EQUILIBRIUM STUDIES IN THE SYSTEM FeO-AI2O3,-SiO2*

Equilibrium relationships on the liquidus surface in the system Fe0-Al₂O₃SiO₂ have been established by a modified quenching procedure. The crystal phases which separate from melts heated in iron crucibles are fayalite (2FeO·SO₂), hercynite (FeO·Al₂O₃), tridymite and cristobalite (SiO₂), mullite (3Al₂O₃·2SiO₂), corundum (Al₂O₃), and wastite (approximately FeO). A considerable portion of this system is liquid at 1400°C. Diagrams show the isotherms and the index of refraction of the glasses formed. Two quintuple points have been established in this investigation. One point is at the composition, SiO₂ 42% by weight, Al₂O₃13%, and FeO 45%, and is a eutectic involving the phases fayalite, hercynite, and tridymite at 970°C. ± 200C. The preferred composition of the second quintuple point is 48% of SO₂, 23% of Al₂O₃, and 29% of FeO; it is a peritectic, and the crystal phases are mullite, hercynite, and tridyrnite. Crystallization from this melt without a change in the weight composition calls for the resorption of mullite at a temperature of 1100°C. ±20°C.     

Beneficial effect of adding γ-AlOOH to the γ-Al2O3 washcoat of a PdO catalyst for methane oxidation

The beneficial effect of adding γ-AlOOH to the γ-Al₂O₃ washcoat of a ceramic cordierite (2MgO · 2Al₂O₃ · 5SiO₂) monolith, used to support a PdO catalyst, is reported for methane oxidation in the presence of water at low temperature (<500°C). The mini-monolith (400 cells per square inch (CPI), 1 cm diameter × 2.54 cm length; ~52 cells) was washcoated using a suspension of γ-Al₂O₃ plus boehmite (γ-AlOOH), followed by calcination and then deposition of Pd by wet impregnation. An optimum solid content of 25 wt% in the washcoat suspension was used to obtain a ~25 wt% washcoat on the monolith. The presence of γ-AlOOH enhanced the thermal and mechanical stability of the washcoat, provided that the γ-AlOOH content was <8 wt%. Temperature-programmed methane oxidation (TPO) showed that the addition of γ-AlOOH to the γ-Al₂O₃ washcoat decreased the catalyst activity. However, when H₂O (2 vol% and 5 vol%) was present in the feed gas, the γ-AlOOH improved the catalyst activity and stability. A γ-AlOOH content of ~5 wt% in the washcoat was determined to provide the highest catalyst activity and stability for CH₄ oxidation in the presence of water.     

Deactivation and coke formation on palladium and platinum catalysts in vegetable oil hydrogenation

Deactivation of palladium and platinum catalysts due to coke formation was studied during hydrogenation of methyl esters of sunflower oil. The supported metal catalysts were prepared by impregnating γ-alumina with either palladium or platinum salts, and by impregnating α-alumina with palladium salt. The catalysts were reused for several batch experiments. The Pd/γ-Al₂O₃ catalyst lost more than 50% of its initial activity after four batch experiments, while the other catalysts did not deactivate. Samples of used catalysts were cleaned from remaining oil by repeated extractions with methanol, and the amount of coke formed on the catalysts was studied by temperature-programmed oxidation. The deactivation of the catalyst is a function of both the metal and the support. The amount of coke increased on the Pd/γ-Al₂O₃ catalyst with repeated use, but the amount of coke remained approximately constant for the Pt/γ-Al₂O₃ catalyst. Virtually no coke was detected on the Pd/α-Al₂O₃ catalyst. The formation of coke on Pd/α-Al₂O₃ may be slower than on the Pd/γ-Al₂O₃ owing to the carrier’s smaller surface area and less acidic character. The absence of deactivation for the Pt/γ-Al₂O₃ catalyst may be explained by slower formation of coke precursors on platinum compared to palladium.     

Transesterification of soybean oil to biodiesel using CaO as a solid base catalyst

In this study, transesterification of soybean oil to biodiesel using CaO as a solid base catalyst was studied. The reaction mechanism was proposed and the separate effects of the molar ratio of methanol to oil, reaction temperature, mass ratio of catalyst to oil and water content were investigated. The experimental results showed that a 12:1 molar ratio of methanol to oil, addition of 8% CaO catalyst, 65 °C reaction temperature and 2.03% water content in methanol gave the best results, and the biodiesel yield exceeded 95% at 3 h. The catalyst lifetime was longer than that of calcined K₂CO₃/γ-Al₂O₃ and KF/γ-Al₂O₃ catalysts. CaO maintained sustained activity even after being repeatedly used for 20 cycles and the biodiesel yield at 1.5 h was not affected much in the repeated experiments.     

Transesterification of castor oil assisted by microwave irradiation

Microwave assisted transesterification of castor bean oil was carried out in the presence of methanol or ethanol, using a molar ratio alcohol/castor bean oil of 6:1, and 10% w/w of acidic silica gel or basic alumina (in relation to the oil mass) as catalyst. Under acid catalysis, the reaction occurred with satisfactory yields using H₂SO₄ immobilized in SiO₂, methanol under conventional conditions (60 °C for 3 h) as well as using microwave irradiation for 30 min. The best results were obtained under basic conditions (Al₂O₃/50% KOH) using methanol and conventional (60 °C, stirring, 1 h) or microwave conditions (5 min). In comparison with conventional heating, the catalyzed alcoholysis assisted by microwaves is much faster and leads to higher yields of the desired fatty esters.     

生态化利用油页岩制备白炭黑和氧化铝

利用油页岩为原料,首先采用碱溶-沉淀法制备了白炭黑,降低了油页岩中的SiO₂的含量,具体工艺条件为：NaOH/SiO₂（物质的量）＝4,水/油页岩（质量）＝1,100℃,6 h,粒径≥0.15 mm。然后采用酸浸法,制备了γ-Al₂O₃,降低了油页岩中的Al₂O₃和Fe₂O₃的含量,具体条件为：酸浸液中用NaOH溶液调整到pH＝12.0,过滤分离,再用HCl调整溶液pH＝6.0,使Al₂O₃和Fe₂O₃完全分离。最后得到了含量为71.6％的干酪根,并经FT-IR验证。     

Unusual Activity Enhancement of NO Conversion over Ag/Al2O3 by Using a Mixed NH3/H2 Reductant Under Lean Conditions

Addition of H₂ to a NO/NH₃/O₂/H₂O feed for selective catalytic reduction of nitrogen oxide over Ag/Al₂O₃ catalysts causes an unusual enhancement of activity, e.g., the marginal activity (<10%) of 1 wt% Ag impregnated on γ-Al₂O₃ or mesoporous Al₂O₃ modifications is boosted to nearly 100% over a broad temperature range from 200 to 550°C at a space velocity of 30,000cm³g^?1h^?1). Contrary, silver on SiO₂ or α-Al₂O₃ shows no improvement of activity in the presence of H₂. The effect is tentatively attributed to a higher percentage of intermediary nano-sized Ag clusters on high-surface area Al₂O₃ in the presence of hydrogen. This promotes oxygen activation and hence NO oxidation to reactive intermediate nitrite species. The required dispersion of Ag cannot be stabilized on SiO₂ or α-Al₂O₃.     

A Pd–Fe/α-Al2O3/cordierite monolithic catalyst for CO coupling to oxalate

A novel Pd–Fe/α-Al₂O₃/cordierite monolithic catalyst was prepared for the synthesis of diethyl oxalate from CO and ethyl nitrite. The palladium-based monolithic catalyst with an optimal thickness (15 μm) of Al₂O₃ washcoat showed excellent catalytic activity and selectivity in a continuous flow, fixed-bed microreactor. The physicochemical properties of catalyst were studied by a variety of characterization techniques. Catalytic performances of Pd–Fe/α-Al₂O₃/cordierite monolithic catalysts were dependent on particle size of alumina-sol, thickness of Al₂O₃ washcoat, pore structure, surface acidity of carrier, and distribution of active metal component on the Al₂O₃ washcoat. Under the mild reaction conditions, CO conversion was 32% and the space–time yield of diethyl oxalate was 429 g/(L h). Pd efficiency (DEO(g)/Pd(g)/h) of the monolithic catalyst (274 h⁻¹) was much higher than that of a reference pellet catalyst (46 h⁻¹), probably due to high dispersion of the Pd nanoparticles on the surface of the monolithic catalyst.     

Hydrotreatment of jatropha oil over noble metal catalysts

Jatropha oil is a promising nonedible feedstock for producing renewable diesel. In this work, the hydrotreatment processing of jatropha oil was investigated. Instead of using conventional alumina-supported Co–Mo, Ni–Mo, and Ni–W catalysts that need sulfidation pretreatment, noble metals such as Pd and Ru were chosen. Trials were performed in an isothermal trickle-bed reactor and the reaction conditions were as follows: temperature 603–663?K, weight hourly space velocity (WHSV) 1 to 4/h, pressure 1.5–3?MPa, and H₂/oil ratio 200–800 (v/v). Yield of n-C₁₅ to n-C₁₈ hydrocarbons was maximized (70.3 and 43.8% for Pd/Al₂O₃ and Ru/Al₂O₃, respectively) at the following conditions: T?=?663 K, WHSV?=?2/h, P?=?3?MPa, and H₂/oil ratio?=?600 (v/v). Since Ru favored cracking reactions to a larger extent than Pd, the yield of C₁₅ to C₁₈ hydrocarbons over Ru/Al₂O₃ was lowered. Using simple first-order plots for oil conversion, activation energies for the hydrotreating process over Pd/Al₂O₃ and Ru/Al₂O₃ were found and they were equal to 109 and 121?kJ/mol, correspondingly.     

Co‐processing of Waste Cooking Oil and Light Cycle Oil with NiW/(Pseudoboehmite + SBA‐15) Catalyst

Light cycle oil (LCO) and waste sunflower cooking oil (WSO) were co‐processed with the aim of obtaining more environmentally friendly fuels. Partial hydrogenation of naphthalene was also investigated as a model reaction. Commercial NiW/SiO₂‐Al₂O₃, as a reference catalyst, and NiW/(pseudoboehmite + SBA‐15), as a new research catalyst, were tested. Liquid products were analyzed by simulated distillation, elemental analysis, and FTIR spectroscopy. Elemental analysis indicated higher efficiency of the research catalyst in hydrodesulfurization, hydrodenitrogenation, and hydrodeoxygenation of pure LCO and mixed feedstock containing WSO. Reactions with pure WSO resulted in less sulfur leaching into the product and a lower degree of deoxygenation compared with the commercial catalyst.     

Experimental phase equilibria study and thermodynamic modelling of the PbO-“FeO”-SiO2-ZnO,PbO-“FeO”-SiO2-Al2O3 and PbO-“FeO”-SiO2-MgO systems in equilibrium with metallic Pb and Fe

Phase equilibria of the PbO-“FeO”-SiO₂-ZnO, PbO-“FeO”-SiO₂-Al₂O₃ and PbO-“FeO”-SiO₂-MgO slags with liquid Pb metal, solid or liquid Fe metal and solid oxides (cristobalite and tridymite SiO₂, willemite (Zn,Fe)₂SiO₄, wustite (Fe,Al)O_1+x, spinel (Fe,Al)₃O₄, olivine Fe₂SiO₄, corundum (Al,Fe)₂O₃, mullite Al₆Si₂O₁₃ and pyroxene (Mg,Fe)SiO₃) were investigated at 1125–1670 °C. These conditions correspond to the minimum solubility of PbO in slag in presence of Pb and Fe metals at reducing conditions and represent the limit of lead smelting and slag cleaning process. High-temperature equilibration on silica, corundum or iron foil substrates, followed by quenching and direct measurement of Pb, Fe, Si, Zn, Al and Mg concentrations in the liquid and solid phases with the electron probe X-ray microanalysis (EPMA) was used. Present data can be used to improve the thermodynamic models for all phases in this system.     

Study on Fe–Al2O3 interaction over precipitated iron catalyst for Fischer–Tropsch synthesis

Two model spherical iron catalysts (100Fe/0Al₂O₃ and 100Fe/15Al₂O₃) with free Cu and K promoters were prepared by the combination of co-precipitation and spray drying method for the application of slurry Fischer–Tropsch synthesis (FTS). The effect of Fe–Al₂O₃ interaction on the reduction/carburization behavior in H₂/CO/syngas, surface basicity and the change of phase structure were comparatively studied by means of H₂ or CO temperature-programmed reduction (TPR), CO₂ temperature-programmed desorption (TPD) and Mössbauer effect spectroscopy (MES). The results showed that the catalyst incorporated with Al₂O₃ exhibits a strong Fe–Al₂O₃ interaction, which obviously weakens the surface basicity, stabilizes the FeO phase and inhibits the reduction of iron catalyst in H₂ or syngas. Furthermore, Fe–Al₂O₃ interaction also restrains the carburization of iron catalyst in CO or syngas. In slurry FTS process, it was found that the strong Fe–Al₂O₃ interaction decreases the FTS activity and suppresses the water gas shift (WGS) reaction, but can stabilize the active sites of iron catalyst and improve its run stability. Due to the strong Fe–Al₂O₃ interaction, the weak surface basicity on the catalyst incorporated with Al₂O₃ greatly decreases the selectivity of heavy hydrocarbon products.     

Transesterification of Rapeseed Oil for Synthesizing Biodiesel by K/KOH/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> as Heterogeneous Base Catalyst

The heterogeneous base catalyst, γ-Al₂O₃ loaded with KOH and K (K/KOH/γ-Al₂O₃) was first prepared and used in the transesterification of rapeseed oil with methanol to produce biodiesel. The prepared catalyst was characterized by X-ray diffraction, scanning electron microscopy, Brunauer–Emmett–Teller method, infrared spectroscopy and X-ray photoelectron spectroscopy. It was found that when γ-Al₂O₃ is loaded with KOH and K, the Al–O–K species is produced, resulting in an increase in the catalytic activity. The impacts of catalyst preparation conditions on the catalytic activities of K/KOH/γ-Al₂O₃ were investigated. The results demonstrate that the catalyst K/KOH/γ-Al₂O₃ has high catalytic activity when the added amounts of KOH and K are 20 and 7.5 wt% respectively. The transesterification of rapeseed oil to biodiesel with the prepared heterogeneous base catalyst was optimized. It was found that the yield of biodiesel can reach as high as 84.52% after 1 h reaction at 60°C, with a 9:1 molar ratio of methanol to oil, a catalyst amount of 4 wt%, and a stirring rate of 270 g.     

The role of Fe on PtPd oxidation catalyst prepared by simultaneous and sequential incipient wetnesses

The roles and effects of Fe on the catalytic performance and physicochemical properties of a PtPd diesel oxidation catalyst prepared by three different methods were investigated by CO oxidation reaction, X-ray diffraction, temperature-programmed reduction (TPR), temperature-programmed oxidation, and BET surface area. It was found that the roles of Fe depended strongly on the sequential order of Fe introduction during the preparation of the PtPd catalyst. The Fe/PtPd/Al₂O₃ catalyst was prepared by introducing Fe onto the PtPd/Al₂O₃, and the PtPd/Fe/Al₂O₃ catalyst was obtained by loading the PtPd onto the Fe/Al₂O₃. The former had a superior activity. From the TPR results, the catalytic activity of CO oxidation was correlated with the oxygen mobility of the iron oxides. For PtPd/Fe/Al₂O₃, the iron interacted preferentially with the alumina support forming FeAlO₃, which resulted in the stabilization of the support and a reduction in the surface area. The major role of Fe was to promote the enhancement of the catalytic activity of PtPd through an intimate interaction between the PtPd and iron oxides, which had lattice oxygens to generate oxygen with oxidation abilities.     

Phosphorus-containing activated carbon as acid support in a bifunctional Pt–Pd catalyst for tire oil hydrocracking

A bifunctional Pt–Pd catalyst supported on phosphorus-containing activated carbon has been prepared, characterized and tested in the hydrocracking of a hydrotreated tire pyrolysis oil. The product has a very interesting composition: 48–78 wt% naphtha and 19–42 wt% diesel fractions, with moderate amounts of aromatics (< 40 wt%) and sulfur (< 250 ppm). The challenge was to prepare a stable, porous, selective and acid carbonaceous catalyst from a waste (olive stone), which has been confirmed from the catalytic properties and product distribution point of view. In fact, phosphate groups in the activated carbon are stable hydrocracking sites, with comparable performance to that of the acid sites present in amorphous SiO₂–Al₂O₃.     

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     

Effect of catalyst preparation and support composition on hydrodesulfurization of dibenzothiophene and Maya crude oil

Hydrodesulfurization (HDS) of dibenzothiophene (DBT) was carried out in a batch reactor at 3.3 MPa and 340 °C. Sulfided catalysts showed a wide range of activity variation as a function of support composition, which established that sulfided active phases strongly depend on the nature and composition of support. The incorporation of MgO, SiO₂, TiO₂ and ZrO₂ with γ-Al₂O₃ alters the nature of active phase interactions on the support surface. Therefore, these oxides play a structural promoting role to the support contribution and its interaction towards the active metal geometry. Different preparation methods of catalysts were carried out by using different additives during the impregnation. It is demonstrated that co-impregnation method found better activity than sequential impregnation. The urea additive prepared catalyst provides promising activity compared with other chelating agents. An Al₂O₃-B₂O₃ mixed oxide supported catalyst was tested at high pressure with real feed (Maya heavy oil diluted with hydrodesulfurized diesel). The mixed oxide supported catalyst showed rapid deactivation with time-on-stream than the alumina supported catalyst that may be due to an enhancement in acidic sites. The activity results demonstrated that the number of catalytic sites is a combination of support composition, additive, impregnation pH, drying and calcinations of catalysts.     

Investigations of Fe-Ru bimetallic catalysts by in situ Mössbauer and EXAFS studies

In situ Mössbauer and EXAFS investigations have shown that the reduction of iron in the monometallic Fe/SiO₂ catalyst is only partial, the reduction being mostly to a ferrous silicate phase. In the bimetallic Fe-Ru/SiO₂ catalysts, the proportion of the FeRu alloy formed on reduction increases markedly with the increase in Ru content; clearly, Ru significantly enhances the reduction of iron on SiO₂. In the Ru-rich compositions (Ru/Fe 1.0), most of the iron is present in the alloy phase and there is no segregation of -Fe. A comparative study of the different supports has shown that -Al₂O₃ and SiO₂ interact with iron strongly at low reduction temperatures while the TiO₂ support interacts at higher temperatures. The presence of traces of Fe³⁺ often found in reduced Fe-Ru catalysts is shown to arise from the oxidation of fine segregated iron particles on the support.Contribution No. 831 from the Solid State and Structural Chemistry Unit.     

CO methanation over supported Mo catalysts in the presence of H2S

The effect of various Mo catalyst supports, i.e., γ-Al₂O₃, SiO₂, SiO₂–Al₂O₃, ZrO₂, yttria-stabilized zirconia (YSZ), CeO₂, and TiO₂, on CO hydrogenation in the presence of H₂S was examined. At 5 wt.% Mo loading, Mo/ZrO₂ was determined to be the most active catalyst for this reaction; its activity was dependent on the number of active sites, as determined via NO chemisorption. Raman spectroscopy revealed that MoO₃ transforms into MoS₂ during the reaction.     

Bio gas oils with improved low temperature properties

During hydrodeoxygenation of triglycerides to motor fuel the isomerization reactions have an important role, since the cold flow properties of the product are improved significantly by increase of isoparaffin content of the product in gas oil boiling range. Accordingly, the aim of our research program was to select and investigate suitable catalyst(s) for producing relatively high isoparaffin containing product for a long time of preserved activity. Both not-presulphided CoMo/Al₂O₃ and NiMo/Al₂O₃ catalysts have isomerization activity, however, in the case of CoMo/Al₂O₃ catalyst triglyceride conversion is higher by 25.1-30.5 abs%, as well as yields by 24.2-24.6 abs% corresponding by 0.18-0.33 higher i-/n-paraffin ratio than for NiMo/Al₂O₃ under favorable conditions. Thereby products with more advantageous cold flow properties can be produced on CoMo/Al₂O₃ catalyst.