现代化工

现代化工 ›› 2025, Vol. 45 ›› Issue (9) : 59-63. DOI: 10.16606/j.cnki.issn0253-4320.2025.09.012

技术进展

基于有机溶剂预处理的木质纤维素组分分离研究进展

李新龙 ¹ ,
侯康 ¹ ,
刘瑞 ¹ ,
张权 ¹^,²^,^*

作者信息 +

Research progress on separation of lignocellulose components based on organic solvent pretreatment

Xin-long LI ¹ ,
Kang HOU ¹ ,
Rui LIU ¹ ,
Quan ZHANG ¹^,²^,^*

Author information +

文章历史 +

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摘要

详细介绍了木质纤维素的组成结构,对常见木质纤维素的组分占比进行了总结。但木质纤维素的复杂结构阻碍了人们对它的分离和利用,需要通过预处理来消除这一障碍。重点介绍了有机溶剂预处理技术,对酸/碱均相和多(两)相预处理组分分离木质纤维素的研究现状进行了概述。针对各体系中溶剂的不同,总结了它们的预处理条件/效果及优缺点,并对有机溶剂高效全组分分离木质纤维纤维素的发展前景进行了展望。

Abstract

This article elaborates on the structural composition of lignocellulose,and summarizes the component proportions of common lignocellulose.However,the complex structure of lignocellulose hinders its separation and utilization,which requires a pretreatment to remove this obstacle.The organic solvent pretreatment technology is introduced briefly,and the current research status in acid/alkali homogeneous and multi-phase pretreatment for separation of lignocellulose components is reviewed.In view of the different solvents in various systems,their pretreatment conditions,effects,advantages and disadvantages are summarized,and the development prospects of efficient full-component separation of lignocellulose based on organic solvent pretreatment technology is predicted.

Graphical abstract

关键词

木质纤维素 / 有机溶剂 / 组分分离 / 预处理

Key words

lignocellulose / organic solvent / components separation / pretreatment

Author summay

李新龙(1995-),男,硕士生。

引用本文

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化石能源的大量消耗导致了诸如CO₂大量排放、环境污染以及能源结构不合理等一系列能源环境问题。在此背景下,通过现代生物炼制的方法对木质纤维素生物质进行开发利用,生产燃料乙醇等生物质能源在国内外备受重视^[1]。然而,木质纤维素生物炼制在实现产业化过程中仍存在诸如预处理成本以及工业酶成本较高、预处理效率及酶解效率较低等难点。目前,克服木质纤维素生物炼制产业化难点的主要策略有提高预处理和酶解效率以降低生产成本,以及木质纤维素全组分开发利用等。其中,木质纤维素生物质全组分开发利用主要是以纤维素组分为原料生产燃料乙醇等生物质能源、以木质素或半纤维素组分为原料制备聚酯、树脂、新型药物、抗菌材料等高附加值产品,通过高附加值产品的“互补作用”降低燃料乙醇生产成本的一种有效策略^[2]。

木质纤维素主要由纤维素、半纤维素和木质素构成。纤维素主要起细胞骨架作用,半纤维素覆盖在纤维素表面起填充纤维素间隙的作用,而木质素能够和碳水化合物通过醚酯键连接形成木质素-碳水化合物复合物,主要起填充和黏合作用,致密的三维网状结构使得木质纤维素具有很强的抗降解屏障^[3],致使其三组分难以得到充分利用。因此,通过预处理方法破坏其致密结构以解聚分离各组分是实现木质素转化利用及木质纤维素全组分生物炼制的前提。

1 木质纤维素组成结构和分类

1.1 木质纤维素组成结构

纤维素是由β-吡喃葡萄糖苷通过β-1-4糖苷键聚合而成的天然高分子化合物,其聚合度因来源不同而有所差异(往往能够达到5 000以上)。纤维素分子内部以及分子之间的氢键相互作用,为纤维素构建了一个稳固的结构基础。半纤维素主要是由木糖及部分阿拉伯糖和葡萄糖等聚合成的非线性复合聚糖,组分含量主要受木质纤维素种类影响。半纤维素是植物细胞壁中仅次于纤维素的碳水化合物组分,与纤维素、木质素之间通过范德华力、氢键力和酯键连接,稳定性相对于纤维素和木质素较低^[4]。木质素是一种天然的芳香族生物聚合物,普遍存在于植物细胞壁中,主要起增强植物细胞壁刚度和强度的作用。其结构基础是苯丙烷单元,这些单元通过C—O和C—C键紧密相连,并通过酯键和醚键与碳水化合物交联。在木质纤维生物质中,根据木质素基本单元中的甲氧基数量,可以分为愈创木基型(G型)、紫丁香基型(S型)和对羟苯基型(H型)^[5-6],这些不同的类型赋予了木质素独特的化学特性。

1.2 常见木质纤维素

如表1所示,根据来源主要分为农业类、林业类及能源植物类木质纤维素。不同种类的生物质中纤维素、半纤维素和木质素的组成比例存在较大差异。纤维素占据了30%~50%的比例,半纤维素占植物细胞壁化学组分的10%~30%。不同木质纤维素中木质素的含量存在较大差异,硬木类生物质中的木质素含量通常介于20%~25%;软木类生物质中的木质素含量一般超过25%;相比之下,草本类植物中的木质素含量相对较低,仅占总质量的10%~15%^[7]。

我国作为农林生产大国,每年都有大量的农林废弃物产生。我国每年主要农作物秸秆产量约7亿t,其中,稻秆、麦秆和玉米秸秆总量近10年的平均占比超过94%^[8]。

2 木质纤维素组分分离策略

通过对木质纤维素原料进行解聚预处理可直接或间接分离得到木质素,常见预处理方法主要有生物、物理、化学、物理化学及综合预处理法,对各种预处理方法的详细介绍和比较已有大量报道^[9-10]。结合现有预处理方法以及木质纤维素全组分生物炼制特点,木质纤维素组分分离可以分为纤维素优先、半纤维素优先、木质素优先和全组分分离策略。

在木质纤维素组分分离策略中,全组分分离更加符合现代生物炼制理念,已受到国内外广泛关注^[11]。在木质纤维素全组分分离方法中,酸性有机溶剂预处理具有较高的半纤维素脱除和纤维素保留特征,木质素的脱除显著受到溶剂体系的影响,构建合适的体系有望实现木质纤维素的一步高效全组分分离。有机溶剂可循环利用,所得木质素具有纯度高、分子质量和多分散系数低、不含硫、保留了大量的β—O—4键以及含有大量的羟基(酚羟基和醇羟基)等^[12]优点,使得酸性溶剂预处理成为一种极具工业化潜力的预处理技术。

3 基于有机溶剂预处理的木质纤维素组分分离现状

有机溶剂预处理一般是利用有机溶剂与酸或者碱混合处理木质纤维素生物质的技术。按溶剂体系可分为醇、酮、酯、酸有机溶剂体系等,按催化剂种类分为酸性有机溶剂和碱性有机溶剂体系,按各组分是否互溶分为均相溶剂体系和多相溶剂体系^[13]。两相体系主要由水不溶有机溶剂(如 2-甲基四氢呋喃、甲基异丁酮、乙二醇苯醚等)、水及酸/碱催化剂组成。如图1所示,解聚的木质素在两相体系中主要溶解在有机溶剂相中,降解的半纤维素糖主要溶解在水相中,通过简单分离即可实现木质纤维素的全组分分离。相对于均相体系,两相体系对产物的分离效率较高,但传热传质效果较差。

3.1 酸性均相溶剂体系

酸性均相体系作为有机溶剂预处理中使用最广泛的体系,对其中的乙醇、乙二醇、甘油、1,4-丁二醇等酸性均相体系的预处理酶解效果进行了总结,结果如表2所示。通过综述文献可以发现,草本、硬木和软木木质纤维素对预处理强度的要求依次增加。水相短链醇(如乙醇)和低成本无机酸(硫酸)是较为常用的溶剂体系和催化剂,主要是因为乙醇等短链醇毒性低、成本低、沸点低且可以回收再利用,还可以有效降低水的黏度并增强溶剂对于木质纤维素生物质的溶解作用^[14]。例如,Hermsdorff等^[15]发现在酸/乙醇预处理中加入CO₂可以降低溶剂的黏度和表面张力,从而增强木质纤维素在溶剂体系中的扩散速度,减少了反应时间,为预处理成本的降低提供了新思路。

虽然乙醇等短链醇具有众多优点,但低沸点、易挥发、易燃性等^[16]特性导致了对预处理设备的高耐压性,进而增加了预处理成本,这一问题至今尚未有合理的解决方法。因此,尽管回收成本相对较高,中高沸点溶剂因具有预处理操作压力低及对木质纤维素原料浸润性更强等优势,目前也已受到国内外广泛关注。例如,Fang等^[17]使用酸性1,4-丁二醇溶剂体系在170℃条件下对杨木和马尾松进行预处理,木质素去除率分别超过83%和70%,且获得了分子质量较低及酚羟基含量较高的高性能木质素,有利于后续的木质素高值化利用。甘油是生物柴油工业的副产品,由于低成本、无毒和泛用性等优点,在工业应用方面有较为强大的潜力^[18]。例如,Song等^[19]研究发现甘油均相体系可以在较温和条件下显著提高半纤维素组分的去除率,同时保证纤维素组分的完整性。得益于较好的传热传质效果,酸性均相体系可轻易拆解半纤维素组分,而高效的木质素脱除则需要选择合适的溶剂,且对于半纤维素和木质素降解组分的后续分离,同样存在一定挑战。

3.2 碱性均相溶剂体系

碱性均相溶液体系的报道相对于酸性均相溶液体系较少,且大部分集中于氢氧化钠的乙醇/甘油预处理,相关预处理酶解效果总结在表3中。Li等^[20]研究发现,碱性乙醇/甘油有机预处理可以有效去除木质纤维素生物质中的木质素,破坏其复杂的内部结构,增加酶对纤维素的可及性,但对于半纤维素的降解作用较弱,因而宗纤维保留效果较好。同时,还有学者研究发现,在体系中加入表面活性剂可以显著提高木质素脱除率和酶水解率^[21]。相对于碱性乙醇/甘油均相体系,Xie等^[22]研究发现,碱性1,4-丁二醇溶剂体系具有更好的木质素脱除效果,且能够在一定程度上抑制木质素的再聚合以及降低对残渣后续酶解的负面影响。除此之外,碱性四氢糠醇体系和碱性三乙二醇均相溶剂体系等也已被报道。例如,Li等^[23]使用碱性三甘醇均相体系预处理甘蔗渣,温和条件下木质素去除率达到82%,残渣72 h酶解率89%,且所得木质素纯度较高,有利于木质素的后续转化利用。相对于水相碱性体系,有机溶剂的使用对木质纤维素组分分离效果的提升有限,这可能也是目前相关报道较少的原因。

3.3 多相溶剂体系

多相溶剂体系是指由水和水不(难)溶有机溶剂组成的预处理体系,常见多相溶剂体系有酸性醇/水(戊醇、丁醇)、酸性2-甲基四氢呋喃/水(2-MTHF)、酸性甲基异丁基酮/水(MIBK)等两相体系,而对碱性多相体系的报道较少,常见两相溶剂体系的预处理酶解效果总结在表4中。2-甲基四氢呋喃是一种可从可再生生物质中获得的生物基溶剂,低毒性、环保性及可再生性使其在木质纤维素预处理组分分离的研究中受到了较多关注^[24]。例如,Zhan等^[13]分别使用2种溶剂对麦秆进行了酸性两相预处理,结果发现半纤维素去除率90%,尽管木质素去除率只有57%,但预处理残渣72 h酶解率高达96%。戊醇具有水溶性低和能够减少木质素副反应发生等优点,是一种高效环保的酸性两相预处理体系^[25]。正丁醇是一种疏水性的中沸点(117℃)绿色醇类溶剂,且易回收,可通过ABE(丙酮/丁醇/乙醇)微生物发酵工艺获得,其酸性两相体系在获得高产率和高活性木质素方面具有较大优势^[26]。同碱性均相体系类似,碱性两相体系中溶剂的参与使木质素去除率和残渣酶解率分别提高了12%和10%^[27],有限的效果提升表明碱性两相体系中溶剂对木质纤维素的组分拆解作用相对较小。酸性两相体系预处理后,半纤维素溶解在水相中,木质素选择性地的溶解在有机相中,纤维素则保留在固体中,简化了木质素和半纤维素降解物的分离步骤、提高了分离效率^[28]。因此,酸性多(两)相溶剂体系更值得深入研究。但相对于均相体系,酸性多(两)相体系的传热传质效果差,相似条件下对木质纤维素的预处理效率较低,开发新型高效酸性多(两)相溶剂体系仍需更多关注。

4 总结与展望

根据现代生物炼制理念,采用全组分分离策略对以农林废弃木质纤维素生物质资源进行高值化开发利用,对缓解当下面临的节能减排问题具有重要意义。对现有常见预处理技术进行综述发现,酸性多(两)相溶剂体系对木质纤维素的全组分分离效率更高,但目前仍存在体系传热传质效果相对较差、中高沸点溶剂回收难以及温和多(两)相体系对木质素组分的去除效果一般等问题。针对有机溶剂预处理木质纤维素技术存在的一些问题,本文中认为:①根据溶度参数,针对性选择对木质素组分溶解能力较强的溶剂,用来构建高效的木质纤维素多(两)相组分分离体系。②选用低沸点溶剂构建多(两)相体系,以解决溶剂组分后续难回收的问题。③结合均相体系传热传质效果好及多相体系产物后续分离简便的优势,构建均相预处理多相组分分离的新型高效溶剂体系,从这些角度出发开发新型溶剂体系,有望实现木质纤维素的高效全组分分离,为推动木质纤维素现代生物炼制技术的发展提供一定借鉴。

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