Theses and Dissertations

Issuing Body

Mississippi State University


Bricka, Ray M.

Committee Member

Toghiani, Hossein D.

Committee Member

DuBien, Janice L.

Committee Member

White, Mark G.

Committee Member

Hernandez, Rafael

Date of Degree


Document Type

Dissertation - Open Access


Chemical Engineering

Degree Name

Doctor of Philosophy


James Worth Bagley College of Engineering


Dave C. Swalm School of Chemical Engineering


This project is primarily focused on improving the storage stability of bio-oils or pyrolysis oils by varying feedstock, reactor, and storage conditions. Pyrolysis oil is a complex medley of oxygenated chemicals (aliphatic and aromatic) that are well known to undergo unstable polymeric reactions (auto-catalyzed) if suitable additives are not utilized. These reactions can be severely detrimental to the long-term storage stability of pyrolysis oils. Hence, a detailed investigation was conducted in four phases namely: 1) pyrolysis oil production 2) additive prescreening 3) concentration optimization and 4) stability testing. During the first phase a lab-scale semi-continuous auger reactor is utilized to produce 16 pyrolysis oils. The reactor variables include pyrolysis temperature and vapor residence time. The feed stocks include pine wood, pine bark, oak wood, and oak bark. During the second phase a range of chemical additives (26) are prescreened to obtain three best performing additives. Anisole, glycerol, and methanol are consequently utilized to perform concentration optimization studies during the third phase. Viscosity, water content, and pH of pyrolysis oils are timely measured to assess the accelerated storage stability of pyrolysis oils during the phases 2-3. During the fourth phase, pyrolysis oils produced from three different reactor systems (lab-scale auger, large-scale auger, and entrained flow) were tested for their storage stability. Viscosity, water content, pH, density, and acid value are timely measured to assess the ambient and accelerated storage stability of pyrolysis oils during phase 4. Extrinsic variables such as light and filtration are utilized during the experimental testing of phase 4. The rheological data (Newtonian/non-Newtonian) enhanced the understanding of pyrolysis oil storage stability both qualitatively and quantitatively. The stability performance of a chemical additive is very much dependent on the concentration and its organic functional group. Consequently, alcohols fared above all the other functional groups in stabilizing the pyrolysis oils. Glycerol is observed to have special blending and homogenizing properties compared to all other additives. Feedstock seems to be the single most important factor affecting storage stability of pyrolysis oils. Consequently, pine wood resulted in the most stable pyrolysis oil whereas pine bark resulted in the least stable pyrolysis oil.