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- 239000002028 Biomass Substances 0.000 claims description 26
- 235000000346 sugar Nutrition 0.000 claims description 23
- 229920002678 cellulose Polymers 0.000 claims description 20
- 239000001913 cellulose Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000012736 aqueous medium Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 241000609240 Ambelania acida Species 0.000 claims description 5
- 239000010905 bagasse Substances 0.000 claims description 5
- 238000001223 reverse osmosis Methods 0.000 claims description 5
- 239000002609 medium Substances 0.000 claims description 4
- 239000012466 permeate Substances 0.000 claims description 4
- 238000001728 nano-filtration Methods 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims 3
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 12
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 description 8
- 238000000227 grinding Methods 0.000 description 7
- 238000010298 pulverizing process Methods 0.000 description 7
- 238000000855 fermentation Methods 0.000 description 6
- 230000004151 fermentation Effects 0.000 description 6
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 description 5
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- LGQKSQQRKHFMLI-SJYYZXOBSA-N (2s,3r,4s,5r)-2-[(3r,4r,5r,6r)-4,5,6-trihydroxyoxan-3-yl]oxyoxane-3,4,5-triol Chemical compound O[C@@H]1[C@@H](O)[C@H](O)CO[C@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)OC1 LGQKSQQRKHFMLI-SJYYZXOBSA-N 0.000 description 4
- LGQKSQQRKHFMLI-UHFFFAOYSA-N 4-O-beta-D-xylopyranosyl-beta-D-xylopyranose Natural products OC1C(O)C(O)COC1OC1C(O)C(O)C(O)OC1 LGQKSQQRKHFMLI-UHFFFAOYSA-N 0.000 description 4
- SQNRKWHRVIAKLP-UHFFFAOYSA-N D-xylobiose Natural products O=CC(O)C(O)C(CO)OC1OCC(O)C(O)C1O SQNRKWHRVIAKLP-UHFFFAOYSA-N 0.000 description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000008103 glucose Substances 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 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 3
- 230000007423 decrease Effects 0.000 description 3
- 230000007071 enzymatic hydrolysis Effects 0.000 description 3
- 238000006047 enzymatic hydrolysis reaction Methods 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- GUBGYTABKSRVRQ-CUHNMECISA-N D-Cellobiose Chemical compound O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-CUHNMECISA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001720 carbohydrates Chemical class 0.000 description 2
- 235000014633 carbohydrates Nutrition 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 150000002772 monosaccharides Chemical class 0.000 description 2
- 229920001542 oligosaccharide Polymers 0.000 description 2
- 150000002482 oligosaccharides Chemical class 0.000 description 2
- 241000219310 Beta vulgaris subsp. vulgaris Species 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021536 Sugar beet Nutrition 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 238000005904 alkaline hydrolysis reaction Methods 0.000 description 1
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 description 1
- PYMYPHUHKUWMLA-WDCZJNDASA-N arabinose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)C=O PYMYPHUHKUWMLA-WDCZJNDASA-N 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 229930182830 galactose Natural products 0.000 description 1
- -1 glucose and xylose Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Description
糖質を原料とした化学品の発酵生産プロセスは、種々の工業原料生産に利用されている。この発酵原料となる糖質として、現在、さとうきび、澱粉、テンサイなどの食用原料に由来するものが工業的に使用されているが、今後の世界人口の増加による食用原料価格の高騰、あるいは食用と競合するという倫理的な側面から、再生可能な非食用資源、すなわちセルロース含有バイオマスからより効率的に糖液を製造するプロセス、あるいは得られた糖液を発酵原料として、効率的に工業原料に変換するプロセスの構築が今後の課題となっている。 Fermentation production processes for chemicals using carbohydrates as raw materials are used to produce various industrial raw materials. Currently, carbohydrates derived from edible raw materials such as sugar cane, starch, and sugar beet are used industrially as raw materials for this fermentation, but the future rise in the price of edible raw materials due to the increase in the world's population, or From the ethical aspect of competition, we are developing a process to more efficiently produce sugar solution from renewable non-edible resources, i.e. cellulose-containing biomass, or efficiently converting the resulting sugar solution into an industrial raw material by using it as a fermentation raw material. The challenge for the future is to create a process to do so.
例えば、セルロースの酵素加水分解速度を向上させるために、セルロース含有物とアルカリ水溶液とを接触させるアルカリ処理を行い、アルカリ性濾液を繰り返し利用する特定の前処理をセルロース含有バイオマスに適用することで糖液が高純度で糖を含有することが開示されている(特許文献1)。 For example, in order to improve the rate of enzymatic hydrolysis of cellulose , a cellulose-containing biomass can be treated with an alkali treatment in which a cellulose-containing material is brought into contact with an alkaline aqueous solution, and a specific pretreatment that repeatedly uses the alkaline filtrate can be applied to cellulose-containing biomass. has been disclosed to contain sugar with high purity (Patent Document 1).
工程(1)で得られる粉砕バイオマスの粉砕度合いとしては、目開き1mmのふるいで通過しない重量割合(乾燥重量%)が乾燥重量で50%程度以下になるまで粉砕し、好ましくは40%程度以上50%程度以下、より好ましくは40%程度以上45%程度以下または45%程度以上50%程度以下になるまで粉砕することで、このような粉砕をしない場合と比較して意外にも固液分離後の含水率が低減し、それにより後段の加水分解時に持ち込まれる前処理バイオマス由来の発酵阻害物質を低減することができる。粉砕度合いは、粉砕バイオマスを乾燥し、含水率20%以下とした後に粉砕バイオマスを目開き1mmのふるいにかけて評価する。なお、本明細書では、目開き1mmのふるいで通過しない粉砕バイオマスの重量割合(乾燥重量%)が低ければ、粉砕度が高いと表現することがある。ふるいの方法・条件はISO 2591-1に従う。 The degree of pulverization of the pulverized biomass obtained in step (1) is pulverized until the weight percentage (dry weight %) that does not pass through a sieve with an opening of 1 mm is about 50% or less by dry weight, preferably about 40% or more. By grinding to about 50% or less, more preferably from about 40% to about 45 % , or from about 45% to about 50%, solid-liquid separation is surprisingly improved compared to when such grinding is not done. The subsequent moisture content is reduced, thereby making it possible to reduce fermentation inhibitory substances derived from the pretreated biomass that are brought into the subsequent hydrolysis. The degree of pulverization is evaluated by drying the pulverized biomass to a moisture content of 20% or less, and then passing the pulverized biomass through a sieve with an opening of 1 mm. In this specification, the degree of pulverization may be expressed as high if the weight proportion (dry weight %) of the pulverized biomass that does not pass through a sieve with an opening of 1 mm is low. The sieving method and conditions comply with ISO 2591-1.
アルカリ性水性媒体のアルカリ濃度は、アルカリ含有性媒体中のアルカリ性物質(水酸化物等のアルカリ固形分)の含有量により算出することができる。アルカリ性水性媒体のアルカリ濃度の上限値は、特に限定されないが、好ましくは3、2、1.5、1、0.7、0.6、0.5、0.4、0.3または0.2重量%程度であり、下限値は、好ましくは0.05、0.1、0.2、0.3、0.4または0.5重量%程度である。また、好ましいアルカリ濃度の範囲は、例えば、0.05重量%程度以上0.3重量%程度以下、0.1重量%程度以上3重量%程度以下、0.1重量%程度以上2重量%程度以下、より好ましい範囲は0.1重量%程度以上2重量%程度以下、0.25重量%程度以上1.5重量%程度以下、0.25重量%程度以上1.5重量%程度以下、さらに好ましい範囲は0.25重量%程度以上1.0重量%程度以下である。 The alkaline concentration of the alkaline aqueous medium can be calculated from the content of alkaline substances (alkaline solid content such as hydroxide) in the alkali-containing medium. The upper limit of the alkaline concentration of the alkaline aqueous medium is not particularly limited, but is preferably 3, 2, 1.5, 1, 0.7, 0.6, 0.5, 0.4, 0.3 or 0. It is about 2% by weight, and the lower limit is preferably about 0.05, 0.1, 0.2, 0.3, 0.4 or 0.5% by weight. Further, preferable alkali concentration ranges are, for example, about 0.05% by weight or more and about 0.3% by weight or less, about 0.1% by weight or more and about 3% by weight or less, and about 0.1% by weight or more and about 2% by weight. The following more preferable ranges are about 0.1 wt% or more and about 2 wt% or less , about 0.25 wt% or more and about 1.5 wt% or less, about 0.25 wt% or more and about 1.5 wt% or less, and A preferable range is about 0.25% by weight or more and about 1.0% by weight or less.
工程(4)では、セルロース含有固形分を加水分解して糖液を得る。加水分解工程では、酸加水分解、アルカリ加水分解、酵素加水分解等の公知の加水分解法を適用することができるが、セルロース含有固形分を水媒体中、酵素で加水分解処理することが好ましい。かかる酵素加水分解工程によって得られる糖液は、例えば、グルコース、キシロース、アラビノース、ガラクトース、キシロビオース、セロビオースをはじめとする、オリゴ糖および/または単糖を含有する水溶液として取得することができる。 In step (4), the cellulose- containing solid content is hydrolyzed to obtain a sugar solution. In the hydrolysis step, known hydrolysis methods such as acid hydrolysis, alkaline hydrolysis, and enzymatic hydrolysis can be applied, but it is preferable to hydrolyze the cellulose- containing solid content with an enzyme in an aqueous medium. The sugar solution obtained by such an enzymatic hydrolysis step can be obtained as an aqueous solution containing oligosaccharides and/or monosaccharides such as glucose, xylose, arabinose, galactose, xylobiose, and cellobiose.
工程(4)で得られる糖液におけるグルコース、キシロースまたはキシロビオースの濃度は、特に限定されず、各工程の反応条件等を調節することにより適宜設定することができる。好適なグルコース濃度としては、例えば、5g/L程度以上1000g/L程度以下、5g/L程度以上700g/L程度以下、5g/L程度以上550g/L程度以下または10g/L程度以上550g/L程度以下である。また、好適なキシロース濃度としては、例えば、1g/L程度以上100g/L程度以下、1g/L程度以上50g/L程度以下または1g/L程度以上10g/L程度以下である。また、好適なキシロビオース濃度としては、例えば、1g/L程度以上100g/L程度以下、1g/L程度以上50g/L程度以下、1g/L程度以上20g/L程度以下または1g/L程度以上15g/L程度以下である。 The concentration of glucose, xylose, or xylobiose in the sugar solution obtained in step (4) is not particularly limited, and can be appropriately set by adjusting the reaction conditions of each step. Suitable glucose concentrations include, for example, about 5 g/L to about 1000 g/L, about 5 g/L to about 700 g/L, about 5 g/L to about 550 g/L, or about 10 g/L to about 550 g/L. It is below that level. Further, a suitable xylose concentration is, for example, about 1 g/L or more and about 100 g/L or less , about 1 g/L or more and about 50 g/L or less, or about 1 g/L or more and about 10 g/L or less. In addition, suitable xylobiose concentrations include, for example, about 1 g/L or more and about 100 g/L or less , about 1 g/L or more and about 50 g/L or less, about 1 g/L or more and about 20 g/L or less, or about 1 g/L or more and about 15 g /L or less.
ナノ濾過膜または逆浸透膜処理とは、工程(4)で製造された糖液をナノ濾過膜または逆浸透膜に通じて濾過し、溶解している糖、特にグルコースやキシロースといった単糖や、キシロビオースやセロビオースといったオリゴ糖を膜の非透過側に阻止または濾別し、糖液に残存する発酵阻害物質を透過液として透過させる処理であり、WO2010/067785号に記載の方法によって実施することできる。 Nanofiltration membrane or reverse osmosis membrane treatment refers to filtering the sugar solution produced in step (4) through a nanofiltration membrane or reverse osmosis membrane to remove dissolved sugars, especially monosaccharides such as glucose and xylose, It is a process in which oligosaccharides such as xylobiose and cellobiose are blocked or filtered to the non-permeable side of the membrane, and fermentation inhibitors remaining in the sugar solution are permeated as a permeate, and it can be carried out by the method described in WO2010/067785. .
比較参考例2:水熱処理時のバガス粉砕度とセルロース含有固形分含水率の関係
粉砕条件としてカッターミルのスクリーン孔径を40mmとする以外は、比較参考例1と同様の条件で実施した。また、粉砕バイオマスを乾燥重量割合測定のため含水率20%に乾燥させ、ISO 2591-1の条件で目開き1mmのふるいにかけ、通過しない重量割合を測定したところ50%であった。また固液分離後のセルロース含有固形分の含水率は73%であった。結果を表2に示す。
Comparative Reference Example 2: Relationship between bagasse grinding degree and cellulose-containing solid moisture content during hydrothermal treatment The grinding was carried out under the same conditions as Comparative Reference Example 1, except that the screen pore diameter of the cutter mill was set to 40 mm as the grinding conditions. In addition, the pulverized biomass was dried to a moisture content of 20% to measure the dry weight percentage, and passed through a sieve with a 1 mm opening under the conditions of ISO 2591-1, and the weight percentage that did not pass was measured, and it was 50%. Further, the moisture content of the cellulose-containing solid after solid-liquid separation was 73%. The results are shown in Table 2.
比較参考例3:水熱処理時のバガス粉砕度とセルロース含有固形分含水率の関係
粉砕条件をカッターミルのスクリーン孔径を50mmとする以外は、比較参考例1と同様の条件で実施した。また、粉砕バイオマスを乾燥重量割合測定のため含水率20%に乾燥させ、ISO 2591-1の条件で目開き1mmのふるいにかけ、通過しない重量割合を測定したところ55%であった。また固液分離後のセルロース含有固形分の含水率は70%であった。結果を表2に示す。
Comparative Reference Example 3: Relationship between bagasse grinding degree and cellulose-containing solid water content during hydrothermal treatment The grinding conditions were the same as in Comparative Reference Example 1, except that the screen pore diameter of the cutter mill was 50 mm. In addition, the pulverized biomass was dried to a moisture content of 20% to measure the dry weight percentage, and passed through a sieve with a 1 mm opening under the conditions of ISO 2591-1, and the weight percentage that did not pass was measured, and it was 55%. Further, the moisture content of the cellulose-containing solid after solid-liquid separation was 70%. The results are shown in Table 2.
表2から分かるとおり、前処理が水熱処理である場合、粉砕バイオマスの目開き1mmのふるいで通過しない割合(乾燥重量%)が低下する(粉砕度が高まる)につれて、固液分離後のセルロース含有固形分含水率(%)が高まり、粉体がスラリー化した排水の処理では粉体の粉砕度が高い程、脱水しにくいという当業者に周知の情報(J.Soc.Powder Technol.,Japan,38,177-183(2001)の表2参照。)と一致する結果であった。一方、前処理がアルカリ処理である場合は、粉砕バイオマスの目開き1mmのふるいで通過しない割合(乾燥重量%)が低下する(粉砕度が高まる)につれて、当業者に周知の情報に反して固液分離後のセルロース含有固形分含水率(%)が低下し、粉砕バイオマスの粉砕度を高めることにより、後段の加水分解で糖液を製造する際に混入する前処理由来の発酵阻害物質を低減できる可能性が見いだされた。 As can be seen from Table 2 , when the pretreatment is hydrothermal treatment, as the proportion (dry weight %) of the pulverized biomass that does not pass through a 1 mm sieve decreases (as the degree of pulverization increases), the cellulose content after solid-liquid separation increases. It is well known to those skilled in the art that in the treatment of wastewater with increased solid water content (%) and powder slurry, the higher the degree of pulverization of the powder, the more difficult it is to dewater (J.Soc.Powder Technol., Japan, 38, 177-183 (2001), Table 2). On the other hand, when the pretreatment is alkaline treatment, as the proportion (dry weight %) of the pulverized biomass that does not pass through a 1 mm sieve decreases (as the degree of pulverization increases), contrary to information well known to those skilled in the art, The water content (%) of cellulose-containing solids after liquid separation decreases, and by increasing the degree of pulverization of the pulverized biomass, it reduces fermentation inhibitors derived from pretreatment that are mixed in when producing sugar solution in the subsequent hydrolysis. A possibility was discovered.
実施例3:バガスからの糖液の製造例(工程(1)~(5)実施)
実施例1で得られた工程(4)の加水分解後の糖液を、遠心分離(斎藤遠心機工業株式会社製、2,000rpm)により固液分離後、精密濾過膜(ミリポア社製、細孔径0.05μmPVDF膜)を使用して濾過を行った後、逆浸透膜(東レ株式会社製、架橋全芳香族ポリアミド系逆浸透膜UTC80)に通じて濃縮液として糖液を回収し、原水の体積の4分の1にまで濃縮されるように透過液として水を回収した。
Example 3: Example of producing sugar solution from bagasse (steps (1) to (5) performed)
The sugar solution obtained in Example 1 after hydrolysis in step (4) was separated into solid and liquid by centrifugation (manufactured by Saito Centrifugal Machinery Co., Ltd., 2,000 rpm), and then filtered through a microfiltration membrane (manufactured by Millipore Corporation, microfiltration membrane). After filtration using a PVDF membrane with a pore size of 0.05 μm, the sugar solution is collected as a concentrated solution through a reverse osmosis membrane (Crosslinked fully aromatic polyamide reverse osmosis membrane UTC80 manufactured by Toray Industries, Inc.), and the raw water is Water was collected as permeate so that it was concentrated to one quarter of the volume .
Claims (9)
工程(1):目開き1mmのふるいで通過しない重量割合が乾燥重量で50%以下になるようにセルロース含有バイオマスを粉砕する工程、
工程(2):工程(1)で得られた粉砕バイオマスをアルカリ性水性媒体に接触させて前処理バイオマスを得る工程、
工程(3):工程(2)で得られた前処理バイオマスに水を添加して固液分離し、含水率が50重量%以上70重量%未満であるセルロース含有固形分を得る工程、および
工程(4):工程(3)で得られたセルロース含有固形分を加水分解して糖液を得る工程、
を含む、方法。 A method for producing a sugar solution using cellulose-containing biomass as a raw material, the method comprising:
Step (1): A step of crushing the cellulose-containing biomass so that the weight percentage that does not pass through a sieve with an opening of 1 mm is 50% or less by dry weight,
Step (2): a step of contacting the pulverized biomass obtained in step (1) with an alkaline aqueous medium to obtain pretreated biomass,
Step (3): Adding water to the pretreated biomass obtained in Step (2) and performing solid-liquid separation to obtain a cellulose-containing solid content with a water content of 50% by weight or more and less than 70% by weight , and a step (4): a step of hydrolyzing the cellulose-containing solid obtained in step (3) to obtain a sugar solution;
including methods.
をさらに含む、請求項1~6のいずれかに記載の糖液の製造方法。 Step (5): The sugar solution obtained in step (4) is filtered through a nanofiltration membrane or a reverse osmosis membrane, the sugar solution is recovered as a non-permeate liquid, and the permeate is used as a pretreated biomass in step (3). The process of reusing water to be added to
The method for producing a sugar solution according to any one of claims 1 to 6, further comprising:
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