NICKEL-COBALT SOLID SOLUTION AND ITS APPLICATIONS AS CATALYSTS FOR CARBON DIOXIDE REFORMING OF METHANE

Global warming issue becomes more significant to human beings and other organisms on the earth. Among many greenhouse gases, carbon dioxide (CO2) has the largest contribution to global warming. To find an effective way to utilize the greenhouse gas is urgent. It is the best way to convert CO2 to useful compounds. CO2 reforming of methane is an attractive process to convert CO2 and methane into synthesis gas (CO/H2), which can be used as a feedstock for gasoline, methanol, and other hydrocarbons. Nickel and cobalt were found to have good activity for CO2 reforming. However, they have a poor stability due to carbon deposition. This research developed efficient Ni-Co solid solution catalysts with excellent activities and high stability for CO2 reforming of methane. First, the structure of binary oxide solid solution of nickel and cobalt was investigated. It was found that while the calcination of Ni(NO3)2 and Co(NO3)2 mixture with 1:1 molar ratio at a high temperature above 800 oC generated NiO-CoO solid solution, only Ni3O4-Co3O4 solid solution was observed after the calcination at a low temperature of 500 oC. Furthermore, if the calcination was carried out at a medium temperature arranged from 600 to 700 oC, both NiO-CoO and Ni3O4-Co3O4 solid solutions can be formed. This occurred because Co3O4 can induce the formation of Ni3O4, whereas NiO can stabilize CoO. In addition, the lattice parameter of Ni3O4, which was predicted by using Vegard’s Law, is 8.2054 Å. As a very important part of this dissertation, Ni-Co solid solution was evaluated as catalysts for CO2 reforming of methane. It was revealed that nickel-cobalt solid solution showed excellent catalytic performance and high stability for CO2 reforming of methane. However, the stability of Ni-Co solid solution catalysts is strongly dependent on their composition and preparation condition. The optimum composition is 50%Ni-50%Co. Furthermore, the structure of Ni-Co catalysts was characterized by XRD, Vvis, TPR, TPD, BET, AES, TEM, XANES and EXAFS. The relationship between the structure and the catalytic performance was established: (1) The reduced NiO-CoO solid solution possesses better catalytic performance and stability than the reduced Ni3O4-Co3O4 solid solution. (2) Ni is richer on surface in Ni-Co catalysts. And (3) the reduction of Ni-Co-O solid solution generated two types of particles, small and large particles. The small ones are dispersed on large ones as catalytic component.

Development of a 1-D Catalyzed Diesel Particulate Filter Model for Simulation of the Performance and the Oxidation of Particulate Matter and Nitrogen Oxides Using Passive Oxidation and Active Regeneration Engine Experimental Data

Back-pressure on a diesel engine equipped with an aftertreatment system is a function of the pressure drop across the individual components of the aftertreatment system, typically, a diesel oxidation catalyst (DOC), catalyzed particulate filter (CPF) and selective catalytic reduction (SCR) catalyst. Pressure drop across the CPF is a function of the mass flow rate and the temperature of the exhaust flowing through it as well as the mass of particulate matter (PM) retained in the substrate wall and the cake layer that forms on the substrate wall. Therefore, in order to control the back-pressure on the engine at low levels and to minimize the fuel consumption, it is important to control the PM mass retained in the CPF. Chemical reactions involving the oxidation of PM under passive oxidation and active regeneration conditions can be utilized with computer numerical models in the engine control unit (ECU) to control the pressure drop across the CPF. Hence, understanding and predicting the filtration and oxidation of PM in the CPF and the effect of these processes on the pressure drop across the CPF are necessary for developing control strategies for the aftertreatment system to reduce back-pressure on the engine and in turn fuel consumption particularly from active regeneration. Numerical modeling of CPF's has been proven to reduce development time and the cost of aftertreatment systems used in production as well as to facilitate understanding of the internal processes occurring during different operating conditions that the particulate filter is subjected to. A numerical model of the CPF was developed in this research work which was calibrated to data from passive oxidation and active regeneration experiments in order to determine the kinetic parameters for oxidation of PM and nitrogen oxides along with the model filtration parameters. The research results include the comparison between the model and the experimental data for pressure drop, PM mass retained, filtration efficiencies, CPF outlet gas temperatures and species (NO2) concentrations out of the CPF. Comparisons of PM oxidation reaction rates obtained from the model calibration to the data from the experiments for ULSD, 10 and 20% biodiesel-blended fuels are presented.