Graduation Year


Document Type




Degree Name

Doctor of Philosophy (Ph.D.)

Degree Granting Department

Chemical Engineering

Major Professor

John N. Kuhn, Ph.D.

Co-Major Professor

Babu Joseph, Ph.D.

Committee Member

Scott Campbell, Ph.D.

Committee Member

Sylvia Thomas, Ph.D.

Committee Member

Matthew M. Yung, Ph.D.


Biogas Reforming, Low Metal Loading, Pt and Pd Catalysts, Alternative Fuels, Waste-to-Energy, Greenhouse Gas Emissions


Global energy demands are constantly increasing and fossil fuels are a finite resource. The shift towards alternative, more renewable and sustainable fuels is inevitable. Furthermore, the increased emissions of greenhouse gases have forced a pressing need to find cleaner, more environmentally friendly sources of fuel. Biomass energy is a promising alternative fuel because it offers several important advantages. It is a renewable energy form, it comes from many sources and produces biogas (CH4 and CO2). Furthermore, it can have a zero carbon footprint; this is due to the fact that the carbon produced is from the same carbon used to make the biomass. In addition, by replacing fossil fuels, the emissions of CH4 and CO2 (both greenhouse gases) is reduced. Biomass-derived syngas (H2 and CO) can be utilized as a feedstock for many important industrial processes such as methanol synthesis, ammonia synthesis and Fischer-Tropsch synthesis (FTS) to produce long chain hydrocarbon fuels.

Municipal solid waste (MSW) biomass is considered as the source of the biomass for this dissertation work. MSW accounts for 20% of man-made methane emissions making it an attractive source for utilization. However, methane reforming to synthesis gas (H2 and CO) typically occurs at temperatures higher than 600°C making it economically challenging at the smaller scale of MSW conversion processes.

This dissertation effort focused on formulating low precious metal loaded heterogeneous catalysts that can reform methane at low temperature (T<500°C) making the process more industrially viable. The effect of select contaminants (siloxanes) in the biogas on the reforming catalysts was studied through accelerated poisoning. Finally, the syngas ratio was improved by combining low temperature dry reforming with steam reforming (termed bi-reforming).

The catalyst system used for this dissertation study was comprised of 1.34wt%Ni- 1.00wt%Mg on a Ceria-Zirconia oxide support (0.6:0.4 ratio respectively). The catalysts were doped with platinum (0-0.64% by mass) and compared to palladium doped catalysts (0-0.51% by mass). The ratio chosen for the support, Ce0.6Zr0.4, was determined to be the best ratio in terms of activity and surface area by previous studies done in this group [1]. Nickel has been widely studied as methane reforming catalyst [2-6]. Alone, nickel atoms are prone to carbon deposition especially during methane decomposition, however, coupling NiO with MgO helps to reduce carbon deposition by reducing agglomeration of Ni crystallites, thereby improving catalyst lifetime [2, 7]. Furthermore, addition of small amounts of noble metals such as Pt or Pd help to drive the reduction of the catalyst to lower temperatures and enhance catalytic activity.

Different metal loadings of Pt and Pd were tested to determine the optimum catalyst that will reform methane at low temperatures, is resistant to deactivation and produces a high syngas ratio (~2:1) which is necessary for processes such as FTS. Preliminary results have shown that in general Pt is superior in this catalyst system for low temperature reforming of methane. It consistently had syngas ratios near the desired ratio compared to Pd, it did not deactivate with extended time on stream and overall had higher turnover frequencies. This catalyst system has potential to make industrial reforming of methane from biomass feedstock more economically viable.