Active Catalysts for the NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> Reduction in a FCC unit

Additives, without noble metals, based in Ce–Al mixed oxides supported on γ-alumina have been investigated as potential catalysts for the NO _x reduction in the FCCU regenerator. The best results were obtained with clusters of Sn–Cu–Al–O interacting with Ce–Al mixed oxides highly dispersed on the γ-Al₂O₃. The strong interaction between the two complex oxides provides a stable catalyst with high activity at high temperature. These additives would be active in the dense phase of the FCC regenerator, being deactivated at oxygen concentrations higher than 2%, but they would be regenerated in the FCC reactor. A. Uzcátegui is in leave to Laboratorio de cinética y catálisis del Departamento de Química, Facultad de Ciencias, Universidad de los Andes, La Hechicera, Merida, Venezuela.     

Effect of pore size on bitumen hydrocracking over Al2O3-AlPO4 supported Ni-Mo catalysts

A study of co-precipitated aluminum oxide-aluminum phosphate (AAP) materials as supports of Ni-Mo heavy oil upgrading catalysts has been completed. Results of both short duration (8 h) and longer duration (up to 200 h) experiments at conditions relevant to the commercial H-Oil process are reported and compared with a commercial NiMo/Al₂O₃ catalyst. The initial activity of the Ni-Mo/AAP catalysts correlates with the catalyst average pore diameter which is determined by the P content of the AAP support. An optimum pore diameter of about 20 run exists for HDM whereas for HDS a pore diameter < 10 nm is desirable. After 100 h operation the HDM conversion of the best Ni-Mo/AAP catalyst was approximately 10 percentage points greater than for the commercial catalyst. The HDS and CCR conversions were comparable over the two catalysts. The difference in performance between the catalysts is attributed primarily to the smaller pore size of the Al₂O₃ support compared to the AAP support. The amount of coke deposited on the Ni-Mo/AAP catalyst was less than that on the commercial catalyst, presumably due to differences in pitch conversion levels.     

Deep hydrodesulphurization and hydrogenation of diesel fuels on alumina-supported and bulk molybdenum carbide catalysts

Deep hydrodesulphurization (HDS) of diesel fuels has been carried out on P (Ni)-promoted or non-promoted Mo₂C-supported γ-Al₂O₃ and bulk Mo₂C under standard industrial conditions (613 K, 3 MPa). The effect of the promoter was investigated for different feedstocks on HDS and hydrogenation (HYD) with very low levels of sulfur. The temperature effect was also followed. The HDS conversion indicates that phosphorus promoted alumina supported carbide catalysts are as active as a commercial Co-Mo/Al₂O₃ catalyst for low levels of sulfur in the feed. Furthermore, the refractory compounds such as 4,6-dimethyldibenzothiophene are only transformed on molybdenum carbide catalyst in industrial conditions for hydrotreated gas oils. With gas oils with less than 50 wt ppm in sulfur, phosphorus promoted molybdenum carbide catalysts become more active than commercial catalysts for the HYD of the aromatic compounds and the HDS or the HDN of the feedstock.     

Methane partial oxidation to synthesis gas over bimetallic cobalt/tungsten carbide catalysts and integration with a Mn substituted hexaaluminate combustion catalyst

Co_0.2W_0.8C_x and supported Co_0.2W_0.8C_x catalysts are shown to be active for the partial oxidation of methane to synthesis gas. The catalyst stability is improved by operating at elevated pressure, or in the presence of excess methane. At atmospheric pressure the Co_0.2W_0.8C_x catalysts deactivate by oxidation, as seen by X-ray diffraction. Manganese substituted hexaaluminate catalysts with different Mn contents have been tested as catalysts for the total combustion of methane. In particular BaMn₂Al₁₀O₁₉ is active and stable for the combustion reaction. The temperature rise observed in the reactor was up to 300 K, depending on the reaction conditions, and complete conversion of oxygen in the feed was achieved. A process for stabilising the carbide catalysts is demonstrated, combining the manganese substituted hexaaluminate total oxidation catalyst, in series before the carbide reforming catalyst: this process leads to stable operation, with no carbon formation in the reactor and no carbide catalyst oxidation observed.     

Toughening of wood particle composites—Effects of sisal fibers

Sisal fibers were added to wood particle composites to enhance their toughness. The selected matrix was a commercial styrene diluted unsaturated polyester thermoset resin. Fracture tests were carried out using single‐edge notched beam geometries. Stiffness, strength, critical stress intensity factor K_IQ, and work of fracture W_f of notched specimens were determined. The incorporation of sisal fibers into wood particle composites significantly changed the fracture mode of the resulting hybrid composite. For the neat matrix and the wood particle composites, once the maximum load was reached, the crack propagated in a catastrophic way. For hybrid composites, fiber bridging and pull‐out were the mechanisms causing increased crack growth resistance. Addition of a 7% wt of sisal fibers almost doubled the K_IQ value of a composite containing 12% wt of woodflour. Moreover, the W_f increased almost 10‐fold, for the same sample. In general, the two composite toughness parameters K_IQ and W_f increased when the fraction of sisal fibers was increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1982–1987, 2006     

Effect of Different Frying Methods on the Total <Emphasis Type="Italic">trans</Emphasis> Fatty Acid Content and Oxidative Stability of Oils

The main objective of this study was to determine the effect of different frying oils and frying methods on the formation of trans fatty acids and the oxidative stability of oils. Sunflower, canola and commercial frying oils, the most commonly used oils for frying potatoes in the fast food industry, were used as the frying medium. The value for total polar compounds was highest when commercial frying oil was used in the microwave oven (22.5 ± 1.1). The peroxide value, as an indicator of oil oxidation, was lowest for microwave oven frying (2.53 ± 0.03). The K₂₃₂ and K₂₇₀ values were 0.41 ± 0.04 and 0.18 ± 0.02, respectively, for commercial frying oil in the microwave oven. The lowest free fatty acid content was recorded for the commercial frying oil used in the deep‐fat fryer at 190 °C. The highest iodine value was measured for sunflower oil used in the deep‐fat fryer (148.14 ± 0.07), indicating a greater degree of unsaturation. The lowest trans fatty acid value was recorded for sunflower oil in the microwave oven (0.17 ± 0.05), with a higher overall amount of total trans fatty acids observed for oils after frying in the electrical deep‐fat fryer compared to the microwave. Sunflower oil was favourable for both frying methods in terms of the trans fatty acid content.     

Catalytic Oxidation of CO over Nanocrystalline La1–xCexNiO3 Perovskite‐Type Oxides

Nanocrystalline La_1–xCe_xNiO₃ (x = 0.1, 0.3, 0.5, 0.7, 0.9) perovskite‐type oxide catalysts prepared by the Pechini method were employed in catalytic CO oxidation and the effect of substitution of La by Ce on CO conversion was evaluated. The results indicated the remarkable effect of La substitution with Ce on the catalytic performance at low temperatures. The reaction temperature had a significant influence on the stability of the catalysts. The La_0.1Ce_0.9NiO₃ sample exhibited the highest activity among the prepared catalysts in CO oxidation reaction. In addition, the influence of different parameters including pretreatment condition, feed ratio, and gas hourly space velocity (GHSV) on the catalytic performance was examined. The optimum catalyst proved high stability under severe reaction conditions in the presence of water vapor and CO₂ in the feed stream.     

Ternary Pt<Subscript>45</Subscript>Ru<Subscript>45</Subscript>M<Subscript>10</Subscript>/C (M=Mn,Mo and W) catalysts for methanol and ethanol electro-oxidation

Ternary Pt₄₅Ru₄₅Mn₁₀/C, Pt₄₅Ru₄₅Mo₁₀/C and Pt₄₅Ru₄₅W₁₀/C catalysts were synthesized and physical and electrochemical properties were characterized. Particle sizes of the catalysts were determined by X-ray diffraction to be 3.9, 4.8 and 4.6 nm for the Mn, Mo and W incorporated catalysts, respectively. Electrochemically active surface areas were calculated from CO stripping results, which were 17.7, 17.2 and 15.7 m²/g _catal for the Pt₄₅Ru₄₅Mn₁₀/C, Pt₄₅Ru₄₅Mo₁₀/C and Pt₄₅Ru₄₅W₁₀/C catalysts, respectively. In methanol electro-oxidation, the Pt₄₅Ru₄₅W₁₀/C catalyst showed highest mass and specific activities of 2.78 A/g _cat. and 177 mA/m², respectively, which were 22 and 100% higher than those of commercial PtRu/C. In the case of ethanol electro-oxidation, the Pt₄₅Ru₄₅Mo₁₀/C catalyst exhibited highest mass and specific activities of 4.8 A/g _catal and 280 mA/m², respectively. Specific activity of the Pt₄₅Ru₄₅Mo₁₀/C catalyst was 56% higher than that of the commercial PtRu/C.     

Experimental Study on Catalytic Biomass Gasification in a Bubbling Fluidized Bed

A bubbling fluidized‐bed gasification system was selected for catalytic steam gasification of rice straw with four Ni‐based catalysts, i.e., Ni/Al₂O₃, Ni/CeO₂, Ni/MnO₂, and Ni/MgO. The effect of temperature, steam/biomass ratio (S/B), and catalyst/biomass ratio (C/B) on the gas composition, char conversion, and hydrogen yield was evaluated. It was found that higher temperature and S/B promote hydrogen production and char conversion. The results also demonstrated that the catalytic activity of Ni/Al₂O₃ under different S/B values is better than those of the other catalysts. Regarding the catalyst activity, all four catalysts exhibited good performance in terms of tar removal and carbon conversion. However, the performance of Ni/Al₂O₃ was superior to that of the other three catalysts.     

Low-temperature catalytic conversion of lignite: 3. Tar reforming using the supported potassium carbonate

Alumina-supported K₂CO₃–LaMn_0.8Cu_0.2O₃ was investigated for the catalytic conversion of tar, produced from lignite, into syngas under inert and steam-reforming conditions. A double-bubble fluidized bed reactor system, equipped with a micro gas chromatograph and a collecting system to analyze permanent gases and condensable species, was developed to screen the catalytic conversion of tar components below 700 °C. The redox properties of catalysts, estimated by hydrogen temperature programmed reduction analyses, were correlated with their catalytic performance in tar conversion. The synthesized catalyst effectively converted tars into hydrogen-rich syngas and also improved tar reforming by inhibiting coke deposition.     

Advanced De-SOx catalyst: Mixed solid solution spinels with cerium oxide

Mixed solid solution spinels impregnated with cerium, Ce/MgO·MgAl_2-xM_xO₄ (M=Fe, V, Cr, x≤0.4), were studied for controlling the SO_x emission from the fluid catalytic cracking (FCC) regenerator. An insufficient sulfur release problem inherent to the earlier De---SO_x catalyst, Ce/MgO·MgAl₂O₄, was effectively overcome by incorporating a transition metal into the spinel structure. Studies of the SO_x pick-up, temperature profile for the sulfate reduction, the thermal analysis, and the De---SO_x cycle test in the batch as well as the automated continuous reactor are discussed to define the role of a transition metal in the mixed spinels for the De---SO_x performance. These advanced De---SO_x catalysts have led to a commercial success for the simultaneous control of SO_x and NO_x emissions from the FCC regenerator.     

Preparation of Highly Active Nickel Catalysts Supported on Mesoporous Nanocrystalline γ‐Al2O3 for Methane Autothermal Reforming

Autothermal reforming (ATR) of methane was carried out over nanocrystalline Al₂O₃‐supported Ni catalysts with various Ni loadings. Mesoporous nanocrystalline γ‐Al₂O₃ powder with high specific surface area was prepared by the sol‐gel method and employed as support for the nickel catalysts. The prepared samples were characterized by X‐ray diffraction, Brunauer‐Emmett‐Teller, temperature‐programmed reduction, temperature‐programmed hydrogenation, and scanning electron microscopy techniques. It is demonstrated that the methane conversion increased with increasing in Ni content and that the catalyst with 25 wt % Ni exhibited the highest activity and a stable catalytic performance in the ATR process, with a low degree of carbon formation. Furthermore, the effects of the reaction temperature, the calcination temperature, the steam/CH₄ and O₂/CH₄ ratios, and the gas hourly space velocity on the catalytic performance of the 25 % Ni/Al₂O₃ catalyst were investigated.     

A model on an entrained bed-bubbling bed process for CO2 capture from flue gas

A simplified model has been developed to investigate effects of important operating parameters on performance of an entrained-bed absorber and bubbling-bed regenerator system collecting CO₂ from flue gas. The particle population balance was considered together with chemical reaction to determine the extent of conversion in both absorber and regenerator. The calculated CO₂ capture efficiency agreed with the measured value reasonably well. Effects of absorber parameters — temperature, gas velocity, static bed height, moisture content of feed gas on CO₂ capture efficiency — have been investigated in a laboratory scale process. The CO₂ capture efficiency decreased as temperature or gas velocity increased. However, it increased with static bed height or moisture concentration. The CO₂ capture efficiency was exponentially proportional to each parameter. Based on the absolute value of exponent of the parameter, the effect of gas velocity, static bed height, and moisture content was one-half, one-third, and one-fourth as strong as that of temperature, respectively.     

Pyrolysis of microalgae biomass over carbonate catalysts

Microalgae are seen as potential biomass to be used in a biorefinery concept. Several technologies can be used to convert microalgal biomass, but pyrolysis is viewed as a unique pathway to obtain valuable chemicals distributed in three phases: liquid (bio-oil), gas (bio-gas) and solid (bio-char). The liquid phase, bio-oil, usually presents higher heating value than raw biomass, but acidity and oxygen content are major drawbacks. In situ catalyzed pyrolysis can help to decrease the oxygen content and acidity of pyrolytic bio-oils. Chlorella vulgaris and Scenedesmus obliquus were pyrolyzed in a fixed-bed reactor using commercial carbonate catalysts (Li₂CO₃, Na₂CO₃, K₂CO₃, MgCO₃, SrCO₃ and MnCO₃). The catalysis pyrolysis temperature (375 °C) was selected from thermal degradation profiles obtained using thermogravimetry under nitrogen flow and corresponds to the maximum degradation rate for both microalgae. In spite of similar volatile and fixed carbon contents, microalgae performed differentially during pyrolysis mainly due to the different contents of carbohydrates, oils and proteins. Chlorella vulgaris and Scenedesmus obliquus showed bio-oil yield in the range 26–38 and 28–50 wt%, respectively. Only sodium carbonate was able to decrease the bio-char yield, confirming that carbonate catalysts prompt simultaneously gasification and carbonization reactions. Fourier transform infrared spectra of produced bio-oils showed a net decrease of acidity, associated with carbonyl species when carbonate catalysts were used. Bio-char morphology, for both microalgae, showed evidence of melting and resolidification of cell structures, which might be due to the lower melting points of the pyrolysis products obtained from proteins and lipids. © 2020 Society of Chemical Industry     

The effect of CO<Subscript>2</Subscript> or steam partial pressure in the regeneration of solid sorbents on the CO<Subscript>2</Subscript> capture efficiency in the two-interconnected bubbling fluidized-beds system

The effect of CO₂ or steam partial pressure in the regeneration of CO₂ solid sorbents was studied in the two-interconnected bubbling fluidized-beds system. Potassium-based dry solid sorbents, which consisted of 35 wt% K₂CO₃ for CO₂ sorption and 65 wt% supporters for mechanical strength, were used. To investigate the CO₂ capture efficiency of the regenerated sorbent after the saturated sorbent was regenerated according to the CO₂ or steam partial pressure in the regeneration, the mole percentage of CO₂ in the regeneration gas was varied from 0 to 50 vol% with N₂ balance and that of steam was varied from 0 to 100 vol% with N₂ balance, respectively. The CO₂ capture efficiency for each experimental condition was investigated for one hour steady-state operation with continuous solid circulation between a carbonator and a regenerator. The CO₂ capture efficiency decreased as the partial pressure of CO₂ in the fluidization gas of the regenerator increased, while it increased as that of steam increased. When 100 vol% of steam was used as the fluidization gas of the regenerator, the CO₂ capture efficiency reached up to 97% and the recovered CO₂ concentration in the regenerator was around 95 vol%. Those results were verified during 10-hour continuous experiment.     

Cu/Ni‐Loaded CeO2‐ZrO2 Catalyst for the Water‐Gas Shift Reaction: Effects of Loaded Metals and CeO2 Addition

Two different types of metals (Cu and Ni) and the effect of CeO₂ addition to produce a CeO₂‐ZrO₂ co‐supporter were investigated through the water‐gas shift (WGS) reaction. It was found that the WGS activity could be enhanced with CeO₂ addition. At relatively high temperature, Ni‐loaded catalysts exhibited higher CO conversion while Cu‐loaded catalysts demonstrated better performance at low temperatures. The stability and yield of the CO₂ and H₂ products of the Cu catalysts were higher than those of the Ni catalysts. These results may be caused by an irreversible adsorption of CO on Ni and the reverse WGS reaction occurring on the Ni catalysts. In situ diffuse‐reflection infrared Fourier transform spectroscopy data suggests that the WGS mechanism likely proceeded via formate species.     

Oxidation of Benzene to Maleic Anhydride in a Fluidized Bed Reactor

In this project, the selective oxidation of benzene to maleic anhydride (MAN) was studied. Gas phase catalytic oxidation of benzene was carried out in a laboratory scale fluidized bed reactor on six different types of catalysts, which have different compositions. Effects of temperature, flow rates of benzene and air and catalyst type on the reaction selectivity were investigated at atmospheric pressure. The experiments were performed over a temperature range of 325 to 400 °C, a space‐time (W/F_A0) range from 11.28 × 10⁵ to 31.9 × 10⁵ g s mol^–1, and benzene/air mole ratio changes between 0.0109 and 0.0477. It was seen that conversion of benzene to MAN increased with increasing temperature for the catalysts supported by silica gel, aluminum oxide and titanium oxide. From the results it was found that conversion increased with increasing flow rate of air. When the comparison of the catalysts were made, it could be said that catalysts supported by silica gel showed higher MAN conversions. So it can be concluded that catalysts supported by silica gel were more suitable catalysts for benzene oxidation to MAN in a fluidized bed reactor.     

Etherification of n-butanol to di-n-butyl ether over H3PMo12 − xWxO40 (x = 0, 3, 6, 9, 12) Keggin and H6P2Mo18 − xWxO62 (x = 0, 3, 9, 15, 18) Wells–Dawson heteropolyacid catalysts

Etherification of n-butanol to di-n-butyl ether was carried out over H₃PMo_12 − xW_xO₄₀ (x = 0, 3, 6, 9, 12) Keggin and H₆P₂Mo_18 − xW_xO₆₂ (x = 0, 3, 9, 15, 18) Wells–Dawson heteropolyacid (HPA) catalysts. Acid strength of H₃PMo_12 − xW_xO₄₀ Keggin and H₆P₂Mo_18 − xW_xO₆₂ Wells–Dawson HPA catalysts was determined by NH₃-TPD (temperature-programmed desorption) measurements. The correlations between desorption peak temperature (acid strength) of the HPA catalysts and catalytic activity revealed that conversion of n-butanol and yield for di-n-butyl ether increased with increasing acid strength of the catalysts, regardless of the identity of HPA catalysts (without HPA structural sensitivity).     

Catalytic conversion of cellulose into ethylene glycol over supported carbide catalysts

In the current paper we present a combined catalytic and surface science studies to evaluate the utilization of carbide catalysts for the conversion of cellulose to polyols, especially to ethylene glycol (EG). Based on catalytic studies over a W₂C catalyst, the EG yield has been optimized by varying H₂ pressure, reaction temperature and time. The catalytic performance has been compared for several types of supported catalysts, including tungsten carbides, molybdenum carbides and platinum on different supports. Among all the catalysts, tungsten carbide supported on activated carbon, W₂C/AC, shows the highest EG yield, which is further enhanced to 61% with the promotion of Ni. The corresponding surface science studies indicate that the enhanced EG yield is at least partially due to a weaker bonding between EG and Ni-promoted tungsten carbide surface.     

Photocatalytic conversion of NO using TiO2–NH3 catalysts in ambient air environment

Photocatalytic conversion of nitric oxide (NO) in ambient air was studied in a continuous-flow photoreactor system at room temperature using different TiO₂ catalysts prepared with different titanium precursors of Ti(SO₄)₂, TiOSO₄, and Ti(O-Bu)₄ by either a moderate-temperature hydrothermal process or a hydrothermal reflux process. The physicochemical properties of the prepared catalysts were characterized by XRD, BET, FTIR, and SEM. Analytical results showed that the crystallinity, morphology, nitrogen adsorption–desorption isotherms, specific surface area, and pore size distribution of catalysts were significantly affected by the precursors and hydrothermal processes, but the crystal structure and crystal size of catalysts were not significantly influenced. The NO conversion experiments demonstrated that the TiO₂ catalysts prepared by the moderate-temperature hydrothermal process without ammonia pretreatment could effectively reduce NO to different low levels, in which the catalysts with longer aging time of more than 12 h performed better than the catalysts with shorter aging time. However, it was found that the NO₂ concentration in outlet gas was gradually increased with extension of an experimental period. Two TiO₂ catalysts (TOSO-NH₃ and TOB-NH₃) prepared by the hydrothermal reflux process with ammonia pretreatment demonstrated a very good performance in NO conversion and also maintained a low level of NO₂ concentration in outlet gas. This study indicated that using the TiO₂ catalysts modified with ammonia pretreatment in photocatalytic reaction could provide a good approach to effectively eliminate the accumulation of NO₂ product from NO oxidation in the system and to achieve a sustainable process, which may be applicable for NO elimination in ambient air environment.