the relative dielectric constant at 25 ° C. was used as a reference.
- a dielectric constant meter for liquid “Model 871” manufactured by RUFUTO
- the present invention is based on the finding that when a sugar liquid containing an organic liquid compound having a relative dielectric constant of 17 or more at 25 ° C. is filtered through a nanofiltration membrane, the sugar permeability of the nanofiltration membrane is reduced. This is presumably because, when the relative dielectric constant of the organic liquid compound is 17 or more, the apparent molecular weight of the sugar molecule increases due to the affinity of the organic liquid compound to the sugar molecule. The reason is not clear.
- the sugar permeability is reduced by including an organic liquid compound having a relative dielectric constant of 17 or more at 25 ° C. in the sugar solution, but the permeability of the above-mentioned fermentation inhibitor is completely different. does not change.
- At least one organic liquid compound having a relative dielectric constant of 17 or more at 25 ° C. is contained in the sugar solution. Therefore, for example, a case where an organic liquid compound having a relative dielectric constant of 17 or more and an organic liquid compound having a relative dielectric constant of less than 17 coexist in the sugar liquid is also included in the present invention.
- the relative dielectric constant at 25 ° C. of the organic liquid compound in the sugar solution used for the nanofiltration membrane is 17 or more, preferably 20 or more, more preferably 25 or more. This is because the organic liquid compound has a relative dielectric constant at 25 ° C. of 17 or more, and an effect of reducing the permeability of the nanofiltration membrane of sugar is observed.
- the upper limit of the relative dielectric constant at 25 ° C. is not particularly limited, but 120 is preferable.
- the nanofiltration membrane permeability of each compound refers to the concentration of each compound contained in the filtrate when the liquid (stock solution) in which each compound is dissolved is passed through the nanofiltration membrane and filtered. , Refers to the value divided by the concentration of each compound contained in the stock solution.
- each compound is affected by the concentration of each compound, the type of separation membrane, the permeation flux, temperature, and pH. Therefore, in this specification, when comparing the effect of reducing the transmittance of each compound (glucose, xylose) by the organic liquid compound in the sugar solution, the conditions of each compound concentration, type of separation membrane, permeation flux, temperature, and pH are set. It shall be constant.
- Examples of the organic liquid compound having a relative dielectric constant of 17 or more include, for example, ethanol (24.8), methanol (32.6), 1-propanol (20.3) 2-propanol (19.8), 1,2-propanediol (30.2), 1,3-propanediol (34.2), glycerin (45.0), 1-butanol (17.4), 2-butanol (17.2), isobutanol (17.5), 1,2-butanediol (29.5), 1,3-butanediol (30.0), 1,4-butanediol (31.
- the concentration range of the organic liquid compound having a relative dielectric constant of 17 or more at 25 ° C. in the sugar solution used for the nanofiltration membrane is preferably 50 ppm to 10,000 ppm, more preferably 500 ppm to 10,000 ppm. More preferably, it is ⁇ 10000 ppm. This is because the effect of reducing the nanofiltration membrane permeability of sugar is seen at 50 ppm or more, and becomes remarkable at 500 ppm, and the effect of reducing the permeability of nanofiltration membrane of sugar reaches the upper limit at 5000 ppm. On the other hand, even if it exceeds 10,000 ppm, the cost for adding the organic liquid compound only increases, and no further effect of reducing the permeability of the nanofiltration membrane of sugar can be obtained.
- the organic liquid compound when the sugar liquid containing the organic liquid compound is filtered through the nanofiltration membrane, most of the organic liquid compound permeates to the filtrate side.
- the organic liquid compound By further filtering the filtrate through a reverse osmosis membrane, the organic liquid compound can be concentrated on the non-permeate side, so that the organic liquid compound can be recovered and reused in the sugar liquid production method of the present invention.
- the filtrate on the permeate side when the sugar solution is filtered through the nanofiltration membrane is usually disposed of as waste liquid. Therefore, it is economically advantageous if it is concentrated by a reverse osmosis membrane and reused as an organic liquid compound. It is.
- the nanofiltration membrane permeability of each compound is included in the filtrate when filtration is performed by passing a liquid (stock solution) in which each compound is dissolved through the separation membrane. It refers to the value obtained by dividing the concentration of each compound by the concentration of each compound contained in the stock solution. Since the nanofiltration membrane permeability of each compound is affected by the permeation flux, liquid temperature, pH, etc., when measuring the nanofiltration membrane permeability in this example, the permeation flux is 0.5 m / day. The temperature was controlled at 25 ° C. and pH 5.
- the permeation flux (m / day) is a value obtained by dividing the permeate flow rate (m 3 / day) by the effective area (m 2 ) of the separation membrane.
- the pH of the solution was adjusted prior to filtration of the nanofiltration membrane using sulfuric acid or sodium hydroxide.
- a cellulase preparation derived from Trichoderma reesei (Accel Lace Duet, manufactured by Genencor) was added in an amount of 1/100 of the dry weight of enzyme protein relative to the dry weight of solids in the slurry, The saccharification reaction was performed at 50 ° C. for 24 hours. Thereafter, a filter press treatment (MO-4, manufactured by Iwata Sangyo Co., Ltd.) was performed to obtain a cellulose-containing biomass-derived sugar solution from which undegraded cellulose or lignin was separated and removed. Further, the present sugar solution was subjected to a microfiltration membrane having a pore diameter of 0.22 ⁇ m to remove insoluble particles of micron order. The cellulose-containing biomass-derived sugar solution thus obtained was used in the following examples.
- Acetic acid analysis conditions The concentration of acetic acid, which is a fermentation inhibitor in the sugar solution, was quantified by comparison with a sample under the HPLC conditions shown below.
- Instrument Hitachi high-performance liquid chromatograph Lachrom elite (manufactured by Hitachi, Ltd.) Column: GL-C610H-S (manufactured by Hitachi, Ltd.)
- Mobile phase 3 mM Perchloric acid reaction solution: Bromothymol blue solution
- Detection method UV-VIS detector flow rate
- Mobile phase 0.5 mL / min Reaction solution: 0.6 mL / min Temperature: 60 ° C.
- Ethanol analysis conditions The ethanol concentration in the sugar solution was quantified by comparison with a sample under the GC conditions shown below.
- Nanofiltration membrane treatment of model sugar solution As model sugar solutions, glucose and xylose as monosaccharides are each 20 g / L, and acetic acid, HMF and vanillin as fermentation inhibitors are each included at 0.5 g / L. An aqueous solution was prepared. This model sugar solution was subjected to cross flow filtration using a nanofiltration membrane (UTC-60, manufactured by Toray Industries, Inc.). The cross flow filtration conditions were a liquid temperature of 25 ° C., a membrane surface linear velocity of 20 cm / second, and the operating pressure was appropriately adjusted so that the permeation flux was 0.5 m / day.
- UTC-60 nanofiltration membrane
- the membrane separator used was a small flat membrane unit (“SEPA CF-II” manufactured by GE Osmonics, effective membrane area 140 cm 2 ) that can be used as a small filtration tester for spiral modules. Since it took time to stabilize the concentration on the filtrate side, the filtrate solution was returned to the raw water side for 20 minutes, the stable filtrate after 20 minutes was sampled, and the transmittance was determined according to Reference Example 1. The obtained results are shown in Table 1.
- Example 1 Nanofiltration membrane treatment of a sugar liquid containing an organic liquid compound having a relative dielectric constant of 17 or more
- the organic liquid compound has a relative dielectric constant of 17 or more at 25 ° C.
- Example 2 Influence of Organic Liquid Compound Concentration
- the organic liquid compounds having a dielectric constant of 17 or more, ethanol, methanol, 1-propanol, 2-propanol, 1,2- Propanediol, 1,3-propanediol, glycerin, 1-butanol, 2-butanol, isobutanol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol , Ethylene glycol, acetone, acetonitrile, acrylonitrile, dimethyl sulfoxide, dimethylformamide at 50 ppm, 500 ppm, 5000 ppm, and 10000 ppm, respectively.
- Table 2 shows the results of determining the permeability of glucose and xylose according to the method of Reference Example 1.
- the model sugar solution contains an organic liquid compound having a dielectric constant of 17 or more, there was an effect of reducing the monosaccharide permeability at a concentration of 50 ppm.
- this effect was further enhanced as the concentration of the organic liquid compound was increased, but it became clear that it almost reached its peak at 5000 ppm.
- Example 3 Nanofiltration membrane treatment of distillation residue liquid after ethanol fermentation of cellulose-containing biomass-derived sugar liquid Obtained by performing ethanol fermentation and distillation using cellulose-containing biomass-derived sugar liquid obtained by the method of Reference Example 2
- the nanofiltration membrane treatment of the distillation residue solution was studied.
- 5 mL of the medium shown in Table 3 was filter sterilized ("Sterriflip” manufactured by Millipore Corporation, average pore diameter 0.22 ⁇ m), and baker's yeast (Saccharomyces cerevisiae) was placed in a test tube at 30 ° C. Cultured with shaking overnight.
- Baker's yeast was recovered from the preculture solution by centrifugation and washed well with 15 mL of sterile water. The washed baker's yeast was inoculated into 100 mL of a cellulose-containing biomass-derived sugar solution obtained by the method of Reference Example 2, and cultured with shaking in a 500 mL Sakaguchi flask for 24 hours (main culture). Solid matter was removed from the main culture solution by centrifugation, and the solution was further applied to a microfiltration membrane ("Sterricup" manufactured by Millipore Corporation, average pore diameter 0.22 ⁇ m) to obtain a clear cellulose sugar fermentation residue.
- a microfiltration membrane (“Sterricup" manufactured by Millipore Corporation, average pore diameter 0.22 ⁇ m)
- Example 4 Nanofiltration membrane treatment of model sugar solution containing various sugars in the presence of ethanol and ethylene glycol
- an organic liquid compound having a relative dielectric constant of 17 or more at 25 ° C Filtration was performed in the same manner as in Comparative Example 3 except that one of ethanol and ethylene glycol was included at a concentration of 5 g / L.
- Table 5 shows the results of determining the transmittance according to Reference Example 1.
- the present invention is useful as a method for increasing the yield of a sugar solution in a method for producing a sugar solution including a step of filtering through a nanofiltration membrane.
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Abstract
Description
(1)糖液をナノ濾過膜に通じて濾過して、非透過側から糖液を回収する工程を含む糖液の製造方法において、25℃における比誘電率が17以上の有機液体化合物を含む糖液をナノ濾過膜に通じて濾過することを特徴とする、糖液の製造方法。
(2)有機液体化合物が、エタノール、メタノール、1-プロパノール、2-プロパノール、1,2-プロパンジオール、1,3-プロパンジオール、グリセリン、1-ブタノール、2-ブタノール、イソブタノール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、2,3-ブタンジオール、エチレングリコール、アセトン、アセトニトリル、アクリロニトリル、ジメチルスルホキシドおよびジメチルホルムアミドからなる群から選ばれる1種類以上であることを特徴とする、(1)に記載の糖液の製造方法。
(3)ナノ濾過膜処理に供する糖液中の25℃における比誘電率が17以上の有機液体化合物の濃度の合計が50ppm以上であることを特徴とする、(1)または(2)に記載の糖液の製造方法。
(4)ナノ濾過膜処理に供する糖液がセルロース含有バイオマス由来であることを特徴とする、(1)~(3)のいずれかに記載の糖液の製造方法。
(5)ナノ濾過膜の透過液を逆浸透膜に通じて濾過し、有機液体化合物を回収することを特徴とする、(1)~(4)のいずれかに記載の糖液の製造方法。
本明細書において各化合物のナノ濾過膜透過率とは、各化合物を溶解した液体(原液)を分離膜に通じ、濾過を行った場合に、濾液に含まれる各化合物の濃度を、原液に含まれる各化合物の濃度で除した値を指す。各化合物のナノ濾過膜透過率は、透過流束、液体の温度、pHなどに影響を受けるため、本実施例でナノ濾過膜透過率を測定する際には、透過流束0.5m/日、温度25℃、pH5に制御した。なお、透過流束(m/日)は、透過流量(m3/日)を、分離膜の有効面積(m2)で除した値である。また、溶液のpHは硫酸または水酸化ナトリウムを使用してナノ濾過膜の濾過に先立って調整した。
セルロース含有バイオマスとして、稲わらを用いた。前記稲わらを4mmの目開きを有するスクリーンで粒度を制御しながらカッターミルを用いて粉砕した。粉砕後、水に浸し、撹拌しながら180℃で5分間オートクレーブ処理(日東高圧株式会社製)した。その際の圧力は10MPaであった。得られたスラリーに、トリコデルマ・リーセイ由来のセルラーゼ製剤(アクセルレース・デュエット、Genencor社製)を、スラリー中の固形物乾燥重量に対し、酵素タンパク質乾燥重量で100分の1の量を添加し、50℃で24時間糖化反応を行った。その後、フィルタプレス処理(薮田産業株式会社製、MO-4)を行い、未分解セルロースあるいはリグニンを分離除去したセルロース含有バイオマス由来の糖液を得た。更に、本糖液を細孔径0.22μmの精密濾過膜に供することにより、ミクロンオーダーの不溶性粒子を除去した。このようにして得られたセルロース含有バイオマス由来糖液を、以下の実施例にて使用した。
1.糖類分析条件
糖液中のグルコース、キシロース濃度は、下記に示す高速液体クロマトグラフィー条件で、標品との比較により定量した。
機器:ACQUITY UPLC システム(Waters社製)
カラム:ACQUITY UPLC BEH Amide 1.7μm 2.1×100mm Column(Waters社製)
移動相:A液;80% アセトニトリル+0.2%TEA、B液;30% アセトニトリル+0.2% TEA
流速:0.3mL/min
温度:55℃。
糖液中の発酵阻害物質である酢酸の濃度は、下記に示すHPLC条件で、標品との比較により定量した。
機器:日立高速液体クロマトグラフ Lachrom elite(株式会社日立製作所製)
カラム:GL‐C610H‐S (株式会社日立製作所製)
移動相:3mM 過塩素酸
反応液:ブロモチモールブルー溶液
検出方法:UV‐VIS検出器
流速 移動相:0.5mL/min 反応液:0.6mL/min
温度:60℃。
糖液中の発酵阻害物質であるHMF、バニリンの濃度は、下記に示すHPLC条件で、標品との比較により定量した。
機器:日立高速液体クロマトグラフ Lachrom elite(株式会社日立製作所製)
カラム:Synergi 2.5μm Hydro‐RP 100A(Phenomenex社製)
検出方法:Diode Array 検出器
流速:0.6mL/min
温度:40℃。
糖液中のエタノール濃度は、下記に示すGC条件で、標品との比較により定量した。
機器:Shimadzu GC-2010(株式会社島津製作所製)
カラム:TC-1(内径0.53mm、長さ15m、膜厚1.50μm(GL サイエンス株式会社製)
検出方法:FID。
モデル糖液として、単糖であるグルコースおよびキシロースをそれぞれ20g/L、発酵阻害物質である酢酸、HMF、バニリンをそれぞれ0.5g/Lずつ含む水溶液を調整した。本モデル糖液を、ナノ濾過膜(UTC-60、東レ株式会社製)を用いて、クロスフロー方式による濾過に供した。クロスフロー濾過条件は、液温25℃、膜面線速度20cm/秒とし、操作圧は透過流束が0.5m/日となるように適宜調節した。また、膜分離装置はスパイラルモジュールの濾過小型試験機として使用できる小型の平膜ユニット(GE Osmonics社製“SEPA CF-II”、有効膜面積140cm2)を使用した。なお、濾液側の濃度は安定するのに時間がかかるため、20分間濾液の液を原水側に戻し、20分経過後の安定した濾液をサンプリングし、参考例1にしたがって透過率を求めた。得られた結果を表1に示す。
参考例4記載のモデル糖液中に、25℃における比誘電率が17以上の有機液体化合物であるエタノール、メタノール、1-プロパノール、2-プロパノール、1,2-プロパンジオール、1,3-プロパンジオール、グリセリン、1-ブタノール、2-ブタノール、イソブタノール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、2,3-ブタンジオール、エチレングリコール、アセトン、アセトニトリル、アクリロニトリル、ジメチルスルホキシド、ジメチルホルムアミドのうちいずれか1種類を、5g/Lの濃度で含むこと以外は、参考例4と同様の方法で濾過を行った。参考例1にしたがって透過率を求めた結果を表1に示す。
参考例4記載のモデル糖液中に、25℃における比誘電率が17未満の有機液体化合物(括弧内は25℃における比誘電率の数値)であるテトラヒドロフラン(THF、7.5)、ベンジルアルコール(11.9)、1-ヘキサノール(12.7)、2-ヘキサノール(11.1)、シクロヘキサノール(15.9)のうちいずれか1種類を、5g/Lの濃度で含むこと以外は、参考例4と同様の方法で濾過を行った。参考例1にしたがって透過率を求めた結果を表1に示す。
参考例4記載のモデル糖液中に、誘電率が17以上の有機液体化合物であるエタノール、メタノール、1-プロパノール、2-プロパノール、1,2-プロパンジオール、1,3-プロパンジオール、グリセリン、1-ブタノール、2-ブタノール、イソブタノール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、2,3-ブタンジオール、エチレングリコール、アセトン、アセトニトリル、アクリロニトリル、ジメチルスルホキシド、ジメチルホルムアミドのうちいずれか1種類を、50ppm、500ppm、5000ppm、10000ppmの各濃度で含む水溶液を調整し、それぞれについて参考例4と同様の方法で濾過を行った。参考例1の方法に従い、グルコース、キシロースの透過率を求めた結果を表2に示す。参考例4の結果および表2から明らかなように、モデル糖液中に誘電率が17以上の有機液体化合物を含む場合では、50ppmの濃度で単糖透過率低減の効果があった。また、この効果は、有機液体化合物の濃度が高くなれば高くなるほど更に高められたが、5000ppmでほぼ頭打ちとなることが明らかとなった。
参考例2の方法により得られたセルロース含有バイオマス由来糖液を用いたエタノール発酵および蒸留を行って得られる蒸留残渣液に含まれる発酵の残糖を回収することを目的として、蒸留残渣液のナノ濾過膜処理について検討した。まず前培養として、表3に示す培地5mLをフィルター滅菌(ミリポア株式会社製“ステリフリップ”、平均細孔径0.22μm)し、試験管中で30℃にてパン酵母(サッカロマイセス・セレビシエ)を一晩振とう培養した。前培養液よりパン酵母を遠心分離により回収し、滅菌水15mLでよく洗浄した。洗浄したパン酵母を、参考例2の方法により得られたセルロース含有バイオマス由来糖液100mLに植菌し、500mL容坂口フラスコで24時間振とう培養した(本培養)。本培養液より固形物を遠心分離により除去し、さらに精密濾過膜(ミリポア株式会社製“ステリカップ”、平均細孔径0.22μm)に供して清澄なセルロース糖発酵残渣液を得た。更にセルロース糖発酵残渣液を、ロータリーエバポレータを用いて蒸留し、得られたセルロース糖由来蒸留残渣液を、参考例4と同様の方法で濾過を行った。セルロース糖蒸留残渣液中の糖(グルコース、キシロース)およびエタノール濃度と、参考例1の方法に従い、グルコース、キシロース、酢酸、HMF、バニリンの透過率を求めた結果を表4に示す。
モデル蒸留残渣液として、実施例3記載のセルロース糖蒸留残渣液と等濃度のグルコース、キシロース、酢酸、HMF、バニリンを含む水溶液を、試薬を用いて調整した。前記モデル蒸留残渣液を、参考例4と同様の方法で濾過を行った。参考例1の方法に従い、各化合物の透過率を求めた結果を表4に示す。
モデル糖液として、マンノース、ガラクトース、フルクトース、アラビノース、キシリトール、ソルビトールをそれぞれ10g/Lずつ、発酵阻害物質である酢酸、HMF、バニリンをそれぞれ0.5g/Lずつ含む水溶液を使用すること以外、参考例4と同様の方法でろ過を行った。参考例1にしたがって透過率を求めた結果を表5に示す。
比較例3記載のモデル糖液中に、25℃における比誘電率が17以上の有機液体化合物であるエタノール、エチレングリコールのうちいずれか1種類を、5g/Lの濃度で含むこと以外は、比較例3と同様の方法で濾過を行った。参考例1にしたがって透過率を求めた結果を表5に示す。
Claims (5)
- 糖液をナノ濾過膜に通じて濾過して、非透過側から糖液を回収する工程を含む糖液の製造方法において、25℃における比誘電率が17以上の有機液体化合物を含む糖液をナノ濾過膜に通じて濾過することを特徴とする、糖液の製造方法。
- 有機液体化合物が、エタノール、メタノール、1-プロパノール、2-プロパノール、1,2-プロパンジオール、1,3-プロパンジオール、グリセリン、1-ブタノール、2-ブタノール、イソブタノール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、2,3-ブタンジオール、エチレングリコール、アセトン、アセトニトリル、アクリロニトリル、ジメチルスルホキシドおよびジメチルホルムアミドからなる群から選ばれる1種類以上であることを特徴とする、請求項1に記載の糖液の製造方法。
- ナノ濾過膜処理に供する糖液中の、25℃における比誘電率が17以上の有機液体化合物の濃度の合計が50ppm~10000ppmであることを特徴とする、請求項1または2に記載の糖液の製造方法。
- ナノ濾過膜処理に供する糖液がセルロース含有バイオマス由来であることを特徴とする、請求項1~3のいずれかに記載の糖液の製造方法。
- ナノ濾過膜の透過液を逆浸透膜に通じて濾過し、有機液体化合物を回収することを特徴とする、請求項1~4のいずれかに記載の糖液の製造方法。
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US14/395,231 US9926613B2 (en) | 2012-04-26 | 2013-04-25 | Method of producing sugar solution |
BR112014026799-5A BR112014026799B1 (pt) | 2012-04-26 | 2013-04-25 | Método de produção de um líquido de açúcar |
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US11053557B2 (en) | 2018-03-15 | 2021-07-06 | Fluid Quip Technologies, Llc | System and method for producing a sugar stream using membrane filtration |
US11519013B2 (en) | 2018-03-15 | 2022-12-06 | Fluid Quip Technologies, Llc | System and method for producing a sugar stream with front end oil separation |
US11505838B2 (en) | 2018-04-05 | 2022-11-22 | Fluid Quip Technologies, Llc | Method for producing a sugar stream |
US10480038B2 (en) | 2018-04-19 | 2019-11-19 | Fluid Quip Technologies, Llc | System and method for producing a sugar stream |
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CA2869298C (en) | 2020-04-07 |
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AU2013253444A1 (en) | 2014-11-27 |
US9926613B2 (en) | 2018-03-27 |
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EP2843061B1 (en) | 2017-06-07 |
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BR112014026799A2 (pt) | 2017-06-27 |
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