Bio-oil Production and Upgrading in Electromagnetic Fields Using Supported Nanostructured Catalysts

摘要：从热解生物油中生产具有商业可行性的生物燃料需要改进加工技术，特别是在提高产品稳定性和催化剂寿命方面。催化剂效能是限制因素。路易斯安那州立大学的多林·博尔多教授和丹尼尔·海耶斯教授根据先前的EAGER奖所做的研究，认为他们有办法改善这种情况。与最先进的热解技术相比，通过直接加热金属颗粒支撑的纳米级催化剂，生物有机聚合物和前体可以迅速分解并转化为高质量的油，产量极高。与目前的反应器设计相反，反应器侧壁被加热，催化剂作为散热器，在这个系统中，来自射频感应线圈或微波源的振荡磁场在支撑的催化剂表面产生涡流，导致感应加热，催化剂的金属核心作为热解的热源，催化剂最有效地用于产品升级。在延长催化剂寿命的同时，单步法有望提高能源效率，提供更高的高价值产品收率。此外，该工艺可以有效地使用各种有机聚合物作为原料。回收的塑料瓶、木屑或农业废弃物等材料可以转化为高价值的生物油。为了使裂解油在功能上有用，通常需要在高温高压下的反应器中进行催化升级和稳定。在升级过程中，不稳定分子倾向于重新聚合成更高分子量的化合物，这些化合物与残留的磷和硫（生物质固有的）相结合，往往会抑制催化剂的活性位点，需要频繁维护并降低催化剂的寿命。在传统反应器中，从热力学角度来看，抑制催化位点是有利的，在传统反应器中，热量由生物油蒸汽携带，催化剂床作为散热器。因此，分子迁移倾向于向催化剂表面进行，而不受远离表面的阻碍。从控制（即加速）反应、优化工艺、延长催化剂寿命的角度出发，合理设计催化剂-热解工艺，使产物侧分子从反应表面迁移，从而产生热力学上有利的分子输运。为了实现这一目标，需要利用催化剂表面或其支撑物作为热源，逆转来自气相载体反应物的热通量。提出的方法包括在不同温度下研究生物质热解，并结合使用表面负载的纳米级金属和沸石催化剂对电磁场进行升级。通过对不同生物质生产的生物油、炭和不可冷凝气体进行定量和定性测量，将对结果和过程性能进行评估；通过反复实验评价催化剂的性能和质量；并为技术经济和工程分析提供数据，以确定扩大工艺的可行性。

Abstract Title: Bio-oil Production and Upgrading in Electromagnetic Fields Using Supported Nanostructured Catalysts The production of commercially viable bio-fuels from pyrolysis bio-oils requires improvement in processing technology, particularly with respect to upgraded product stability and catalyst lifetime. Catalyst effectiveness is the limiting factor. Based on studies performed through a previous EAGER award, Professors Dorin Boldor and Daniel Hayes at the Louisiana State University believe they have an approach to improve the situation. By utilizing direct heating of only the metal particle supported nanoscale catalysts, bio-organic polymers and precursors are rapidly broken down and converted into higher quality oil with extremely high yield compared to state-of-the-art pyrolysis techniques. In contrast to current generation reactor design where the reactor sidewall is heated and the catalyst acts as a heat sink, in this system the oscillating magnetic field from RF induction coils or microwave sources induce eddy currents on the surface of the supported catalyst resulting in induction heating where the metallic core of the catalyst acts as a heat source for pyrolysis and the catalyst works most efficiently for product upgrading. The single step process is expected to be more energy efficient and provide a greater yield of high value product while extending the life of catalyst. Additionally, this process can efficiently use a variety of organic polymers as feedstock. Materials such as recycled plastic bottles, wood chips or agricultural waste can be turned into high value bio-oil. In order to be functionally useful, pyrolysis oil needs to be catalytically upgraded and stabilized, usually in reactors operating at high temperature and pressure. During upgrading, unstable molecules have a tendency to re-polymerize into higher-molecular weight compounds, which, coupled with the residual phosphorus and sulfur (native to the biomass), tend to inhibit the catalyst active sites, requiring frequent maintenance and reducing catalyst lifetime. Inhibition of catalytic sites is thermodynamically favored in conventional reactors, where the heat is carried by the bio-oil vapors, with the catalyst bed acting as a heat sink. Thus, molecular migration is favored to proceed toward the catalyst surface, and is impeded from moving away from the surface. From the perspective of controlling (i.e. accelerating) reactions and optimizing the process while prolonging the catalyst life, it is preferable to rationally design a catalyst-pyrolysis process that is able to generate thermodynamically favorable molecular transport where the molecules on the product side migrate away from the reaction surface. In order to achieve this goal, it is desirable to reverse the thermal flux from the carrier reactants in vapor phase, using the catalyst surface, or logically its support, as a heat source. The proposed approach includes a study of biomass pyrolysis at various temperatures, in conjunction with upgrading in electromagnetic fields using surface supported nanoscale metallic and zeolite catalysts. The results and process performance will be evaluated by quantitative and qualitative measurements of the produced bio-oil, char, and non-condensable gases from different biomass; by evaluating the catalyst performance and quality after repeated experiments; and by providing data for a techno-economic and engineering analysis in order to determine the feasibility of scaling up the process.