He Songbo, Osorio Velasco Jessi, Strien Julian R J, Zhang Zhenlei, Bianchetti Stefanie M, Badr Parniya, Sridharan Balaji, van de Bovenkamp Hendrik H, Venderbosch Robbie H, Bijl Anton, Heeres Hero Jan
Green Chemical Reaction Engineering, Engineering and Technology Institute Groningen, University of Groningen, Nijenborgh 4, Groningen 9747 AG, The Netherlands.
CoRe Pro B.V., Osloweg 4-17, Groningen 9723 BL, The Netherlands.
Energy Fuels. 2024 May 1;38(10):8740-8748. doi: 10.1021/acs.energyfuels.3c04733. eCollection 2024 May 16.
Pyrolysis of lignocellulosic biomass and waste plastics has been intensely studied in the last few decades to obtain renewable fuels and chemicals. Various pyrolysis devices have been developed for use in a laboratory setting, operated either in batch or continuously at scales ranging from milligrams per hour to tenths of g per hour. We report here the design and operation of a novel staged free-fall (catalytic) pyrolysis unit and demonstrate that the concept works very well for the (catalytic) pyrolysis of pinewood sawdust, paper sludge, and polypropylene as representative feeds. The unit consists of a vertical tube with a pretreatment section, a pyrolysis section, a solid residue collection section, a gas-liquid separation/collection section, and a catalytic reaction section to optionally perform ex situ catalytic upgrading of the pyrolysis vapor. The sample is placed in a tube, which is transported by gravity through various sections of the unit. It allows for rapid testing with semicontinuous feeding (e.g., 50 g h) and the opportunity to perform reactions under an (inert) gas (e.g., N) at atmospheric as well as elevated pressure (e.g., 50 bar). Liquid yields for noncatalytic sawdust pyrolysis at optimized conditions (475 °C and atmospheric pressure) were 63 wt % on biomass intake. A lower yield of 51 wt % (on a biomass basis) was obtained for the noncatalytic pyrolysis of paper sludge, likely due to the presence of minerals (e.g., CaCO) in the feed. The possibility of using the unit for ex situ catalytic pyrolysis (pyrolysis at 475 °C and catalytic upgrading at 550 °C) was also successfully demonstrated using paper sludge as the feed and H-ZSM-5 as the catalyst (21 wt % catalyst on biomass). This resulted in a biphasic liquid product with 25.6 wt % of an aqueous phase and 11 wt % of an oil phase. The yield of benzene, toluene, and xylenes was 1.9 wt % (on a biomass basis). Finally, the concept was also proven for a representative polyolefin (polypropylene), both noncatalytic as well as in situ catalytic pyrolysis using H-ZSM-5 as the catalyst at 500 °C. The liquid yield of thermal, noncatalytic plastic pyrolysis was as high as 77 wt % on plastic intake, while in situ catalytic pyrolysis gave a combined 7.8 wt % yield of benzene, toluene, and xylenes on plastic intake.
在过去几十年中，人们对木质纤维素生物质和废塑料的热解进行了深入研究，以获取可再生燃料和化学品。已经开发了各种热解装置用于实验室环境，这些装置可以间歇或连续运行，规模从每小时几毫克到每小时十分之几克不等。我们在此报告一种新型分级自由落体（催化）热解装置的设计和运行，并证明该概念对于松木锯末、纸污泥和聚丙烯等代表性原料的（催化）热解非常有效。该装置由一个垂直管组成，带有预处理段、热解段、固体残渣收集段、气液分离/收集段以及一个催化反应段，用于对热解蒸汽进行非原位催化升级。样品放置在管中，通过重力输送通过装置的各个部分。它允许通过半连续进料（例如，50 g/h）进行快速测试，并有机会在常压以及高压（例如，50 bar）下的（惰性）气体（例如，N）中进行反应。在优化条件（475°C和常压）下，非催化锯末热解的液体产率以生物质进料计为63 wt%。纸污泥的非催化热解产率较低，为51 wt%（以生物质为基础），这可能是由于进料中存在矿物质（例如，CaCO）。以纸污泥为原料，H-ZSM-5为催化剂（催化剂用量为生物质的21 wt%），成功证明了该装置用于非原位催化热解（475°C热解，550°C催化升级）的可能性。这产生了一种双相液体产物，其中水相为25.6 wt%，油相为11 wt%。苯、甲苯和二甲苯的产率为1.9 wt%（以生物质为基础）。最后，该概念也被证明适用于代表性聚烯烃（聚丙烯），包括非催化热解以及在500°C下使用H-ZSM-5作为催化剂的原位催化热解。热的、非催化塑料热解的液体产率以塑料进料计高达77 wt%，而原位催化热解以塑料进料计苯、甲苯和二甲苯的总产率为7.8 wt%。
