TWI614288B - Organosolv Pretreatment Method of Lignocellulosic Biomass with Low Water Footprint Feature - Google Patents

Organosolv Pretreatment Method of Lignocellulosic Biomass with Low Water Footprint Feature Download PDF

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TWI614288B
TWI614288B TW105140287A TW105140287A TWI614288B TW I614288 B TWI614288 B TW I614288B TW 105140287 A TW105140287 A TW 105140287A TW 105140287 A TW105140287 A TW 105140287A TW I614288 B TWI614288 B TW I614288B
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solvent
lignin
lignocellulose
low water
cellulose
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TW201821499A (en
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顏豐裕
陳信宏
郭家倫
詹明峰
陳文華
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行政院原子能委員會核能研究所
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Abstract

一種低水足跡之木質纖維素溶劑前處理方法,係使用溶劑與水進行木質纖維素組成之解聚分離之低水足跡前處理方法,藉由添加少量無機酸,於適當之反應溫度、壓力下,將木質素予以溶解且將半纖維素予以水解,兩者皆溶於液相,留下纖維素固渣。本發明係利用溶劑與水相對揮發性之差異,特別是相對低溫條件下,以低溫抽氣乾燥之方式輔助進行纖維素固渣之溶劑去除與回收,據此可顯著降低製程之用水量以及後續廢水處理量,達成製程低水足跡之目的,同時亦可達成原有溶劑前處理法所欲達成之酵素水解效率目標。而含有木質素與半纖維素水解產物之溶液則可藉由蒸發或稀釋之方式將溶劑濃度降低以析出木質素固體,藉以達成木質纖維素之三個主要組成之有效分離,達成木質纖維素之多元與充分利用之目的。A low water footprint lignocellulose solvent pretreatment method, which is a low water footprint pretreatment method for depolymerization separation of lignocellulose by using a solvent and water, by adding a small amount of inorganic acid at a suitable reaction temperature and pressure The lignin is dissolved and the hemicellulose is hydrolyzed, both of which are dissolved in the liquid phase, leaving the cellulose solid residue. The invention utilizes the difference of the relative volatility of the solvent and the water, in particular, under the relatively low temperature condition, assists in the solvent removal and recovery of the cellulose solid residue by means of low temperature air drying, thereby significantly reducing the water consumption of the process and subsequent The amount of wastewater treatment can achieve the goal of low water footprint of the process, and at the same time achieve the goal of enzyme hydrolysis efficiency that the original solvent pretreatment method is to achieve. The solution containing lignin and hemicellulose hydrolysate can reduce the solvent concentration by evaporation or dilution to precipitate lignin solids, thereby achieving effective separation of the three main components of lignocellulose, and achieving lignocellulose. Diversification and full use.

Description

低水足跡之木質纖維素溶劑前處理方法Lignocellulosic solvent pretreatment method with low water footprint

本發明係有關於一種低水足跡之木質纖維素溶劑前處理方法,尤指涉及一種改善木質纖維素溶劑移除程序之方法,特別係指可降低製程之用水量,達成低水足跡之目的者。The invention relates to a lignocellulosic solvent pretreatment method with low water footprint, in particular to a method for improving the lignocellulose solvent removal procedure, in particular to a person who can reduce the water consumption of the process and achieve a low water footprint. .

農林廢棄物即所謂木質纖維素(lingo-cellulose)料源,其係由三種主要成分所構成,即纖維素(cellulose)、半纖維素(hemicellulose)與木質素(lignin),其中纖維素、半纖維素分別主要由六碳葡萄糖(glucose)、與五碳木糖(xylose)等可發酵單糖所鏈結構成,而木質素則由三種不同之類苯基丙烷單體(phenylpropanoid monomers)所組成,就生物資源之角度而言,其皆有後續利用之價值。然而,由於生質物在生長之過程中,為了保護水分、糖分不被外來之動物或細菌所破壞而逸失,它會自成一個複雜之構造與輸送機構來自我保護,因此欲從木質纖維素中提煉有價值之產品,最大之難題便在於克服其頑強結構(recalcitrant structure)。 自木質纖維素中進行物質之轉換目前主要有兩種途徑,即糖化平台與熱化學平台。該糖化平台中之關鍵解聚糖化製程,以解聚糖化之角度而言,由於木質纖維素中纖維素與半纖維素之結構強度差異,因此目前已知較可行之解聚方法係選擇先將半纖維素水解為木糖為主之可發酵單糖,然後傾向採用酵素水解法進行纖維素轉化葡萄糖程序,以完備整個解聚糖化製程。 對於木質纖維素之料源而言,採用常見之稀酸前處理法,可將料源中之半纖維素先水解為可發酵單糖,並有效破壞所殘留之纖維素與木質素為主之固體結構,以達成較佳之纖維素酵素水解效率,此法相較於另一種常見之鹼前處理法,可解決其大量廢液產生之缺點。但由於木質纖維素中之木質素及半纖維素所構成之複雜基質(complex matrix)會使得酵素難以接近纖維素之活化位置,此複雜基質亦有吸附酵素之特性,導致對於木質素含量較豐之料源而言,不但其纖維素與木質素結構之破壞更形困難,過多木質素之存在亦將導酵素之吸附與抑制作用,使得酵素水解效率顯著降低。以溶劑與水進行木質纖維素組成之解聚分離通常稱為溶劑前處理法,其係藉由添加少量無機酸,於適當之反應溫度、壓力下,可將木質素予以溶解且將半纖維素予以水解,留下純度相當高之纖維素固渣,據此可以較低之酵素劑量進行纖維素之水解,有效解決木質素含量較高料源所導致酵素抑制現象,同時亦可分離出具有高價值之高純度木質素或木糖及其衍生物。然而,在此方法中,由於纖維素固渣中溶劑之殘留亦將顯著抑制酵素水解之進行 ,因此酵素水解前必須進行溶劑移除與回收,習知方法係常以水洗之方式進行溶劑之移除,製程中必須使用大量清水進行纖維素固渣之多次水洗以去除大部分殘留溶劑,再添加酵素將纖維素水解為葡萄糖,做為後續發酵產製生質燃料或生質化學品之原料,惟其後續回收與廢水處理等問題,存在著成本、環保、水資源取得與配置之疑慮;故,ㄧ般習用者係無法符合使用者於實際使用時之所需。Agricultural and forestry waste, the so-called lingo-cellulose source, consists of three main components, namely cellulose, hemicellulose and lignin, of which cellulose and half Cellulose is mainly composed of a chain of fermentable monosaccharides such as hexaglucose and xylose, and lignin is composed of three different kinds of phenylpropanoid monomers. In terms of biological resources, they all have the value of subsequent use. However, since the biomass is in the process of growing, in order to protect the water and the sugar is not destroyed by the foreign animals or bacteria, it will become a complex structure and transport mechanism from my protection, so it is intended to be from lignocellulose. The biggest challenge in refining valuable products is to overcome their recalcitrant structure. There are two main ways to convert substances from lignocellulose, namely the saccharification platform and the thermochemical platform. The key saccharification process in the saccharification platform, in terms of saccharification, due to the difference in structural strength between cellulose and hemicellulose in lignocellulose, it is known that the more feasible depolymerization method is selected first. Hemicellulose is hydrolyzed into xylose-based fermentable monosaccharides, and then the enzyme hydrolysis process is used to carry out the cellulose conversion glucose process to complete the entire glycolytic process. For the source of lignocellulose, the common dilute acid pretreatment method can be used to hydrolyze the hemicellulose in the source to fermentable monosaccharides, and effectively destroy the residual cellulose and lignin. Solid structure to achieve better cellulase hydrolysis efficiency, this method can solve the shortcomings of its large amount of waste liquid compared to another common alkali pretreatment method. However, due to the complex matrix of lignin and hemicellulose in lignocellulose, it is difficult for the enzyme to access the activation site of cellulose. This complex matrix also has the property of adsorbing enzymes, resulting in a high content of lignin. In terms of the source of the material, not only the destruction of its cellulose and lignin structure is more difficult, but the presence of too much lignin also adsorbs and inhibits the enzyme, which makes the enzyme hydrolysis efficiency significantly lower. The depolymerization separation of lignocellulose composition with solvent and water is generally referred to as solvent pretreatment, which can dissolve lignin and hemicellulose at a suitable reaction temperature and pressure by adding a small amount of inorganic acid. It is hydrolyzed to leave a cellulose slag with a relatively high purity. According to this, the hydrolysis of cellulose can be carried out at a lower enzyme dosage, and the enzyme inhibition phenomenon caused by the high lignin content source can be effectively solved, and the separation can be high. High purity lignin or xylose and its derivatives. However, in this method, since the residual solvent in the cellulose slag will also significantly inhibit the hydrolysis of the enzyme, the solvent must be removed and recovered before the hydrolysis of the enzyme, and the conventional method is usually carried out by washing in a solvent manner. In addition, a large amount of water must be used in the process to wash the cellulose residue to remove most of the residual solvent, and then add the enzyme to hydrolyze the cellulose into glucose, which is used as a raw material for the subsequent fermentation to produce biofuel or biochemical. However, problems such as subsequent recycling and wastewater treatment have doubts about cost, environmental protection, and acquisition and allocation of water resources; therefore, the general users cannot meet the needs of users in actual use.

本發明之主要目的係在於,克服習知技藝所遭遇之上述問題並提供一種改善木質纖維素溶劑移除程序之方法,可降低製程之用水量,達成低水足跡目的之低水足跡之木質纖維素溶劑前處理方法。 本發明之次要目的係在於,提供一種利用溶劑與水相對揮發性之差異 ,特別是相對低溫條件下,以抽氣乾燥之方式輔助進行纖維素固渣之溶劑去除與回收,據此可顯著降低製程之用水量以及後續廢水處理量,達成製程低水足跡之目的,同時亦可達成原有溶劑前處理法所欲達成之酵素水解效率目標之低水足跡之木質纖維素溶劑前處理方法。 本發明之另一目的係在於,提供一種含有木質素與半纖維素水解產物之溶液可藉由蒸發或稀釋之方式將溶劑濃度降低以析出木質素固體,藉以達成木質纖維素之三個主要組成之有效分離,達成木質纖維素之多元與充分利用目的之低水足跡之木質纖維素溶劑前處理方法。 本發明之再一目的係在於,提供一種可分離出純度相當高之纖維素、木質素及半纖維素水解產物,鑒於其係屬可高值應用之標的,因此對於料源成本單價較高與木質素含量較豐之木質纖維素更具有實施之價值,同時本發明方法有效降低製程用水量,對於水資源取得不易之廠域,亦有實施效益之低水足跡之木質纖維素溶劑前處理方法。 為達以上之目的,本發明係一種低水足跡之木質纖維素溶劑前處理方法,其程序包括:木質纖維素料源步驟:提供一木質纖維素料源,該木質纖維素料源係包含纖維素、半纖維素與木質素之生質物,且該木質纖維素料源之木質素含量係大於10%者;料源切碎步驟:將該木質纖維素料源粗切至所需尺寸;溶劑混合加熱反應步驟:將切碎後之木質纖維素料源與包含醇類、水及酸液之溶劑均勻攪拌混合,並於反應器中進行高溫高壓反應,反應溫度介於120~160°C、反應時間介於20~120分鐘;固液分離步驟:當上述溶劑混合加熱反應步驟完成時,係將該反應器內容物予以固液分離,分離得到高纖維素含量之纖維素固渣與含木質素與木糖之水解液;木質素析出步驟:將該水解液以蒸發或稀釋溶劑濃度之方式進行木質素析出與木糖液之分離;溶劑回收步驟:當上述木質素析出步驟完成時,進行溶劑回收;抽氣乾燥步驟:將該纖維素固渣以低溫乾燥為主要方式進行溶劑之移除並回收至溶劑回收步驟,其抽氣乾燥之溫度係介於10~50°C、壓力係介於10~150mbar;以及酵素水解步驟:對抽氣乾燥處理後之纖維素固渣,係使用纖維水解酵素(cellulase)進行酵素水解,其纖維酵素水解糖化效率可達80%以上。 於本發明上述實施例中,該木質纖維素料源係為木片或蔗渣。 於本發明上述實施例中,該溶劑中之醇類溶劑濃度係介於40~75%、水係介於25~60%、及酸液濃度係介於0.5~3%,且該酸液係為無機酸或有機酸,而該溶劑與該木質纖維素料源重量比值係介於4~12之間。 於本發明上述實施例中,該無機酸係包含硫酸、鹽酸或醋酸。 於本發明上述實施例中,該溶劑中之醇類溶劑係包括甲醇、乙醇、異丙醇、正丁醇、或異丁醇。 於本發明上述實施例中,該木質素析出步驟中之稀釋係包含添加相異於醇類之溶劑,並可為水。 於本發明上述實施例中,該抽氣乾燥步驟係之抽氣乾燥時間係介於0.5至12小時。 於本發明上述實施例中,該酵素水解步驟係使用10~30 (FPU/g cellulose)纖維水解酵素,於反應溫度介於45~52°C、反應時間介於24~72hr下進行酵素水解。 於本發明上述實施例中,該固液分離步驟係可進一步進行稀釋液之添加。 於本發明上述實施例中,該稀釋液之組成係包含水、醇類、酸或其組合。The main object of the present invention is to overcome the above problems encountered in the prior art and to provide a method for improving the lignocellulose solvent removal procedure, which can reduce the water consumption of the process and achieve a low water footprint for low water footprint. Solvent pretreatment method. A secondary object of the present invention is to provide a difference in relative volatility between a solvent and water, particularly in a relatively low temperature condition, in a manner of suction drying to assist in solvent removal and recovery of cellulose slag, thereby significantly Reduce the water consumption of the process and the amount of subsequent wastewater treatment, achieve the purpose of low water footprint of the process, and at the same time achieve the low water footprint of the original solvent pretreatment method to achieve the low water footprint of the lignocellulose solvent pretreatment method. Another object of the present invention is to provide a solution containing lignin and hemicellulose hydrolyzate by lowering the solvent concentration by evaporation or dilution to precipitate lignin solids, thereby achieving the three main components of lignocellulose. Effective separation, a lignocellulose solvent pretreatment method that achieves the diversification of lignocellulose and the low water footprint for the purpose of full utilization. A further object of the present invention is to provide a cellulose, lignin and hemicellulose hydrolysate which can be separated into a relatively high purity, and in view of the high value application of the system, the unit price of the source is higher. The lignocellulose with rich lignin content has more practical value. At the same time, the method of the invention effectively reduces the water consumption of the process, and the lignocellulosic solvent pretreatment method for implementing the low water footprint of the water resources for the plant area which is difficult to obtain water resources . For the purposes of the above, the present invention is a low water footprint lignocellulose solvent pretreatment process, the process comprising: a lignocellulosic material source step: providing a source of lignocellulosic material comprising fibers Biomass of hemicellulose, hemicellulose and lignin, and the lignin content of the lignocellulosic material source is greater than 10%; source shredding step: crudely cutting the lignocellulosic material source to a desired size; solvent Mixing and heating reaction step: uniformly mixing and mixing the chopped lignocellulosic material source with a solvent containing an alcohol, water and an acid solution, and performing a high temperature and high pressure reaction in the reactor at a reaction temperature of 120 to 160 ° C, The reaction time is between 20 and 120 minutes; the solid-liquid separation step: when the solvent mixing and heating reaction step is completed, the content of the reactor is solid-liquid separated, and the cellulose residue and wood containing high cellulose content are separated. a hydrolyzate of the quality and the xylose; a step of precipitating the lignin: separating the lignin precipitation from the xylose solution by evaporating or diluting the solvent concentration; the solvent recovery step: when When the quality precipitation step is completed, the solvent recovery is performed; the air drying step is: the cellulose solid residue is removed by low temperature drying, and the solvent is removed to the solvent recovery step, and the temperature of the air drying is between 10 and 10 50 ° C, pressure system between 10 ~ 150 mbar; and enzyme hydrolysis step: the cellulose slag after suction drying, using cellulase (cellulase) for enzyme hydrolysis, its fiber enzyme hydrolysis saccharification efficiency up to 80 %the above. In the above embodiment of the invention, the lignocellulosic material source is wood chips or bagasse. In the above embodiment of the present invention, the concentration of the alcohol solvent in the solvent is 40 to 75%, the water system is between 25 and 60%, and the acid concentration is between 0.5 and 3%, and the acid solution is It is a mineral acid or an organic acid, and the weight ratio of the solvent to the lignocellulosic material source is between 4 and 12. In the above embodiment of the invention, the inorganic acid comprises sulfuric acid, hydrochloric acid or acetic acid. In the above embodiment of the invention, the alcohol solvent in the solvent includes methanol, ethanol, isopropanol, n-butanol, or isobutanol. In the above embodiment of the present invention, the dilution in the lignin precipitation step comprises adding a solvent different from the alcohol, and may be water. In the above embodiment of the present invention, the evacuation drying step is performed by a drying time of 0.5 to 12 hours. In the above embodiment of the present invention, the enzyme hydrolysis step uses 10 to 30 (FPU/g cellulose) fiber hydrolyzing enzyme, and the enzyme is hydrolyzed at a reaction temperature of 45 to 52 ° C and a reaction time of 24 to 72 hr. In the above embodiment of the present invention, the solid-liquid separation step may further perform the addition of the diluent. In the above embodiment of the invention, the composition of the diluent comprises water, an alcohol, an acid or a combination thereof.

本發明係從基於生物發酵轉化程序之糖化平台切入,探討糖化平台中之關鍵解聚糖化製程,亦即採用適當方法將木質纖維素中之纖維素及半纖維素予以有效地轉換為可發酵單糖,供作後續發酵或其他應用。因此本發明即以改善此溶劑移除程序為目的,進行溶劑移除與回收方法之改良,據以降低製程之用水量以及後續廢水處理量。 請參閱『第1圖』所示,係本發明低水足跡之木質纖維素溶劑前處理方法之實施例一流程示意圖。如圖所示:本發明係一種低水足跡之木質纖維素溶劑前處理方法,係使用溶劑與水之纖維原料前處理分離法 ,其程序包括: 木質纖維素(lingo-cellulose)料源步驟s101:提供一木質纖維素料源,該木質纖維素料源係包含纖維素(cellulose)、半纖維素(hemicellulose)與木質素(lignin)之生質物,且該木質纖維素料源之木質素含量係大於10%,例如非糧木質纖維原料木片或蔗渣。 料源切碎步驟s102:將該木質纖維素料源粗切至1~2公分尺寸。 溶劑混合加熱反應步驟s103:將切碎後之木質纖維素料源與包含醇類 、水及酸液之溶劑以適當比例均勻攪拌混合,並於反應器中進行高溫高壓反應,反應溫度介於120~160°C、反應時間介於20~120分鐘。其中該醇類溶劑係包括甲醇、、乙醇、異丙醇、正丁醇或異丁醇,該酸液係為無機酸或有機酸,而該無機酸係包含硫酸、鹽酸或醋酸,可經由任意調整其中之醇類溶劑濃度介於40~75%、水介於25~60%、及酸液濃度介於0.5~3%之比例,且該溶劑與該木質纖維素料源重量比值係介於4~12之間。 固液分離步驟s104:當上述步驟s103完成時,係將該反應器內容物予以固液分離,分離得到高纖維素含量之纖維素固渣與含木質素與木糖之水解液。 木質素析出步驟s105:將該水解液以蒸發或稀釋溶劑濃度之方式進行木質素析出與木糖液之分離;其中稀釋包含添加相異於醇類之溶劑,如水。 溶劑回收步驟s106:當上述步驟s105完成時,進行溶劑回收。 抽氣乾燥步驟s107:將該纖維素固渣以低溫乾燥為主要方式進行溶劑之移除並回收至步驟s106,其抽氣乾燥之溫度係介於10~50°C、壓力係介於10~150mbar、時間係介於0.5至12小時。 酵素水解步驟s108:對抽氣乾燥處理後之纖維素固渣,使用10~30 (FPU/g cellulose)纖維水解酵素(cellulase),於反應溫度介於45~52°C、反應時間介於24~72hr下進行酵素水解,其纖維酵素水解糖化效率可達80%以上。如是,藉由上述揭露之流程構成一全新之低水足跡之木質纖維素溶劑前處理方法。 以下,基於實施例對本發明進一步具體地進行說明,但本發明未受以下實施例之任何限定。 [實施例一] 請參閱『第2~4圖』所示,係分別為本發明以實施例一流程所獲得之纖維固渣與所析出木質素之組成含量分析結果示意圖、本發明以實施例一流程利用不同方法進行溶劑移除後之酵素水解結果示意圖、及本發明在不同溫度下乙醇與水之相對揮發度趨勢圖。如圖所示:本實施例以木質纖維素原料木片為料源,其尺寸經切碎至1~1.5公分,與水30~50%、醇類溶劑50~70%均勻混合,並添加1~2%硫酸,形成溶劑與木質纖維素料源重量比值為10之固液相,並置入反應器進行135~160°C、50~80分鐘之反應。如第2圖所示,其中黑色柱狀代表纖維素含量、斜線柱狀圖代表半纖維素含量、及白色柱狀圖代表木質素含量。反應完成經固液分離後,木質素移除率可達90%以上,其固體之纖維素含量達86%以上,水解液部分經木質素析出步驟後,其木質素純度達93%以上。反應後固渣以無水洗或以相同體積之水進行水洗一次、兩次、三次及抽氣乾燥之方式進行處理後,再以纖維水解酵素以15(FPU/g cellulose)之劑量於50°C反應72小時,分別可得到1%、69%、88%、90%及83%之纖維素糖化效率,如第3圖所示。其中,抽氣乾燥之溫度係在30°C以下,壓力係在100mbar以下,以乙醇溶劑為例,此時溶劑與水之相對揮發度約為2.5,有利於溶劑之移除,乾燥後固渣之溶劑殘餘量可在3%以下,如第4圖所示。值得注意的是,抽氣乾燥之條件仍可再進一步優化,預期糖化效率可望再向上提升。 [實施例二] 請參閱『第5圖』所示,係本發明低水足跡之木質纖維素溶劑前處理方法之實施例二流程示意圖。如圖所示:本實施例可配合木質素析出程序進行製程之改良,如第5圖所示,若木質素析出步驟需添加少量稀釋液以利析出效率之提升,此方法可於反應後之固液分離階段進行稀釋液之添加,再搭配本方法所採用之抽氣乾燥將固渣之殘餘溶劑予以移除。此處之稀釋液之組成可為水、溶劑(如醇類)、酸或其組合。 本發明為一種低水足跡之木質纖維素溶劑前處理方法,係提供一種改善木質纖維素溶劑移除程序之方法,可降低製程之用水量,達成低水足跡之目的。藉由將木質纖維素與水及低沸點之溶劑一同混合,並添加少量無機酸後,於適當之反應溫度、壓力下,將木質素予以溶解且將半纖維素予以水解,使其溶於液相,留下纖維素固渣。有別於一般習知方法係以大量清水進行纖維素固渣水洗以去除大部分殘留溶劑,再添加酵素將纖維素水解為葡萄糖,做為後續發酵產製生質燃料或生質化學品之原料,本發明係利用溶劑與水相對揮發性之差異,特別是相對低溫條件下,以抽氣乾燥之方式輔助進行纖維素固渣之溶劑去除與回收,據此可顯著降低製程之用水量以及後續廢水處理量,達成製程低水足跡之目的,同時亦可達成原有溶劑前處理法所欲達成之酵素水解效率目標。而含有木質素與半纖維素水解產物之溶液則可藉由蒸發或稀釋之方式將溶劑濃度降低以析出木質素固體,藉以達成木質纖維素之三個主要組成之有效分離,達成木質纖維素之多元與充分利用之目的。採用本發明之前處理方法,若採用醇類與水以適當比例混合為溶液,並添加適當無機酸,其木質素移除率可大於90%,所得纖維素固渣之葡聚糖(glucan)成分純度可大於85%,而所析出之木質素固體純度亦可大於90%。所得固渣若經2~3次清水洗滌以去除溶劑,所得纖維素固渣之酵素水解效率可大幅提升至80~90%間,而採用本發明所提低溫乾燥之方式,其酵素水解亦可大於80%,但可節省纖維素固渣重量約10~20倍之清水用量,大幅降低製程用水量,因此本發明不但能提高木質纖維素之糖化效率,有效達成纖維素、半纖維素及木質素之分離,並可降低製程用水量,達成低水足跡之目標。 綜上所述,本發明係一種低水足跡之木質纖維素溶劑前處理方法,可有效改善習用之種種缺點,本發明方法可分離出純度相當高之纖維素 、木質素及半纖維素水解產物,鑒於其係屬可高值應用之標的,因此對於料源成本單價較高與木質素含量較豐之木質纖維素更具有實施之價值,同時本發明方法有效降低製程用水量,對於水資源取得不易之廠域,亦有實施之效益,進而使本發明之□生能更進步、更實用、更符合使用者之所須,確已符合發明專利申請之要件,爰依法提出專利申請。 惟以上所述者,僅為本發明之較佳實施例而已,當不能以此限定本發明實施之範圍;故,凡依本發明申請專利範圍及發明說明書內容所作之簡單的等效變化與修飾,皆應仍屬本發明專利涵蓋之範圍內。The invention cuts into a key saccharification process in a saccharification platform from a saccharification platform based on a bio-fermentation conversion program, that is, an appropriate method for efficiently converting cellulose and hemicellulose in lignocellulose into a fermentable single Sugar for subsequent fermentation or other applications. Therefore, the present invention improves the solvent removal and recovery method for the purpose of improving the solvent removal process, thereby reducing the amount of water used in the process and the amount of subsequent wastewater treatment. Please refer to FIG. 1 , which is a schematic diagram of a first embodiment of a lignocellulosic solvent pretreatment method with low water footprint according to the present invention. As shown in the figure: the present invention is a low water footprint lignocellulose solvent pretreatment method, which uses a solvent and water fiber raw material pretreatment separation method, and the procedure includes: a lignin-cellulose source step s101 Providing a lignocellulosic material source comprising a biomass of cellulose, hemicellulose and lignin, and the lignin content of the lignocellulosic material source More than 10%, such as non-grain wood fiber raw wood chips or bagasse. Source shredding step s102: The lignocellulosic material source is roughly cut to a size of 1 to 2 cm. Solvent mixing and heating reaction step s103: uniformly mixing and mixing the chopped lignocellulosic material source with a solvent containing an alcohol, water and an acid solution in an appropriate ratio, and performing a high temperature and high pressure reaction in the reactor at a reaction temperature of 120 ~160 ° C, the reaction time is between 20 and 120 minutes. Wherein the alcohol solvent comprises methanol, ethanol, isopropanol, n-butanol or isobutanol, the acid liquid is an inorganic acid or an organic acid, and the inorganic acid comprises sulfuric acid, hydrochloric acid or acetic acid, and can be optionally Adjusting the ratio of the alcohol solvent concentration to 40 to 75%, the water to 25 to 60%, and the acid concentration to 0.5 to 3%, and the ratio of the solvent to the lignocellulosic source is Between 4 and 12. Solid-liquid separation step s104: When the above step s103 is completed, the reactor contents are subjected to solid-liquid separation, and a cellulose content residue having a high cellulose content and a hydrolyzate containing lignin and xylose are separated. The lignin precipitation step s105: separating the lignin precipitation from the xylose solution by evaporating or diluting the solvent concentration; wherein the dilution comprises adding a solvent different from the alcohol, such as water. Solvent recovery step s106: When the above step s105 is completed, solvent recovery is performed. The air drying step s107: removing the solvent from the cellulose residue by low-temperature drying and recovering to the step s106, the temperature of the air drying is between 10 and 50 ° C, and the pressure system is between 10 and 150 mbar, time is between 0.5 and 12 hours. Enzyme hydrolysis step s108: 10~30 (FPU/g cellulose) fiber hydrolysate (cellulase) is used for the cellulose slag after the air drying treatment, the reaction temperature is between 45 and 52 ° C, and the reaction time is between 24 The hydrolysis of the enzyme is carried out at ~72 hr, and the efficiency of hydrolysis and saccharification of the fibrin is up to 80%. If so, a new low water footprint lignocellulose solvent pretreatment process is formed by the above disclosed process. Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited by the following examples. [Example 1] Please refer to "Fig. 2 to 4" for the analysis results of the composition analysis of the fiber slag and the precipitated lignin obtained by the first embodiment of the present invention, and the present invention is an example. A schematic diagram of the hydrolysis results of the enzyme after solvent removal by different methods, and the relative volatility trend of ethanol and water at different temperatures of the present invention. As shown in the figure: in this embodiment, the lignocellulosic material wood chip is used as a material source, and the size thereof is chopped to 1 to 1.5 cm, uniformly mixed with water 30-50%, alcohol solvent 50-70%, and added 1~ 2% sulfuric acid, forming a solid liquid phase with a solvent to lignocellulose source weight ratio of 10, and placed in a reactor for 135-160 ° C, 50-80 minutes reaction. As shown in Fig. 2, the black column represents the cellulose content, the oblique bar graph represents the hemicellulose content, and the white histogram represents the lignin content. After the reaction is completed, the lignin removal rate can reach over 90%, the solid cellulose content is over 86%, and the lignin purity is over 93% after the lignin precipitation step. After the reaction, the solid residue is washed with water or washed with water of the same volume once, twice, three times and air-dried, and then treated with fibrinolytic enzyme at a dose of 15 (FPU/g cellulose) at 50 °C. After 72 hours of reaction, cellulose saccharification efficiencies of 1%, 69%, 88%, 90% and 83%, respectively, were obtained, as shown in Fig. 3. The temperature of the air drying is below 30 ° C, and the pressure is below 100 mbar. Taking the ethanol solvent as an example, the relative volatility of the solvent and water is about 2.5, which is beneficial to the removal of the solvent, and the solid residue after drying. The residual amount of solvent may be below 3%, as shown in FIG. It is worth noting that the conditions for pumping and drying can still be further optimized, and it is expected that the saccharification efficiency will increase upwards. [Embodiment 2] Please refer to FIG. 5, which is a schematic flow chart of the second embodiment of the lignocellulosic solvent pretreatment method of the present invention with low water footprint. As shown in the figure: this embodiment can be combined with the lignin precipitation program to improve the process, as shown in Figure 5, if the lignin precipitation step needs to add a small amount of diluent to improve the precipitation efficiency, this method can be solid after the reaction The addition of the diluent is carried out in the liquid separation stage, and the residual solvent of the solid residue is removed by the air-drying method used in the method. The composition of the diluent herein may be water, a solvent such as an alcohol, an acid or a combination thereof. The invention relates to a lignocellulose solvent pretreatment method with low water footprint, which provides a method for improving the solvent removal process of lignocellulose, which can reduce the water consumption of the process and achieve the goal of low water footprint. By mixing lignocellulose with water and a solvent having a low boiling point, and adding a small amount of a mineral acid, the lignin is dissolved at a suitable reaction temperature and pressure, and the hemicellulose is hydrolyzed to dissolve it. Phase, leaving cellulose slag. Different from the conventional method, the cellulose residue is washed with a large amount of water to remove most of the residual solvent, and the enzyme is added to hydrolyze the cellulose into glucose, which is used as a raw material for the subsequent fermentation to produce raw fuel or raw chemicals. The invention utilizes the difference of relative volatility between solvent and water, especially under relatively low temperature conditions, assists in solvent removal and recovery of cellulose solid residue by means of suction drying, thereby significantly reducing the water consumption of the process and subsequent The amount of wastewater treatment can achieve the goal of low water footprint of the process, and at the same time achieve the goal of enzyme hydrolysis efficiency that the original solvent pretreatment method is to achieve. The solution containing lignin and hemicellulose hydrolysate can reduce the solvent concentration by evaporation or dilution to precipitate lignin solids, thereby achieving effective separation of the three main components of lignocellulose, and achieving lignocellulose. Diversification and full use. According to the previous treatment method of the present invention, if the alcohol and water are mixed in a proper ratio as a solution, and a suitable inorganic acid is added, the lignin removal rate can be more than 90%, and the obtained cellulose slag glucan component can be obtained. The purity may be greater than 85%, and the purity of the precipitated lignin solids may also be greater than 90%. If the obtained solid residue is washed by 2 to 3 times of water to remove the solvent, the hydrolysis efficiency of the obtained cellulose residue can be greatly increased to 80 to 90%, and the enzyme can be hydrolyzed by the method of low temperature drying according to the present invention. More than 80%, but can save about 10-20 times the weight of cellulose slag, and greatly reduce the water consumption of the process. Therefore, the invention can not only improve the saccharification efficiency of lignocellulose, but also effectively achieve cellulose, hemicellulose and wood. The separation of quality and the reduction of water consumption in the process to achieve the goal of low water footprint. In summary, the present invention is a low water footprint lignocellulose solvent pretreatment method, which can effectively improve various disadvantages of the conventional use, and the method of the invention can separate cellulose, lignin and hemicellulose hydrolysate with relatively high purity. In view of the fact that it is the target of high-value applications, it has more practical value for the higher the unit cost of the source and the lignocellulose content, and the method of the invention effectively reduces the water consumption of the process. The difficult factory area also has the benefits of implementation, which in turn makes the life of the invention more progressive, more practical, and more in line with the needs of the user. It has indeed met the requirements of the invention patent application and has filed a patent application according to law. However, the above is only the preferred embodiment of the present invention, and the scope of the present invention is not limited thereto; therefore, the simple equivalent changes and modifications made in accordance with the scope of the present invention and the contents of the invention are modified. All should remain within the scope of the invention patent.

s101~s108‧‧‧步驟S101~s108‧‧‧Steps

第1圖,係本發明低水足跡之木質纖維素溶劑前處理方法之實施例 一流程示意圖。 第2圖,係本發明以實施例一流程所獲得之纖維固渣與所析出木質 素之組成含量分析結果示意圖。 第3圖,係本發明以實施例一流程利用不同方法進行溶劑移除後之 酵素水解結果示意圖。 第4圖,係本發明在不同溫度下乙醇與水之相對揮發度趨勢圖。 第5圖,係本發明低水足跡之木質纖維素溶劑前處理方法之實施例 二流程示意圖。Fig. 1 is a schematic view showing an embodiment of a method for pretreating a lignocellulosic solvent having a low water footprint according to the present invention. Fig. 2 is a schematic view showing the results of analysis of the composition of the fiber slag and the precipitated lignin obtained by the first embodiment of the present invention. Fig. 3 is a schematic view showing the results of hydrolysis of an enzyme after solvent removal by a different method in the first embodiment of the present invention. Figure 4 is a graph showing the relative volatility of ethanol and water at different temperatures in the present invention. Fig. 5 is a schematic view showing the second embodiment of the method for pretreating a lignocellulose solvent having a low water footprint according to the present invention.

s101~s108‧‧‧步驟 S101~s108‧‧‧Steps

Claims (10)

一種低水足跡之木質纖維素溶劑前處理方法,其程序包括:木質纖維素(lingo-cellulose)料源步驟:提供一木質纖維素料源,該木質纖維素料源係包含纖維素(cellulose)、半纖維素(hemicellulose)與木質素(lignin)之生質物,且該木質纖維素料源之木質素含量係大於10%者;料源切碎步驟:將該木質纖維素料源粗切至所需尺寸;溶劑混合加熱反應步驟:將切碎後之木質纖維素料源與包含醇類、水及酸液之溶劑均勻攪拌混合,並於反應器中進行高溫高壓反應,反應溫度介於120~160℃、反應時間介於20~120分鐘;固液分離步驟:當上述溶劑混合加熱反應步驟完成時,係將該反應器內容物予以固液分離,分離得到高纖維素含量之纖維素固渣與含木質素與木糖之水解液;木質素析出步驟:將該水解液以蒸發或稀釋溶劑濃度之方式進行木質素析出與木糖液之分離;溶劑回收步驟;當上述木質素析出步驟完成時,進行溶劑回收;抽氣乾燥步驟:將該纖維素固渣以低溫乾燥為主要方式進行溶劑之移除並回收至溶劑回收步驟,其抽氣乾燥之溫度係介於10~50℃、壓力係介於10~150mbar;以及酵素水解步驟:對抽氣乾燥處理後之纖維素固渣,係使用纖維水解酵素(cellulase)進行酵素水解,其纖維酵素水解糖化效率可達80%以上。 A lignocellulosic solvent pretreatment method with low water footprint, the procedure comprising: a lignin-cellulose source step: providing a source of lignocellulosic material comprising cellulose , hemicellulose (hemicellulose) and lignin (lignin) of the biomass, and the lignocellulosic material source lignin content is greater than 10%; source shredding step: the lignocellulosic material source is roughly cut to The required size; solvent mixing heating reaction step: the chopped lignocellulosic material source and the solvent containing the alcohol, water and acid solution are uniformly stirred and mixed, and the high temperature and high pressure reaction is carried out in the reactor, and the reaction temperature is between 120 ~160 ° C, reaction time is between 20 and 120 minutes; solid-liquid separation step: when the solvent mixing and heating reaction step is completed, the reactor contents are solid-liquid separated, and the cellulose content of high cellulose content is separated. a slag and a hydrolyzate containing lignin and xylose; a lignin precipitation step: separating the lignin precipitation from the xylose solution by evaporating or diluting the solvent concentration; a solvent recovery step; When the lignin precipitation step is completed, the solvent recovery is performed; the air drying step is: the cellulose slag is removed by low temperature drying as a main method, and the solvent is removed to the solvent recovery step, and the temperature of the air drying is introduced. At 10~50 °C, the pressure system is between 10 and 150 mbar; and the hydrolysis step of the enzyme: the cellulose slag after the air-drying treatment is hydrolyzed by the cellulase, and the efficiency of hydrolysis and saccharification of the fiber enzyme can be More than 80%. 依申請專利範圍第1項所述之低水足跡之木質纖維素溶劑前處理 方法,其中,該木質纖維素料源包含木片或蔗渣。 Lignocellulosic solvent pretreatment with low water footprint as described in item 1 of the patent application The method wherein the lignocellulosic feed source comprises wood chips or bagasse. 依申請專利範圍第1項所述之低水足跡之木質纖維素溶劑前處理方法,其中,該溶劑中之醇類溶劑濃度係介於40~75%、水係介於25~60%、及酸液濃度係介於0.5~3%,且該酸液包含無機酸或有機酸,而該溶劑與該木質纖維素料源重量比值係介於4~12之間。 a lignocellulosic solvent pretreatment method according to the low water footprint described in claim 1, wherein the solvent has an alcohol solvent concentration of 40 to 75%, a water system of 25 to 60%, and The acid concentration is between 0.5 and 3%, and the acid solution comprises a mineral acid or an organic acid, and the weight ratio of the solvent to the lignocellulosic source is between 4 and 12. 依申請專利範圍第3項所述之低水足跡之木質纖維素溶劑前處理方法,其中,該酸係包含硫酸、鹽酸或醋酸。 A method for pretreating a lignocellulose solvent having a low water footprint as described in claim 3, wherein the acid comprises sulfuric acid, hydrochloric acid or acetic acid. 依申請專利範圍第1項所述之低水足跡之木質纖維素溶劑前處理方法,其中,該溶劑中之醇類溶劑係包括甲醇、乙醇、異丙醇、正丁醇或異丁醇。 A lignocellulose solvent pretreatment method according to the low water footprint of claim 1, wherein the alcohol solvent in the solvent comprises methanol, ethanol, isopropanol, n-butanol or isobutanol. 依申請專利範圍第1項所述之低水足跡之木質纖維素溶劑前處理方法,其中,該木質素析出步驟中之稀釋係包含添加相異於醇類之溶劑。 A lignocellulose solvent pretreatment method according to the low water footprint of claim 1, wherein the dilution in the lignin precipitation step comprises adding a solvent different from the alcohol. 依申請專利範圍第1項所述之低水足跡之木質纖維素溶劑前處理方法,其中,該抽氣乾燥步驟係之抽氣乾燥時間係介於0.5至12小時。 A lignocellulosic solvent pretreatment method according to the low water footprint of claim 1, wherein the evacuation drying step is performed for 0.5 to 12 hours. 依申請專利範圍第1項所述之低水足跡之木質纖維素溶劑前處理方法,其中,該酵素水解步驟係使用10~30(FPU/g cellulose)纖維水解酵素,於反應溫度介於45~52℃、反應時間介於24~72hr下進行酵素水解。 A lignocellulose solvent pretreatment method according to the low water footprint described in claim 1 wherein the enzyme hydrolysis step uses 10 to 30 (FPU/g cellulose) fiber hydrolyzing enzyme at a reaction temperature of 45~ The enzyme was hydrolyzed at 52 ° C and the reaction time was between 24 and 72 hr. 依申請專利範圍第1項所述之低水足跡之木質纖維素溶劑前處理方法,其中,該固液分離步驟係可進一步進行稀釋液之添加。 A lignocellulose solvent pretreatment method according to the low water footprint described in claim 1 wherein the solid-liquid separation step further performs the addition of the diluent. 依申請專利範圍第9項所述之低水足跡之木質纖維素溶劑前處理方法,其中,該稀釋液之組成係包含水、醇類、酸或其組合。 A method for pretreating a lignocellulose solvent having a low water footprint as described in claim 9 wherein the composition of the diluent comprises water, an alcohol, an acid or a combination thereof.
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