Characterization of some perovskite oxides based on YBa2Cu3O7 − x in relation to their use in methanol production

The oxidized and weakly reducible perovskite oxide YBa₂Cu₃O_{7 − x} (YBCO) has been prepared as a catalyst, supported on γ‐Al₂O₃. It was further modified by (i) impregnation with Ru and Pd and (ii) cobalt incorporation via co‐precipitation. All the catalysts were either 20% (w/w) YBCO/γ‐Al₂O₃ or 2% (w/w) Ru, Pd or Co/20% (w/w) YBCO/γ‐Al₂O₃. The catalysts were characterized using temperature programmed reduction (TPR), surface area measurements and X‐ray diffraction (XRD) studies before and after various treatments. They were studied as catalysts in the pressure range 20–50 atmospheres and in the temperature range 523–573 K in an autoclave equipped with a spinning basket catalyst container. The Pd‐, Ru‐ and Co‐modified catalysts gave predominantly methanation products, along with some C₂–C₄ hydrocarbons. However the YBCO/γ‐Al₂O₃ catalyst exhibited significant methanol selectivity at 50 atmospheres and at 523 K X‐ray diffraction studies revealed the presence of Cu(0), Cu(I) and Cu(II) after reduction and the species Cu(0) and Cu(I) are probably essential to CH₃OH production. © 2000 Society of Chemical Industry     

Dibenzothiophene hydrodesulfurization using in situ generated hydrogen over Pd promoted alumina-based catalysts

Catalytic hydrodesulfurization (HDS) of dibenzothiophene (DBT) was carried out in a temperature range of 320-?400 °C using in situ generated hydrogen via steam reforming of ethanol and the effect of some organic additives was studied for the first time. Four kinds of alumina-based catalysts, i.e. Co?-Mo/Al₂O₃, Ni-Mo/Al₂O₃ and their corresponding Pd promoted catalysts Pd-?Co-?Mo/Al₂O₃ and Pd-?Ni-?Mo/Al₂O₃, prepared through incipient impregnation method, were used for the desulfurization process. Catalytic activity was investigated in a batch autoclave reactor in the complete absence of external hydrogen gas. Experiments showed that organic additives like diethylene glycol (DEG), phenol, naphthalene, anthracene, o-xylene, tetralin, decalin and pyridine can affect the HDS activity of the catalysts in different ways, and only naphthalene is inhibitive for the catalytic activity towards HDS. The results showed that Ni-based catalysts are more active than Co-based ones while Pd shows a high promotion effect. DBT conversion of up to 97% was achieved with Pd-?Ni-?Mo/Al₂O₃ catalyst at 380 °C temperature and 13 h reaction time. Catalyst systems followed the HDS activity order of: Pd-?Ni-?Mo/Al₂O₃ > Ni-?Mo/Al₂O₃ > Pd-?Co-?Mo/Al₂O₃ > Co?-Mo/Al₂O₃ at all conditions. Qualitative analysis of the products stream was carried out using GC?-MS technique. The present HDS process using in situ generated hydrogen might be applied as an alternative approach for the catalytic HDS of DBT on industrial level due to its cost effectiveness, mild operating conditions and high activity of the catalysts.     

Hydrogenation of the Aromatics and Olefins in FCC Gasoline During Deep Desulphurisation

The applicability of four catalyst with different composition (conventional and new generation CoMo/Al₂O₃, new composition Pt,Pd/USY, Pt/H-Mordenite) catalysts was investigated for selective desulphurization of different sulphur containing FCC gasolines. The new generation CoMo/Al₂O₃ and the new composition Pt,Pd/USY were found to have favourable hydrodesulphurisation activity. The reactions of some C₅-C₆ olefin and aromatic hydrocarbons are discussed under the conditions of deep desulphurisation, highlighting the effects of that on the octane number.     

Nitrogen Tolerant Hydrodesulfurization Catalysts Based on Rh and Ru Promoted Mo/Al2O3

Rh and Ru promoted Mo/Al₂O₃ catalysts were tested in HDS of thiophene in the presence of different amounts of pyridine and compared with CoMo/Al₂O₃. The Rh and Ru promoted catalysts were more nitrogen tolerant and in the presence of pyridine showed higher HDS activities than CoMo/Al₂O₃. This was explained by higher C–N bond hydrogenolysis activity and high nitrogen tolerance of the free Rh and Ru sulfides in the promoted catalysts.     

Novel inexpensive transition metal phosphide catalysts for upgrading of pyrolysis oil via hydrodeoxygenation

Supported molybdenum/molybdenum‐phosphides as inexpensive catalysts for bio‐oil hydrodeoxygenation (HDO) were in‐house prepared using different support materials, i.e., Al₂O₃, activated carbon (AC), MgAl₂O₄, and Mg₆Al₂(CO₃)(OH)₁₆. The HDO activity of these catalysts were investigated using a 100 mL bench‐scale reactor operating at 300°C with an initial hydrogen pressure of 50 bar for 3 h with a pyrolysis oil (PO). The catalytic efficiencies for bio‐oil HDO for the catalysts were compared with the expensive but commercially available Ru/C catalyst. Addition of small amount of P to the Mo catalysts supported on either AC and Al₂O₃ led to increased degree of deoxygenation (DOD) and oil yield compared with those without P. MoP supported on AC (MoP/AC) demonstrated bio‐oil HDO activity comparable to the Ru/C catalyst. Furthermore, three AC‐supported metal phosphides for PO HDO were compared under the same conditions, and they were found to follow the order of NiP/AC > CoP/AC > MoP/AC. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3664–3672, 2016     

Catalytic Hydroprocessing of p-Cresol: Metal, Solvent and Mass-Transfer Effects

A systematic study of the comparative performances of supported Pt, Pd, Ru and conventional CoMo/Al₂O₃, NiMo/Al₂O₃, NiW/Al₂O₃ catalysts as well as the effects of solvent, H₂ pressure and temperature on the hydroprocessing activity of a representative model bio-oil compound (e.g., p-cresol) is presented. With water as solvent, Pt/C catalyst shows the highest activity and selectivity towards hydrocarbons (toluene and methylcyclohexane), followed by Pt/Al₂O₃, Pd and Ru catalysts. Calculations indicate that the reactions in aqueous phase are hindered by mass-transfer limitations at the investigated conditions. In contrast, with supercritical n-heptane as solvent at identical pressure and temperature, the reactant and H₂ are completely miscible and calculations indicate that mass-transfer limitations are eliminated. All the noble metal catalysts (Pt, Pd and Ru) show nearly total conversion but low selectivity to toluene in supercritical n-heptane. Further, conventional CoMo/Al₂O₃, NiMo/Al₂O₃ and NiW/Al₂O₃ catalysts do not show any hydrodeoxygenation activity in water, but in supercritical n-heptane, CoMo/Al₂O₃ shows the highest activity among the tested conventional catalysts with 97?% selectivity to toluene. Systematic parametric investigations with Pt/C and Pt/Al₂O₃ catalysts indicate that with water as the solvent, the reaction occurs in a liquid phase with low H₂ availability (i.e., low H₂ surface coverage) and toluene formation is favored. In supercritical n-heptane with high H₂ availability (i.e., high H₂ surface coverage), the ring hydrogenation pathway is favored leading to the high selectivity to 4-methylcyclohexanol. In addition to differences in H₂ surface coverage, the starkly different selectivities between the two solvents may also be due to the influence of solvent polarity on p-cresol adsorption characteristics.     

Conversion of isopropanol and mixed alcohols to hydrocarbons using HZSM‐5 Catalyst in the MixAlco™ process

HZSM‐5 (SiO₂/Al₂O₃=280 mol/mol) is used to produce hydrocarbons from reagent‐grade isopropanol and mixed alcohols made from lignocellulosic biomass (waste office paper and chicken manure) using the MixAlco? process. All studies were performed at 101 kPa (abs). The experiments were conducted in two sets: (1) vary temperature (300–T_max°C) at weight hourly space velocity (WHSV)=1.31 h^–1, and (2) vary WHSV (0.5–11.5 h^–1) at T=370°C. For isopropanol, T_max=450°C and for mixed alcohols T_max=520°C. For isopropanol, higher temperatures produced more gaseous products and more aromatics. High WHSV gives high concentration of C6+ olefins, whereas low WHSV gives high concentrations of C9 aromatics. For mixed alcohols, changes in temperature affected the product distribution similar to isopropanol. In contrast, WHSV did not affect the concentration of reaction products; only dehydration products were observed. © 2013 American Institute of Chemical Engineers AIChE J, 59: 2549–2557, 2013     

Selective hydrogenation of (E)-2-hexenal to (E)-2-hexen-1-ol over Co-based bimetallic catalysts

Hydrogenation of (E)-2-hexenal was carried out in a liquid phase using Co-based bimetallic catalysts (M–Co/Al₂O₃, M=Pd, Pt, Ru, Rh, Sn, Fe, or Cu). Pd–Co/Al₂O₃ showed the highest activity among the catalysts tested and catalyzed the hydrogenation of CC bond predominantly to produce hexanal and 1-hexanol. Pt–Co/Al₂O₃ was more active than monometallic Co/Al₂O₃ for the hydrogenation of CO bond. The excellent result, 92% selectivity to (E)-2-hexen-1-ol formation at 90% conversion, was obtained by the hydrogenation over Pt–Co/Al₂O₃ bimetallic catalyst. No improved activities were observed for the other bimetallic catalysts.     

Effect of different air-abrasion protocols on topography,surface wettability and adhesion of MDP monomer-based resin cement to zirconia

This study evaluated the effect of air-abrasion protocols on the topography, surface wettability and adhesion of resin cement to zirconia. Ceramic specimens (N?=?49; n?=?7) (15?mm × 2?mm) were randomly allocated to seven groups to be treated with: (1) Air-abrasion with 45?μm Al₂O₃ (A45), (2) 80?μm Al₂O₃ (A80), (3) 30?μm Al₂O₃ coated with SiO₂ (CoJet) (C30), (4) 30?μm Al₂O₃ coated with SiO₂ (Rocatec Soft) (R30), (5) 110?μm Al₂O₃ coated with SiO₂ (Rocatec Plus) (R110); (6) R110R30 (Rocatec) (R110R30) and (7) control, no conditioning (NC). Air-abrasion was performed using a chairside air-abrasion device (2.5?bar, 10?mm, 90?s). Contact angle measurements were performed using goniometry (n?=?5). MDP-based dual resin cement (Panavia F2.0) was bonded on four locations after air-abrasion protocols (n?=?20 per group). Half of the specimens were tested after 24?h and the other half after thermal cycling (×3000, 5–55?°C). Data were analyzed using 1-, 2-way ANOVA and Tukey’s test (alpha = 0.05). Significantly lower contact angle values were observed for groups C30 (62.6?±?0.91), R30 (61.91?±?1.05) and R110R30 (61.54?±?1.02) compared to those of other groups (65.5?±?0.9–110.61?±?0.9) (p?<?0.05). In dry conditions, surface conditioning methods tested did not show significant effect on bond strength (MPa) (10.57?±?1.42–16.86?±?2.54) (p?=?0.238). After thermocycling, bond strength results decreased significantly (p?<?0.05) (12.6–51.2%). R110 (7.18?±?1.34) and A80 (4.92?±?1.53) showed significantly higher bond strength compared to other groups (2.13?±?0.73–4.16?±?1.34) (p?<?0.05). The best wettability and adhesion results with MDP-based resin cement to zirconia was achieved with A80 and R110 air-abrasion.     

Conversion of canola oil to various hydrocarbons over Pt/HZSM-5 bifunctional catalyst

Canola oil conversion was studied at atmospheric pressure over Pt/HZSM-5 catalyst (0.5 mass% Pt) in a fixed bed micro-reactor. The operating conditions were: temperature range of 400?500°C, weight hourly space velocity (WHSV) of 1.8 and 3.6 h^?1 and steam/oil ratio of 4. The objective was to optimize the amount of gasoline range hydrocarbons in the organic liquid product (OLP) and the selectivity towards olefins and isohydrocarbons in the gas product. The gas yields varied between 22–65 mass% and were higher in the presence of steam compared to the operation without steam. The olefin/paraffin mass ratio of C₂-C₄ hydrocarbon gases varied between 0.31–0.79. The isohydrocarbons/n-hydrocarbons ratio was higher with Pt/HZSM-5 (1.6–4.8) compared with pure HZSM-5 catalyst (0.2–1.0). The OLP yields with Pt/HZSM-5 (20–55 mass% of canola oil) were slightly lower compared to HZSM-5 (40–63 mass% of canola oil) under similar conditions. The major components of OLP were aliphatic and aromatic hydrocarbons. A scheme postulating the reaction pathways for the conversion of canola oil over Pt/HZSM-5 catalyst is also presented.     

Mathematical modeling of the partial hydrogenation of vegetable oil in a monolithic stirrer reactor

Experimental and theoretical studies on the partial hydrogenation of vegetable oil in a monolithic stirrer reactor are reported. A complete mathematical model of the reactor was developed, including hydrogenation and isomerization kinetics, catalyst deactivation, external gas–liquid and liquid–solid as well as internal mass transfer. The experimental studies were carried out in a Pd/Al₂O₃/Al monolithic stirrer reactor, at a wide range of temperatures (353–373 K), pressures (414–552 kPa), and catalyst loadings (0.00084–0.00527 kg_Pd,exp m^?3). Based on this model, simulated data can be used to evaluate the catalyst (Pd/Al₂O₃/Al) and the hydrogenation process in consecutive catalytic tests under different operating conditions. © 2014 American Institute of Chemical Engineers AIChE J, 60: 3524–3533, 2014     

Synthesis,characterization and evaluation of Ni–Mo/Zr–Al2O3 catalyst for hydro-conversion of lignite-based heavy carbon resources

NaOH depolymerized products (SDP) of Shengli lignite was used as lignite-based heavy carbon resources in this study. Hydrotreatment of SDP over Ni–Mo/Al₂O₃ and Ni–Mo/Zr–Al₂O₃ catalysts was investigated. It was found that the incorporation of Zr to Ni–Mo/Al₂O₃ catalyst results in the easy reduction of metal oxides and the increase of the stacking degree and length of MoS₂ slabs. Both of Ni–Mo/Al₂O₃ and Ni–Mo/Zr–Al₂O₃ catalysts show better performance for hydrogenation of SDP and can be used repeatedly. The incorporation of Zr to Ni–Mo/Al₂O₃ catalyst significantly inhibits the formation of tetrahydrofuran insolubles (THFI), promotes the formation of two-ring aromatics and increases HS yield compared to that over Ni–Mo/Al₂O₃ catalyst.     

Characterisation and microstructure of Pd and bimetallic Pd–Pt catalysts during methane oxidation

The catalytic oxidation of methane was studied over Pd/Al₂O₃ and Pd–Pt/Al₂O₃. It was found that the activity of Pd/Al₂O₃ gradually decreases with time at temperatures well below that of PdO decomposition. The opposite was observed for Pd–Pt/Al₂O₃, of which the activity decreases slightly with time. Morphological studies of the two catalysts showed major changes during operation. The palladium particles in Pd/Al₂O₃ are initially composed of smaller, randomly oriented crystals of both PdO and Pd. In oxidising atmospheres, the crystals become more oxidised and form larger crystals. The activity increase of Pd–Pt/Al₂O₃ is probably related to more PdO being formed during operation. The particles in Pd–Pt/Al₂O₃ are split into two different domains: one with PdO and the other likely consisting of an alloy between Pd and Pt. The alloy is initially rich in palladium, but the composition changes to a more equalmolar Pd–Pt structure during operation. The ejected Pd is oxidised into PdO, which is more active than its metallic phase. The amount of PdO formed depends on the oxidation time and temperature.     

Co–Pd/γ‐Al2O3 catalyst for heavy oil upgrading: Desorption kinetics,reducibility and catalytic activity

The influence of Pd on a Co–Pd/γ‐Al₂O₃ heavy oil upgrading catalyst is investigated using different physicochemical and reactive Characterization techniques. Nitrogen adsorption isotherm analysis shows that the specific surface area and porosity of the support alumina is significantly decreased due to the blockage of the pores by the loaded cobalt species. The estimated activation energy of NH₃ desorption is found to be less for Co–Pd/γ‐Al₂O₃ sample, which confirms improved acidity due to Pd. TPR experiments show that the reducibility of the catalyst is significantly improved with the presence of Pd. Higher metal dispersion and hydrogen spillover effects are the main reasons for the enhanced reducibility of the Pd promoted catalyst as revealed by the H₂‐pulse chemisorptions study. When evaluated using VGO as feed stock, the Co–Pd/γ‐Al₂O₃ displayed superiority both in hydrodesulphurisation (HDS) and hydrocracking (HC) activities as compared to the unpromoted Co/γ‐Al₂O₃ catalyst. The coke deposition on the spent catalyst is also found to be low due to the Pd promotional effects. This is an encouraging result, given that higher hydrogenation activity of the catalyst can be achieved without compromising the cracking activity and sustained activity of the catalyst.     

XANES investigation of the enhanced chemical stability of Pd in supported Pd–Mo catalysts

The XANES (X-ray absorption near edge structure) technique was used to study Pd and Mo catalysts deposited on supported Al₂O₃/SiO₂ and Al₂O₃/Si-MCM-41 in the form of monometallic and bimetallic systems. The results indicate that Pd has stronger chemical stability when in the presence of Mo and is always in the metallic form, which is surprising, because the samples were not subjected to reducing conditions prior to the measurements. The increased stability was attributed to the formation of a core-shell structure with a Pd rich core and a Mo rich surface.     

Fischer-Tropsch synthesis and the generation of DME in situ

Ternary physical mixtures comprised a Fischer-Tropsch catalyst, a methanol synthesis catalyst and a zeolite employed in the hydrocarbon synthesis from syngas. Two Fe-based catalysts (i.e., one promoted by K and the other by Ru), two HY zeolites with different acidities, a commercial HZSM-5 and Cu/ZnO/Al₂O₃ (methanol synthesis catalyst) were used in these systems. The main products obtained were dimethyl ether, methanol and hydrocarbons. First of all, it was observed that by adding Cu/ZnO/Al₂O₃ catalyst to a binary physical mixture comprised of a Fischer-Tropsch catalyst and HZSM-5, the CO conversion increases more than 20 times. Second, during the reaction transient period the dimethyl ether selectivity decreases as the conversion increases. Third, the hydrocarbons synthesized followed the ASF distribution in the C₁-C₁₂ range and finally, it was also verified that the Y zeolites and the Fischer-Tropsch synthesis catalyst promoted by Ru generated the most active physical mixtures. The results showed that the role of zeolites in the ternary physical mixture is only associated with the dimethyl ether synthesis. The following reaction pathway was suggested: first, methanol is synthesized from syngas using Cu/ZnO/Al₂O₃ catalyst; after that, this alcohol is dehydrated by an acid catalyst generating DME; and lastly, DME initiates Fischer-Tropsch synthesis, which is then propagated by CO.     

Palladium-Based Catalysts with Improved Sulphur Tolerance for Diesel-Engine Exhaust Systems

Palladium-based catalysts have been developed for the diesel exhaust system with an emphasis on their sulphur tolerance during the simultaneous oxidation of CO and HC. Promising materials include Au–Pd–Pt, Co–Pd–Pt and Ni–Pd–Pt supported on Al₂O₃ or TiO₂ and Pd–Pt/MoO₃–Al₂O₃ with the Al₂O₃ support modified with MoO₃ monolayer.     

Hydrogen Production from Partial Oxidation and Steam Reforming of N‐octane Over Alumina‐supported Ni and Ni‐Pd Catalysts

Hydrogen production by partial oxidation and steam reforming (POSR) of n‐octane was investigated over alumina‐supported Ni and Ni‐Pd catalysts. It showed that Ni‐Pd/Al₂O₃ had higher activity and hydrogen selectivity than the nickel catalyst under the experimental conditions, which indicated Ni‐Pd/Al₂O₃ could be an effective catalyst for the production of hydrogen from hydrocarbons.     

On the Production of Hydrogen from Bio-Oil: A Representative Study Using Propylene Glycol

In a bio-refinery focused on fast pyrolysis, hydrogen (H₂) producible from reforming of the aqueous fraction of bio-oil with steam can be utilized for upgrading pyrolytic lignin into fuels by hydrotreatment. In this work, propylene glycol (PG) was chosen as a typical compound symbolizing higher polyols in the bio-oil aqueous fraction. Catalytic processing of PG into H₂ at low temperature (T = 500°C) was investigated using several commercial catalysts such as Ni/Al₂O₃, Ru/Al₂O₃, Ru/C, Pt/C, and Pd/C in a laboratory-scale fixed-bed reactor. The efficiencies of the catalysts were presented as selectivity to CO, CO₂, CH₄ and H₂, and PG conversion into gaseous phase. Wide ranges of temperature (300–500°C), W/F_O (18.6–92.9 g h/mol), and S/C ratio (5.6–12.7 mol/mol) were examined using Ni/Al₂O₃. At T = 500°C, H₂ selectivity (73.7%) and PG conversion (66.2%) were maximized using ratios of catalyst mass to molar flow rate of PG (W/F_O) = 18.6 g h/mol and steam to carbon (S/C) = 12.7 (10 wt% PG solution). It was found that Ni/Al₂O₃ demonstrates stable operation for at least 6 h of time-on-stream. Finally, a plausible reaction pathway for PG reforming was proposed.     

Hydrogenation of Sunflower Oil over M/SiO2 and M/Al2O3 (M = Ni,Pd, Pt,Co, Cu) Catalysts

This work is aimed at evaluating the performance of several catalysts in the partial hydrogenation of sunflower oil. The catalysts are composed of noble (Pd and Pt) and base metals (Ni, Co and Cu), supported on both silica and alumina. The following order can be proposed for the effect of the metal on the hydrogenation activity: Pd > Pt > Ni > Co > Cu. At a target iodine value of 70 (a typical value for oleomargarine), the production of trans isomers is minimum for supported nickel catalysts (25.7–32.4 %, depending on the operating conditions). Regarding the effect of the support, Al₂O₃ allows for more active catalysts based on noble metals (Pd and Pt) and Co, the effect being much more pronounced for Pt. Binary mixtures of catalysts have been studied, in order to strike a balance between catalyst activity and product distribution. The results evidence that Pd/Al₂O₃–Co/SiO₂ mixture has a good balance between activity and selectivity, and leads to a very low production of trans isomers (11.8 %) and a moderate amount of saturated stearic acid (13.5 %). Consequently, the utilization of cobalt‐based catalysts (or the addition of cobalt to other metallic catalysts) could be considered a promising alternative for the hydrogenation of edible oil.