Results for “DOE catalyst study” — Page 8

DOE OSTI2015

Mechanism of CO 2 Hydrogenation on Pd/Al 2 O 3 Catalysts: Kinetics and Transient DRIFTS-MS Studies

The hydrogenation of CO 2 was investigated over a wide range of reaction conditions, using two Pd/γ-Al 2 O 3 catalysts with different Pd loadings (5% and 0.5%) and dispersions (~11% and ~100%, respectively). Turnover rates for CO and CH 4 formation were both higher over 5% Pd/Al 2 O 3 with a larger average Pd particle size than those over 0.5% Pd/Al 2 O 3 with a smaller average particle size. The selectivity to methane (22-40%) on 5% Pd/Al 2 O 3 was higher by a factor of 2-3 than that on 0.5% Pd/Al 2 O 3 . The drastically different rate expressions and apparent energies of activation for CO and CH 4 formation lead us to conclude that reverse water gas shift and CO 2 methanation do not share the same rate-limiting step on Pd, and that the two pathways are probably catalyzed at different surface sites. Measured reaction orders in CO 2 and H 2 pressures were similar over the two catalysts, suggesting that the reaction mechanism for each pathway does not change with particle size. In accordance, the DRIFTS results reveal that the prevalent surface species and their evolution patterns are comparable on the two catalysts during transient and steady-state experiments, switching feed gases among CO 2 , H 2 and CO 2 +H 2 . The DRIFTS and MS results also demonstrate that no direct dissociation of CO 2 takes place over the two catalysts, and that CO 2 has to first react with surface hydroxyls on the oxide support. The thus-formed bicarbonates react with dissociatively adsorbed hydrogen on Pd particles to produce adsorbed formate species (bifunctional catalyst: CO 2 activation on the oxide support, and H 2 dissociation on the metal particles). Formates near the Pd particles (most likely at the metal/oxide interface) can react rapidly with adsorbed H to produce CO, which then adsorbs on the metallic Pd particles. Two types of Pd sites are identified: one has a weak interaction with CO, which easily desorbs into gas phase at reaction temperatures, while the other interacts more strongly with CO, which is mainly in multi-bound forms and remains stable in He flow at high temperatures, but is reactive towards adsorbed H atoms on Pd leading eventually to CH 4 formation. 5% Pd/Al 2 O 3 contains a larger fraction of terrace sites favorable for forming these more stable CO species than 0.5% Pd/Al 2 O 3 . Consequently, we propose that the difference in the formation rate and selectivity to CH 4 on different Pd particle sizes stems from the different concentrations of the reactive intermediate for the methanation pathway on the Pd surface. JS gratefully acknowledges the financial support of this work by the US Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2014

Jointly Sponsored Research Program on Energy Related Research

Cooperative Agreements, DE-FC26-08NT43293, DOE-WRI Cooperative Research and Development Program for Fossil Energy-Related Resources began in June 2009. The goal of the Program was to develop, commercialize, and deploy technologies of value to the nation’s fossil and renewable energy industries. To ensure relevancy and early commercialization, the involvement of an industrial partner was encouraged. In that regard, the Program stipulated that a minimum of 20% cost share be achieved in a fiscal year. This allowed WRI to carry a diverse portfolio of technologies and projects at various development technology readiness levels. Depending upon the maturity of the research concept and technology, cost share for a given task ranged from none to as high as 67% (two-thirds). Over the course of the Program, a total of twenty six tasks were proposed for DOE approval. Over the period of performance of the Cooperative agreement, WRI has put in place projects utilizing a total of $\$$7,089,581 in USDOE funds. Against this funding, cosponsors have committed $\$$7,398,476 in private funds to produce a program valued at $\$$14,488,057. Tables 1 and 2 presented at the end of this section is a compilation of the funding for all the tasks conducted under the program. The goal of the Cooperative Research and Development Program for Fossil Energy-Related Resources was to through collaborative research with the industry, develop or assist in the development of innovative technology solutions that will: • Increase the production of United States energy resources – coal, natural gas, oil, and renewable energy resources; • Enhance the competitiveness of United States energy technologies in international markets and assist in technology transfer; • Reduce the nation's dependence on foreign energy supplies and strengthen both the United States and regional economies; and • Minimize environmental impacts of energy production and utilization. Success of the Program can be measured by several criteria. Using the deployment of the federal funding with industrial participation as a performance criterion, over the course of the program, the cosponsors contributed more dollars than the federal funds. As stated earlier, a little more than half of the funding for the Program was derived from industrial partners. The industrial partners also enthusiastically supported the research and development activities with cash contribution of $\$$4,710,372.67, nearly 65% of the required cost share. Work on all of the tasks proposed under the Cooperative Agreement has been completed. This report summarizes and highlights the results from the Program. Under the Cooperative Agreement Program, energy-related tasks emphasized petroleum processing, upgrading and characterization, coal and biomass beneficiation and upgrading, coal combustion systems development including oxy-combustion, emissions monitoring and abatement, coal gasification technologies including gas clean-up and conditioning, hydrogen and liquid fuels production, and the development of technologies for the utilization of renewable energy resources. Environmental-related activities emphasized cleaning contaminated soils using microbial fuel cells, development of processes and sorbents for emissions reduction and recovery of water from power plant flue gas, and biological carbon capture and reuse. Technology enhancement activities included resource characterization studies, development of improved methods, monitors and sensors. In general the goals of the tasks proposed were to enhance competitiveness of U.S. technology, increase production of domestic resources, and reduce environmental impacts associated with energy production and utilization. Technologies being brought to commercialization as a result of the funds provided by the Cooperative Agreement contribute to the overall goals of the USDOE and the nation. Each has broad applicability both within the United States and abroad, thereby helping to enhance the competitiveness of U.S. energy technologies in international markets and assisting in technology transfer. Under the Cooperative Agreement Program, WRI has furthered the development of two different coal upgrading technologies. River Basin Energy technology was scaled-up and demonstrated at a nominal 40 tpd size. Similarly, WRI’s patented mercury removal technology further developed into WRITE Coal technology which was then integrated into oxy-combustion and gasification systems for IGCC and fuels production. Integrated systems with WRITE Coal technology applied at the front end represent substantial environmental and efficiency gains. A variation of the RBE coal upgrading technology is being commercialized as a torrefaction technology for woody biomass. WRI worked with EPRI and NIST to develop and improve mercury calibration standards for emissions monitoring. Working with Chart Energy and Chemicals, WRI scaled-up compact reactor technology for the synthesis of fuels and chemicals from syngas. Compact reactor technology represents a five-fold increase in productivity over conventional reactors making smaller-scale distributed synthesis plants an economical viability. Similarly, WRI's patented mixed alcohol synthesis catalyst production is being scaled-up in collaboration with a commercial catalyst manufacturer.

99 GENERAL AND MISCELLANEOUS↗