Dissertation
CONTRIBUTIONS TO THE DEVELOPMENT OF PYROLYSIS OIL BIOREFINERIES
Washington State University
Doctor of Philosophy (PhD), Washington State University
01/2022
DOI:
https://doi.org/10.7273/000004441
Handle:
https://hdl.handle.net/2376/118851
Abstract
Pyrolysis oil is a mixture of water, oligomers, sugars, phenols, furans, carbonyl compounds, acids and esters, making it very unstable. The main route explored for bio-oil upgrading is the two-stage hydrotreatment. This technology has technical challenges, such as high hydrogen consumption, coke formation, high aromatic content fuel, and absence of co-products. Alternative techniques have been investigated, but there is a lack of complete biorefinery configurations. In this work, we contribute to the development of bio-oil refineries. The first part of the dissertation comprises a holistic analysis of bio-oil biorefineries. We reviewed refining technologies, bio-oil chemistry and the challenges associated with its use. Then, we used Process-graph to access new biorefineries. P-graph generated over 300 configurations, calculated total costs, and ranked the optimum pathways in terms of profit. We showed that refining of the aqueous phase represents an interesting opportunity for bio-oil industry. At our model conditions, production of levoglucosan and glycolaldehyde achieved over $23 k$/h and 10 k$/h of profit, respectively. The second part of this work focused on the challenges of converting the water insoluble fraction (WIS) into fuels. Detailed analysis of bio-oil WIS and hydrothermal liquefaction biocrude reveled that bio-oil WIS contains more oxygen in the form or carboxylic groups than the biocrude. In order to take advantage of existing infrastructure, we proposed to co-hydrotreat bio-oil WIS with vegetable oils on HEFA units. An experimental design showed that the yield of the hydrotreatment products was mainly affected by the temperature, while the yield of the distillation products increased with the hydrogen pressure and catalyst loading. Higher temperature was correlated with lower oxygen content in kerosene, therefore, we selected the highest hydrogen pressure (7MPa), catalyst load (1.3 g), and temperature (380°C) as recommended operating conditions. Compared with previous studies, the conditions herein identified increased the yield of kerosene from 11 to 23.7 wt. % and reduced the yield of coke from 8.7 to 2.7 wt. % (on feedstock basis). The resulting fuel fractions were characterized. This dissertation proposes a biorefinery concept based on the water extraction of bio-oil, and the use of its fractions to produce fuels and chemicals.
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Details
- Title
- CONTRIBUTIONS TO THE DEVELOPMENT OF PYROLYSIS OIL BIOREFINERIES
- Creators
- Anamaria Paiva Pinheiro Pires
- Contributors
- Manuel Garcia-Perez (Advisor)Peter H. Pfromm (Committee Member)Hanwu Lei (Committee Member)Su Ha (Committee Member)
- Awarding Institution
- Washington State University
- Academic Unit
- Biological Systems Engineering, Department of
- Theses and Dissertations
- Doctor of Philosophy (PhD), Washington State University
- Publisher
- Washington State University
- Number of pages
- 249
- Identifiers
- 99900883437301842
- Language
- English
- Resource Type
- Dissertation