CN102787149B - 处理木质纤维素生物质的方法 - Google Patents

处理木质纤维素生物质的方法 Download PDF

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CN102787149B
CN102787149B CN201210287568.7A CN201210287568A CN102787149B CN 102787149 B CN102787149 B CN 102787149B CN 201210287568 A CN201210287568 A CN 201210287568A CN 102787149 B CN102787149 B CN 102787149B
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Abstract

描述了采用浓氨水(加入或不加入无水氨)处理生物质,以提供更具可及性和/或可消化性的结构性碳水化合物的方法。所述方法优选采用蒸汽来从所述生物质汽提回收氨。从所述结构性碳水化合物获得单糖的产率良好,具体地通过结构性碳水化合物的酶水解测定。单糖用作动物饲料和乙醇生产的能源。

Description

处理木质纤维素生物质的方法
本申请是以下申请的分案申请:申请日:2007年4月30日;申请号:2007800253944(PCT/US2007/010415);发明名称:处理木质纤维素生物质的方法。
相关申请的交叉引用
本申请要求2006年5月1日提交的美国临时申请60/796,375的优先权,所述申请通过引用其整体内容结合于本文中。
关于联邦资助研究或开发的申明
不适用
关于政府权利的申明
不适用
发明背景
(1)发明领域
本发明涉及采用浓氨水、优选采用氨气处理木质纤维素生物质来提高结构性碳水化合物(多糖)的可获得性的方法。优选采用加压蒸汽从生物质中汽提回收氨。具体地讲,本发明涉及使多糖有效转变成单糖(优选通过酶水解)的方法。
(2)相关技术描述
已采用许多方法(例如浓或稀酸或碱、高温、各种形式的辐射)对木质纤维素生物质进行预处理来提取结构性碳水化合物,所述结构性碳水化合物用于获得用于不同用途的单糖。这些预处理的目标是提高随后通过化学或生物化学手段如酸催化、酶催化、发酵或动物消化从结构性碳水化合物获得单糖的速率和/或产率。通常,这些预处理由于以下几个原因达不到所需经济和技术性能:1)许多预处理使一些糖降解成例如酸或醛,因此减少了产率并抑制了随后剩余糖的生物转化;2)当化学品用于预处理时,通常难以合理的成本回收这些化学品;3)残余化学品会负面影响下游转化工序;和4)许多预处理的效率有限,使得获得的结构性碳水化合物最终转化率(与糖降解反应导致的损失产率无关)对于竞争性工艺而言在经济上仍为不足。因此,存在许多现有技术的方法,但它们具有包括上述的许多缺点。
来自可再生植物生物质的足够廉价单糖可替代石油和其它矿物原料而成为化学和燃料工业的基础。需要有效、经济的预处理来以高产率和可接受成本获得这些单糖。
现有技术中广泛采用无水液氨或氨水溶液对植物生物质进行预处理。实例有以下专利和参考文献:
Dale的美国专利4,600,590
Chou的美国专利4,644,060
Dale的美国专利5,037,663
Holtzapple等的美国专利5,171,592
Holtzapple等的美国专利5,865,898
Karsents等的美国专利5,939,544
Bredereck等的美国专利5,473,061
Karstens的美国专利6,416,621
Dale等的美国专利6,106,888
Dale等的美国专利6,176,176
Felix,A.等,Anim.Prod.(畜牧业)5147-61(1990)
Waiss,A.C,Jr.等,Journal of Animal Science(畜牧杂志)35No.1,109-112(1972)。所有这些专利和公开物整体内容都结合于本文中。
具体地讲,氨纤维爆裂(AFEX)代表用于将木质纤维素生物转化成乙醇的一种独特、有效的预处理(Dale,B.E.,1986.美国专利5,037,663;Dale,B.E.,1991.美国专利4,600,590;Alizadeh,H.,F.Teymouri,T.I.Gilbert,B.E.Dale,2005,Pretreatmentof Switchgrass by Ammonia Fiber Explosion(通过氨纤维爆裂进行柳枝稷预处理),Applied Biochemistry and Biotechnology(应用生物化学和生物技术),121-124:1133-1141;Dale,B.E.,1991.美国专利4,600,590;Dale,B.E.,1986.美国专利5,037,663)。AFEX预处理中,将木质纤维素生物质暴露于在足以保持氨为液相的压力和适当温度(如约100℃)下的浓氨中。AFEX反应器中的停留时间通常不到30分钟,将预处理生物质减压(闪蒸)来终止AFEX反应。AFEX法不局限于对无水氨实施AFEX处理。在开始AFEX处理时,将一些水加到生物质,使得所有无水氨立即转化成浓氨水混合物。
当将AFEX结合到更广生物质转化工艺设计中时,主要目标是回收AFEX预处理中所用的氨。如图1所述,现有氨回收设计(Eggeman,T.2001.Ammonia FiberExplosion Pretreatment for Bioethanol Production(用于生物乙醇生产的氨纤维爆裂预处理),National Renewable Energy Laboratory(NREL)Subcontract No.LCO-1-31055-01)(国家可再生能源实验室转包合同LCO-1-31055-01)要求将氨压缩(通过闪蒸工艺蒸发)并通过在干燥器中蒸发将仍接触已预处理固体的液氨分离。然后将所得蒸气(还包含水)输送到蒸馏柱以纯化氨。将来自塔的氨泵抽到一定压力,并与经压缩闪蒸的氨一起回收到AFEX反应器。图1显示了现有的氨回收方法。
图1显示了包括密闭AFEX反应容器12的现有技术***10,加压将生物质、水和氨引入密闭AFEX反应容器12中。阀V1用来释放容器12的压力。将已处理生物质传送到热干燥器14。将经干燥的生物质转移出干燥器14以进行后道处理。通过冷凝器22将来自干燥器14的氨冷凝并输送到浆柱16。通过冷凝器18除去水并冷凝。氨在冷凝器20中冷凝并循环到容器12。在压缩机24中将氨气增压、冷凝并循环到容器12中。
问题是所述方法将制备低产率的单糖和/或需要大量液氨或氨水溶液。
发明目的
因此本发明的一个目标是提供将采用浓氨水萃取结构性碳水化合物和有效回收所述氨有效地结合的方法。此外,本发明的一个目标是提供能从所述结构性碳水化合物高产率地生产单糖的经济方法。通过参考以下说明书和附图,这些和其它目标将变得显而易见。
发明概述
本发明涉及处理木质纤维素生物质中结构性碳水化合物的方法,所述方法包括:(a)在50℃以上、大气压以上压力的密闭容器中,使生物质和热的氨水溶液(具有浓度超过约30%重量的氨)反应,同时控制温度、氨与干生物质的质量比及水与干生物质的质量比来提高所述结构性碳水化合物的可消化性和/或可及性;(b)快速释放容器中的压力;(c)从所述生物质和溶液中回收至少一些氨和氢氧化铵;和(d)任选通过酶、微生物转化或动物消化法进一步加工经处理生物质。优选在步骤(d)中将结构性碳水化合物作为葡萄糖、木糖、***糖和其它糖的混合物回收。优选所得结构性碳水化合物可通过进一步处理利用,所述进一步处理为产生有机酸、醇和其它副产物的微生物转化方法。优选通过所述方法可获得的碳水化合物通过动物消化法用于反刍动物或非反刍动物饲料。优选密闭容器中氨、生物质和水混合物的温度为约50℃-120℃。优选密闭容器中的压力为约4-50atm。优选将氨气加入容器中来填充容器中的所有空隙空间。氨处理不直接使大部分生物质溶解。大约20%半纤维素(主要为木聚糖聚合物)可被增溶,但基本上没有葡聚糖结构的多糖(纤维素)被增溶。它们被“活化”或提供了高得多的水解可能性。术语“结构性碳水化合物”是指纤维素和半纤维素。
本发明还涉及处理含植物生物质(包含结构性碳水化合物和天然存在于生物质中的水)的木质纤维来制备更具可消化性或可及性的结构性碳水化合物的方法,所述方法包括:(a)在较高压力和较高温度的密闭容器中,使生物质和热的氨水溶液(所述氨水溶液具有超过约30%重量氨)反应,同时不使所述木质纤维素降解,来将结构性碳水化合物从生物质中移到溶液中,其中生物质提供的水量超过生物质的1%重量但少于50%重量;(b)释放容器中生物质中的压力;(c)将生物质与结构性碳水化合物的浆料从容器中移出;和(d)从所述浆料中汽提氨水溶液和氨来提供在浆料中的结构性碳水化合物,其中结构性碳水化合物中超过85%的可用葡萄糖可通过结构性碳水化合物的酶水解回收。优选使氨循环。优选所述糖包括木糖和葡萄糖的混合物。优选密闭容器中氨、生物质和水混合物的温度为约50-120℃。优选将氨气加入容器中来填充容器中的所有空隙空间。优选迅速释放压力。优选压力为约6.9-20.7atm。
本发明还涉及从木质纤维素生物质的氨纤维爆裂(AFEX)处理回收氨的方法,所述方法包括:(a)在密闭反应容器中用氨水溶液加压处理生物质以形成浆料;(b)释放反应容器中的压力并将所得浆料泵送到汽提柱;(c)采用加压蒸汽从汽提柱上部将氨汽提出来,并从该柱下部将经汽提浆料移走;(d)将来自该柱上部的汽提氨引入混合器中,并将水加压加入该混合器中形成稀氨水溶液;(e)将来自混合器的稀氨水溶液冷却;和(f)将经冷却的氨水溶液与其它生物质加压引入反应容器中。优选反应是连续的。本发明还涉及实施本文所述方法的***。
通过参考以下附图和说明书,本发明的主旨和优点会变得显而易见。
附图简述
图1是带有回收和循环氨的工艺的现有技术AFEX预处理工艺流程图。
图2是带有有效回收氨工艺的本发明AFEX预处理的工艺流程图。
优选实施方案描述
纤维素生物质包含大量结构性碳水化合物或多糖(纤维素、半纤维素等),所述结构性碳水化合物或多糖可提供非常廉价的单糖来发酵或非生物转化成多种产品或作为改良的动物饲料。然而,难以获得这些多糖。本发明提供采用高压浓氨水来提高纤维素生物质的多糖的可及性/可消化性的预处理方法。本发明优选采用无水氨和浓氨水溶液组合来获得通过稀氨水或无水氨单独作用不可能获得的结果。
本发明中,用氨水溶液中含有超过30%重量的浓氢氧化铵处理木质纤维素材料。如实施例中,所述方法可在连续反应器中或间歇反应器中进行。
所述生物质包含天然存在的水。通常该天然水占所述生物质的约1%-20%重量。该天然水通常结合于所述生物质中,因此主要需要的水为通过氨水溶液加入的水。水也可加到生物质,如果这样,则其与氨水混合得到氨水溶液。加入的水可占生物质的至多50%。
术语“木质纤维素生物质”是指天然木质素和纤维素基材料。例如这类材料有苜蓿、麦草、玉米秸秆、木纤维等。优选将所述材料在最长尺寸方向上粉碎成微粒。
术语“结构性碳水化合物”是指包含通过水解可获得的单糖部分的多糖材料。
木质纤维素生物质与氨的质量比优选为1比1。
反应温度优选为90℃;然而,温度可为50℃-120℃。
压力优选为100psia-300psi(6.9-20.7atm);然而,可使用4-50atm的压力。
可将热氨水溶液或热氨蒸气/水蒸气加到在容器中的磨碎的木质纤维素生物质来获得50℃以上,优选90℃的最终混合物温度。优选氨与干生物质的质量比为约0.2-1.0。优选水与干生物质质量比为约0.4-1.0。
图2显示了带有AFEX反应容器的改进***100。将浆料直接送到汽提柱104,在冷凝器106中冷凝并送到混合器108以加入水。在汽提柱104中采用高压蒸汽来从浆料移走氨。从汽提柱底部移走热的含水浆料。冷凝器110和112用来冷却水和氨的混合物,所述混合物将被循环到容器102。通过对比图1和2,可以看出这种方法更有效。
实施例1-20
首先用一定质量的、打湿到表1中所示的所需湿度水平的玉米秸秆填充300ml压力容器102,将容器102密封。然后在另一压力容器将正确比例的无水氨和水混合制备浓氨水混合物,将该混合物加入300ml反应容器102中的玉米秸秆,来得到所需最终水平的氨和水。这种情况中,目标为1kg氨/kg干生物质和0.6kg水/kg干生物质。接着将氨、水和生物质的混合物加热到90℃,在此温度保持5分钟并迅速释放压力。
将所得固体水解成包含例如葡萄糖、木糖和***糖的单糖混合物。
本发明的结果显示于表1实施例2-15中。
表1-氨处理的玉米秸秆用纤维素酶水解168hr(7天)后的葡萄糖和木糖产率。采用不同氨浓度。都以如下条件进行实验:1kg NH3:1Kg干秸秆(BM),90℃反应器温度,0.6Kg水/Kg干秸秆(除实验17-20这最后4个外)和5分钟停留时间。15FPU纤维素酶/g BM中葡聚糖。
注:除实验16-19(其压力为大气压)外,其他压力为约100psia-约300psia
(a)对比实施例1显示了Dale的美国专利4,600,590和5,037,663中描述的AFEX法,图1所示。对比实施例16-19(b)显示了用氨水在大气压下得到的结果,实施例20(c)显示了不用氨的方法。
表1显示了以下用氨和水处理,玉米秸秆转化成葡萄糖和木糖的结果。所有情况下水、氨和生物质的总量和***温度相同。用1kg氨/1kg干生物质(未处理秸秆的水分含量为干基重的约15%)处理生物质。实验在90℃进行,在该温度保持5分钟并用15滤纸单位的纤维素/g秸秆中纤维素将实施例1的已处理材料水解。从秸秆经受的最终条件来看,这些条件是相同的。
表的前两(2)列显示这是如何进行的。例如标题为“加入氨”的列显示氨(NH3)作为无水氨或者氨水(氨/水)加入。例如“全部NH3”意味着如实施例1中将全部氨作为无水液氨直接从压力罐加到生物质。“全部NH4OH”意味着全部氨作为氨水溶液加入。
第二列显示直接将水加到秸秆或者作为氨水的部分加入。第一行中“全部NH3”和“全部BM中的水”意味着如实施例1中全部氨作为无水氨加入且所有水在生物质中。最后一行为“全部NH4OH”,意味着全部氨作为氨水加入且将水加到秸秆或与氨水一起加入。
因此,根据如何加入氨和水,得到非常不同的结果。85%纤维素转化成葡萄糖为在成本上具有竞争力的方法的最低值。采用该标准,最后列显示了水解168小时后的葡萄糖(G)和木糖(X)%的产率。当全部水作为氨水加入(相对更稀氨水)时不能达到85%标准。
表1显示:铵浓度是重要的。与生物质天然结合的水不会起着可用来稀释氨的游离水的作用。
本发明方法的具体特征如下所述比现有技术更有利:(1)它不会使任何生物质碳水化合物降解,从而产率不会由于该预处理而受到影响;(2)获得高的葡萄糖总产率(接近理论的100%)和85%的木糖理论产率;(3)可在较低的其它昂贵水解酶的使用率下获得这些产率,(4)残余氨可用作后道发酵或动物饲养工艺的氮气源;(5)经处理的生物质和多糖可以非常高的固体水平进料到后道加工工序,从而提高了所有产品的浓度并减少了从所得多糖生产其它化学品的开支;和(6)采用氨和氨水组合与氨回收工序很好地融合到一起。
可采用本发明的市场包括:(1)美国化工行业,其开始不采用石油作为化学原料并对廉价单糖作为新的可持续方法的平台化合物感兴趣;(2)发酵行业,特别是燃料乙醇生产行业,其也对来自植物生物质的廉价糖感兴趣;和(3)动物饲料行业,其受到可获得碳水化合物/制备各种动物饲料的热量的成本影响很大。
以下实施例16描述了相对现有AFEX预处理氨回收设计减少了工艺能量需求的两个设计特征:(1)经预处理的材料的蒸汽汽提;和(2)氨蒸气的水骤冷冷凝。图2代表更广的AFEX预处理设计中的这些特征的工艺流程图。
预处理材料的蒸汽汽提
AFEX预处理完成后,如现有设计中,将已预处理的材料闪蒸到较低压力。然而与现有设计不同,本发明采用将所得预处理固体的蒸汽汽提来回收残余的氨。该特征能消除图1设计中所用的高能耗固体干燥。处理设备可与用于直接蒸汽干燥固体的设备相同,现有越来越多的这种设备的商品实例(Kudra,T.,A.S.Mujumdar,2002.Advanced Drying Technologies(高级干燥技术),New York,NY:Marcel Dekker,Inc.;Pronyk,C,S.Cenkowski,2003."Superheating Steam Drying Technologies(过热蒸汽干燥技术),"ASAE Meeting Presentation(ASAE会议报告),Paper Number RRV03-0014.)。
氨蒸气的水骤冷冷凝
使来自氨回收蒸汽汽提柱的氨蒸气和产自AFEX后闪蒸工艺的氨蒸气结合,并通过如下冷凝:首先在混合器中加入水,然后在两步骤(首先用冷水,然后用冷冻水)中间接将水溶液冷却。接着通过液泵抽将冷凝的含水混合物增压并循环到AFEX反应器。这些步骤消除了用于图1设计中的氨蒸气压缩需求。
本发明的应用
根据图1和2方法的Aspen Plus(建模软件产品)过程模拟,如表2中所示,相对现有设计,本发明显著减少了过程能量。此外,预计本发明还将产生较低的加工成本。
表2过程能量需求对比:对比本发明方法与现有技术的带氨回收的
AFEX预处理1,2
1达到AFEX反应温度所需的能量完全通过反应器中氨和水之间的混合热满足。
2两种设计都采用相同的氨和水负载:0.3g NH3/g生物质;0.5g H2O/g生物质。
尽管本文中参考图示实施方案对本发明进行描述,应该理解本发明不局限于此。本领域技术人员和将使用本发明教导的技术人员会认识到属于本发明范围的其它改进和实施方案。因此,本发明受到所附权利要求书的限定。

Claims (23)

1.一种处理含有结构性碳水化合物的木质纤维素生物质的方法,所述方法包括:
将热氨蒸气和水蒸气加到密闭容器中的磨碎的木质纤维素生物质,使得在所述木质纤维素生物质中的结构性碳水化合物更易于发生水解,其中所述密闭容器是在大气压至较高压力下操作。
2.权利要求1的方法,其中所得到的最终混合物的温度为50℃以上。
3.权利要求2的方法,其中所述最终混合物的温度为90℃。
4.权利要求3的方法,其中在所述氨蒸气中的氨与干燥木质纤维素生物质的重量比为0.2:1至1:1。
5.权利要求4的方法,其中水与干生物质的比率为0.4:1至1:1。
6.权利要求1的方法,其中所述较高压力被释放。
7.权利要求1的方法,其中所述水蒸气中的水与所述木质纤维素生物质的重量比为0.4:1至1:1。
8.权利要求1的方法,其中所述密闭容器中的氨、生物质和水的混合物的温度是较高温度,其中所述较高温度为50至120℃。
9.权利要求8的方法,其中所述较高压力为4至50atm。
10.权利要求9的方法,其中所述较高压力为6.9至20.7atm。
11.权利要求1的方法,其进一步包括从经过处理的所述木质纤维素生物质获得单糖。
12.权利要求11的方法,其中所述单糖是通过酶水解、微生物转化和/或动物消化来获得的。
13.权利要求11的方法,其中所述单糖是作为葡萄糖、木糖、***糖和其它糖的混合物回收。
14.权利要求12的方法,其中所述酶水解是采用纤维素酶进行的。
15.权利要求12的方法,其中所述微生物转化产生有机酸、醇和其它副产物。
16.权利要求12的方法,其中所述动物消化用于反刍动物或非反刍动物饲料。
17.权利要求1的方法,其中所述压力被快速释放。
18.一种处理生物质的方法,包括:
将氨蒸气和水蒸气加到密闭容器中的干的植物生物质,使得在所述干燥植物生物质中的结构性碳水化合物更易于发生水解,其中所述水蒸气中的水与所述干燥植物生物质的重量比为0.4:1至1:1。
19.权利要求18的方法,其中所述密闭容器是在较高压力下操作。
20.权利要求19的方法,其中所述较高压力为4至50atm。
21.权利要求19的方法,其中所述较高压力被释放。
22.权利要求18的方法,其中所述氨蒸气中的氨与所述干燥植物生物质的重量比为0.2:1至1:1。
23.权利要求18的方法,其中所述干燥植物生物质为玉米秸秆或柳枝稷。
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