Budarin Vitaliy L, Clark James H, Henschen Jonatan, Farmer Thomas J, Macquarrie Duncan J, Mascal Mark, Nagaraja Gundibasappa K, Petchey Tabitha H M
Green Chemistry Centre of Excellence, Department of Chemistry, University of York, Heslington, York, YO10 5DD, UK.
Department of Chemistry, University of California Davis, 1 Shields Avenue, Davis, CA, 95616, USA.
ChemSusChem. 2015 Dec 21;8(24):4172-9. doi: 10.1002/cssc.201501319. Epub 2015 Nov 25.
The lignin by-product of the conversion of lignocellulosic biomass to 5-(chloromethyl)furfural (CMF) has been characterised by thermogravimetric analysis, N2 physisorption porosimetry, attenuated internal reflectance IR spectroscopy, elemental analysis and solid-state NMR spectroscopy. The lignin (LCMF) has a moderate level of mesoporosity before thermal treatment and a surface area of 63 m(2) g(-1) , which increases dramatically on pyrolysis at temperatures above 400 °C. An assessment of the functionality and textural properties of the material was achieved by analysing LCMF treated thermally over a range of pyrolysis temperatures. Samples were sulfonated to test their potential as heterogeneous acid catalysts in the esterification of levulinic acid. It was shown that unpyrolysed catalysts gave the highest ester yields of up to 93 %. To the best of our knowledge, this is the first example of mesoporous lignin with an appreciable surface area that is produced directly from a bio-refinery process and with further textural modification of the material demonstrated.
木质纤维素生物质转化为5-(氯甲基)糠醛(CMF)过程中产生的木质素副产物已通过热重分析、N₂物理吸附孔隙率测定、衰减全反射红外光谱、元素分析和固态核磁共振光谱进行了表征。木质素(LCMF)在热处理前具有中等程度的介孔率,表面积为63 m² g⁻¹,在400℃以上温度热解时表面积会急剧增加。通过分析在一系列热解温度下热处理的LCMF,对该材料的官能团和结构性质进行了评估。将样品磺化以测试其作为乙酰丙酸酯化反应中多相酸催化剂的潜力。结果表明,未热解的催化剂酯产率最高可达93%。据我们所知,这是首次直接从生物炼制过程中生产出具有可观表面积的介孔木质素,并展示了对该材料进行进一步结构改性的实例。