The influence of mordenite characteristics in mordenite mixed with alumina on cracking of vacuum gas oil

Catalytic cracking of vacuum gas oil has been investigated at 500 ‡C over mixed catalysts in a micro-activity tester. The catalyst consists of mordenite treated by either HCl/steam or HF and alumina prepared at pH of 9.5 or 7.8. The catalysts retaining mordenite in which SiO₂/Al₂O₃ weight ratio ranged from 15 to 20 show the max-imum activity and selectivity for gasoline. Both the activity and selectivity for gasoline seem to depend strongly on both acid strength of mixed catalysts and mesopore volume of the mordenite. It is found, however, that the selectivity of kerosene+diesel in liquid product as well as the yield of aromatics in gasoline are influenced more by mesopore volume of mordenite than by acid properties of mordenite in the catalyst of mordenite/alumina.     

Facile synthesis of Y-doped graphitic carbon nitride with enhanced photocatalytic performance

Yttrium-doped graphitic carbon nitride (Y/g-C₃N₄) catalysts were prepared via a facile pyrolysis method with urea used as a precursor and yttrium nitrate as the Y source. Characterization results show that an appropriate doping ratio of Y can be embedded into in-planes of g-C₃N₄. The Y/g-C₃N₄ catalysts are characterized by hierarchical porosity, large specific surface area, and large pore volume. Introduction of Y species effectively extends the spectral response of g-C₃N₄ from ultraviolet to visible region and decelerates the recombination of photogenerated electrons and holes. Because of these properties, the Y/g-C₃N₄ catalysts show an enhanced photocatalytic performance in rhodamine B degradation under visible light.     

Catalysis on cobalt-containing sodium zeolite Y

A number of cobalt-containing sodium zeolite Y catalysts were prepared by (i) impregnation using a dilute solution of CO₂(CO)₈ in pentane and (ii) by ion-exchange using dilute aqueous cobalt nitrate followed by further impregnation using aqueous NaOH. Different cobaltimpregnated catalysts could be prepared depending on the method of post-treatment, and all samples were characterised for activity in the hydrogenation and ethylation of benzene. In both series of samples good reduction catalysts were obtained, while only the hydroxide impregnated series exhibited any alkylation activity.     

Properties of zeolite Y in various forms and utilization as catalysts or supports for cerium oxide in ethanol oxidation

Zeolite Y in sodium form (NaY) was synthesized using silica source from rice husk, transformed to ammonium form (NH₄Y), and calcined to convert to proton form (HY). The direct conversion of NH₄Y to HY resulted in loss of the zeolite crystallinity and lower surface area. Thus, the NH₄Y was further used in the preparation of cerium (Ce) catalysts. The NH₄Y was also treated with a basic solution in an attempt to generate mesopores but only site defects were likely formed. The supported Ce catalysts with good Ce dispersion were prepared by wetness impregnation of Ce precursor solution on NaY, NH₄Y, and base-treated NH₄Y. Upon calcination, the generated catalysts were notated as Ce/NaY, Ce/HY, and Ce/YB. In catalytic testing on ethanol oxidation at varying temperature in a continuous laboratory-scale fixed-bed reactor, all the zeolites gave low ethanol conversion at 100–300 °C. The catalytic activity significantly improved with the presence of Ce. The Ce/YB showed the higher ethanol conversion and CO₂ yield than Ce/NaY and Ce/HY probably because of the presence of more local site defects on the zeolite.     

Preparation and properties of nickel preimpregnated CYCTS supports for hydrotreating coker gas oil

The citric treated Y zeolite composite titania–silica (CYCTS) supports and nickel (Ni) preimpregnated CYCTS supports (NiCm, m is the Ni content by weight) were prepared by sol–gel combined with CO₂ supercritical drying method. Effects of the Ni concentration on the structure, physical and chemical properties were examined using BET, H₂-TPR, XRD, and UV–vis DRS. Hydrotreating catalysts were prepared with CYCTS or NiCm as supports and Ni–tungsten (W) as metal components. The hydrotreating performances of the catalysts were examined with Liaohe coker gas oil (CGO) as feedstock. The results indicated that the Ni preimpregnated supports had suitable mesoporous structure and surface area, and the TiO₂ particles size become smaller. At the same time, the Ni preimpregnation method could promote the formation of highly active nickel species in octahedral sites and improved the dispersivity of WO₃. The hydrotreating performances of the Ni–W catalysts using the NiCm supports for Liaohe CGO had been remarkably promoted, especially the hydrodenitrogenation (HDN) performance.     

Catalytic Activity of Y Zeolite Supported CeO2 Catalysts for Deep Oxidation of 1, 2-Dichloroethane (DCE)

Three Y zeolites supported CeO₂ catalysts (CeO₂/USY, CeO₂/HY, CeO₂/SSY) were prepared and used for deep oxidation of 1,2-dichloroethane (DCE) in low concentration (about 1,000 ppm). The catalysts were characterized by XRD, N₂ adsorption/desorption and H₂-TPR. The results showed that the catalytic activity of the supported CeO₂ catalysts was much higher than that of Y zeolites, in particular, CeO₂/USY exhibited the highest activity, T_98% values of DCE was about 270 °C. And the catalytic activity was strongly related to the interaction between CeO₂ and Y zeolites.     

Hydrocracking of heavy oil using zeolites Y/Al-SBA-15 composites as catalyst supports

A series of Y/Al-SBA-15 composites were prepared by a two-step synthesis procedure in mild acidic medium. The materials were characterized by powder X-ray diffraction (XRD), N₂ sorption isotherms and TEM techniques. Catalytic cracking of cumene and 1,3,5-tri-isopropylbenzene was carried out as the probing reactions on these composites. The XRD results showed that these materials are composites of Al-SBA-15 and Y zeolite. N₂ sorption isotherms and TEM displayed that these composites were abundant in micropores and mesopores. At the same time, the mesopores may communicate with the␣micropores in some domains, which may result in the high catalytic activities of Y/Al-SBA-15 composites for the␣cracking of both small-molecule (cumene) and large-molecule (1,3,5-tri-isopropylbenzene) hydrocarbons. The existence of mesopores may also make the acid sites easily accessible for reactants. Catalysts of W–Ni supported on Y/Al-SBA-15 and modified Y zeolites with mesopores were prepared by impregnation method, and the hydrocracking of heavy oil was performed on these catalysts. The catalyst using zeolite Y/mesoporous Al-SBA-15 composites as support gave higher yield of diesel compared to the catalysts using modified zeolite Y as support. In addition, the higher aromatics potential of heavy naphtha and the significantly lower BMCI (U.S. Bureau of Correlation Index) of tail oil revealed Y/Al-SBA-15 composite catalyst possessed integrated performance in the hydrocracking of heavy oil. These results proved that the combination of Y zeolites and mesoporous Al-SBA-15 plays a great role in improving the performance of catalysts for hydrocracking heavy oils.     

Catalysis over bimetallic zeolites: Influence of copper on the catalytic behaviour of nickel in sodium and hydrogen Y zeolites

The catalytic activity of a range of bimetallic nickel/copper zeolite catalysts prepared from NaY and NH₄Y as starting materials has been investigated; the reactions chosen were alkylation of toluene with methanol and the hydrogenation of benzene. The samples prepared from NH₄Y did not reduce benzene although they contained metallic nickel; this is attributed to nickel migration and agglomeration. All the catalysts were active in alkylation and there is evidence that a Cu:Ni ratio of 3:2 favours the formation of intrazeolitic clusters and confers increased acidity on the catalysts.     

Activity tests of various catalysts for hydrocracking of coal by means of high pressure differential thermal analysis

The activities of fourteen kinds of catalysts for the hydrocracking of Taiheiyo coal were examined by a high pressure differential thermal analytical method. Exothermic peaks appeared at low temperatures (420–430°C) when MoO₃TiO₂, NiY zeolite and CoY zeolite were used as catalysts, indicating that these catalysts are highly active compared with other catalysts including MoO₃CoOAl₂O₃. The qualitative analysis of gas and liquid products revealed that MoO₃TiO₂ and CoY are good catalysts for the liquefaction reaction. The hydrogenation ability of the catalyst is concluded to be more important than its acidic property.     

Catalytic curing agents

Summary The BY₃ (Y=F, Cl, Br, I, NCS, H) adducts with the tertiary amines N,N-dimethyl-n-octylamine (DMOA) and N,N-dimethyl-benzylamine (DMOA) were prepared, characterized and tested as catalytic curing agents for epoxy (DGEBA) and epoxy-isocyanate resins.Evaluation of the storage stability and reactivity of the resins showed that the BBr₃, BCl₃, BI₃ and B(NCS)₃ adducts were good latent catalysts. No correlation could be found between the temperature of decomposition of the catalysts in an inert atmophere or in contact with air and the catalytic properties. Consequently the reaction medium was involved in the activation process.     

Nanosized HY zeolite-alumina composite support for hydrodesulfurization of FCC diesel

A series of hydrodesulfurization (HDS) NiMo catalysts supported on Al₂O₃-NY (denoted as ANY) composites with various amounts of nanosized H-type Y zeolite (denoted as NY) were prepared. The samples were characterized by XRD, BET, TPD, TPR, HRTEM, and FT-IR spectroscopy of pyridine adsorption. The characterization results showed that, compared with NiMo/Al₂O₃, the addition of NY reduced the Metal-support interaction and made the MoS₂ stacking degree higher, slabs shorter and dispersion of edge and corner Mo atoms bigger. The addition of NY also enhanced the overall acidity and the ratio of Brönsted acid to Lewis acid of these catalysts. The fluidized catalytic cracking (FCC) diesel HDS activity was increased with the addition of NY in these catalysts compared with NiMo/Al₂O₃ catalysts. The optimal NY content was found to be 20 wt% in ANY composite support. The highest HDS activity of NiMo/ANY20 was attributed to the synergy of hydrogenation activity, acid amount and textural properties.     

Catalytic decomposition of N2O over supported rhodium catalysts: high activities of Rh/USY and Rh/Al2O3 and the effect of Rh precursors

The catalytic decomposition of nitrous oxide to nitrogen and oxygen has been studied over Al₂O₃-supported and zeolite-supported Rh catalysts. The activities of Rh/Al₂O₃ and Rh/USY (ultrastable Y zeolite) catalysts prepared from Rh(NO₃)₃ were higher than those of Rh/ZSM-5 and Rh/ZnO reported in the literature, while the activity of a Rh/Al₂O₃ catalyst prepared from RhCl₃ was suppressed severely in spite of the high H/Rh and CO/Rh values. The catalytic activity of N₂O decomposition was sensitive not only to the Rh dispersion but also to the preparation variables such as the Rh precursors and the supports used. This revised version was published online in July 2006 with corrections to the Cover Date.     

Aldol condensation in gaseous phase by zeolite catalysts

Vapour-phase reactions of, in situ, prepared formaldehyde with methyl propionate were studied using X, Y and ZSM-5 zeolite catalysts. Base properties of these zeolites were enhanced by KOH or NaN₃ treatment. The niobium and molybdenum ZSM-5 zeolite supported oxides were also tested for their catalytic activity. The results are discussed in terms of an ability of zeolite catalysts to synthesize methyl methacrylate.     

Methanol synthesis pathway over Cu/ZrO2 catalysts: a time‐resolved DRIFT 13C‐labelling experiment

X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) have been used to characterize a series of Cu/Ce/Al₂O₃ catalysts. Catalysts were prepared by incipient wetness impregnation using metal nitrate and alkoxide precursors. Catalyst loadings were held constant at 12 wt% CuO and 5.1 wt% CeO₂. Mixed oxide catalysts were prepared by impregnation of cerium first, followed by copper. The information obtained from surface and bulk characterization has been correlated with CO and CH₄ oxidation activity of the catalysts. Cu/Al₂O₃ catalysts prepared using Cu(II) nitrate (CuN) and Cu(II) ethoxide (CuA) precursors consist of a mixture of copper surface phase and crystalline CuO. The CuA catalyst shows higher dispersion, less crystalline CuO phase, and lower oxidation activity for CO and CH₄ than the CuN catalyst. For Cu/Ce/Al₂O₃ catalysts, Ce has little effect on the dispersion and crystallinity of the copper species. However, Cu impregnation decreases the Ce dispersion and increases the amount of crystalline CeO₂ present in the catalysts, particularly in Ce modified alumina prepared using cerium alkoxide precursor (CeA). Cerium addition dramatically increases the CO oxidation activity, however, it has little effect on CH₄ oxidation. This revised version was published online in July 2006 with corrections to the Cover Date.     

Hydroisomerization of n-Heptane Over Cr Promoted Pt-bearing H3PW12O40 Catalysts Supported on Dealuminated USY Zeolite

The Pt-bearing H₃PW₁₂O₄₀ (PW) catalysts, promoted by Cr or La, supported on dealuminated USY zeolite were prepared and their catalytic activities were evaluated in the hydroisomerization of n-heptane with an atmospheric fixed-bed reactor. The catalysts were characterized by XRD, BET, IR and H₂-chemisorption. The results showed that the dealuminated USY support retained the Y zeolite structure and the PW well kept its Keggin structure in the supported PW catalysts and the doping of Cr or La into the catalysts enhanced the dispersion of Pt on the catalyst surface. The Pt-bearing PW catalysts doped with Cr or La, especially Cr, exhibited much higher catalytic activity and selectivity than the catalysts without dopants. Both the conversion and selectivity were discussed in relation with physicochemical properties of catalysts.     

Effect of EDTA on hydrotreating activity of CoMo/γ-Al2O3 catalyst

γ-Al₂O₃ supported Co (0–4.5 wt%) Mo (9.0 wt%) sulfide catalysts were prepared in the presence and the absence of ethylenediaminetetraacetic acid (EDTA). The hydrodenitrogenation (HDN) activity of these catalysts was studied in the model reaction of 2,6-dimethylaniline (DMA) at 300 °C under 4 MPa. The CoMo/Al₂O₃ catalysts prepared with the EDTA showed higher HDN of DMA than those prepared without EDTA. The maximum of 36% increase in rate constant of HDN of DMA was observed over the catalyst with 3% Co prepared using EDTA. The FT-IR spectroscopy of adsorbed CO on CoMo catalysts showed that EDTA addition promoted the formation of catalytically active “CoMoS” phase as evidenced from increases in intensity of band at 2070 cm⁻¹, which is maximum for 3% Co loaded catalysts. The HDN and hydrodesulfurization (HDS) activity of 3% Co loaded catalyst prepared using EDTA was tested and compared with those catalyst prepared without EDTA in a trickle bed reactor using heavy gas oil derived from Athabasca bitumen in the temperature range 370–400 °C and 8.8 MPa. Improved HDN and HDS conversion of heavy gas oil was obtained for the catalyst prepared with EDTA.     

Methanol Decomposition to Synthesis Gas Over Supported Pd Catalysts Prepared from Hydrotalcite Precursors

Supported Pd catalysts were prepared by solid-phase crystallization (spc) starting from MgAl hydrotalcite anionic clay minerals as the precursors, and were tested for the methanol decomposition to synthesis gas. The precursors based on [Mg₆Al₂(OH)₁₆CO₃ ^2-] · 4H₂O were prepared by coprecipitation from raw materials containing Pd²⁺, Mg²⁺ and Al³⁺ ions as the components of hydrotalcite. The precursors were thermally decomposed and reduced to afford supported Pd catalysts on MgAl mixed oxide. Pd-supported catalysts as a reference were also prepared by the impregnation (imp) method. The spc-Pd catalysts thus prepared afforded highly dispersed Pd metal particles and showed higher activity as well as lower activation energy than the imp-Pd catalysts. When the precursor was prepared under mild conditions, finer particles of Pd metal were formed over the catalyst, resulting in a high activity. In the case of spc-Pd catalysts, carbon monoxide adsorbed on Pd easily desorbed, compared with imp-Pd catalysts. It is likely that the high activity is due to the highly dispersed and stable Pd metal particles and the easy desorption of carbon monoxide.     

Promoted Fe2O3‐Al2O3‐CuO Chromium‐Free Catalysts for High‐Temperature Water‐Gas Shift Reaction

Promoted Fe₂O₃‐Al₂O₃‐CuO (FAC) chromium‐free catalysts were prepared for high‐temperature water‐gas shift reactions and characterized by X‐ray diffraction (XRD), Brunauer‐Emmett‐Teller method (BET), temperature‐programmed reduction (TPR), and transmission electron microscopy (TEM) techniques. The catalytic results revealed that among the investigated promoted catalysts with Ce, La, Zn, Y, and Mn as promoters, the Mn‐promoted sample showed higher activity compared to the other promoted catalysts. Increasing the Mn content improved the surface area and catalytic activity. The FAC catalyst promoted with a high Mn content exhibited maximum activity and relatively high stability in high‐temperature water‐gas shift reaction.     

Ring-opening polymerization of ε-caprolactone and l-lactide using organic amino calcium catalyst

Poly (ε-caprolactone) (PCL) and poly (l-lactide) (PLA) were prepared by ring-opening polymerization catalyzed by organic amino calcium catalysts (Ca/PO and Ca/EO) which were prepared by reacting calcium ammoniate Ca(NH₃)₆ with propylene oxide and ethylene oxide, respectively. The catalysts exhibited high activity and the ring-opening polymerization behaved a quasi-living characteristic. Based on the FT-IR spectra and the calcium contents of the catalysts, and based on the ¹H NMR end-group analysis of the low molecular weight PCL prepared using catalysts Ca/PO and Ca/EO, it was proposed that the catalysts have the structure of NH₂-Ca-O-CH(CH₃)₂ and NH₂-Ca-O-CH₂CH₃ for Ca/PO and Ca/EO, respectively. The ring-opening polymerization of CL and LA follows a coordination-insertion mechanism and the active site is the Ca-O bond.     

Production of hydrogen by steam reforming of bio-oil over Ni/Al2O3 catalysts: Effect of addition of promoter and preparation procedure

Catalytic steam reforming of bio-oil was investigated in a fixed bed tubular reactor for production of hydrogen. Two series of nickel/alumina (Ni/Al₂O₃) supported catalysts promoted with ruthenium (Ru) and magnesium (Mg) were prepared. Each catalyst of the first series (Ru–Ni/Al₂O₃) was prepared by co-impregnation of nickel and ruthenium on alumina. They were examined to investigate the effect of adding ruthenium on the performance of the catalysts for hydrogen production. The effect of the temperature, the most effective parameter in the steam reforming of bio-oil, on the activity of the catalysts was also investigated. Each catalyst of the second series (Ni–MgO/Al₂O₃) was prepared by consecutive impregnation using various preparation procedures. They were tested to determine the effect of adding magnesium as well as the effect of the preparation procedure on the outlet gas concentrations. It was shown that in both series, the catalysts were more efficient in hydrogen production as well as carbon conversion than Ni/Al₂O₃ catalysts. The highest hydrogen yield was 85% which was achieved over Ru–Ni/Al₂O₃ at 950 °C. It was also found that the effect of adding a small amount of ruthenium was superior to that of nickel on the yield of hydrogen when the nickel content was equal to or greater than 10.7%.