Effect of Palladium on Iron Fischer–Tropsch Synthesis Catalysts

Studies were conducted to investigate the effect of Pd on the Fischer–Tropsch Synthesis (FTS) selectivity, activity and kinetics as well as on the water–gas shift activity of an iron catalyst. Two palladium promoted catalysts (Pd0.002/Fe100 and Pd0.005/Fe100) were prepared from a base Fe100/Si5.1 (atomic ratio) catalyst. Results of FTS over the two palladium promoted catalysts were compared to those obtained from the K/Fe/Si base catalyst and a Cu/K/Fe/Si catalyst. The results indicate that Pd enhanced the FT activity while the selectivity for CO₂ and CH₄ changed little compared to the results for the base catalyst and the Cu promoted catalyst. Palladium promotion had a negative effect on the C₂—C₄ olefin to paraffin ratio. Pd promotion led to a higher WGS rate than the other two catalysts at high syngas conversions. A higher WGS rate compared to the FTS rate was obtained only for the Pd promoted catalysts. The FTS rate constant for the Pd promoted catalyst is higher than the base catalyst but lower than for the Cu promoted catalyst.     

Iron catalyst supported on carbon nanotubes for Fischer-Tropsch synthesis: Effects of Mo promotion

Our studies on the application of carbon nanotubes (CNTs) as support have shown that iron catalysts supported on CNTs are active and selective catalysts for Fischer-Tropsch synthesis (FTS). However, these catalysts experienced deactivation as a result of active site agglomerations. In order to control the agglomeration of active site, which is an important step in developing a novel catalyst supported on carbon-based supports, the effects of Mo promotion on deactivation behavior of iron catalysts supported on CNTs were studied. In this work the properties and catalytic performance of unpromoted iron catalysts were compared with a promoted catalyst with different Mo contents (0.5, 1, 5, and 12 wt%). Based on TEM and XRD analyses, promotion of the catalysts with Mo resulted in production of smaller metal particles compared to the unpromoted iron catalyst. According to XRD analysis, Mo species were deposited in their amorphous structure. TPR analyses showed that addition of Mo increased reduction temperature significantly. Based on TEM and XRD analyses, the particle size of the iron oxides in the unpromoted catalyst increased from 16 to 25 nm under FT operating conditions, while the particle size of the iron oxide in the Mo promoted catalysts (∼12-14 nm) did not change noticeably under the same operating conditions. Activity, selectivity and stability of the unpromoted and Mo promoted catalysts showed that addition of 0.5-1 wt% Mo resulted in a more stable catalyst. Higher contents of Mo (5 and 12 wt%) decreased the activity of the catalysts due to catalytic site coverage and lower extent of reduction. Mo promotion (0.5-12 wt%) increased the selectivity of the catalysts toward lighter hydrocarbons. The promotion of the iron catalyst with 0.5 wt% of Mo stabilized the activity of the catalyst with minimal increase (2%) in methane selectivity.     

Fischer-Tropsch synthesis: Impact of potassium and zirconium promoters on the activity and structure of an ultrafine iron oxide catalyst

Slurry phase Fischer-Tropsch synthesis was conducted with an ultrafine iron oxide catalyst promoted with either 0.5 at% K or 1.0 at% Zr or both. Pretreatment in CO yielded higher conversions and a more stable catalyst than activation in hydrogen or synthesis gas. Hydrogen pretreatment of K promoted catalysts and synthesis gas activation in general were less effective. Mössbauer spectroscopy and XRD showed-Fe₅C₂ and -Fe_2.2C were formed during pretreatment in CO and did not depend on promoters present. Catalysts pretreated in H2 were reduced to metallic Fe and Fe₃O₄; promotion with K and Zr decreased the extent of reduction. Hydrogen pretreated catalysts, promoted with K, lost surface area and carbided rapidly under synthesis conditions. Activation in synthesis gas reduced all catalysts to Fe₃O₄. Subsequent synthesis did not affect the phase present for the unpromoted and Zr promoted catalysts while those promoted with K formed -Fe₅C₂ and -Fe_2.2C. It is concluded that pretreatment type is more important to the catalyst activity during the early period of synthesis than the impact of promotion with K and/or Zr and that changes in the bulk composition of iron catalysts do not necessarily correlate with changes in activity.     

Effect of reducing agents on microstructure and catalytic performance of precipitated iron-manganese catalyst for Fischer–Tropsch synthesis

Effects of reducing agents on the textural properties and bulk/surface phase compositions of a precipitated iron-manganese catalyst were investigated by N₂-physisorption, X-ray photoelectron spectroscopy (XRD), Mössbauer effect spectroscopy (MES), X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy (LRS). Fischer–Tropsch synthesis (FTS) was performed in a slurry-phase continuously stirred tank reactor. The characterization results indicated that the hematite in the fresh catalyst was converted mainly to magnetite in H₂ atmosphere without the formation of intermediate metallic iron. Large amounts of Fe₃O₄ and small amounts of ε′-Fe_2.2C and χ-Fe_2.5C were formed after syngas pretreatment. In contrast, CO activation led to the formation of large amounts of χ-Fe_2.5C and carbonaceous species on the surface of magnetite. In the FTS reaction, the CO-activated catalyst presented the highest initial activity compared to the H₂ and syngas-reduced catalysts, and remained unchanged in the activity following the transformation of iron carbides to Fe₃O₄. Furthermore, the FTS activity of the H₂-reduced catalyst increased gradually accompanied with the conversion of magnetite to iron carbides. All of the results suggested that the formation of iron carbides (especially for χ-Fe_2.5C) on the surface layers provides probably the active sites for FTS, whereas the Fe₃O₄ formed plays a negligible role in the FTS activity.     

Inorganic polymers made of fayalite slag: On the microstructure and behavior of Fe

The microstructure of inorganic polymers (IP) formed from fayalite slag was investigated as a function of the composition of different activating solutions. The starting slag was 80 wt% amorphous, and after activation using sodium silicate solutions with varying SiO₂/Na₂O molar ratios, the amorphous phase dissolved and a binder phase was formed. The morphology of this binder, including the population and size of remnant particles and pores, was dependent on the particular activating solution used, and became denser as the level of silicate rose. ⁵⁷Fe Mössbauer spectroscopy revealed that the IP synthesis reaction is combined with the oxidation of Fe²⁺ from the fayalite slag to Fe³⁺ in the inorganic polymer binder. The reaction extent varied and could be quantified using the absorption areas of these ions. Data corroborate that the Fe²⁺ ions in the amorphous part of the fayalite slag and the Fe³⁺ ions in the new binder phase had an average oxygen‐coordination number of 5.     

Transformation of doped Fe in pitch sphere in carbonization and activation processes

Ferrocene was added into the starting pitch in order to produce the pitch-based spherical activated carbon with mesopore (PSAC-M) forms of doped Fe in different stages—stabilization, carbonization, and activation—during the preparation process of the PSAC-M being analyzed using Mössbauer spectroscopy (MES), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). Ferrocene was oxidized into -Fe₂O₃ at the stabilization step. The major portion of -Fe₂O₃ was reduced into -Fe during carbonization at 900°C, which was subsequently transformed into Fe₃C by 1200°C. No obvious sintering or agglomeration of iron particles occurred during carbonization process even when the carbonization temperature was as high as 1200°C. The activation re-oxidized -Fe into γ-Fe₂O₃, which aggregated and grew up along with the activation time and iron content.     

Synthesis and characterization of chemically and electrochemically prepared conducting polymer/iron oxalate composites

Poly(3-octyl-thiophene) (POT) and polypyrrole (PPy) iron oxalate composites were synthesized through a post-polymerization oxidative treatment. The composite of the latter has been prepared also by electrochemical polymerization. The samples have been characterized by X-ray diffraction (XRD), impedance spectroscopy, scanning electron microscope (SEM) combined with energy dispersive X-ray (EDX) spectroscopy, Mössbauer spectroscopy, cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM). In case of PPy, two peaks in the XRD spectra show the presence of iron containing composite, while with POT only the layered structure originating from the octyl side-chain interactions was modified by the composite formation. The assumption of the weakening of short- and long-range interactions was proven by the decrease in conductivity of the composite. The successful electrochemical synthesis resulted a composite of ∼5% iron content, determined by EDX. Mössbauer spectroscopy measurements evidenced a composite containing mixed valence iron oxalate doping ions, which supports the indirect EQCM data.     

Preparation,characterisation and activity of an iron/sodalite catalyst for the oxidation of methane to methanol

An iron sodalite catalyst similar to that reported to have good selectivity for the oxidation of methane to methanol by Lyons et al. has been prepared, tested and characterised. In a limited range of temperature at 34 bar total pressure the selectivity of the catalyst to methanol is a little better than that of an empty silica glass reactor. Before reaction, X-ray powder diffraction and Mössbauer spectroscopy confirm the presence of Fe(III) in the sodalite framework. After reaction Mössbauer spectroscopy identifies Fe(II) and also small particles of iron(III) oxide, < 1 m in size.     

Surface modification of carbon-supported iron catalyst during the wet air oxidation of phenol: Influence on activity, selectivity and stability

Catalytic wet air oxidation (CWAO) of phenol with iron/activated carbon catalysts (Fe/AC) at temperature of 400 K and 8 atm of total pressure is an efficient treatment to oxidize a resistant pollutant such as phenol into biodegradable species, mainly short chain acids. Extended studies employing activated carbon catalysts point out significant changes in the carbon as a consequence of the CWAO process. After the long-term experiments carried out in this work it was concluded that these modifications consist of loss of microporosity, temporary decrease of the mesoporosity, decrease of the carbon/oxygen ratio on the catalyst surface, more acidic pH_slurry values, and aggregation of the -Fe₂O₃ crystallites. The causes that provoke these changes and the reasons why they do not alter significantly the CWAO efficiency were analyzed. The way of exposition of Fe/AC catalyst to the reactants plays an important role in its activity and selectivity towards complete mineralization, namely oxidation to CO₂ and H₂O.     

Application of in situ Mössbauer spectroscopy to investigate the effect of precipitating agents on precipitated iron Fischer–Tropsch catalysts

The type of the precipitating agent used during the preparation of a precipitated iron-based Fischer–Tropsch (FT) catalyst affects the catalyst pore structure, crystallite size, phase composition and catalytic behavior. Catalysts prepared by using precipitating agents, that contain carbonate ions, have pores that are larger than those of catalysts prepared using precipitating agents that contain hydroxides. Precipitation at pH>8, using aqueous NH₃ solution as a precipitating agent, results in the formation of large crystallites of FeOOH, which are not observed when Na₂CO₃ and K₂CO₃ are used. Higher % CO conversion during FT synthesis was observed with the catalyst prepared by using aqueous NH₃ solution. However, this is correlated with a low selectivity for the formation of olefins. For all catalysts, in situ Mössbauer spectra recorded during FT synthesis show that the % CO conversion increases with the formation of iron carbides, viz. ′-Fe_2.2C and χ-Fe_2.5C.     

Fischer-Tropsch synthesis with an iron catalyst: Incorporation of ethene into higher carbon number alkanes

Tracer studies with C labeled ethene show that for synthesis over a doubly promoted iron catalyst at 7 atm and ca. 60% CO conversion, higher carbon number products are formed from ethene initiation. About 10% of the added ethene (ethene/CO 0.02) is incorporated into C ₅ ⁺ products and that ca. 85% of the ethene that is incorporated does so by initiating chain growth.     

Mössbauer spectroscopy and neutron activation analysis of ancient Chinese glazes

The optical spectra of the glaze of Ru porcelain made in the Chinese Northern Song Dynasty (AD 960–1126) were measured by the chromatometer to determine the relations between glaze color and its dominant wavelength (λ_D). The concentrations of 30 coloring elements in the glaze were determined by neutron activation analysis (NAA). Iron was the dominant coloring element. Mössbauer spectroscopy detected that iron existed in the state of structural Fe²⁺ and Fe³⁺ ions. A relationship between λ_D of various colored glazes and the Fe²⁺/Fe³⁺ ratio was established. As the Fe²⁺/Fe³⁺ ratio gradually increases, the glaze color of Ru porcelain will gradually change from pea green to sky green. All the Ru porcelains were fired in a reducing atmosphere. The sky green Ru porcelain was fired in the most reducing atmosphere and at the highest temperature, the powder green in a more reducing atmosphere and at a lower temperature and the pea green in a lightly reducing atmosphere and at the lowest temperature.     

Effect of iron counter-ions on the reducibility of the Keggin type molybdophosphoric heteropolyacid: Part II. A theoretical study

Quantum-chemical calculations of the interaction of the molybdophosphoric Keggin heteropolyanion with the iron counter-ion are performed to explain the influence of the latter on the reducibility of iron-doped acid. It is shown that the electron transfer heteropolyanion→iron counter-ion becomes possible only under hydration of the solid. The microscopic mechanism of this transfer is due to the modification of the relative position of the counter ion which enters into strong interaction with terminal oxygens of the heteropolyanion.     

Technological characterization of kaolin: Study of the case of the Borborema–Seridó region (Brazil)

The technological characterization of kaolin from the Borborema–Seridó region has shown that it is predominantly kaolinitic, pseudoplastic and thixotropic; approximately 50% of its particles size is less than 2 μm. By using electronic paramagnetic resonance (EPR) and Mössbauer spectroscopy (ME), it was observed that Fe²⁺ and Fe³⁺ substitute Al³⁺ in octahedral sites of kaolinite. After magnetic separation followed by chemical bleaching, kaolin reached a brightness index of 87.72% ISO and an opacity index of 85.58% ISO, indicating that it can be used mainly as a filler and a coating in the paper industry, paint and pottery, among other industries.     

La(1−x)SrxCo1−yFeyO3 perovskites prepared by sol–gel method: Characterization and relationships with catalytic properties for total oxidation of toluene

La_(1−x)Sr_xCo_(1−y)Fe_yO₃ samples have been prepared by sol–gel method using EDTA and citric acid as complexing agents. For the first time, Raman mappings were achieved on this type of samples especially to look for traces of Co₃O₄ that can be present as additional phase and not detect by XRD. The prepared samples were pure perovskites with good structural homogeneity. All these perovskites were very active for total oxidation of toluene above 200 °C. The ageing procedure used indicated good thermal stability of the samples. A strong improvement of catalytic properties was obtained substituting 30% of La³⁺ by Sr²⁺ cations and a slight additional improvement was observed substituting 20% of cobalt by iron. Hence, the optimized composition was La_0.7Sr_0.3Co_0.8Fe_0.2O₃. The samples were also characterized by BET measurements, SEM and XRD techniques. Iron oxidation states were determined by Mössbauer spectroscopy. Cobalt oxidation states and the amount of O⁻ electrophilic species were analyzed from XPS achieved after treatment without re-exposition to ambient air. Textural characterization revealed a strong increase in the specific surface area and a complete change of the shape of primary particles substituting La³⁺ by Sr²⁺. The strong lowering of the temperature at conversion 20% for the La_0.7Sr_0.3Co_(1−y)Fe_yO₃ samples can be explained by these changes. X photoelectron spectra obtained with our procedure evidenced very high amount of O⁻ electrophilic species for the La_0.7Sr_0.3Co_(1−y)Fe_yO₃ samples. These species able to activate hydrocarbons could be the active sites. The partial substitution of cobalt by iron has only a limited effect on the textural properties and the amount of O⁻ species. However, Raman spectroscopy revealed a strong dynamic structural distortion by Jahn–Teller effect and Mössbauer spectroscopy evidenced the presence of Fe⁴⁺ cations in the iron containing samples. These structural modifications could improve the reactivity of the active sites explaining the better specific activity rate of the La_0.7Sr_0.3Co_0.8Fe_0.2O₃ sample. Finally, an additional improvement of catalytic properties was obtained by the addition of 5% of cobalt cations in the solution of preparation. As evidenced by Raman mappings and TEM images, this method of preparation allowed to well-dispersed small Co₃O₄ particles that are very efficient for total oxidation of toluene with good thermal stability contrary to bulk Co₃O₄.