Fischer–Tropsch Synthesis: Deuterium Kinetic Isotope Study for Hydrogenation of Carbon Oxides Over Cobalt and Iron Catalysts

Abstract  

The hydrogenation of CO₂ using Pt promoted Co/γ-Al₂O₃ and doubly (Cu, K) promoted iron catalysts exhibits an inverse isotope effect (r ^H/r ^D < 1). The observed inverse isotope effect for hydrogenation of CO₂ shows that hydrogen addition to CO₂ should be involved in the kinetically relevant step. The systematic increase of inverse isotope effect with carbon number of products obtained during H₂–D₂–H₂ switching experiments suggests the possible existence of a common intermediate (CH _x O) for hydrogenation of CO₂ over both cobalt and iron FT catalysts. The magnitude of the inverse isotope effect is lower for CO₂ compared to CO hydrogenation under similar reaction conditions. The deuterium isotope effect does not provide a definite conclusion regarding the mechanism which CO₂ hydrogenation follows (alkyl, enol, or alkylidine mechanisms).     

Selective Oxidation of Ethane Over Mo–V–Al–O Oxide Catalysts: Insight to the Factors Affecting the Selectivity of Ethylene and Acetic Acid and Structure-activity Correlation Studies

Catalysts of general formula, MoVAlO _x were prepared with the initial elemental composition of 1:0.34:0.167 (Mo:V:Al) at a pH value in the range of 1–4. The elemental analysis showed that the final composition of the catalysts is pH dependant. The performance of the catalysts was tested for selective oxidation of ethane to give ethylene and acetic acid. While all of them were active for ethane oxidation with a moderate conversion, the catalyst prepared at pH 2 showed a highest activity with 23% ethane conversion and a combined selectivity of 80.6% to ethylene and acetic acid. The catalyst prepared at pH 4 was least selective to ethylene and acetic acid. Various techniques like powder XRD, SEM, Raman, UV–Vis and EPR were used to characterize the catalysts and to identify the active phases responsible for the selective oxidation of ethane. The powder XRD data showed that the catalysts prepared at pH 1 and 2 contain mainly of MoO₃ and MoV₂O₈ along with traces of Mo₄O₁₁. The amount of MoO₃ was slightly higher in the catalyst prepared at pH 1. However, the catalyst prepared at pH 3 contains mainly of MoV₂O₈ with no trace of MoO₃. The catalyst prepared at pH 4 showed V₂O₅ as the major phase along with MoVAlO₄ phase. The Raman data corroborated the XRD results. EPR and UV–Vis studies indicated the presence of traces of V⁴⁺ in pH 1 and 2 catalysts and significant amount of Mo⁵⁺ in all the catalysts. Thus, the high activity and selectivity to ethylene and acetic acid are attributed to the presence of MoV₂O₈ phase and other reduced species like Mo₄O₁₁ phase supported on MoO₃. The presence of V and Mo ions in a partially reduced form seems to play a crucial role in the selective oxidation of ethane.     

Hydrogenolysis of Glycerol to Propanediols Over Highly Active Ru–Re Bimetallic Catalysts

Several supported Ru–Re bimetallic catalysts (Ru–Re/SiO₂, Ru–Re/ZrO₂, Ru–Re/TiO₂, Ru–Re/H-β, Ru–Re/H–ZSM5) and Ru monometallic catalysts (Ru/SiO₂, Ru/ZrO₂, Ru/TiO₂, Ru/H-β, Ru/H–ZSM5) were prepared and their catalytic performances were evaluated in the hydrogenolysis of glycerol to propanediols (1,2-propanediol and 1,3-propanediol) with a batch type reactor (autoclave) under the reaction conditions of 160 °C, 8.0 MPa and 8 h. Compared with Ru monometallic catalysts, the Ru–Re bimetallic catalysts showed much higher activity in the hydrogenolysis of glycerol, and Re exhibited obvious promoting effect on the performance of the catalysts. The supported Ru monometallic catalysts and Ru–Re bimetallic catalysts were characterized by N₂ adsorption/desorption, XRD, TEM-EDX, H₂-TPR and CO chemisorption for obtaining some physicochemical properties of the catalysts, such as specific surface areas, crystal phases, morphologies/microstructure, reduction behaviors and dispersion of Ru metal. The results of XRD and CO chemisorption indicate that the addition of Re component could improve the dispersion of Ru species on supports. The measurements of H₂-TPR revealed that the coexistence of Re and Ru components on supports changed the respective reduction behavior of Re or Ru alone on the supports, indicating the existence of synergistic effect between Ru and Re species on the bimetallic catalysts. The hydrogenolysis of some products (such as 1,2-propanediol, 1,3-propanediol, 1-propanol and 2-propanol) were also examined over Ru and Ru–Re catalysts for evaluating influence of Re–Re on the reaction routes during glycerol hydrogenolysis. The results showed that over Ru–Re catalysts, glycerol was favorable to be converted to 1,2-propanediol, but not favorable to ethylene glycol, while 1,2-propanediol and 1,3-propanediol were favorable to be converted to 1-propanol. The influence of glycerol concentration in its aqueous solution on the catalytic performance was also evaluated over Ru and Ru–Re catalysts.     

Room Temperature Photocatalytic Oxidation of Carbon Monoxide Over Pd/TiO2–SiO2 Catalysts

The photocatalytic oxidation of carbon monoxide over TiO₂–SiO₂ and Pd/TiO₂–SiO₂ catalysts was studied. The catalyst samples were synthesized by using sol–gel technique coupled with hydrothermal treatment and all samples were hydrothermally treated before calcination in air. The catalyst samples were characterized by XRD, BET and DRIFTS techniques. The photocatalytic activity of the samples was determined by using circulated batch photoreactor coupled with in line gas transmission FTIR cell charged with 2,000 ppm carbon monoxide in air initially over 0.5 g of catalyst sample under 33 W (254 nm) irradiation power. XRD and BET results confirmed the presence of anatase phase and the decrease on the crystallite size of TiO₂ with SiO₂ addition which yield higher surface area and better dispersion of TiO₂ over mesoporous SiO₂. DRIFTS results indicated the presence of surface hydroxyls coordinated to Ti⁴⁺ and Si–O–Ti sites. All samples containing 10–90 % TiO₂ over SiO₂ exhibited significant photo oxidation activity at room temperature. The photocatalytic oxidation rate of carbon monoxide is favored by SiO₂ addition due to high surface area, better dispersion of TiO₂ particles and higher surface defects. The addition of PdO improves the photocatalytic activity significantly and the synergy between the TiO₂ and PdO phases.     

Selective Hydrogenolysis of Glycerol to 1, 2 Propanediol Over Cu–ZnO Catalysts

A series of Cu–ZnO catalysts with varying Cu to Zn weight ratio are prepared by co-precipitation method. The catalysts were characterized by surface area, XRD, TPR and N₂O chemisorption to measure Cu metal area. These catalysts were evaluated for hydrogenolysis of glycerol. The catalyst with Cu to Zn ratio of 50:50 is highly active under relatively low H₂ pressure. The catalysts are highly selective towards 1,2 propanediol (>93%). The glycerol conversion depends upon the bifunctional nature of catalyst where it requires both acidic sites and metal surface. The presence of sufficient amount with small particle size of ZnO and Cu are required for high conversion of glycerol and selectivity to 1,2 propanediol. Different reaction parameters are studied in order to optimize the reaction conditions.     

Selective Catalytic Reduction of NO x Over Nano-Sized Gold Catalysts Supported on Alumina and Titania and Over Bimetallic Gold–Silver Catalysts Supported on Alumina

The reduction of NO with octane under lean conditions was examined over gold supported on alumina and titania and over alumina supported bimetallic gold–silver catalysts. The silver loading was either 1.2 or 1.9 wt% whereas 0.3, 1 or 5 wt% gold was used. The catalysts were characterized by means of EDXS, N₂-adsortion, UV–Vis and TEM to correlate recorded results with different preparation methods. UV–Vis measurements indicated that gold was present in the form of fine Au particles, single Au ions and small (Au)_n ^δ+ clusters on the catalysts and silver was mainly present in the form of single Ag ions. The highest NO to N₂ reduction activity was recorded over the 0.3Au–Al₂O₃ catalyst. The Au–TiO₂ catalysts did not result in significant NO to N₂ reduction.     

Catalytic Purification of Exhaust Gases Over Pd–Rh Alloy Catalysts

Three-way catalysts with low content of Pd–Rh alloy particles used as active components were synthesized and studied. Monometallic and bimetallic mixed catalysts with corresponding precious metals loading were chosen as reference samples. The catalytic activity was tested in oxidation of carbon monoxide, hydrocarbons, and in nitrogen oxides reduction. The stability of the samples was estimated by prompt thermal aging in situ technique. Ethane hydrogenolysis testing reaction was used to determine the surface concentration of Pd and Rh, and to confirm the alloy formation. Photoluminescence and electron paramagnetic resonance spectroscopy were applied to clarify the possible reasons of deactivation and to elucidate the mechanism of stabilization. It was shown that Pd–Rh alloyed catalyst is characterized by comparable activity and enhanced stability. While the Pd and Rh particles of monometallic samples were found to interact with support at high temperatures resulting in sintering and bulk diffusion, the particles of alloy type kept their initial state of dispersion and catalytic activity.     

Studies on Carbon Deposition in CO2Reforming of CH4over Nickel–Magnesia Solid Solution Catalysts

Carbon formation behavior under CH₄-CO₂reaction and through CH₄decomposition and CO disproportionation was investigated over Ni_0.03Mg_0.97O solid solution, supported Ni/MgO, and NiO-Al₂O₃catalysts by means of thermogravimetric analysis (TGA) and transmission electron microscopy (TEM). Ni_0.03Mg_0.97O showed high resistance to carbon formation in CO₂reforming of methane and the selectivity to carbon formation was much lower than two other catalysts. It is suggested that CO₂plays an important role in the inhibition of carbon formation on Ni_0.03Mg_0.97O through the activation of CO₂at the interface between small nickel particles and the support surface.     

Studies of Heterogeneous Hydrothermal Stripping from Iron-loaded Naphthenic Acid–Alcohol–Kerosen

The technique of hydrothermal stripping from mixed aqueous-organic systems is a promising method for synthesizing oxide ceramic powders for high-performance applications. Some factors influencing heterogeneous hydrothermal stripping with water from iron-loaded organic phase of naphthenic acid–isooctyl alcohol–kerosene, such as initial concentrations of iron and naphthenic acid, concentration of Fe2O3 “seed”, temperature and time, were investigated. Based on the experimental results, the rate equation was established. Nano-ferric oxide powders were obtained by the technique of hydrothermal stripping from the iron-loaded organic phase. The results suggest that the heterogeneous hydrothermal stripping proceeds in 3 steps: adsorption of naphthenic acid dimers and naphthenic complex of iron onto the surface of “seed”, hydrolysis of adsorbed complex of iron, and condensation of hydrolyzed complex. The process activation energy is 115 kJ/mol and the heterogeneous hydrothermal stripping is controlled by a chemical reaction (the hydrolysis of naphthenic complex of iron).     

Oxidative Dehydrogenation of Ethylbenzene to Styrene with CO2 Over V2O5–Sb2O5–CeO2/TiO2–ZrO2 Catalysts

Utilization of CO₂ as a soft oxidant in the oxidative dehydrogenation of ethylbenzene to styrene, a remarkable V₂O₅–Sb₂O₅–CeO₂/TiO₂–ZrO₂ catalyst has been accomplished. Preparation of TiO₂–ZrO₂ support by co-precipitation followed by a single step deposition of V and Ce and Sb as stabilizers yielded a highly active and selective catalyst. Acid–base and redox properties including sustained stability of active species (V⁵⁺) are responsible for high activity of V₂O₅–Sb₂O₅–CeO₂/TiO₂–ZrO₂ catalyst. The redox cycle is related to the dispersed V⁵⁺ and lattice reduced vanadium site in the VSbO₄ phase. The antimony oxide inhibits the easy redox cycle between different vanadia species.     

Crystalline Mo-V–W-mixed Oxide with Orthorhombic and Trigonal Structures as Highly Efficient Oxidation Catalysts of Acrolein to Acrylic Acid

We succeeded in introducing W in Mo₃VO_x with keeping the orthorhombic, trigonal, and amorphous structures. Synthesized crystalline Mo(W)₃VO_x with orthorhombic and trigonal structures, both of which possess heptagonal channels, showed catalytic activity for gas-phase selective acrolein oxidation to acrylic acid superior to amorphous Mo(W)₃VO_x and to tetragonal Mo₃VO_x. The results strongly suggest that the crystalline Mo(W)₃VO_x with orthorhombic and trigonal structures are real active phase of industrial acrolein oxidation catalysts based on Mo, W, and V oxides. Furthermore, we found that the resulting W-containing catalyst showed less-dependency of water partial pressure in the reactant feed on the acrolein conversion.     

Oxidative Dehydrogenation of Ethane to Ethylene with Carbon dioxide over Cr–Ce/SBA-15 Catalysts

Chromium oxide supported on SBA-15 was modified with Ce species by an incipient method. The effect of Ce on the activity of Cr/SBA-15 catalyst in the dehydrogenation of ethane with CO₂ was investigated. The activity is enhanced for Ce modified Cr/SBA-15 catalyst for the dehydrogenation of ethane with CO₂. The cycle between Cr⁶⁺ and Cr³⁺ species can be carried out viaing the dehydrogenation of ethane and oxidation of CO₂ processes.