School of Environmental Engineering, University of Seoul, Seoul 02504, Republic of Korea.
Department of BioEnvironmental Energy, Pusan National University, Miryang 50463, Republic of Korea.
Environ Res. 2019 May;172:658-664. doi: 10.1016/j.envres.2019.03.014. Epub 2019 Mar 7.
Lignocellulosic biomass is an abundant renewable energy source that can be converted into various liquid fuels via thermochemical processes such as pyrolysis. Pyrolysis is a thermal decomposition method, in which solid biomass are thermally depolymerized to liquid fuel called bio-oil or pyrolysis oil. However, the low quality of pyrolysis oil caused by its high oxygen content necessitates further catalytic upgrading to increase the content of oxygen-free compounds, such as aromatic hydrocarbons. Among the three different types of lignocellulosic biomass components (hemicellulose, lignin, and cellulose), lignin is the most difficult fraction to be pyrolyzed because of its highly recalcitrant structure for depolymerization, forming a char as a main product. The catalytic conversion of lignin-derived pyrolyzates is also more difficult than that of furans and levoglucosan which are the main pyrolysis products of hemicellulose and cellulose. Hence, the main purpose of this study was to develop a bench-scale catalytic pyrolysis process using a tandem catalyst (both in-situ and ex-situ catalysis mode) for an efficient pyrolysis and subsequent upgrading of lignin components. While HZSM-5 was employed as an ex-situ catalyst for its excellent aromatization efficiency, the potential of the low-cost additives of bentonite, olivine, and spent FCC as in-situ catalysts in the Kraft lignin pyrolysis at 500 °C was investigated. The effects of these in-situ catalysts on the product selectivity were studied; bentonite resulted in higher selectivity to aromatic hydrocarbons compared to olivine and spent FCC. The reusability of HZSM-5 (with and without regeneration) was examined in the pyrolysis of lignin mixed with the in-situ catalysts of bentonite, olivine, and spent FCC. In the case of using bentonite and spent FCC as in-situ catalysts, there were no obvious changes in the activity of HZSM-5 after regeneration, whereas using olivine as in-situ catalyst resulted in a remarkable decrease in the activity of HZSM-5 after regeneration.
木质纤维素生物质是一种丰富的可再生能源,可以通过热化学过程(如热解)转化为各种液体燃料。热解是一种热分解方法,其中固体生物质通过热解聚解为称为生物油或热解油的液体燃料。然而,由于其高含氧量,热解油的质量较低,需要进一步催化升级以增加无氧化合物(如芳烃)的含量。在三种不同类型的木质纤维素生物质成分(半纤维素、木质素和纤维素)中,木质素是最难热解的部分,因为其结构高度稳定,难以解聚,形成主要产物焦。木质素衍生热解产物的催化转化也比呋喃和左旋葡聚糖更难,呋喃和左旋葡聚糖是半纤维素和纤维素的主要热解产物。因此,本研究的主要目的是开发一种使用串联催化剂(原位和异位催化模式)的中试规模催化热解工艺,以实现木质素成分的高效热解和随后的升级。虽然 HZSM-5 因其优异的芳烃生成效率而被用作异位催化剂,但研究了廉价添加剂膨润土、橄榄石和废 FCC 在 Kraft 木质素 500°C 热解中的原位催化潜力。研究了这些原位催化剂对产物选择性的影响;与橄榄石和废 FCC 相比,膨润土导致芳烃的选择性更高。考察了 HZSM-5(是否再生)在木质素与原位催化剂膨润土、橄榄石和废 FCC 混合热解中的重复使用性。在使用膨润土和废 FCC 作为原位催化剂的情况下,再生后 HZSM-5 的活性没有明显变化,而在使用橄榄石作为原位催化剂的情况下,再生后 HZSM-5 的活性明显下降。