Changes in the hydrogenative ring-opening mechanism of cyclohexene oxide over Cu/SiO2 resulting from the addition of cyclohexene, a major product

The ring-opening mechanism influencing effect of a major product in the cyclohexene oxide–D₂ system was investigated over a Cu/SiO₂ catalyst. This product is cyclohexene, thus, the hydrogenative ring opening of a 1:1 cyclohexene oxide–cyclohexene mixture was studied in the presence of D₂ at 403 K in a closed circulation reactor. It was found that the mechanism of single C–O scission was not affected, but that of the double C–O scission was changed. Simultaneous bond cleavage was the major route of ring opening in the additive-free system and it became consecutive on cyclohexene addition. Added cyclohexene was hydrogenated with a very low rate, but it transformed the surface of the catalyst and, thus, facilitated the change in the mechanism. An explanation concerning the seemingly anomalous lack of deuterium in a product (cyclohexane) not seen in the additive-free system is also suggested. This revised version was published online in November 2006 with corrections to the Cover Date.     

Hydrodeoxygenation of Furfural Over Supported Metal Catalysts: A Comparative Study of Cu,Pd and Ni

Abstract  

The hydrodeoxygenation of furfural has been investigated over three different metal catalysts, Cu, Pd and Ni supported on SiO₂, on a continuous-flow reactor under atmospheric pressure of hydrogen in the 210–290 °C temperature range. The distribution of products is a strong function of the metal catalyst used. High selectivity to furfuryl alcohol is obtained over Cu/SiO₂, with the formation of only small amounts of 2-methyl furan at the highest reaction temperature studied. In contrast to Cu catalyst, the conversion of furfural over Pd/SiO₂ mainly produces furan by decarbonylation. Furan can further react with hydrogen to form tetrahydrofuran (THF). Finally, on Ni/SiO₂ catalysts ring opening products (butanal, butanol and butane) can be obtained in significant amounts. The different product distributions are explained in terms of the strength of interaction of the furan ring with the metal surface and the type of surface intermediates that each metal is able to stabilize.     

Mediatory role of K,Cu and Mo over Ru/SiO2 catalysts for glycerol hydrogenolysis

SiO₂ supported ruthenium catalysts with and without modifiers were prepared, characterized and tested for glycerol hydrogenation. Addition of K, Cu and Mo affects the reducibility and acidity of the Ru/SiO₂ catalyst. Characterization data shows that Cu and Mo-modified Ru/SiO₂ have stronger acidity. On the contrary, K element on a passive effect on the acidity of Ru based catalyst had been observed. A comparison with the pure Ru/SiO₂ indicates the Cu-promoted specimen has better selective to the desired products, acetol, 1,2-propanediol and ethyl glycol, although the reactivity is slightly lower.     

Study of an iron-manganese Fischer–Tropsch synthesis catalyst promoted with copper

The metal–silica interaction and catalytic behavior of Cu-promoted Fe–Mn–K/SiO₂ catalysts were investigated by temperature-programmed reduction/desorption (TPR/TPD), differential thermogravimetric analysis, in situ diffuse reflectance infrared Fourier transform analysis, and Mössbauer spectroscopy. The Fischer–Tropsch synthesis (FTS) performance of the catalysts with or without copper was studied in a slurry-phase continuously stirred tank reactor. The characterization results indicate that several kinds of metal oxide–silica interactions are present on Fe–Mn–K/SiO₂ catalysts with or without copper, which include iron–silica, copper–silica, and potassium–silica interactions. In addition to the well-known effect of Cu promoter on easing the reduction of iron-based FTS catalysts, it is found that Cu promoter can increase the rate of carburization, but does not vary the extent of carburization during the steady-state FTS reaction. The basicity of the Cu and K co-promoted catalyst is greatly enhanced, as demonstrated by CO₂-TPD results. In the FTS reaction, Cu improves the rate of catalyst activation and shortens the induction period, whereas the addition of Cu has no apparent influence on the steady-state activity of the catalyst. Promotion of Cu strongly affects hydrocarbon selectivity. The product distribution shifts to heavy hydrocarbons, and the olefin/paraffin ratio is enhanced on the catalyst due to the indirect enhancement of surface basicity by the copper promotion effect.     

The effect of the reduction temperature on the structure of Cu/ZnO/SiO2 catalysts for methanol synthesis

The structure of Cu/SiO₂ and Cu/ZnO/SiO₂ catalysts was studied after reduction at 450–1300 K. The influence of the ZnO promoter on the exposed Cu surface area and metal cluster size was determined by N₂O chemisorption and X-ray diffraction. After reduction at 450 K, the metal surface area amounted to 9 m²/g_cat for both catalysts. Oxygen uptake during N₂O chemisorption increased significantly up to reduction temperatures of 800–900 K. This increase was most prominent for the ZnO-promoted catalyst, although no oxygen uptake was observed for a similarly treated ZnO/SiO₂ sample. The behaviour of the promoted catalyst can be explained by formation of Zn⁰, surface alloying, and segregation of ZnO_x species on top of Cu clusters. The high thermostability of the catalysts was confirmed by in situ XRD measurements. The Cu crystallite size in both catalysts was about 4 nm, and did not increase when the reduction temperature was raised to 1100 K for 1 h.     

Creation of the active site for methanol synthesis on a Cu/SiO2 catalyst

The effect of ZnO/SiO₂ in a physical mixture of Cu/SiO₂ and ZnO/SiO₂ on methanol synthesis from CO₂ and H₂ was studied to clarify the role of ZnO in Cu/ZnO-based catalysts. An active Cu/SiO₂ was prepared by the following procedure: the Cu/SiO₂ and ZnO/SiO₂ catalysts with a different SiO₂ particle size were mixed and reduced with H₂ at 523-723 K, and the Cu/SiO₂ was then separated from the mixture using a sieve. The methanol synthesis activity of the Cu/SiO₂ catalyst increased with the reduction temperature and was in fairly good agreement with that previously obtained for the physical mixture of Cu/SiO₂ and ZnO/SiO₂. These results indicated that the active site for methanol synthesis was created on the Cu/SiO₂ upon reduction of the physical mixture with H₂. It was also found that ZnO itself had no promotional effect on the methanol synthesis activity except for the role of ZnO to create the active site. The active site created on the Cu/SiO₂ catalyst was found not to promote the formation of formate from CO₂ and H₂ on the Cu surface based on in situ FT-IR measurements. A special formate species unstable at 523 K with an OCO asymmetric peak at ~1585 cm^-1 was considered to be adsorbed on the active site. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of Ag, Cu, and Au Incorporation on the Diesel Soot Oxidation Behavior of SiO2: Role of Metallic Ag

The catalytic behaviors of Ag, Cu, and Au loaded fumed SiO₂ have been investigated for diesel soot oxidation. The diesel soot generated by burning pure Mexican diesel in laboratory was oxidized under air flow in presence of catalyst inside a tubular quartz reactor in between 25 and 600 °C. UV–Vis optical spectroscopy was utilized to study the electronic states of Ag, Cu, and Au(M) in M/SiO₂ catalysts. The soot oxidation was seen to be strongly enhanced by the presence of metallic silver on 3 % Ag/SiO₂ surface, probably due to the formation of atomic oxygen species during the soot oxidation process. The catalyst is very stable due to the stability of Ag⁰ species on the catalyst surface and high thermal stability of SiO₂. Obtained results reveal that though the freshly prepared 3 % Cu/SiO₂ is active for soot oxidation, it gets deactivated at high temperatures in oxidizing conditions. On the other hand, 3 % Au/SiO₂ catalyst does not present activity for diesel soot oxidation in the conventional soot oxidation temperature range. The catalytic behaviors of the supported catalyst samples have been explained considering the electron donating ability of the metals to generate atomic oxygen species at their surface.     

Effect of the Ratio of Precipitated SiO2 to Binder SiO2 on Iron-based Catalysts for Fischer–Tropsch Synthesis

The effects of the ratio of precipitated SiO₂ to binder SiO₂ (Si(P)/Si(B)) on the reduction, carburization and catalytic behavior of precipitated Fe–Cu–K–SiO₂ catalysts for Fischer–Tropsch synthesis (FTS) were investigated by N₂ physisorption, temperature-programmed reduction/desorption (TPR/TPD) and Mössbauer effect spectroscopy (MES). FTS performances of the catalysts were tested in a continuous stirred tank reactor (CSTR). It is found that the increase of Si(P)/Si(B) ratio (Si(P)/Si(B) = 0/25 ～ 15/10) decreases the crystallite size of the catalysts, improves the surface basicity, enhances the reduction and carburization of the catalysts, and increases the activity of the catalyst. However, when Si(P)/Si(B) ratio is further increased (Si(P)/Si(B) = 25/0), the catalyst exhibits a restrained reduction and carburization behavior, which may be attributed to the stronger metal–support interaction. Based on the present work, a catalyst with a suitable ratio of Si(P)/Si(B), for example Si(15)/Si(10) displays an optimal FTS performances.     

An in situ high pressure FT-IR study of CO2/H2 interactions with model ZnO/SiO2, Cu/SiO2 and Cu/ZnO/SiO2 methanol synthesis catalysts

In situ FT-IR spectroscopy allows the methanol synthesis reaction to be investigated under actual industrial conditions of 503 K and 10 MPa. On Cu/SiO₂ catalyst formate species were initially formed which were subsequently hydrogenated to methanol. During the reaction a steady state concentration of formate species persisted on the copper. Additionally, a small quantity of gaseous methane was produced. In contrast, the reaction of CO₂ and H₂ on ZnO/SiO₂ catalyst only resulted in the formation of zinc formate species: no methanol was detected. The interaction of CO₂ and H₂ with Cu/ZnO/SiO₂ catalyst gave formate species on both copper and zinc oxide. Methanol was again formed by the hydrogenation of copper formate species. Steady-state concentrations of copper formate existed under actual industrial reaction conditions, and copper formate is the pivotal intermediate for methanol synthesis. Collation of these results with previous data on copper-based methanol synthesis catalysts allowed the formulation of a reaction mechanism.     

Effect of SiO2 content on iron-based catalysts for slurry Fischer–Tropsch synthesis

A study has been carried out to investigate the effects of binder SiO₂ content on catalytic behavior of spray-dried precipitated Fe/Cu/K/SiO₂ catalysts for Fischer–Tropsch synthesis (FTS). The catalysts were characterized by means of N₂ physisorption, H₂ temperature-programmed reduction (TPR), scanning electron microscopy (SEM), and Mössbauer effect spectroscopy (MES). The Fischer–Tropsch synthesis performances (activity, selectivity and stability) of the catalysts were studied in a slurry-phase continuously stirred tank reactor (CSTR). The results indicated that the increase of SiO₂ content stabilizes Fe₃O₄ phase and suppresses the further reduction and carburization of the catalysts in syngas. Long time on stream FTS performances showed that the catalyst with SiO₂ improves its reaction stability. The selectivities to light hydrocarbons (methane, C₂–C₄, C₅–C₁₁) are enhanced whereas those to heavy hydrocarbons (C₁₂⁺) are suppressed with increasing SiO₂ content. The results were explained to the interactions of Fe–SiO₂ and K–SiO₂. From the present study, it is found that a catalyst with composition of 100Fe/5Cu/4.2K/25SiO₂ on mass basis displays both better FTS performances and a good attrition resistance, which is suitable for the use in CSTRs or SBCRs (Slurry Bubble Column Reactors) for FTS reaction.     

Methanol synthesis over Cu/SiO2 catalysts

The rates of CO and CO/CO₂ hydrogenation at 4.2 MPa and 523 K are reported for a series of Cu/SiO₂ catalysts containing 2 to 88 wt.% Cu. These catalysts were prepared on a variety of silica sources using several different Cu deposition techniques. In CO/CO₂ hydrogenation, the rate of methanol formation is proportional to the exposed Cu surface area of the reduced catalyst precursor, as determined by N₂O frontal chromatography. The observed rate, 4.2×10^–3 mole CH₃OH/Cu site-sec, is within a factor of three of the rates reported by others over Cu/ZnO and Cu/ZnO/Al₂O₃ catalysts under comparable conditions. These results suggest that the ZnO component is only a moderate promoter in methanol synthesis. Hydrogenation of CO over these catalysts also gives methanol with high selectivity, but the synthesis rate is not proportional to the Cu surface area. This implies that another type of site, either alone or in cooperation with Cu, is involved in the synthesis of methanol from CO.     

A Study of the Activated Decomposition of CO2 on the Cu Component of a Cu/ZnO/Al2O3 Catalyst

The decomposition of CO₂ over the Cu component of two ZnO/Al₂O₃ supported Cu catalysts, having different Cu areas, has been studied over the temperature range 393–513 K. The time dependence of the evolution of CO from a CO₂/He stream (10% CO₂, 101 kPa) which was dosed continuously over the catalyst showed two peak maxima, the first of which moved to shorter times on raising the temperature. The activation energy for the decomposition of CO₂ on the ZnO/Al₂O₃ supported polycrystalline copper was obtained from a plot of the logarithm of the time to the peak maximum of the first peak against the reciprocal of the dosing temperature. The value so obtained was 83±10 kJ mol^-1 (catalyst A) and 86±10 kJ mol^-1 (catalyst B) for fresh catalysts reduced in H₂ at 513 K. This value fell to 49 ±4 kJ mol^-1 (catalyst A) and 55±5 kJ mol^-1 (catalyst B) after CO reduction at 473 K of the Cu which had been oxidised by the decomposition of the CO₂. This lowering of the activation energy for the second CO₂ decomposition is considered to be due to the original morphology of the Cu not being restored by reduction in CO after the oxygen-driven reconstruction of the Cu deriving from the decomposition of the CO₂.     

Copper catalysts in the selective hydrogenation of soybean and rapeseed oils: IV. Copper on silica gel,phase composition and preparation

Phase composition of a copper on silica gel catalyst was studied with X-ray diffraction analysis. Activity measurements showed three periods of activity, the first two of which were ascribed to a copper surface subjected to reduction and the third one to the reduced form of the catalyst. Hydrogenation reaction over Cu/SiO₂ catalyst has a complex pressure dependence with a rate maximum at 6 atm in the low pressure range. Preparation of the catalyst was studied. On the basis of a proposed reaction model, a catalyst mixture was prepared and tested with good results. In rapeseed oil hydrogenation, Cu/SiO₂ catalysts were shown to be superior to copper chromite catalysts. In soybean oil the two types of catalyst were rather equivalent.     

Selective Hydrogenation of Soybean Oil on Copper Catalysts as a Tool Towards Improved Bioproducts

The liquid-phase soybean oil hydrogenation was studied on silica-supported Cu and ternary Cu–Zn–Al catalysts. Cu/SiO₂ samples were prepared by incipient-wetness impregnation (Cu/SiO₂-Imp) and chemisorption-hydrolysis (Cu/SiO₂-CH), while two Cu–Zn–Al mixed oxides containing 8 (Cu(8)–Zn–Al) and 15?% Cu (Cu(15)–Zn–Al), respectively, were prepared by coprecipitation. Copper dispersion (D _Cu) was 23?% on Cu/SiO₂-CH, and this sample showed a high activity for soybean oil hydrogenation; in contrast, Cu/SiO₂-Imp was inactive, probably because Cu was poorly dispersed (D _Cu?=?2?%). The oil hydrogenation activity on Cu(15)–Zn–Al (D _Cu?=?9?%) was lower than on Cu/SiO₂-CH, while Cu(8)–Zn–Al (D _Cu?=?23?%) was inactive. Citral hydrogenation used as a test reaction showed that the intrinsic Cu⁰ activity was not significantly changed by the kind of support or the catalyst preparation method. These latter results suggested that the observed differences in soybean oil hydrogenation may be explained as changes in accessibility of the triglyceride molecules to Cu active sites. In ternary Cu–Zn–Al samples, access to catalytic sites was hampered by the narrower pore structure of the catalyst. Copper exhibited unique properties for obtaining proper lubricants from soybean oil hydrogenation because selectively hydrogenated unsaturated linolenic (C18:3) and linoleic (C18:2) fatty acids to unsaturated oleic acid (C18:1) without forming saturated stearic acid (C18:0).     

Kinetic study of higher alcohol synthesis directly from syngas over CoCu/SiO2 catalysts

Higher alcohol synthesis (HAS) directly from syngas is one of the most promising approaches for utilizing nonoil resources cleanly and efficiently. A series of bimetallic CoCu catalysts with different Co/Cu ratios were prepared using a SiO₂ support. The structure of Cu modified Co catalysts was characterized using HRTEM, in/ex situ X‐ray diffraction, and temperature‐programmed reduction. It was evidenced that nanoscale metal particles were formed and the reduction of Co oxide at above 673 K. Meanwhile, the interaction between Co and Cu on the surface was assumed to be responsible for the enhanced selectivity to HAS. The intrinsic kinetics for this reaction was performed over a CoCu/SiO₂ catalyst under realistic conditions. The kinetic parameters, including apparent activation energies and reaction orders, were calculated through power‐law models. With the combination of chain growth probability and kinetics, the effect of temperatures on the reaction mechanism and the Cu promotional effects on Co catalysts were elaborated. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1797–1809, 2014     

Synergy of ruthenium and cobalt in SiO2-supported catalysts on ethylene hydroformylation

Dynamic hydroformylation of ethylene at atmospheric pressure and 150°C has been studied in a fixed bed reactor over ruthenium- and cobalt-containing SiO₂-supported catalysts (1% Ru loading). Any combination of ruthenium and cobalt precursors leads to significant improvement of hydroformylation activity with respect to those of monometallic catalysts. The optimal atomic ratio of Co:Ru is estimated to be 3:1 for ideal catalytic activity. A catalyst derived from Ru₃(CO)₁₂ and Co₂(CO)₈ is most active. A catalyst derived from metal carbonyls is generally more active than a catalyst prepared from metal salts. Metal chlorides retard the preparation of active catalysts in most cases. The catalysts studied exhibit fairly good catalytic stability. The determined rate enhancement of ethylene hydroformylation suggests a synergy of ruthenium and cobalt, which is understood as catalysis by bimetallic particles or ruthenium and cobalt monometallic particles in intimate contact. The synergy causes high ethylene hydrogenation activity while giving enhanced ethylene hydroformylation activity. Meanwhile, the potential of the ruthenium-based catalysts is evaluated from both catalytic performances and cost by comparison with the corresponding rhodium-based ones.     

Silica Gel-Supported, Metal-Promoted MoS2 Catalysts for HDS Reactions

Silica-supported, metal-promoted MoS₂ catalysts were prepared. Sol–gel method was used for providing the SiO₂ support as well as for including the catalyst precursors and promoter in one single step of preparation. The general idea in this approach is to obtain the promoted MoS₂ catalyst phase finely and uniformly distributed in the SiO₂ support. Scanning electron microscopy of the obtained catalysts shows a fine and homogeneous distribution of the metal-promoted MoS₂ particles on the SiO₂ matrix with surface area between 62 and 104m²/g. Metal promoter affects the surface area, pore size distribution and the hydrodesulfurization (HDS) activity and selectivity. When different promoters were used at the same amount, the highest selectivity for direct C–S bound cleavage is observed for Ru/MoS₂/SiO₂ catalyst, and at different amounts of Co the highest selectivity was occurred with Co/MoS₂/SiO₂ at 12% of Co/MoS₂, X-ray diffraction studies showed that the catalysts are poorly crystallized with a very weak intensity of the (002) line of 2H-MoS₂. Comparison on the catalytic activities of the catalysts with different metal promoters was made. Catalytic activity results showed the method of preparation used in this study is successful in producing very efficient catalysts for the HDS of dibenzothiophene (DBT). Silica-supported, cobalt-promoted MoS₂ catalyst showed the highest activity.     

Comparative study of iron-based Fischer–Tropsch synthesis catalyst promoted with potassium or sodium

FeCu/SiO₂ catalysts, in which K or Na promoter is incorporated respectively, are prepared by a combination method of continuous co-precipitation and spray drying technology. The catalysts were characterized by temperature-programmed desorption and Mössbauer spectroscopy. The Fischer–Tropsch synthesis (FTS) performance of the catalysts was studied in a continuously stirred tank slurry reactor. The basicity of the K-promoted catalyst is enhanced, as demonstrated by CO₂-TPD results. MES results show that sodium can weaken the dispersion of α-Fe₂O₃ phase; either potassium or sodium can promote carburization of the catalyst, while the effect of sodium is weaker. FTS results indicate that the addition of K or Na can improve the catalyst activity, and shift the product distribution to heavy hydrocarbons to the different extent.     

Partial oxidation of ethane over K2MoO4/SiO2 and potassium promoted MoO3/SiO2 catalyst

Silica supported K₂MoO₄ and potassium-promoted MoO₃ were used as catalysts for the partial oxidation of ethane in fix-bed continuous-flow reactor at 770–823 K using N₂O as oxidant. The main products of the oxidation reaction were ethylene, acetaldehyde, CO and CO₂. Addition of various compounds of potassium to the MoO₃/SiO₂ greatly enhanced the conversion of ethane and influenced the product distribution. The highest rate and selectivity for acetaldehyde formation was found on a K₂MoO₄/SiO₂ catalyst.     

The difference in the active sites for CO2 and CO hydrogenations on Cu/ZnO-based methanol synthesis catalysts

The effect of Zn in copper catalysts on the activities for both CO₂ and CO hydrogenations has been examined using a physical mixture of Cu/SiO₂+ZnO/SiO₂ and a Zn-containing Cu/SiO₂ catalyst or (Zn)Cu/SiO₂. Reduction of the physical mixture with H₂ at 573–723 K results in an increase in the yield of methanol produced by the CO₂ hydrogenation, while no such a promotion was observed for the CO hydrogenation, indicating that the active site is different for the CO₂ and CO hydrogenations. However, the methanol yield by CO hydrogenation is significantly increased by the oxidation treatment of the (Zn)Cu/SiO₂ catalyst. Thus it is concluded that the Cu–Zn site is active for the CO₂ hydrogenation as previously reported, while the Cu–O–Zn site is active for the CO hydrogenation.