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Fast Pyrolysis of Woody Biomass in a Pyroprobe Reactor: Effect of Torrefaction on the Pyrolysis Products

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Fast Pyrolysis of Woody Biomass in a Pyroprobe Reactor: Effect of Torrefaction on the Pyrolysis Products Fast Pyrolysis of Woody Biomass in a Pyroprobe Reactor: Effect of Torrefaction on the Pyrolysis Products Christos Tsekos Delft University of TechnologyofDelft University Challenge the future Fast Pyrolysis of Woody Biomass in a Pyroprobe Reactor: Effect of Torrefaction on the Pyrolysis Products By Christos Tsekos 4417011 In partial fulfilment of the requirements for the degree of Master of Science in Sustainable Energy Technology at the Delft University of Technology, department of Process & Energy December 2016 Supervisor: Prof. Dr. ir. Wiebren de Jong Thesis committee: Prof. Dirk Roekaerts Dr. Maria Cuellar Soares Daily supervisors: Ir. George Archimidis Tsalidis Dr. Kostas Anastasakis Abstract The future depletion of conventional fossil fuel reserves, the ever increasing need for energy self – reliance and the global concern around environmental change caused by their use, have made heat and power generation from alternative and sustainable sources a primary research focus worldwide. Biomass is such a source, constituting a clean and renewable fuel, while being the third fuel resource in the world after coal and oil in terms of abundance. Through thermochemical processes biomass can be employed for energy, chemicals and transport fuel production. Pyrolysis is the thermochemical process of biomass decomposition into various useful products in the absence of an oxidation medium. Torrefaction is a mild pyrolysis process, typically carried out in a temperature range between 230oC and 300oC. This pretreatment process offers benefits with respect to biomasses energy density, while reducing the oxygen and hydrogen to carbon ratios and its hygroscopic nature. In this work untreated and torrefied biomass species were pyrolysed under different final temperatures in a Pyroprobe 5200 reactor. In particular, raw and torrefied (at 250oC and 265oC) wood ash (Fraxinus excelsior) and raw and torrefied (at 300oC) Torrcoal, which consists of mixed wood residues, were investigated. The feed was reduced to a particle size less than 75 μm and the experiments were performed with a sample size of 30 mg in the temperature range of 600oC to 1000oC at a heating rate of 600oC/s, in order to achieve fast pyrolysis conditions. The main purpose of these experiments was to determine the effect of final pyrolysis temperature and torrefaction to the yield and nature of pyrolysis final products. In terms of individual gases, CO, CO2, CH4 and H2 were identified using a micro GC. Tar compounds (phenol and PAHs) were identified and quantified using a HPLC system. The aforementioned experiments produced mass closure values between 65% and 84%, which can be considered as satisfactory due to the difficulties in measuring gravimetrically pyrolytic water, higher hydrocarbon gases and light tar compounds. Increasing pyrolysis temperatures had a negative effect on char yield, however above 800oC it appeared to stabilize. Maximum values of the liquid yield were obtained at 600oC and 700oC before attaining a decreasing trend for the ash materials and stabilizing for Torrcoal materials at 900oC. Gas yields increased until 900oC for Torrcoal species and ash torrefied at 265, but for the rest species the increase continued until 1000oC. CO was o the major gas produced above 800 C overtaking CO2 at that temperature, while CH4 and H2 yields became significant above 700oC and 800oC respectively. Torrefaction and increased torrefaction severity led to an increase of the char yield of the pyrolysis process. Their effect on the liquid yield was the opposite. In terms of total gases production the differences were minimal and only noticeable above 800oC. However, the quality of the pyrolysis gas was higher for the torrefied species. Regarding the tar compounds analysis, phenol yield decreased until 800oC before reaching a plateau thereafter. PAH species yield increased steeply between 800oC and 900oC. Their production still increased above that temperature but at a slower rate. Naphthalene was the major PAH produced. Torrefaction seemed to favour phenol production while its effect on PAHs was not significant. Between the two biomass species studied, the higher phenol yield of Torrcoal pyrolysis along with its higher char and lower liquid yield are indicative of higher lignin content for this biomass. Acknowledgments From this position, I would like to express my gratitude to the people that supported me and helped me throughout the conduction of this MSc thesis project. Their assistance was essential for the realization of this work. First of all, I would like to express my gratitude to my daily supervisor Ir. George Archimidis Tsalidis for his support, attention and guidance. His constant availability and willingness to elaborate on my doubts and questions and his well – aimed remarks, were crucial for the completion of my project. Additionally, I would also like to thank Dr. Konstantinos Anastasakis for his help in getting familiar with the setup and the realization of the HPLC analyses. Despite the fact that he was not my direct supervisor, he was always available to discuss any theoretical or practical issue raised from the performance of the experiments. Furthermore, I would like to extend my gratitude to Prof. Wiebren de Jong, for giving me the opportunity to work in a challenging project and providing me with any necessary means for that. His constructive remarks and useful feedback helped me expand the scope of my thesis and led me to improve my academic and research knowledge. Last but not least, I would like to thank my friends and family who stood beside me constantly and unconditionally all this time. Without them it would be impossible to achieve my goals. Christos Tsekos Delft University of Technology November 29, 2016 Table of Contents 1. Introduction ........................................................................................................................................ 1 1.1 Biomass formation and composites.............................................................................................. 1 1.2 Biomass pyrolysis .......................................................................................................................... 3 1.2.1 Pyrolysis products .................................................................................................................. 5 1.2.2 Types of pyrolysis ................................................................................................................... 7 1.2.3 Pyrolysis end product ............................................................................................................. 9 1.3 Fundamentals of torrefaction ..................................................................................................... 12 1.3.1 Advantages of torrefaction .................................................................................................. 16 1.4 Tars .............................................................................................................................................. 17 1.4.1 Basics and classification ....................................................................................................... 17 1.4.2 Phenol .................................................................................................................................. 20 1.4.3 PAH formation...................................................................................................................... 20 1.4.4 Tar removal and conversion ................................................................................................ 22 1.5 Research questions and methodology ........................................................................................ 25 2. Materials and methods ..................................................................................................................... 26 2.1 Biomass feedstocks ..................................................................................................................... 26 2.2 Pyroprobe ................................................................................................................................... 26 2.3 Thermogravimetric analysis (TGA) .............................................................................................. 32 2.4 Gas and tar analysis .................................................................................................................... 32 3. Experimental results ......................................................................................................................... 33 3.1 Fuels analysis............................................................................................................................... 33 3.1.1 TGA results ........................................................................................................................... 33 3.1.2 Ultimate analysis .................................................................................................................. 36 3.2 Pyroprobe results ........................................................................................................................ 37 3.2.1 Mass balances ...................................................................................................................... 37 3.2.2 Solid product ........................................................................................................................ 39 3.2.3 Liquid product .....................................................................................................................
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