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Bio-Energy with Carbon Capture and Storage (BECCS)- Production of H2 with Suppressed CO2 Formation via Alkaline Thermal Treatment

Stonor, Maxim Richard Alphonse

The demand for energy continues to grow but concerns over climate change means that conventional fossil fuels will eventually need to be replaced. The solution to the energy crisis will require a combination of both conventional energy sources with CO2 capture and renewable technologies. While many renewable technologies exist, it is not common that CO2 capture is incorporated into the process.
Biomass is an ideal feed-stock for bio-energy production as it is CO2 neutral. Many thermochemical conversion technologies exist, but the Alkaline Thermal Treatment (ATT) reaction is particularly interesting because it combines conventional thermochemical conversion with CO2 capture in order to create a process that is potentially CO2 negative. By reacting biomass with a metal hydroxide, high purity H2 can be produced while simultaneously locking the carbon as a stable carbonate, which is a form of Bio-energy with Carbon Capture & Storage (BECCS). The H2 can then be used for applications ranging from Fischer-Tropsch synthesis to PEM fuel cells.
Group I & II hydroxides were investigated for their ability to react with cellulose (a biomass model compound) in the ATT reaction scheme. Comparison between both groups indicated that NaOH and Ca(OH)2 were the best hydroxides from groups I & II respectively. However, the amount of H2 produced during the ATT of cellulose with Ca(OH)2 is considerably lower than with NaOH. A 10% Ni/ZrO2 catalyst was then added to increase the yield of H2 from the reaction between cellulose and Ca(OH)2. It was found that at 20% catalyst loading, the amount of H2 produced and the suppressed level of CO2 was similar to the ATT with NaOH.
Several other catalytic metals were also investigated and found to have the following H2 production activity: Ni > Pt≈Pd > Co > Fe, Cu. Since Ni was the most active and has a considerably lower cost than noble metals it was chosen for additional studies. The ATT reaction in the presence of Ni has two distinct steps in the formation of H2 from cellulose. The presence of Ca(OH)2 enhances the formation of linear oxygenates from cellulose. These oxygenates are then reformed over the Ni-based catalyst to H2 and CO2, the latter of which is captured by Ca(OH)2 to form CaCO3. If either Ca(OH)2 or Ni was removed from the reaction, the yield H2 fell significantly.
Although the reactants and the catalyst are all solid materials, they do not need to be physically mixed. The Ni-based catalyst produced H2 primarily through the reforming of gaseous species and therefore could be placed ex-situ of the cellulose and Ca(OH)2 mixture. However, placing the catalyst away from Ca(OH)2 prevented CO2 capture. In order to remedy this Ca(OH)2 was mixed with the Ni-based catalyst and mixture was placed ex-situ of pure cellulose. This created a process whereby cellulose could be decomposed thermally followed by a single gas-phase Alkaline Thermal Treatment (GATT) reforming step of the pyrolysis vapors to H2 with suppressed CO2.

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More About This Work

Academic Units
Chemical Engineering
Thesis Advisors
Chen, Jingguang G.
Degree
Ph.D., Columbia University
Published Here
March 6, 2017
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