Continuous Gas‐Phase Hydroformylation of 1‐Butene using Supported Ionic Liquid Phase (SILP) Catalysts

The concept of supported ionic liquid phase (SILP) catalysis has been extended to 1‐butene hydroformylation. A rhodium‐sulfoxantphos complex was dissolved in [BMIM][n‐C₈H₁₇OSO₃] and this solution was highly dispersed on silica. Continuous gas‐phase experiments in a fixed‐bed reactor revealed these SILP catalysts to be highly active, selective and long‐term stable. Kinetic data have been acquired by variation of temperature, pressure, syngas composition, substrate and catalyst concentration. A linear dependency in rhodium concentration could be established over a large concentration range giving another excellent hint for truly homogeneous catalysis in the SILP system. Compared to former studies using propene, the SILP system showed significantly higher activity and selectivity with 1‐butene as feedstock. These findings could be elucidated by solubility measurements using a magnetic microbalance.     

Biphasic and Flow Systems Involving Water or Supercritical Fluids

Two processes are described for improving reaction rates for relatively hydrophobic substrates in aqueous biphasic systems. In the first, 1-octyl-3-methylimidazolium bromide ([Octmim]Br) increases the rate of hydroformylation of 1-octene from 8% conversion in 24 h to full conversion of 1.5 h. Phase separation is fast and catalyst retention is good. 1-Hexyl-3-methylimidazolium bromide gives little rate enhancement, whilst 1-decyl-3-methylimidazolium bromide gives stable emulsions., The mechanism of action of these additives is discussed. In the second approach, functionalising PPh₃ with amidine groups allows the rhodium catalysed hydroformylation of 1-octene in toluene with a very high reaction rate. The catalyst can be switched between toluene and water by bubbling CO₂ and back into toluene by bubbling N₂ at 60 °C. This switching has been used to separate the catalyst from hydrophobic (from 1-octene) or hydrophilic (from allyl alcohol) aldehydes obtained from hydroformylation reactions. CO₂ expanded liquids have been shown to be effective media for transporting substrates and catalysts over supported ionic liquid phase (SILP) catalysts. The advantages offered over all gas phase and liquid phase catalysts are discussed.     

n‐butane carbonylation to n‐pentanal using a cascade reaction of dehydrogenation and SILP‐catalyzed hydroformylation

A novel gas‐phase process has been developed that allows direct two‐step conversion of butane into pentanals with high activity and selectivity. The process consists of alkane dehydrogenation over a heterogeneous Cr/Al₂O₃ catalyst followed by direct gas‐phase hydroformylation using advanced supported ionic liquid phase (SILP) catalysis. The latter step uses rhodium complexes modified with the diphosphite ligands biphephos (BP) and benzopinacol to convert the butane/butene mixture from the dehydrogenation step efficiently into aldehydes. The use of the BP ligand results in improved yields of linear pentanal because SILP systems with this ligand are active for both isomerization and hydroformylation. © 2014 American Institute of Chemical Engineers AIChE J, 61: 893–897, 2015     

Continuous acylation of anisole by acetic anhydride in mesoporous solid acid catalysts: Reaction media effects on catalyst deactivation

The acylation of anisole with acetic anhydride was carried out in a continuous slurry reactor over mesoporous supported Nafion^® (SAC-13) and heteropolyacid (HPA) catalysts. At 70 °C, using an anisole-rich feed molar ratio of 5:1 and a space velocity of 1.6 g_{acetic anhydride} g⁻¹_cat. h⁻¹, acetic anhydride conversions of 40–50% with excellent selectivity (>95%) toward the primary product, p-methoxyacetophenone (p-MOAP), were observed at time on stream (TOS) of a few hours. However, all the catalysts deactivated completely during liquid-phase operation in less than 24 h. It was observed that the Keggin ions from the supported HPA-based catalyst (70% HPA/SiO₂) leached out into the solution, as confirmed by elemental analysis. The 50% Cs_2.5-HPA/SiO₂ catalyst, on the other hand, was more leach-resistant, yet deactivated rapidly during liquid-phase operation. SAC-13-type catalysts, which displayed the best combination of stability and leach resistance during liquid-phase operation, were evaluated in CO₂-expanded liquids (CXLs) to better enhance the transport properties and potentially mitigate deactivation. It is observed that the CXL media gave lower conversion and surprisingly, faster deactivation compared with liquid-phase operation, indicating that CO₂ had a detrimental effect despite the use of polar cosolvents like nitromethane. The spent catalysts were subjected to Soxhlet extraction with polar solvents like nitromethane. Such treatment did not restore catalyst activity. BET surface area, pore volume of the fresh and spent catalysts, GC/MS analysis of the Soxhlet extract, and IR analysis of the spent catalyst (before and after Soxhlet extraction) indicate that the deactivation could be caused by the primary product, p-MOAP and/or multiply acetylated products in the micropores of Nafion^® catalyst aggregates. Treating the spent catalyst with boiling HNO₃ solution restored complete activity of the SAC-13-type catalysts. The high TON (∼400) achieved with these catalysts before deactivation and their ability to regain complete activity for acylation reactions indicate that Nafion^® catalysts are promising alternatives to the conventional homogeneous Lewis acids like AlCl₃.     

Rhodium complexes supported on nanoporous activated carbon for selective hydroformylation of olefins

Activated carbon with nanoporous structure, high surface area (2500 m²/g) and total pore volume (2.35 cm³/g) was prepared from Mango seed shell (Mangifera indica L.) via chemical activation method and used as support to impregnate active hydroformylation rhodium complexes HRhCO(PPh₃)₃ and Rh(acac)(CO)₂. The prepared catalysts were characterized by XRD, SEM, TEM, NMR, IR, TGA, and N₂ adsorption/desorption techniques. The supported catalysts have shown excellent selectivity for aldehydes (~ 99%) in the hydroformylation of olefins with good stability and recyclability up to 4 cycles.     

Biosynthesized Au/TiO<Subscript>2</Subscript>@SBA-15 catalysts for selective oxidation of cyclohexane with O<Subscript>2</Subscript>

A variety of TiO₂@SBA-15 supporters with various TiO₂ loadings were synthesized using a facile sol-gel method. Gold (Au)-based catalysts were prepared with an environmentally benign and economical bioreduction method via Cacumen Platycladi (CP) leaf extract and immobilized on various TiO₂@SBA-15 supporters with different TiO₂ loadings. The as-prepared biosynthesized Au catalysts were applied in the liquid-phase cyclohexane oxidation. The results showed that the Au nanoparticles were well-dispersed on TiO₂@SBA-15, and the Au existed as Au⁰. These biosynthesized Au catalysts are promising for cyclohexane oxidation, achieving a turnover frequency up to 3,426 h^?1 with a 14.1% cyclohexane conversion rate.     

Phenoxaphosphino‐Modified Xantphos‐Type Ligands in the Rhodium‐Catalysed Hydroformylation of Internal and Terminal Alkenes

The solubility of the modifying ligand is an important parameter for the efficiency of a rhodium‐catalysed hydroformylation system. A facile synthetic procedure for the preparation of well‐defined xanthene‐type ligands was developed in order to study the influence of alkyl substituents at the 2‐, and 7‐positions of the 9,9‐dimethylxanthene backbone and at the 2‐, and 8‐positions of the phenoxaphosphino moiety of ligands 1 – 16 on solubility in toluene and the influence of these substituents on the performance of the ligands in the rhodium‐catalysed hydroformylation. An increase in solubility from 2.3 mmol⋅L⁻¹ to >495 mmol⋅L⁻¹ was observed from the least soluble to the most soluble ligand. A solubility of at least 58 mmol⋅L⁻¹ was estimated to be sufficient for a large‐scale application of these ligands in hydroformylation. Highly active and selective catalysts for the rhodium‐catalysed hydroformylation of 1‐octene and trans‐2‐octene to nonanal, and for the hydroformylation of 2‐pentene to hexanal were obtained by employing these ligands. Average rates of >1600 (mol aldehyde) × (mol Rh)⁻¹×h⁻¹ {conditions: p(CO/H₂) = 20 bar, T = 353 K, [Rh] = 1 mM, [alkene] = 637 mM} and excellent regio‐selectivities of up to 99% toward the linear product were obtained when 1‐octene was used as substrate. For internal olefins average rates of >145 (mol aldehyde)×(mol Rh)⁻¹×h⁻¹ {p(CO/H₂) = 3.6–10 bar, T = 393 K, [Rh] = 1 mM, [alkene] = 640–928 mM} and high regio‐selectivities up to 91% toward the linear product were obtained.     

Study on catalysis by carbonyl cluster-derived SiO2-supported rhodium for ethylene hydroformylation

Atmospheric hydroformylation of ethylene was studied under differential conditions over Rh₄(CO)₁₂-derived Rh/SiO₂ catalysts. The specific activities as functions of Rh dispersions show that ethylene hydroformylation is structure sensitive and ethylene hydrogenation structure insensitive. These structural dependences and in situ IR observations show that Rh⁰ is the unique active site for catalytic ethylene hydroformylation on Rh/SiO₂. The reactions of Rh⁰-coordinated CO and Rh⁰-adsorbed CO with C₂H₄ + H₂ at 293 K were monitored by IR spectroscopy. The linear CO adsorbed on Rh⁰/SiO₂ is consumed with formation of propanal, whereas the coordinated CO in Rh₆(CO)₁₆/SiO₂ and its derivative do not participate in CO insertion. IR study of the thermal decomposition of Rh₆(CO)₁₆/SiO₂ indicates that the cluster can be stabilized on the surface up to 548 K by gaseous CO under hydroformylation conditions. Moreover, the Rh₆(CO)₁₆/SiO₂ system exhibits increased catalytic hydroformylation activity with reducing coordinated CO. These results show that coordinative unsaturation on the Rh⁰ surface is necessary for heterogeneously rhodium-catalyzed hydroformylation and that totally decarbonylated Rh⁰/SiO₂ is most effective. In addition, the oxidation of Rh⁰ by surface OH^? is discussed.     

Organometallics derived (Pd + Ln)/SiO2 catalysts for the reactions of synthesis gas conversion

C₃H₆ hydroformylation and CH₃OH synthesis on organometallics derived (Pd + Ln)/ SiO₂ and Pd/SiO₂ catalysts have been studied. The activity and selectivity towards methanol in CO + H₂ reaction were observed to increase for all the modified catalysts while both the hydroformylation activity and selectivity towards oxygenates in C₃H₆ hydroformylation decreased for the catalysts in comparison to those of Pd/SiO₂. The FTIR, TPD data and characteristic catalytic properties of the catalysts studied allow to suggest that C₃H₆ hydroformylation on (Pd + Ln)/SiO₂ catalysts occurs on monometallic Pd clusters without participation of mixed active sites and CO complexes activated thereon.     

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.     

Could readily silanized silica particles substitute silica coating and silanization in conditioning zirconium dioxide for resin adhesion?

This study investigated the effect of particle types with different morphology and surface properties on the wettability and adhesion of resin cement to zirconia. Zirconia specimens (5 × 5 × 1 mm³) were wet polished. Specimens were randomly assigned to one of the following protocols (N = 36, n = 9 per group): Group CON: Control, no surface conditioning; Group AL: Chairside air-abrasion with aluminium trioxide (50 μm Al₂O₃) + silane; Group SIL: Chairside air-abrasion with alumina particles coated with silica (SIL) (30 μm SiO2, SilJet) + air-drying + silane; Group 4: Chairside air-abrasion with readily silanized silica particles (SILP) (30 μm SiO_2, SilJet Plus). Adhesive resin was applied and resin cement (Variolink II, Ivoclar) was bonded using polyethylene moulds and photo-polymerized and aged (thermocycling, 6.000 cycles, 5–55 °C). Shear bond test was performed using Universal Testing Machine (1 mm/min). Pretest failures were considered 0 MPa. Contact angle measurements were performed (n = 2/group, sessile drop with water). Data (MPa) were analyzed (ANOVA, Tukey’s (α = 0.05). Two-parameter Weibull distribution values including the Weibull modulus, scale (m) and shape (0), values were calculated. Contact angle measurements were in descending order as follows: SIL (74°)^c < CON (60°)^c < AL (51°)^b < SILP (40°)^a. Bond strength (MPa) with SIL (17.2 ± 4)^a and SILP (17.3 ± 1.9)^a demonstrated no significant difference (p > 0.05), being higher than AL (8.4 ± 1.5)^b and CON (0)^c (p < 0.05). Failure types were exclusively adhesive in all groups. Weibull distribution presented the highest shape (0) for SILP (10.8). SILP presented better wettability than AL. SILP provided similar bond strength to SIL. Readily silanized silica particles may substitute for conventional silica coating and silanization.     

Cobalt(III) Acetylacetonate Chemisorbed on Aluminum-Nitride-Modified Silica: Characteristics and Hydroformylation Activity

Co/AlN/SiO₂ catalysts were prepared by the saturative chemisorption of cobalt(III) acetylacetonate (Co(acac)₃). The support was bare silica or silica that had been modified with aluminum nitride (AlN) by repeated separate, saturated chemisorptions of trimethylaluminum and ammonia two or six times. Chemisorption of Co(acac)₃ occurred on all the supports up to a saturation ligand density of 2.7 acac nm^-2; the amount of bonded cobalt decreased from 2.1 to 1.5 at_Co nm^-2 with increasing extent of AlN modification of the support. Ligand exchange reaction, releasing Hacac, occurred less on AlN-modified silica than on bare silica. This induced difference in the reduction behavior of the catalysts, and catalytic activity in gas-phase hydroformylation of ethene, was lower with Co/AlN/SiO₂ than with Co/SiO₂ catalyst.     

Gas-Phase Hydroformylation of Propene over Silica-Supported PPh3-Modified Rhodium Catalysts

Heterogeneous rhodium catalysts supported on SiO₂ were modified with PPh₃ for the gas-phase hydroformylation of propene to produce n- and isobutanal. High selectivity to aldehydes was achieved, with no propane or alcohols formed. Investigation of the effects of reaction temperature, reactant partial pressures, total pressure, and PPh₃/Rh ratio suggested that the supported catalyst behaved similarly to the homogeneous catalyst. In particular, the supported catalyst showed similar activation energies and partial and total pressure dependences of the reaction rates to those observed in homogeneous, liquid-phase reactions. The first order dependence of the hydroformylation rate on the partial pressures of propene, CO, and H₂ individually led to a cubic dependence of butanal formation on total pressure for equimolar reactant mixtures. High regioselectivity with a typical n/i ratio of 14 was achieved.     

The beneficial effect of alkali metal salt on supported aqueous-phase catalysts for olefin hydroformylation

Alkali metal salt modified SAP (supported aqueous-phase) rhodium catalysts prepared by coimpregnation method using alkali metal chloride were found to be active and selective for olefin hydroformylation. The salt addition promoted the formation of aldehydes with high selectivity, the aldehyde yield being increased more than 2.5 times at a proper salt/Rh ratio. Changes in stretching frequency of the carbonyl species were detected during ethene hydroformylation, which appeared at ca. 1625 cm^–1 on the non-modified SAP catalyst sample, while at ca. 1586 cm^–1 on the KCl-modified one, as shown by in situ IR spectroscopy. The results of a deuterium isotope effect experiment showed that the hydroformylation rate for aldehyde formation on SAP rhodium catalyst under atmospheric pressure of CO/D₂ was about 1.3 times faster than that under CO/H₂, implying that the rate-determining step involved in aldehyde formation is most probably a step related with hydrogen. The role of the alkali metal salt is discussed in relation with the reaction mechanism.     

Titania-Supported Pd–Cu Bimetallic Catalyst for the Reduction of Nitrite Ions in Drinking Water

Titania-supported palladium–copper bimetallic catalysts (Pd–Cu/P25) are prepared by liquid-phase chemical reduction method and then applied in liquid-phase catalytic reduction of nitrite ions (NO₂ ^-). Compared with the conventional impregnation method, which usually needs a post-thermal reduction procedure to eliminate the introduced anions, liquid-phase chemical reduction at ambient temperature was proved to inhibit the aggregation of metal active components by means of TEM and DSC analysis in this work, and the catalyst exhibited superior catalytic activity. The conversion of nitrite reached a high level (1×10^-4 mol min^-1 g_cat ^-1) and is about 14 times than that reported recently. The influences on the conversion of NO₂ ^- by support materials and the molar ratio of palladium to copper are also investigated, and further, the reaction mechanisms are discussed according to the characterization results of XPS and in situ FT-IR.     

Selective synthesis of alcohols from syngas and hydroformylation of ethylene over supported cluster-derived cobalt catalysts

Hydroformylation of ethylene and CO hydrogenation were studied over cobalt-based catalysts derived from reaction of Co₂(CO)₈ with ZnO, MgO and La₂O₃ supports. At 433 K a similar activity sequence was reached for both reactions: Co/ ZnO > Co/La₂O₃ > Co/MgO. This confirms the deep analogy between hydroformylation and CO hydrogenation into alcohols. In the CO hydrogenation the selectivity towards alcohol mixture (C₁-C₃) was found to be near 100% at 433 K for a conversion of 6% over the Co/ZnO catalyst; this catalyst showed oxo selectivity higher than 98% in the hydroformylation of ethylene. Magnetic experiments showed that no metallic cobalt particles were formed at 433 K. It is suggested that the active site for the step that is common to both reactions is related to the surface homonuclear Co²⁺/[Co(CO)₄]^– ion-pairing species.     

Support and precursor effects on the preparation of new heterogenized Pt/Sn catalysts for the selective hydroformylation of 1-pentene

New heterogenized Pt/Sn catalysts selective for the hydroformylation of 1-pentene have been synthesized. The complex cis-[PtCl₂(PPh₃)₂] and the SnCl₂.2H₂O or SnC₂O₄ precursors have been anchored on silica-, magnesia- and alumina-carriers. X-ray photoelectron spectroscopy was used to determine the surface composition and the nature of the anchored species. The hydroformylation activity was found to depend on the type of support and tin precursor used. Only the silica supported catalysts were active in the hydroformylation reaction. Samples prepared from SnCl₂-2H₂O were 200-fold more active than those prepared from SnC₂O₄. Selectivity ton-hexanal of the silica-supported catalyst prepared from SnCl₂-2H₂O was as high as 94.4% at 39.2% conversion of 1-pentene.     

Bioreactors Based on Monolith‐Supported Ionic Liquid Phase for Enzyme Catalysis in Supercritical Carbon Dioxide

Bioreactors with covalently supported ionic liquid phases (SILP) were prepared as polymeric monoliths based on styrene–divinylbenzene or 2‐hydroxyethyl methacrylate–ethylene dimethacrylate, and with imidazolium units loadings ranging from 54.7 to 39.8 % wt IL per gram of polymer. The SILPs were able to absorb Candida antarctica lipase B (CALB), leading to highly efficient and robust heterogeneous biocatalysts. The bioreactors were prepared as macroporous monolithic mini‐flow systems and tested for the continuous flow synthesis of citronellyl propionate in supercritical carbon dioxide (scCO₂) by transesterification. The catalytic activity of these mini‐flow‐bioreactors remained practically unchanged for seven operational cycles of 5 h each in different supercritical conditions. The best results were obtained when the most hydrophobic monolith, M‐SILP‐ 8 ‐CALB, was assayed at 80 °C and 10 M Pa, reaching a total turnover number (TON) of 35.8×10⁴ mol product/mol enzyme. The results substantially exceeded those obtained for packed‐bed reactors with supported silica‐CALB‐Si‐4 catalyst under the same experimental conditions.     

Micellar Effects in Olefin Hydroformylation Catalysed by Neutral,Calix[4]arene‐Diphosphite Rhodium Complexes

The combination of calixarene‐derived surfactants and neutral rhodium complexes containing a hemispherical “1,3‐calix‐diphosphite” ligand led to efficient catalysts for the hydroformylation of octene and other olefins in water. While the surfactants allowed the formation of micelles that dissolve both the catalyst and the alkene, thereby resulting in high olefin:rhodium ratios, the diphosphite provided a tight envelope about the catalytic centre able to drive the reaction towards the linear aldehydes. Best results in the hydroformylation of 1‐octene were obtained when using [tetra(p‐sulfonato)]‐(tetra‐n‐butoxy)‐calix[4]arene as surfactant. With this additive remarkable linear to branched aldehyde ratios of up to 62 were obtained, the corresponding activities being higher than those observed when operating in an organic solvent [turnover frequencies (TOFs) up to 630 mol(converted 1‐octene)⋅ mol(Rh)⁻¹⋅h⁻¹].     

Komplexkatalyse mit Technetiumverbindungen: Hydroformylierung mit Technetiumcarbonyl-Katalysatoren

Complex Catalysis with Technetium Compounds. Hydroformylation with Technetiumcarbonyl Catalysts The hydroformylation reaction of cyclohexene ( 1 ), propene ( 2 ) and 1-octene ( 3 ) was studied using Tc₂(CO)₁₀ and Tc(CO)₁₀/P(n-C₄H₉)₃, resp., as catalysts in solution. For comparison experiments have also been made with Mn₂(CO)₁₀, Mn₂(CO)₁₀/P(n-C₄H₉)₃ and Re₂(CO)₁₀/P(n-C₄H₉)₃ as catalysts for the hydroformylation of 1 . There is always a competition between hydrogenation and hydroformylation. Tc₂(CO)₁₀/P(n-C₄H₉)₃ gave the best results in activity and selectivity within the subgroup VII complexes studied, but is a rather poor catalyst compared with the cobalt or rhodium compounds.