- Title
- The effect of silica on the reduction of precipitated iron-based fischer-tropsch catalysts
- Creator
- Coombes, Matthew
- Subject
- Fischer-Tropsch process Reduction (Chemistry)
- Subject
- Catalysts
- Date Issued
- 2016
- Date
- 2016
- Type
- Thesis
- Type
- Doctoral
- Type
- PhD
- Identifier
- http://hdl.handle.net/10948/14873
- Identifier
- vital:27888
- Description
- Iron Fischer-Tropsch (FT) catalysts are typically prepared as iron oxides which are reduced to FT-active iron metal and iron carbide prior to FT synthesis. The iron oxides contain a variety of different chemical and structural promoters to alter FT-activity. Silica is a common structural promoter which stabilises the formation of small crystallites and provides mechanical integrity to the catalyst. However, silica inhibits the reduction of the oxide precursor to the FT-active phases. This ultimately affects catalyst activity and product selectivity. It has been proposed that the silica interacts with the iron to form encapsulating shells of fayalite (Fe2SiO4), or fayalite rafts between the iron oxide and the silica support. In this study, six silica-promoted iron oxide samples were prepared using a simple co-precipitation technique. Samples contain varying amounts of silica, and the samples are named 100/x Fe/SiO2, where x is the weight of silica for 100 weight iron, with x taking on values of 0, 10, 25, 50, 100 and 200. The resulting iron oxides were characterised using scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray powder diffraction (XRPD), M¨ossbauer spectroscopy (MS), magnetic susceptibility measurements (MM), Raman spectroscopy, thermal gravimetric analysis (TGA) and nitrogen physisorption. Their reduction in a hydrogen atmosphere was investigated using temperature programmed reduction (TPR), in situ XRPD and TEM. The reduction in hydrogen of 100/0 Fe/SiO2 and 100/10 Fe/SiO2 was also studied using in situ gas flow TEM cells. These cells allow the samples to be studied in the electron microscope at temperature and pressure conditions approaching those experienced in a real reactor environment. In the absence of a silica promoter (100/0 Fe/SiO2), hematite particles are formed with mean particle diameters of 39 ± 12 and 52.7 ± 0.2 nm determined using TEM and XRPD respectively. MM data reveals a magnetic transition (Morin transition) at≈230 K, consistent with a mean particle size of≈50 nm. In a hydrogen atmosphere, the hematite reduces to metallic iron via a two-step process viz. hematite → magnetite → iron. The final iron particles have an average crystallite size of 68.0 ± 0.2 nm. The presence of lower amounts of silica in the samples 100/10 Fe/SiO2, 100/25 Fe/SiO2 and 100/50 Fe/SiO2 results in the formation of silicasubstituted 2-line ferrihydrite particles. Bands in the Raman spectra of these samples shift on increasing silica content, which indicates an increasing number of Fe-O-Si bonds within the ferrihydrite framework. MM reveals typical superparamagnetic (SPM) behaviour above a blocking temperature in the range 39 - 68 K which gives mean particle sizes of 4.2, 3.6 and 3.5 nm for 100/10 Fe/SiO2, 100/25 Fe/SiO2 and 100/50 Fe/SiO2 respectively, in good agreement with particle sizes determined using TEM (3.1±0.4, 2.4±0.3 and 2.4±0.3 nm respectively). MS data at 300 K and 4.2 K were fitted with distributions of ∆EQ and Bhf respectively. The median values of Bhf decrease with increasing silica content, indicating greater degrees of distortion in the Fe3+ environments induced by increased silica substitution. The reduction to metallic iron occurs via a three-step process viz. hematite → magnetite → wu¨stite → iron, with the silica stabilising the wu¨stite phase. The increasing amount of Fe-O-Si bonds on increasing silica content shifts reduction to higher temperatures broadens each reduction step as a result of local Fe-O-Si concentration variations. Fractions of each sample are not completely reduced even at 1000°C, with the relative proportion increasing with increasing silica content. In situ gas flow TEM studies reveal that the mechanism of reduction involves the liberation of atomic iron atoms from the silica-substituted iron oxides which agglomerate and grow into final iron particles. This leaves a poorly crystalline Fe-O-Si bonded framework behind. STEM-EDS and STEM-EELS reveal low concentrations of silicon at the surface of the resulting iron particles, however they do not form encapsulating shells of fayalite as previously suggested. The majority of the silica remains in the Fe-O-Si material which may crystallise into separate fayalite particles at elevated temperature. The presence of silica in high proportions (100/100 Fe/SiO2 and 100/200 Fe/SiO2) results in the formation of a two-phase system consisting of silicasubstituted 2-line ferrihydrite particles which are encapsulated in an ironinfused amorphous silica network. As with the other silica-bearing samples, there is an increase in Fe-O-Si bonds and an increase in the degree of distortion at Fe3+ sites with increasing silica content. The large amount of silica suppresses the blocking temperature of the SPM crystallites. In a hydrogen atmosphere, the reduction to metallic iron follows the same three step process as the other silica-bearing samples. Reduction temperatures are further shifted to higher values and given reduction steps are considerably broader with increasing silica content. The fraction of iron not fully reduced also increases. Iron particle diameters are very small, since encapsulation by the silica matrix prevents growth of particles.
- Format
- xxxi, 296 leaves : illustrations
- Format
- Publisher
- Nelson Mandela Metropolitan University
- Publisher
- Faculty of Science
- Language
- English
- Rights
- Nelson Mandela Metropolitan University
- Hits: 2282
- Visitors: 2346
- Downloads: 203
Collections
NMMU School of Computer Science, Mathematics, Physics and Statistics
| Thumbnail | File | Description | Size | Format | |||
|---|---|---|---|---|---|---|---|
| View Details Download | SOURCE1 | The effect of silica on the reduction of precipitated iron-based fischer-tropsch catalysts | 48 MB | Adobe Acrobat PDF | View Details Download |