摘要
生物质热化学转化利用的技术和设备一直在快速地发展和更新,其向绿色能源燃料和高附加值化学品转化的高值化利用研究也已全面展开。生物质中木素大分子的化学结构最为复杂,其热解过程和反应途径也相对较为复杂。因此,对生物质原料中木素组分的分离、分级定向转化过程是必然途径,深入地研究木素的热裂解特性和反应途径的调控,为实现生物质热解的目标产物的合理调控提供理论指导。
以禾本科植物中具有代表性的毛竹和稻草为原料,采用比较成熟的纤维素酶酶解/温和酸解法进行木素的分离,对分离后得到的高纯度和高得率的木素进行热解规律和热解产物进行深入研究。
1.采用元素分析、凝胶色谱(gel chromatography,GPC)、傅里叶红外光谱(Fourier transform infrared spectrometer,FT-IR)、氢谱(~1H),碳谱(~(13)C)和定量磷谱(~(31)P)核磁共振(nuclear magnetic resonance,NMR)等精密分析技术对木素的物理化学性质进行了全面表征。分析结果表明,分离得到的酶解/温和酸解木素(enzymatic hydrolysis/mild acidolysis lignin,EMAL)在分离过程中的结构破坏程度较小,具有原本木素的大分子结构。毛竹和稻草EMAL中主要存在愈疮木基(guaiacyl,G)丙烷和紫丁香基(syringyl,S)丙烷结构单元,并含有少量的对羟基苯基(para-hydroxyphenyl,p-H)丙烷结构单元。其中,稻草EMAL结构中愈疮木基单元占有主要地位,而毛竹EMAL中紫丁香基结构单元的含量相对较多;β-O-4型芳基醚键联接是毛竹和稻草EMAL结构单元的一个重要特征,除此之外,稻草EMAL还含有较多的β-β、β-5、α-O-4型联接,而毛竹EMAL则含有较多的β-1、α-O-4和β-5型联接。
2.借助于热重分析法(thermogravimetric analysis,TGA)、热解气质联用技术(pyrolysis-gas chromatopraphy/mass spectrometry,Py-GC/MS)和小型管式炉热解技术等对木素热裂解的反应途径以及产物的形成规律进行深入研究。TGA实验结果表明木素的热解反应发生在一个较长的温度范围,主热解反应主要集中在400～600℃温区;依据热失重数据进一步求算出木素热解动力学参数,并建立动力学一级反应模型。热重-傅里叶红外联用(TG-FT-IR)技术揭示了毛竹和稻草EMAL在热解过程中小分子气体的释放规律,在300～500℃的主反应温区各小分子气体产物大量生成,CO_2的产率明显高于其他气体分子。在毛竹和稻草EMAL的管式炉热裂解试验中,液体焦油的得率明显高于焦炭和气体,且500℃时达到最高。随着热解温度的升高,气体得率显著增加,焦炭得率逐渐减少,并且焦炭的芳香性和微晶结构特征逐渐增强。木素在高温热解时产生较多的CO、H_2和CH_4。研究还发现,稻草EMAL热裂解的产物得率与G-型木素模型物相近,由此印证了木素的自身结构与其热解行为和热解产物分布规律有着密切的关系。
3.酚类化合物是木素热裂解的典型特征产物,其含量最高约占热解产物的60%。一般地说,总酚的相对含量在600℃时达到最高;随着热解温度的升高,产物中G-型酚和S-型酚的相对含量逐渐减少,p-H-型酚逐渐增加;尤其苯酚和4-甲基苯酚在600～800℃时生成量迅速增加,这是由G-型酚和S-型酚在高温时发生二次裂解所致。催化剂金属盐和人造沸石的添加,加深了木素分子结构的裂解程度,使G-和S-型酚类化合物结构上的官能团(如甲氧基、羧基、羰基及醇羟基)分裂更加彻底,生成更多小分子化合物、苯系物、苯酚和烷基取代苯酚。催化剂的添加对改善生物质热裂解产物的组分有着重要意义。
Thermochemical conversion techniques and equipments for biomass has been developing quickly, and an ever increasing attention has been paid to the high-value utilization of biomass applied to green bio-energy and high value-added chemicals. The structure of lignin are the most complicated macromolecules in biomass constitute, thus pyrolysis and reaction pathways of lignin are relatively more complex. Therefore, it is truly necessary to separate lignin from the biomass feedstock and then grade pyrolysis for directional conversion. To in-depth deliberate pyrolysis characteristic and reaction pathways of lignin would be required, which provided the theoretical guidance for the control of the desired products on line.
Feedstock of bamboo and straw were representative in grass plants, enzymatic hydrolysis/mild acidolysis method was used to isolated lignin from feedstock, the obtained enzymatic hydrolysis/mild acidolysis lignin (named EMAL) had a higher purity and yield. The behavior of EMAL pyrolysis and pyrolytic products distribution were highlighted in this thesis.
The physical and chemical characteristics of EMAL were comprehensively investigated in this paper by using elemental analysis, GPC, FT-IR, ~1H-NMR, ~(13)C-NMR, quantitative ~(31)P-NMR and other sophisticated analytical techniques. The results revealed that EMAL with an unbroken molecular structure was in close proximity to original lignin; EMAL contained main guaiacyl propane unit (G-type), syringyl propane unit (S-type) and a handful of para-hydroxyphenyl propane unit (p-H-type), moreover, G-type unit was superior in structural units of rice straw EMAL and S-type unit was major in bamboo EMAL.β-O-4 ether linkage is an important feature of structural units in bamboo and rice straw EMAL. In addition, rice straw EMAL contained someβ-β,β-5 andα-O-4 bonds and banboo EMAL also possesedβ-1,α-O-4 andβ-5 bonds.
The reaction path of lignin pyrolysis and the formation of pyrolyzate were revealed by means of thermogravimetric analysis (TGA), pyrolysis coupled with gas chromatopraphy/ mass spectrometry (Py-GC/MS) and small tube furnace pyrolysis apparatus. TGA studies showed that lignin pyrolysis took place in a long temperature range, and the sharp pyrolysis reactions mainly concentrated at temperature from 400℃to 600℃. Besides, kinetic parameters of lignin pyrolysis was obtained according to TGA data, and a dynamic order reaction model for lignin pyrolysis was established. TG-FT-IR was applied to detect release rules of gas products from bamboo and rice straw EMAL pyrolysis, which confirmed that most of the gas products were released within a temperature range from 300℃to 500℃, and CO_2 production was significantly higher than other gas molecules. Bamboo and rice straw EMAL were pyrolyzed on a tube furnace pyrolyzing furnace to collect bio-oil, char and gas products. the yield of obtained bio-oil was significantly higher than that of char and gas, to the highest 60% at 500℃. As the pyrolysis temperature increased, the gas yield increased significantly yet char yield decreased, and the aromaticity of char gradually heightened. Besides, lignin pyrolysis at high temperature also produced more CO, H_2 and CH_4. It was also discoverded that pyrolysate yield from rice straw EMAL agreed with that from G-type lignin model, which affirmed that the pyrolysis behaviors and products were closely related to lignin structure.
Phenolic compounds were the characteristics products from lignin pyrolysis, accounted for 60% around. In general, the relative content of total phenolics reached maxima at 600℃. As the pyrolysis temperature increased, G- and S-type phenol content decreased yet p-H-type phenol content gradually increased; in particular, phenol and 4-methylphenol formed rapidly during 600～800℃, which resulted from the secondary cracking of G- and S-type phenol at high temperature. Catalysts of metal salts and permutite added to lignin pyrolysis enhanced the cleavage levels of lignin structure, and caused a thorough split of functional groups (methoxyl, carboxyl, and carbonyl group) from G- and S-type phenolics to produce more small molecules, i.e. the gaseous, benzenes, phenol and alkyl-phenols. It was a great significance for catalytic pyrolysis improved pyrolysate components from biomass pyrolysis.
引文
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