Studies on the Catalysts in Process of Hydrogen Production by Aqueous-phase Reforming of Glycerol The top priority for all of the

world is developing new type of energy. Biomass energy may be one of the best options as its huge and renewable reserves. Hydrogen energy, the most efficient and cleanest secondary energy source, is considering as the best energy carrier. The energy strategy taking biomass as the energy and hydrogen as the energy carrier is approved and supported by most of the countries in the world. Glycerol, the main by-product of biodiesel production process, is increasing rapidly with the development of biodiesel industry. Its utilization is one of the main options to be considered to lower the overall cost of the biodiesel production. It is worth to be considered to produce hydrogen from glycerol. In this sense, biodiesel would be fully integrated in the renewable fuel concept through its own use as biofuel, and that of the H2 from the glycerol by-product, as clean fuel for fuel cell devices.In this thesis, a series of novel catalysts were designed and prepared and used for hydrogen production by aqueous-pahse reforing of glycerol. The main research results are achived as follows:1. Pt loaded MgO, Al2O3, CeO2, TiO2 and SiO2 catalysts were prepared by loading pre-synthesized Pt colloids on support and used for the aqueous-phase reforming (APR) of glycerol to investigate the influence of support properties on catalytic performance. The conversion of glycerol, rate of hydrogen production and composition of gaseous products were measured for the APR process of 5 wt% glycerol. It was found that the overall catalytic activities for APR of glycerol decreased in the following order for Pt based catalysts: Pt/MgO> Pt/Al2O3> Pt/CeO2> Pt/TiO2> Pt/SiO2. The WGS reactions were also examined over these five catalysts. The relationship between WGS and APR was discussed and found that WGS played a key role in the process of APR, both are related to the surface properties: the basic sites are prefer for water-gas shift and further enhanced the APR process. Typical solid basic magnesium and alumina mixed oxides supporting Pt catalysts were also tested and exhibited the best APR activity.2. PtM (M=Fe, Co, Ni, Cu) bimetallic alloy nanoparticles loaded-Al2O3 catalysts were prepared by loading pre-synthesized PtM colloids on support and used for the aqueous-phase reforming (APR) of glycerol to investigate the influence of bimetallic alloy on catalytic performance. The XRD, BET, TEM and in situ FTIR were adopted for charaterization. The conversion of glycerol, rate of hydrogen production and composition of gaseous products were measured for the APR process of 5 wt% glycerol. It was found that the overall catalytic activities for APR of glycerol decreased in the following order Pt1Fe1> PtPt1Ni1Pt1Co1>>Pt1Cu1. The catalytic activies of PtFe bimetallic alloy with different Pt/Fe ratio were also investigated. The Pt1Fe1 bimetallic alloy showed the best activity. According to the in situ FTIR study, a possible mechanism was proposed on the supported PtFe bimetallic alloy catalyst. The activeation of H2O and desorption of formate species in the WGS reaction play important roles in the APR reaciton.3. A Ni-B amorphous alloy catalyst (AP Ni) was prepared and used in an aqueous-phase reforming (APR) of glycerol. Higher stability and higher selectivity towards H2 were obtained when compared with Raney Ni. After 130 hon stream aqueous-phase reforming of glycerol, the amorphous Ni-B catalyst was transformed to hexagonal closed-packed (hcp) Ni crystallites. The high selectivity towards hydrogen and catalytic stability may be due to the formation of hcp Ni crystallites during reaction and the protection of B2O3. The AP Ni catalyst was found to be 35-50% more active in terms of the H2 production rate and 17-31% more selective toward H2 as compared to Raney Ni. The reforming reaction at

different reaction temperature, feedstock concentration, feedstock flow rate and other biomass derivatives i.e., ethylene glycol and sorbitol, were also investigated over AP Ni catalyst.4. The hexagonal close-packed (hcp) Ni nanoparticles have been synthesized successfully in triethylene glycol with high ionic Ni concentration under the presence of protective agent (PVP or PEG). The protective agent (PVP or PEG) played an important role in the formation of hcp Ni. The crystal structure of nickel can be tuned by changing the concentration of Ni ions, reaction temperature and amount of protectors. The X-ray diffraction and magnetic studies revealed the formation of pure hcp Ni. The VSM study showed that the magnetic properties of hcp Ni is quite different from that of face-centered cubic (fcc) Ni. The hcp Ni nanoparticle had a low saturation magnetization, while the coercivity value of hcp Ni was nearly the same as that of fcc Ni. A stable hcp Ni supported on-Al2O3 catalyst was also prepared successfully for the first time and its catalytic activity was investigated in the aqueous-phase reforming of glycerol. The achieved conversion of glycerol and selectivity to hydrogen was high up to 52% and 64%, while the selectivity to methane was only 5%, indicating the preventing of methanation on hcp Ni. Reference: Medical information: http://www.nlm.nih.gov/medlineplus/ medical questions answered: http://www.healthqas.org health news: http://www.medicalnewstoday.com