Significant Improvement in Activity and Stability of Pt/TiO2 Catalyst for Water Gas Shift Reaction Via Controlling the Amount of Na Addition

Na promoted Pt/TiO₂ catalysts have been studied under high severity, near equilibrium, conditions for use as a single stage WGS catalyst. Addition of 3 wt% Na to a 1 wt% Pt/TiO₂ catalyst has been found to improve water gas shift activity significantly compared to Pt/TiO₂, Pt/CeO₂, and Pt–Re/TiO₂ catalysts. This catalyst is stable when the reaction temperature is higher than 250 °C. Deactivation occurred when the reaction temperature was lower than 250 °C, however, returning the temperature to higher than 250 °C fully recovered activity. TEM observations revealed that addition of Na inhibited Pt particle sintering. These results suggest that Na promoted Pt/TiO₂ is a promising single stage water gas shift catalyst for small scale hydrogen production.     

Study of the Suitability of a Pt-Based Catalyst for the Upgrading of a Biomass Gasification Syngas Stream via the WGS Reaction

In this article, the catalytic activity of a Pt-based water gas shift (WGS) catalyst is presented. The experimental study has been conducted under realistic conditions typical of pressurised oxygen gasification. The effect of temperature, space velocity, steam to carbon monoxide ratio, and gas composition on the performance of the catalyst is investigated. Despite the high CO content in the feed gas, ranging from 32% to 60% v/v, dry basis, the catalyst has shown very good performance at intermediate temperature, 300–450 °C. Carbon monoxide concentration at the reactor outlet reached values below 3% what is comparable with conventional high-temperature, first-stage WGS catalysts.     

Differences Between Al2O3 and Ag/Al2O3 for Lean Reduction of NO x with Dimethyl Ether

Lean reduction of NO _x with DME occurs with high selectivity to N₂ over Al₂O₃ between 300 °C and 550 °C with a maximum of 47% at 380 °C, and with lower selectivity over Ag/Al₂O₃ between 250 °C and 400 °C due to the catalysts’ sensitivity to gas phase radical reactions and activity for NO _x reduction with methanol.     

Steam reforming of ethanol over skeletal Ni‐based catalysts: A temperature programmed desorption and kinetic study

An investigation on reaction scheme and kinetics for ethanol steam reforming on skeletal nickel catalysts is described. Catalytic activity of skeletal nickel catalyst for low‐temperature steam reforming has been studied in detail, and the reasons for its high reactivity for H₂ production are attained by probe reactions. Higher activity of water gas shift reaction and methanation contributes to the low CO selectivity. Cu and Pt addition can promote WGSR and suppress methanation, and, thus, improve H₂ production. A reaction scheme on skeletal nickel catalyst has been proposed through temperature programmed reaction spectroscopy experiments. An Eley‐Rideal model is put forward for kinetic studies, which contains three surface reactions: ethanol decomposition, water gas shift reaction, and methane steam reforming reaction. The kinetics was studied at 300–400°C using a randomized algorithms method and a least‐squares method to solve the differential equations and fit the experimental data; the goodness of fit obtained with this model is above 0.95. The activation energies for the ethanol decomposition, methane steam reforming, and water gas shift reaction are 187.7 kJ/mol, 138.5 kJ/mol and 52.8 kJ/mol, respectively. Thus, ethanol decomposition was determined to be the rate determining reaction of ethanol steam reforming on skeletal nickel catalysts. © 2013 American Institute of Chemical Engineers AIChE J 60: 635–644, 2014     

Effect of Mo and Re Promoters on the Activity and Stability of a Pt/ZrO2 Water-Gas Shift Catalyst (Part 1)

The activity and stability of Pt catalysts for the water-gas shift (WGS) reaction can be profoundly influenced by the presence of promoters. We present the results on the promotion of a Pt/doped ZrO₂ catalyst by Mo and Re. The CO conversion rate of the catalysts is approximately 3-times higher in the presence of the promoters after reduction at temperatures higher than 325 °C. The stability of the catalysts against sintering under reaction conditions is significantly enhanced by the promoters as well. The active phase is unstable in the presence of steam, even in presence of hydrogen at temperatures as high as 300 °C but is re-formed at higher temperatures in reformate. A detailed FTIR investigation reveals that Pt–Re–Mo alloy is the active phase for the material under investigation. The alloy decomposes reversibly below 300 °C, but reforms in reformate above 325 °C restoring catalytic activity.     

Conversion of Synthesis Gas to Dimethylether Over Gold-based Catalysts

It is shown that Au?Czinc oxide?Calumina catalysts are suitable for the water?Cgas shift reaction and for methanol (MeOH) and DME synthesis, indicating their use in a direct single-stage process for converting syngas to a DME?+?methanol mixture. Temperatures above 340?°C were required in order to obtain reasonable catalytic activity. A 67?% DME selectivity was achieved at 380?°C with a low space velocity 0.75?dm³?h^?1?g^?1 and 50?bar. The lower CO conversions at the higher temperature of 460?°C was probably due to the MeOH equilibrium limitation in the range of temperatures 340 to 460?°C, but deactivation is observed as well, above 460?°C. Au/ZnO/??-Al₂O₃ is more stable than traditional copper-based catalysts, which are stable below about 300?°C, and then only in the absence of water. The gold composite catalyst was mainly selective toward DME, MeOH and CH₄, and to C₂ to C₅ hydrocarbons. An analysis of the main reactions involved indicates that only the methanol synthesis reaction reaches a near-equilibrium situation, with the other reactions being under kinetic control.     

Effect of Molybdenum on the Sulfur-Tolerance of Cerium–Cobalt Mixed Oxide Water–Gas Shift Catalysts

As traditional sources of energy become depleted, significant research interest has gone into conversion of biomass into renewable fuels. Biomass-derived synthesis gas typically contains concentrations ranging from ~30 to 600 ppm H₂S. H₂S is a catalyst poison which adversely impacts downstream processing of hydrogen for gas-to-liquid plants and the deactivation of water–gas shift catalysts by sulfur is typical. Novel catalysts are needed to remain active in the presence of sulfur in order to boost efficiency and mitigate costs. Previous studies have shown molybdenum to be active in concentrations of sulfur >300 ppm. Cobalt has been shown to be active as a spinel in concentrations of sulfur <240 ppm. Ceria has received attention as a catalyst due to its oxygen donating properties. In this study, mixed oxide catalysts were synthesized via Pechini’s method into various blends of metal oxide solutions. Activity testing at low steam-to-carbon ratios (1:1) produced near equilibrium conversions at a GHSV of 6,300 h^?1 and over a temperature range of 350–400 °C for a Ce–Co mixed oxide even after an 800 ppm sulfur treatment. The addition of molybdenum to the Ce–Co base had little effect on sulfur tolerance, but it did lead to a reduction in selectivity for methanation. Specific surface areas generally increased following the sulfur treatments and X-ray diffraction patterns confirmed that bulk sulfiding did not occur.     

Selective Production of H2 from Ethanol at Low Temperatures over Rh/ZrO2–CeO2 Catalysts

A series of Rh catalysts on various supports (Al₂O₃, MgAl₂O₄, ZrO₂, and ZrO₂–CeO₂) have been applied to H₂ production from the ethanol steam reforming reaction. In terms of ethanol conversion at low temperatures (below 450 °C) with 1wt% Rh catalysts, the activity decreases in the order: Rh/ZrO₂–CeO₂ > Rh/Al₂O₃ > Rh/MgAl₂O₄ > Rh/ZrO₂. Support plays a very important role on product selectivity at low temperatures (below 450 °C). Acidic or basic supports favor ethanol dehydration, while ethanol dehydrogenation is favored over neutral supports at low temperatures. The Rh/ZrO₂–CeO₂ catalyst exhibits the highest CO₂ selectivity up to 550 °C, which is due to the highest water gas shift (WGS) activity at low temperatures. Among the catalysts evaluated in this study, the 2wt% Rh/ZrO₂–CeO₂ catalyst exhibited the highest H₂ yield at 450 °C, which is possibly due to the high oxygen storage capacity of ZrO₂–CeO₂ resulting in efficient transfer of mobile oxygen species from the H₂O molecule to the reaction intermediate.     

A Novel Method for Measuring Active Sites of Fe3O4 for WGS Reaction

Phase transformation among iron oxides was investigated. Pure magnetite material was obtained by reducing iron oxide with diluted hydrogen in a narrow temperature window and with steam to prevent over-reduction. A pulse chromatographic method with N₂O decomposition over magnetite surface to determine active sites of iron oxide based catalysts for water gas shift reaction has been developed. N₂O decomposes over activated Fe₃O₄ surface to N₂ and leaves oxygen species at oxygen vacancy on the catalyst surface, which is the same site for water gas shift reaction. Lower temperature for N₂O decomposition is required to avoid magnetite bulk oxidation. An oxygen coverage on the active sites θ = 1 corresponded to a surface stoichiometry of N₂O/Fe²⁺ = 0.5 was estimated. A linear correlation between water gas shift reaction rate and the quantity of decomposed N₂O over the corresponded catalysts was observed.     

Hydrothermal Solubilization–Hydrolysis–Dehydration of Cellulose to Glucose and 5-Hydroxymethylfurfural Over Solid Acid Carbon Catalysts

Solid acid catalysts based on graphite-like mesoporous carbon material Sibunit were developed for the one-pot solubilization–hydrolysis–dehydration of cellulose into glucose and 5-hydroxymethylfurfural (5-HMF). The catalysts were produced by treating Sibunit surface with three different procedures to form acidic and sulfo groups on the catalyst surface. The techniques used were: (1) sulfonation by H₂SO₄ at 80–250 °C, (2) oxidation by wet air or 32 v/v% solution of HNO₃, and (3) oxidation-sulfonation what meant additional sulfonating all the oxidized carbons at 200 °C. All the catalysts were characterized by low-temperature N₂ adsorption, titration with NaOH, TEM, XPS. Sulfonation of Sibunit was shown to be accompanied by surface oxidation (formation of acidic groups) and the high amount of acidic groups prevented additional sulfonation of the surface. All the Sibunit treatment methods increased the surface acidity in 3–15 times up to 0.14–0.62 mmol g^?1 compared to pure carbon (0.042 mmol g^?1). The catalysts were tested in the depolymerization of mechanically activated microcrystalline cellulose at 180 °C in pure water. The main products 5-HMF and glucose were produced with the yields in the range of 8–22 wt% and 12–46 wt%, respectively. The maximal yield were achieved over Sibunit sulfonated at 200 °C. An essential difference in the composition of main products obtained with solid acid Sibunit carbon catalysts (glucose, 5-HMF) and soluble in water H₂SO₄ catalysts (formic and levulinic acids) as well as strong dependence of the reaction kinetics on the morphology of carbon catalysts argue for heterogenious mechanism of cellulose depolymerization over Sibunit.     

Ethanol oxidation on a high temperature PBI-based DEFC using Pt/C, PtRu/C and Pt3Sn/C as catalysts

A high temperature ethanol-fed polymer electrolyte membrane fuel cell has been implemented by using H₃PO₄-doped m-polybenzimidazole as polymeric electrolyte. Commercial Pt/C, PtRu/C and Pt₃Sn/C catalysts are used in the anode. The performance was assessed in terms of polarization curves at different temperatures, feeding the cell with a high concentration ethanol solution (water/ethanol mass ratio of 2). The product distribution was measured with the support of a gas chromatograph. The use of bimetallic catalysts increased the current density. PtRu/C showed the best performance up to 175 °C, but it is outperformed by Pt₃Sn/C at 200 °C. In terms of oxidation products, higher temperatures and current densities favour the oxidation of ethanol. However, Pt₃Sn/C promoted the generation of more oxidized products compared to PtRu/C (in which most of the ethanol is oxidized to acetaldehyde), especially at high temperature. This accounts for the large current density. In terms of complete oxidation of ethanol to CO₂, Pt/C was by far the most efficient catalyst for C–C scission, achieving percentages of 56 % of CO₂, although operating above 175 °C dramatically boosted an undesirable methanation process that slashed the efficiency. The combination of fuel cell results and product distribution helped to suggest the different oxidation routes on the surface of the different catalysts.     

Catalytic decomposition of biomass tars with iron oxide catalysts

Catalytic gasification of wood (Cedar) biomass was carried out using a specially designed flow-type double beds micro reactor in a two step process: temperature programmed non-catalytic steam gasification of biomass was performed in the first (top) bed at 200–850 °C followed by catalytic decomposition gasification of volatile matters (including tars) in the second (bottom) bed at a constant temperature, mainly 600 °C. Iron oxide catalysts, which transformed to Fe₃O₄ after use possessed catalytic activity in biomass tar decomposition. Above 90% of the volatile matters was gasified by the use of iron oxide catalyst (prepared from FeCl₃ and NH_3aq) at SV of 4.5 × 10³ h^?1. Tar was decomposed over the iron oxide catalysts followed by water gas shift reaction. Surface area of the iron oxide seemed to be an important factor for the catalytic tar decomposition. The activity of the iron oxide catalysts for tar decomposition seemed stable with cyclic use but the activity of the catalysts for the water gas shift reaction decreased with repeated use.     

Surface Modification of Pd/α-Si3N4 Catalysts Through the Solvent Used During Synthesis. Implications on the CO Chemisorption Properties and Catalytic Performances

Palladium catalysts supported on α-Si₃N₄ were prepared by impregnation with Pd(II)-acetate dissolved either in toluene or in water. The mean metal particle size of ~0.5 wt% Pd catalysts was similar (~5 nm) and independent of the way of preparation. Nevertheless, the two catalysts present very different chemisorption behaviour chemisorptive and catalytic properties. Fourier transformed infrared (FTIR) spectra of adsorbed CO at different temperatures (ranging from room temperature to 300 °C) show a very different behaviour for both catalysts. While the CO adsorption states on the Pd/α-Si₃N₄ prepared in toluene are very similar to those generally measured for silica and/or alumina supported palladium catalysts, CO chemisorbs less strongly on Pd/α-Si₃N₄ prepared in water and on different adsorption sites. The Pd/α-Si₃N₄ catalyst obtained by aqueous impregnation is much less efficient for the methane total oxidation. It is less active and less stable: it deactivates strongly after 3 h on stream at 650 °C. The two catalysts present about the same activity for the 1,3-butadiene hydrogenation after stabilisation at 20 °C. But, the catalyst prepared in water shows a much better selectivity to butenes. The results are discussed in terms of the possible migration of silicon atoms from the silicon nitride support to the surface of the palladium particles, when the catalyst is prepared in water. This is not the case when prepared in an organic solvent.     

Nickel Oxide Based Supported Catalysts for the In-situ Reactions of Methanation and Desulfurization in the Removal of Sour Gases from Simulated Natural Gas

Supported nickel oxide based catalysts were prepared by wetness impregnation method for the in-situ reactions of H₂S desulfurization and CO₂ methanation from ambient temperature up to 300 °C. Fe/Co/Ni (10:30:60)–Al₂O₃ and Pr/Co/Ni (5:35:60)–Al₂O₃ catalysts were revealed as the most potential catalysts, which yielded 2.9% and 6.1% of CH₄ at reaction temperature of 300 °C, respectively. From XPS, Ni₂O₃ and Fe₃O₄ were suggested as the surface active components on the Fe/Co/Ni (10:30:60)–Al₂O₃ catalyst, while Ni₂O₃ and Co₃O₄ on the Pr/Co/Ni (5:35:60)–Al₂O₃ catalyst.     

Flame-Made Pt/K/Al2O3 for NO x Storage–Reduction (NSR) Catalysts

High surface area Pt/K/Al₂O₃ catalysts were prepared with a 2-nozzle flame spray method resulting in Pt clusters on γ-Al₂O₃ and amorphous K storage material as evidenced by Raman spectroscopy. The powders had a high NO _x storage capacity and were regenerated fast in a model exhaust gas environment. From 300 to 400 °C no excess NO _x was detected in the off gas during transition from fuel lean to fuel rich conditions, resulting in a highly effective NO _x removal performance. Above 500 °C, the NSR activity was lost and not recovered at lower temperatures as K-compounds were partially crystallized on the catalyst.     

Fischer–Tropsch Synthesis: Effect of K Loading on the Water–Gas Shift Reaction and Liquid Hydrocarbon Formation Rate over Precipitated Iron Catalysts

The effect of K loading on the water–gas shift (WGS) reaction and hydrocarbon formation rate during Fischer–Tropsch synthesis (FTS) was studied over 100 Fe/5.1 Si/2 Cu/x K (x = 1.25 or 3) precipitated catalysts using a 1-L continuously stirred tank reactor. The catalysts were tested over a wide range of experimental conditions: 260–270 °C, 1.3 MPa, H₂/CO = 0.67 and 20–90 % CO conversions. On the low K loading (1.25 % K) Fe catalyst, the H₂ deficiency required for the FTS reaction was made up by the WGS reaction only at high CO conversion level, i.e. >70 %; however, increasing potassium loading to 3 % dramatically improved the WGS reaction rate which provided enough hydrogen for the FTS reaction even at low CO conversion level, i.e. 30 %. Kinetic analysis suggests that increasing K loading resulted in significant increases in the WGS rate constant relative to that of FTS, which is a major cause of the high WGS activity on the high K loading catalyst. Both the low and high potassium containing iron catalysts have high liquid oil and solid wax formation rates, i.e. 0.78–0.93 g/g-cat/h at 260 °C, 1.3 MPa, H₂/CO = 0.67 and 50 % CO conversion, but increasing potassium loading from 1.25 to 3 % shifted the primary product to wax (70 %) from oil (73.5 %). The wax fraction increased with increasing CO conversion for both iron catalysts. The effect of K loading on initial FTS activity and hydrocarbon distribution/selectivity of the Fe catalysts was also studied. High K loading, i.e. 3 % K, increased the iron carburization rate and significantly shortened the induction period of the FTS reaction. Secondary reactions of olefins were remarkably suppressed and the olefin content was greatly enhanced with increasing K loading from 1.25 to 3 %, consistent with a number of studies in the open literature.     

Reaction coupling of diethylbenzene dehydrogenation with water–gas shift over alumina-supported iron oxide catalysts

Starting from the thermodynamic analysis of the coupling of diethylbenzene (DEB) dehydrogenation to divinylbenzene (DVB) with reverse water–gas shift, the dehydrogenation of DEB in the presence of carbon dioxide over alumina-supported iron oxide catalysts was carried out at 450–650 °C under atmospheric pressure with CO₂/DEB mole ratio of 10–70 and DEB liquid space velocity (LHSV) of 0.2–1.2 h⁻¹. The effects of reaction temperature, LHSV, CO₂/DEB ratio, as well as iron loading and addition of promoters upon DEB conversion and DVB selectivity were investigated. It was revealed that the yield of DVB and ethylstyrene (EST) could be greatly improved by the reaction coupling due to the simultaneous elimination of the hydrogen produced in the dehydrogenation by reverse water–gas shift. A typical result with EST + DVB selectivity of 90.3%, DVB yield of 43.9% and EST yield of 38.0% was obtained at 550 °C with DEB LHSV of 0.4 h⁻¹ and CO₂/DEB mole ratio of 40.     

Microchannel Autothermal Reforming of Methane to Synthesis Gas

Autothermal reforming of methane to synthesis gas (CO and H₂) is studied in a microchannel reactor comprised of Pt- and Rh-based catalysts that are coated on opposite walls of the channel. The effects of operating parameters and microchannel catalyst configuration on methane conversion and CO selectivity are analyzed. The parameters considered are the residence time of the reactants (12.9–25.7 ms), reaction temperature (500–650 °C), molar steam-to-carbon (S/C = 0–3.0) and oxygen-to-carbon (O₂/C = 0.47–0.63) ratios at the inlet. Doubling the residence time leads to ca. 10 % increase in methane conversion, but has only a 4 % contribution to the CO selectivity. Higher O₂/C ratios improve extent of methane oxidation, but reduce selectivity due to CO₂ production. When the temperature is raised from 500 to 650 °C, conversion increases from 12.8 to 46.6 % and selectivity increases from 20.1 to 35.7 %. S/C ratio has the greatest effect on the outlet H₂/CO ratio, which is found to vary between 0.93 and 2.68, via the water–gas shift reaction. Comparison of the present catalyst configuration with the use of bimetallic Pt–Rh coating in the microchannel under identical conditions shows that the latter can improve conversion by 20 % and CO selectivity by 33 %.     

在工业催化剂上水煤气变换反应宏观动力学

用内循环式无梯度反应器,在不同的反应条件下,测定了B106及B109两种型号的原粒度工业变换催化剂的宏观反应速率.根据实验数据关联出两种催化剂都适用的宏观动力学方程,求定了相应的模型参数.该式可用以模拟工业变换反应器.此外,并由实验数据计算了各种情况下的有效因子.整个实验及计算结果表明,这两种催化剂对气体的内扩散阻力都是相当大的.     

Effects of Reaction Variables on Fischer–Tropsch Synthesis with Co-Precipitated K/FeCuAlO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Catalysts

Abstract  

The effects of reduction temperature and reaction temperature, pressure and space velocity on iron-based K/FeCuAlO _x Fischer–Tropsch catalysts prepared by co-precipitation were investigated. The catalyst reduced at 150 °C deactivated quickly due to an abundance of unreduced iron species. With increasing reduction temperature, the iron oxide’s phase transformed from hematite (α-Fe₂O₃) to magnetite (Fe₃O₄) and finally to metallic iron (α-Fe). The induction period to reach steady-state catalytic activity was reduced at increased reduction temperatures due to in situ reduction by syngas during reaction. CO conversion increased with increasing reaction temperature, and selectivity to C₅+ decreased with increasing reaction pressure and space velocity. At reaction temperatures up to of 300 °C, CO₂ formation by the water–gas shift reaction was linearly correlated with the extent of CO conversion, and CO₂ formation was slightly suppressed at ≥350 °C by a reverse water–gas shift reaction.