Preparation methods and promoters effects on α-Al2O3 supported Fe-Mn based FT catalysts for light olefin production

Atik, Özge
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Graduate School
Most countries do have not sufficient fossil resources. So, they need to develop alternative and environmental processes to prevent their dependence on other foreign countries, and also reduce carbon emissions. Fischer-Tropsch synthesis was developed in Germany in 1923 with the increasing demand for liquid fuel during World War. Fischer-Tropsch (FT) which process is the conversion of synthesis gas (CO, H2) has become one of the most important processes for industry. It is possible to obtain a wide range of products with Fischer-Tropsch catalysts from single-carbon methane to more carbon-containing products. These hydrocarbons obtained can be subjected to various processes and then converted into fuels and convenient chemicals. Hydrocarbons obtained as a result of Fischer-Tropsch synthesis also do not contain harmful chemicals and contain a small amount of aromatic structure compared to known fuels. The most important member of the hydrocarbons belonging to the organic compound's family are olefins known as alkenes. Olefins are divided into two main groups light olefins (C2-C4) and heavy olefins (C5+) according to the number of carbons they contain. Light olefins which are the raw materials of many products we encounter many times in our daily lives are very important components of the chemical industry. Commonly preferred metals for Fischer-Tropsch catalysts are iron, nickel, cobalt, and ruthenium. Iron-based catalysts are much cheaper than other active-metal-based catalyst. Also produces less methane and higher amounts of olefins. The product selectivity of the catalyst depends on many factors such as promoter, support material, and also many other parameters (for example; flow, pressure and gas composition, etc). The subject of this study, "Development of Catalyst and Reactor for the Production of Light Olefin from Cleaned Synthesis Gas" is a project carried out together with TUBITAK-MAM Energy Institute and ITU SENTEK Catalysis Laboratory. Within the scope of the project, iron was selected as the active metal due to its many advantages, and a catalyst was developed. In this work, the effect of promoter and solvent-aided impregnation on FT-Olefin synthesis performance was investigated for 15% Fe-based alumina-supported catalysts. In the synthesized 50 different Fe-based α-Al2O3 supported catalysts manganese (Mn), copper (Cu), potassium (K), and nickel (Ni) were used as promoters. These catalysts were prepared using three different solvents in the impregnation step. So in this work, we examined the catalyst preparation method (solvent effect) and promoter effects. Catalyst performances were tested in the atmospheric and high-pressure test systems at 310 ⁰C, H2/CO=2. After the atmospheric tests, the best catalysts were selected and tested in a high-pressure test system at 10 bar at 310 ⁰C in the flow of H2/CO=2. After performance tests, the catalysts were characterized to explore catalysts' behavior physically and structurally by these characterization methods; Brunauer–Emmett–Teller (BET), X-ray diffraction (XRD), H2-Temperature Programmed Reduction (H2-TPR), Scanning Electron Microscope (SEM). In this study, Mn which has been studied extensively in the literature as it enhances the light olefin selectivity was selected as the first promoter. Different Mn percentages (x= 0.05, 0.1, 0.2, 0.3, 0.4, 0.5) by molecular weight were tested and the highest light olefin selectivity and CO conversion were observed in 0.3 wt.% Mn. After choosing the optimum amount for the Mn promoter, the effect of Cu, Ni, and K metals on 15Fe0.3Mn/α-Al2O3 with the amounts as x= 0.5, 1, 1.5, 2, 2.5 weight percent was investigated. It was observed that the best results for Cu, Ni, and K promoters were 0.5 weight percent. To analyze the solvent effect on catalyst preparation isopropyl alcohol, n-pentane, and deionized water was used in this study. The addition of Mn promoter to iron catalyst (15Fe0.3Mn/α-Al2O3) increased olefin selectivity by 25% compared to unpromoted catalyst. CO conversion of Mn-promoted catalyst prepared with n-pentane was higher and more stable than the unpromoted sample. 15Fe0.3Mn/α-Al2O3-NP had 63% CO conversion. Cu loading had positively affected the catalyst olefin selectivity and CO conversion. Cu promoter led to catalyst stability and higher reaction performance. Cu-promoted catalysts` CO conversions are equal to 88 and 93 for water and pentane, respectively. The highest olefin selectivity and olefin-to-paraffin ratio among all catalysts in this work belong to the K-promoted catalyst. The olefin selectivity and olefin to-paraffin ratio are 49.83% and 7.3% respectively. The addition of Ni shifted the product selectivity to paraffin and CH4. Ni promoted catalysts paraffin ratio equals 30% which has the highest paraffin selectivity. The catalyst promoted with Cu and K (15Fe0.3Mn0.5Cu0.5K) showed synergistic interaction including the stability and activity decrease from the K promoter effect but the Cu promoter balanced the CO conversion. The K promoter prevented the secondary hydrogenation reactions so the olefin selectivity and O/P ratio increased. In this context, for industrial applications, A0.5Cu and A0.5K catalysts were chosen due to the CO conversion, high olefin selectivity, low methane selectivity, and high olefin to paraffin ratio during the catalyst performance tests.
Thesis (M.Sc.) -- İstanbul Technical University, Graduate School, 2022
Anahtar kelimeler
catalysts, manganese, olefines, promoters