Autothermal Reforming of Acetic Acid to Hydrogen and Syngas on Ni and Rh Catalysts

The autothermal reforming (ATR) of acetic acid (HAc) as a model bio-oil compound is examined via bench scale experiments and equilibrium modelling to produce hydrogen and syngas. This study compares the performance of nickel (Ni-Al, Ni-CaAl) vs. rhodium (Rh-Al) for particulate packed bed (PPB), and of Rh-Al in PPB vs. Rh with and without Ceria for honeycomb monolith (‘M’) catalysts (R-M and RC-M). All PPB and M catalysts used Al2O3 as main support or washcoat, and when not pre-reduced, exhibited good performance with more than 90% of the HAc converted to C1-gases. The maximum H2 yield (6.5 wt.% of feed HAc) was obtained with both the Rh-Al and Ni-CaAl catalysts used in PPB, compared to the equilibrium limit of 7.2 wt.%, although carbon deposition from Ni-CaAl at 13.9 mg gcat−1 h−1 was significantly larger than Rh-Al’s (5.5 mg gcat−1 h−1); close to maximum H2 yields of 6.2 and 6.3 wt.% were obtained for R-M and RC-M respectively. The overall better performance of the Ni-CaAl catalyst over that of the Ni-Al was attributed to the added CaO reducing the acidity of the Al2O3 support, which provided a superior resistance to persistent coke formation. Unlike Rh-Al, the R-M and RC-M exhibited low steam conversions to H2 and CH4, evidencing little activity in water gas shift and methanation. However, the monolith catalysts showed no significant loss of activity, unlike Ni-Al. Both catalytic PPB (small reactor volumes) and monolith structures (ease of flow, strength, and stability) offer different advantages, thus Rh and Ni catalysts with new supports and structures combining these advantages for their suitability to the scale of local biomass resources could help the future sustainable use of biomasses and their bio-oils as storage friendly and energy dense sources of green hydrogen.

Stabilization of Pt in SiO2–Al2O3 Microspheres at High Mechanical Resistance, Promoted with W Oxides for the Combustion of CO

This study shows the development of a combustion promoter for the oil-refining process called fluid catalytic cracking (FCC). The investigation of a catalyst prepared for the combustion of CO composed of 0.05 wt% Pt supported on SiO2–Al2O3–0.5 wt% W microspheres with high mechanical resistance, promoted with tungsten oxides (WOx) that can inhibit the sintering of Pt, is reported. The addition of WOx in SiO2–Al2O3 inhibited the decrease in the specific area when calcined from 550 °C to 950 °C. SiO2–Al2O3 support in the form of calcined microspheres with average diameters between 70–105 µm were produced by spray drying, using two atomization discs with vanes of different geometry: a straight rectangular blade disc (DAR) and a curved rectangular vanes disc (DAC). The DAR disk produced whole microspheres, while the DAC had hollow and broken microspheres. The microspheres were characterized by XRD, SEM, optical microscopy, N2 physisorption (BET area) and fracture resistance tests. The Pt catalysts were evaluated by TPR, H2 chemisorption and CO combustion. The catalyst of 0.05 wt% Pt/SiO2–Al2O3–0.5 wt% turned out to be the most stable. A thermal stabilization effect was observed at contents lower than 1 wt% W that allowed it to inhibit the sintering of the Pt catalyst.

Carbon-Supported KCoMoS2 for Alcohol Synthesis from Synthesis Gas

KCoMoS2 was supported on various carbon support materials to study the support effect on synthesis gas conversion. Next to two activated carbons with high micropore volume, a traditional alumina (γ-Al2O3) support and its carbon coated form (CCA) were studied for comparison. Coating alumina with carbon increases the selectivity to alcohols, but the AC-supported catalysts show even higher alcohol selectivities and yields, especially at higher temperatures where the conversions over the AC-supported catalysts increase more than those over the γ-Al2O3-based catalysts. Increasing acidity leads to decreased CO conversion yield of alcohols. The two activated-carbon-supported catalysts give the highest yield of ethanol at the highest conversion studied, which seems to be due to increased KCoMoS2 stacking and possibly to the presence of micropores and low amount of mesopores.

Quantum chemical study of NO reduction mechanism on Ag /Al2O3 catalysts

It was shown that N2O content among NO reduction products increases with an increase of the silver concentration in the catalyst because the nature of the catalytic centers changes and leads to a subsequent change in the mechanism of the reaction. Two reaction mechanisms were proposed and studied by means of quantum chemistry: a two-stage mechanism that proceeds via NO dimer formation on catalysts with high (above 2 wt. %) silver concentration and a parallel mechanism with isocyanates involved on catalysts with low (below 2 wt. %) silver concentration. It was demonstrated that on catalysts with high silver concentration mechanism that involves stepwise NO reduction via N2O to N2 is realised. Moreover, the final stage is complicated by the fact that formed intermediates and N2O are likely to desorb from the catalyst surface. In the case of catalysts with low silver concentration, the formation of both products (N2O and N2) proceeds in parallel and the lower activation barriers of the reaction leading to N2, as well as the thermodynamic profitability of its formation, lead to the predominance of the target product. The competition between the proposed mechanisms was studied in the case of catalytic centers represented by silver dimers. It was shown that activation barriers of reaction proceeding via NO dimer formation are lower than the corresponding barriers of the reaction with isocyanates involved, which confirms the prevalent realisation of the first process and the predominance of N2O among the final products. The obtained results explain the experimental data and are significant for further modelling of the mechanism of nitrogen oxides catalytic reduction considering the Al2O3 support.

Catalytic Activity Enhancement of Cu-Zn-Based Catalyst for Methanol Steam Reforming with Magnetic Inducement

Magnetic inducement was applied during metal loading to enhance Cu-Zn catalysts for methanol steam reforming in the temperature range of 200–300 °C. The supports used in this study were the γ-Al2O3 support and CeO2-Al2O3 supports prepared under different magnetic environments. Cu-Zn loading between the north and south poles (N-S) on the CeO2-Al2O3 support, prepared between two north poles (N-N), led to the highest H2 production at 300 °C (2796 ± 76 µmol/min), which is triple that of Cu-Zn/CeO2-Al2O3 prepared without magnetic inducement and ~11-fold the activity of the Cu-Zn/Al2O3 reference catalyst. The N-S magnetic environment during metal loading leads to lower reduction temperatures and larger Cu(1+):Cu(2+) ratio. These results showed that the pole arrangement of magnets during metal loading could affect the catalytic activity of the Cu-Zn catalyst owing to its influence on the reducibility and the oxidation state of Cu active metal.

Preparation and Investigation of Pd and Bimetallic Pd-Sn Nanocrystals on γ-Al2O3

One of the key factors for producing highly dispersed controlled nanoparticles is the method used for metal deposition. The decomposition of metal-organic precursors is a good method for deposition of metal nanoparticles with very small sizes and narrow size distributions on the surface of various supports. The preparation process of Pd and bimetallic Pd-Sn nanoparticles supported onto γ‑Al2O3 is considered. The samples were prepared by diffusional co-impregnation of the γ‑Al2O3 support by using organometallic Pd(acac)2 and Sn(acac)2Cl2 precursors. To achieve the formation of Pd and bimetallic Pd-Sn nanoparticles on the support surface, the synthesized samples were then subjected to thermal decomposition under Ar (to decompose the organometallic bound to the surface while keeping the formed nanoparticles small) followed by an oxidation in O2 (to eliminate the organic compounds remaining on the surface) and a reduction in H2 (to reduce the nanoparticles oxidized during the previous step). A combination of methods (ICP-OES, TPR-H2, XPS, TEM/EDX) was used to compare the physical-chemical properties of the synthesized Pd and bimetallic Pd-Sn nanoparticles supported on the γ‑Al2O3. The three samples exhibit narrow size distribution with a majority on nanoparticles between 3 and 5 nm. Local EDX measurements clearly showed that the nanoparticles are bimetallic with the expected chemical composition and the measured global composition by ICP-OES. The surface composition and electronic properties of Pd and Sn on the γ-Al2O3 support were investigated by XPS, in particular the chemical state of palladium and tin after each step of thermal decomposition treatments (oxidation, reduction) by the XPS method has been carried out. The reducibility of the prepared bimetallic nanoparticles was measured by hydrogen temperature programmed reduction (TPR-H2). The temperature programmed reduction TPR-H2 experiments have confirmed the existence of strong surface interactions between Pd and Sn, as evidenced by hydrogen spillover of Pd to Sn (Pd-assisted reduction of oxygen precovered Sn). These results lead us to propose a mechanism for the formation of the bimetallic nanoparticles.

Pervaporative Dehydration of Organic Solvents Using High-Silica CHA-Type Zeolite Membrane

A high-silica chabazite (CHA) type zeolite membrane was prepared on the porous α-Al2O3 support tube by the secondary growth of seed particles. The dehydration performances of the membrane were determined using methanol, ethanol, 2-propanol, acetone, acetic acid, methyl ethyl ketone (MEK), tetrahydrofuran (THF), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methyl-2-pyrolidone (NMP) at 303–373 K. As a result, the dehydration performances of the membrane were categorized to following three types: (1) 2-propanol, acetone, THF, and MEK; (2) ethanol and acetic acid; and (3) methanol, DMF, and DMSO, and NMP. The adsorption isotherms of water, methanol, ethanol, and 2-propanol were determined to discuss the influences of the organic solvents on the permeation and separation performances of the membrane. For 2-propanol, acetone, MEK, and THF solutions, the high permeation fluxes and separation factors were obtained because of the preferential adsorption of water due to molecular sieving. In contrast, the permeation fluxes and separation factors were relatively low for methanol, DMF, and DMSO, and NMP solutions. The lower dehydration performance for the methanol solution was due to the adsorption of methanol. The permeation fluxes for ethanol and acetic acid solution were ca. 1 kg m−2 h−1. The significantly low flux was attributed to the similar molecular diameter to the micropore size of CHA-type zeolite.