Catalytic Activity of a Thermoregulated, Phase-Separable Pd(II)-perfluoroalkylphthalocyanine Complex in an Organic/Fluorous Biphasic System: Hydrogenation of Olefins

A fluoroalkene-soluble tetrakis[heptadecafluorononyl]-substituted Pd(II)-phthalocyanine complex has been studied for olefin (styrene, 1-octene, trans-2-octene and cyclohexene) hydrogenation with molecular hydrogen in an organic/fluorous biphasic system [n-hexane/perfluoromethylcyclohexane (PFMCH)]. The palladium complex was found to be an active catalyst for styrene (100% conversion, TON = 634) and 1-octene (92%, TON = 596) at 80 °C and 15 bar of H₂ after 6 h of reaction time. The catalyst was recycled in nine consecutive reactions for the hydrogenation of styrene without the loss of activity or metal contamination.     

Preparation of Rh-containing cellulose acetate films and the chemistry of Rh in cellulose acetate

RhCl [P(C₆H₅)₃]₃ complexes have been incorporated in cellulose acetate as a dispersion medium using cosolvent (tetrahydrofuran). The interactions between Rh (I) complexes and cellulose acetate (CA) are examined by infrared spectroscopy and thermal analysis. The chemical reactivities of Rh–CA films have been investigated by reacting Rh sites with CO, H₂, O₂, and C₂H₄ in the temperature range 90–150°C and at a pressure of less than 1 atm. Three different Rh-carbonyls and a Rh-hydride species formed in CA are characterized by their infrared spectra. Treatment of 10 or 20 wt % Rh–CA films with hydrogen (600 torr) at 150°C produces small Rh metal particles of ca. 10 Å or less in diameter in CA, which show catalytic activities under mild conditions in various reactions such as hydrogenation of C₂H₄, oxidation of CO, and Fischer–Tropsch type reactions.     

Esterification of Hemicelluloses from Poplar Chips in Homogenous Solution of N,N- Dimethylformamide/Lithium Chloride

Abstract

Hemicelluloses, extracted from the delignified poplar chips with 8.0% NaOH-1.0% Na₂B₄O₇-10H₂O, were esterified with various acyl chlorides in the homogeneous N,N-dimethylformamide/lithium chloride system. Comparative reactions were performed with different molar ratios of acyl chloride/anhydroxylose, different concentrations of triethylamine, various reaction times, and reaction temperatures between 45°C and 75°C. The degree of substitution was controlled between 0.32 and 1.51. Under optimum conditions (sample 8, molar ratio 3:1, TEA% 280), over 75% of the hydroxyl groups in native hemicelluloses were stearoylated. The preparations were characterized by FT-IR and GPC techniques as well as their solubilities in various organic solvents. The molecular weight measurements showed minimal degradation of the hemicelluloses during the rapid reactions at 45-75° C for 30-45 min.     

Cobalt Particle Size Effects in the Fischer–Tropsch Synthesis and in the Hydrogenation of CO2 Studied with Nanoparticle Model Catalysts on Silica

We have investigated the effect of cobalt nanoparticle size in Fischer–Tropsch synthesis (CO/H₂) and have compared it to data obtained for carbon dioxide hydrogenation (CO₂/H₂) using model catalysts produced by colloidal methods. Both reactions demonstrated size dependence, in which we observed an increase of the turnover frequency with increasing average particle size. In both case, a maximum activity was found for cobalt particles around 10–11 nm in size. Regarding the selectivity, no size-dependent effect has been observed for the CO₂ hydrogenation, whereas CO hydrogenation selectivity depends both on the temperature and on the size of the particles. The hydrogenation of CO₂ produces mainly methane and carbon monoxide for all sizes and temperatures. The Fischer–Tropsch reaction exhibited small changes in the selectivity at low temperature (below 250 °C) while at high temperatures we observed an increase in chain growth with the increase of the size of cobalt particles. At 250 °C, large crystallites exhibit a higher selectivity to olefin than to the paraffin equivalents, indicating a decrease in the hydrogenation activity.     

Pressure and temperature effects on the hydrogenation of coal-derived asphaltene

Pressure and temperature effects on hydrogenation reactions were examined using coal-derived asphaltene at 390,420 and 450 °C, under 3 and 10 MPa of hydrogen partial pressure. Higher conversion was obtained at higher reaction temperatures. Benzene-insoluble material (Bl) was formed at higher temperatures especially at low hydrogen pressure, this Bl being one-third of the reaction product at 450 °C. From structural analysis of unreacted asphaltenes and product oils, at 390 °C, it was concluded that smaller molecular components convert to oil initially and the larger molecules remain as unreacted asphaltene. Under higher hydrogen pressure for all temperatures carbon aromaticity (f_a) and number of aromatic ring per structural unit (R_aus) in unreacted asphaltenes were lower than those under lower hydrogen pressure suggesting that hydrogenation of the aromatic nucleus was promoted by higher pressure. At lower hydrogen pressure, R_aus for asphaltenes at higher temperature is larger than that at lower temperature. This suggests that at lower hydrogen pressure, dehydrogenation or condensation reactions occur more easily. A large effect at higher hydrogen pressure was a reduction in the extent of condensation reactions. Higher reaction temperatures contribute to splitting of bridged linkages so reducing molecular size and degree of aromatization.     

Polymerization of glycidyl methacrylate with poly(ethylene terephthalate) fibers using Fe+2–H2O2 redox system

Fe⁺²–H₂O₂ redox system initiated polymerization reactions of glycidyl methacrylate (GMA) from aqueous solution with poly(ethylene terephthalate) fibers (PET) were investigated. The polymer add-on is greatly influenced by H₂O₂ concentration, GMA concentration, as well as reaction time and temperature. Polymer add-on was directly related to H₂O₂ concentration up to 30 meq/L and GMA concentration up to 4%. Further increase in concentrations of H₂O₂ and GMA resulted in lower polymer add-on. Raising the reaction temperature from 65°C to 95°C caused a significant enhancement in the rate of polymerization, the latter follows the order 95 > 85 > 75 > 65°C. However, at 65°C, the polymerization reaction showed an induction period of about 120 min, in contrast with reactions at 75°C, 85°C, and 95°C, where no induction period was observed though the polymer add-on was quite low at 75°C during the initial stages of the reaction. Using dimethylformamide (DMF) alone or mixed with water as polymerization medium offset the polymerization reaction. Incorporation of thioureadioxide in the polymerization system decreased the polymer add-on significantly.     

Hydrogenation of conjugated dienes over ZrO2 by H2 and cyclohexadiene

Hydrogenation of 1,3-butadiene and 2-methyl-1,3-butadiene and equilibration reaction of H₂D₂ were carried out over ZrO₂ using H₂ and Cyclohexadiene as hydrogen sources. Reaction rates were measured by changing the activation temperature of the catalyst. While the hydrogenation with H₂ and H₂D₂ equilibration reaction gave an optimum activity at 600 °C, another optimum was obtained for transfer hydrogenation at 800 °C. Hence it is concluded that the sites responsible for the transfer hydrogenation are not the same as those which catalyze hydrogenation with H₂ and H₂D₂ equilibration. Product distributions in n-butenes and methylated butenes were compared on ZrO₂, ThO₂, La₂O₃, and MgO and were also compared in direct hydrogenation with H₂ and transfer hydrogenation with Cyclohexadiene. Assuming an ionic intermediate, selectivity changes in the monoolefins produced over different catalysts and by different hydrogen sources were interpreted in terms of the variation of the anionic character of the intermediate and the shift of anionic to neutral or cationic intermediate, respectively.     

Effect of pyrite and pyrrhotite on free radical formation in coal

The effects of pyrite (FeS₂) and pyrrhotite (Fe₇S₈) on free radical formation in a coal sample (81% carbon content) have been investigated by electron spin resonance (e.s.r.) spectroscopy. Changes in the e.s.r. parameters (spin concentration g^-1, n, linewidth ΔH and g-value) were monitored in samples of coal, coal+8% FeS₂ and coal+8% Fe₇S₈, as these samples were heated in vacuum or in hydrogen from room temperature to 500 °C, in steps of 50 °C for a residence time of 30 min at each temperature. In vacuum heating, changes in n begin to occur at 400 °C, 350 °C and 300 °C respectively for coal, coal+8%Fe₇S₈ and coal+8% FeS₂ samples whereas in H₂, the corresponding temperatures are 250 °C, 200 °C and 150 °C. Changes in ΔH and g were also observed at these temperatures. The maximum increase in n occured for coal+8% FeS₂ samples whereas the minimum increase was observed for the pure coal sample. It is argued that enhancement in n is due to two mechanisms: the pyrite to pyrrhotite conversion and the presence of pyrrhotite itself. The detailed nature of the catalytic activity of pyrrhotite is not known.     

Coal gasification studies: Part I. Single stage complete gasification of coal using water as the hydrogen source

The complete gasification of coal to low molecular weight hydrocarbons has been achieved in a single stage process using water as the source of hydrogen. Reaction times of one hour, and a temperature of 600°C were required. The reactions were carried out in a stainless steel reactor with iodine or FeI₂ as a catalyst. It is shown that FeI₂ is a catalyst for the reaction Stainless Steel + H₂O → H₂ + Metal Oxide and also for the coal hydrogenation reaction. The apparent excellent reduction efficiency is probably a consequence of the good contact between the coal sample and the catalyst, which at the reaction temperature has a significant vapor pressure.     

The chemistry of Pd in cellulose acetate

Pd(OAc)₂ complex has been incorporated in cellulose acetate (CA) as a dispersion medium using cosolvent (THF). The interactions Pd(II) complexes and cellulose acetate are examined by infrared spectroscopy and thermal analysis (DSC). The chemical reactivities of Pd–CA films have been investigated by reacting Pd sites with CO, H₂, O₂, and C₂H₄ in the temperature range 25–150°C and at the pressure of less than 1 atm. Two different Pd-carbonyls and a Pd(O)-hydride species formed in CA are characterized by their infrared spectra. Treatment of 10 wt % Pd–CA films with hydrogen (600 torr) at 70°C produces small Pd metal particles of ca. 30–60 Å in diameter in CA, which show catalytic activities under mild conditions in the reactions such as hydrogenation of C₂H₄ and oxidation of CO.     

Analysis and removal of heteroatom containing species in coal liquid distillate over NiMo catalysts

Heteroatom containing molecules in South Banko coal liquid (SBCL) distillate were identified with a gas chromatograph equipped with an atomic emission detector (GC-AED). Thiophenes and benzothiophenes were found to be the major sulfur compounds. Pyridines, anilines, and phenols were the major nitrogen and oxygen compounds, respectively. Reactivities of heteroatom containing species in hydrotreatment over conventional NiMoS/Al₂O₃, NiMoS/Al₂O₃–SiO₂ catalysts were very different according to their cyclic structure as well as the kind of heteroatom in the species. The sulfur species were completely desulfurized over the catalysts examined in the present study by 60 min at 360 °C under initial hydrogen pressure of 5 MPa. However, hydrodenitrogenation was more difficult than hydrodesulfurization even at 450 °C. Anilines were found the most refractory ones among the nitrogen species. Hydrodeoxygenation of SBCL was also difficult in the hydrotreatment conditions examined in the present study. Dibenzofuran was the most refractory molecule among the oxygen species. A two-stage reaction configuration at 340 and 360 °C improved HDN and HDO reactivities, although the conversions were still insufficient. Increasing the acidity of the support as well as the loading of the metals on the NiMoS/Al₂O₃ catalysts improved very much the heteroatom reduction to achieve complete removal of nitrogen by two-stage reaction configuration at 340–360 °C and oxygen at 360 °C, respectively. The addition of H₂S in the reaction atmosphere inhibited the HDN reaction but increased markedly the HDO conversion. The acidic support increased the activity in hydrotreatment through enhancing the hydrogenation activity, while H₂S maintained the catalyst in a sufficiently sulfided state.     

Valorization of α-olefins: Double bond shift and skeletal isomerization of 1-pentene and 1-hexene on zirconia-based catalysts

Several catalysts consisting of Pt supported on sulfated or tungstated zirconia (one of them supported on alumina) have been characterized by different techniques, such as elemental and XRD analyses, N₂ adsorption, TPD of ammonia, TPR and H₂ chemisorption. All these catalysts were active in the transformation of two α-olefins, 1-pentene and 1-hexene, both present in most of FCC naphthas, whose conversion to internal and branched olefins is of a great interest for their use in reformulated gasolines and as intermediate chemicals. At low reaction temperatures (200–250 °C), both hydrogenation and double bond shift compete to give n-paraffins and internal olefins, respectively. As the temperature rises (>350 °C) the catalytic activity for the isomerization reactions increases, yielding a higher amount of internal and branched olefins. The product composition depends on the particular catalyst and reaction conditions used. The high activity of the sulfated zirconia, is remarkable and clearly indicates the participation of acid sites in these reactions.     

Catalytic hydrogenation of alkenes on acidic zeolites: Mechanistic connections to monomolecular alkane dehydrogenation reactions

Brønsted acid sites in zeolites (H-FER, H-MFI, H-MOR) selectively hydrogenate alkenes in excess H₂ at high temperatures (>700 K) and at rates proportional to alkene and H₂ pressures. This kinetic behavior and the De Donder equations for non-equilibrium thermodynamics show that, even away from equilibrium, alkene hydrogenation and monomolecular alkane dehydrogenation occur on predominantly uncovered surfaces via microscopically reverse elementary steps, which involve kinetically-relevant (C–H–H)⁺ carbonium-ion-like transition states in both directions. As a result, rate constants, activation energies and activation entropies for these two reactions are related by the thermodynamics of the overall stoichiometric gas-phase reaction. The ratios of rate constants for hydrogenation and dehydrogenation reactions do not depend on the identity or reactivity of active sites; thus, sites within different zeolite structures (or at different locations within a given zeolite) that favor alkane dehydrogenation reactions, because of their ability to stabilize the required transition states, also favor alkene hydrogenation reactions to the exact same extent. These concepts and conclusions also apply to monomolecular alkane cracking and bimolecular alkane–alkene reaction paths on Brønsted acids and, more generally, to any forward and reverse reactions that proceed via the same kinetically-relevant step on vacant surfaces in the two directions, even away from equilibrium. The evidence shown here for the sole involvement of Brønsted acids in the hydrogenation of alkoxides with H₂ is unprecedented in its mechanistic clarity and thermodynamic rigor. The scavenging of alkoxides via direct H-transfer from H₂ indicates that H₂ can be used to control the growth of chains and the formation of unreactive deposits in alkylation, oligomerization, cracking and other acid-catalyzed reactions.     

Phosphonitrilic chloride: 23. Substitution reaction of phosphonitrilic chloride trimer with sodium hydroxymethylphenolate and polymerization of substitution products

Chlorine substitution reactions of phosphonitrilic chloride trimer (PNCl₂)₃ with 2-, 3- or 4- HOH₂CC₆H₄ONa and 2-NaOH₂CC₆H₄ONa were carried out in dioxane solvent under various experimental conditions. All reactions were completed in 40–200 min in the temperature range 60° to 100°C. The chemical shifts of P atom were measured by ³¹P n.m.r. spectroscopy of P₃N₃(2-HOH₂CC₆H₄O)₆ (I), P₃N₃(3-HOH₂CC₆H₄O)₆ (II), P₃N₃(4-HOH₂CC₆H₄O)₆ (III) and P₃N₃(2-OH₂CC₆H₄O)₃ (IV). The ³¹P n.m.r. spectra showed the singlet peak. Water vapour and formaldehyde were detected by gas chromatography and polymers were formed when (I), (II) and (III) were heated from 150°C to 250°C. The polymers were stable towards water. Further, thermal balance measurements showed that the polymer formed from (I) was the most stable. The resistivity of films formed when (I), (II) and (III) were heated at about 300°C for 2 min was $\text{1–10 × 10}{}^{13}\text{Ω-}\text{cm}$. Thermal decomposition occurred rather than ring cleavage reaction when (IV) was heated from 150°C to 250°C.     

Influence of Particle Size on Reaction Selectivity in Cyclohexene Hydrogenation and Dehydrogenation over Silica-Supported Monodisperse Pt Particles

The role of particle size during the hydrogenation/dehydrogenation of cyclohexene (10 Torr C₆H₁₀, 200–600 Torr H₂, and 273–650 K) was studied over a series of monodisperse Pt/SBA-15 catalysts. The conversion of cyclohexene in the presence of excess H₂ (H₂: C₆H₁₀ ratio = 20:60) is characterized by three regimes: hydrogenation of cyclohexene to cyclohexane at low temperature (<423 K), an intermediate temperature range in which both hydrogenation and dehydrogenation occur; and a high temperature regime in which the dehydrogenation of cyclohexene dominates (>573 K). The rate of both reactions demonstrated maxima with temperature, regardless of Pt particle size. For the hydrogenation of cyclohexene, a non-Arrhenius temperature dependence (apparent negative activation energy) was observed. Hydrogenation is structure insensitive at low temperatures, and apparently structure sensitive in the non-Arrhenius regime; the origin of the particle-size dependent reactivity with temperature is attributed to a change in the coverage of reactive hydrogen. Small particles were more active for dehydrogenation and had lower apparent activation energies than large particles. The selectivity can be controlled by changing the particle size, which is attributed to the structure sensitivity of both reactions in the temperature regime where hydrogenation and dehydrogenation are catalyzed simultaneously.     

Methanol oxidation on Au/TiO2 catalysts

We have investigated the adsorption and reaction of methanol with Au/TiO₂ catalysts using a pulsed flow reactor, DRIFTS and TPD. The TiO₂ (P25) surface adsorbed a full monolayer of methanol, much of it in a dissociative manner, forming methoxy groups associated with the cationic sites, and hydroxyl groups at the anions. The methoxy is relatively stable until 250 °C, at which point decomposition occurs, producing mainly dimethyl ether by a bimolecular surface reaction. As the concentration of methoxy on the surface diminishes, so the mechanism reverts to a de-oxygenation pathway, producing mainly methane and water (at ~330 °C in TPD), but also with some coincident CO and hydrogen. Au catalysts were prepared by the deposition-precipitation method to give Au loadings between 0.5–3 wt %. The effect of low levels of Au on the reactivity is marked. The pathway which gives methane, which is characteristic of titania, remains, but a new feature of the reaction is the evolution of CO₂ and H₂ at lower temperature (a peak is seen in TPD at 220 °C), and the elimination of the DME-producing state. Clearly this is associated with the presence of Au and appears to be due to the production of a formate species on the surface of the Au component. This formate species is mainly involved in the reaction of methanol with the Au/TiO₂ catalysts which results in a combustion pathway being followed, with complete conversion occurring by ~130 °C.     

Catalytic Oxidation and Reduction of Polycyclic Aromatic Hydrocarbons (PAHs) Present as Mixtures in Hydrothermal Media

The reactivity of fluorene, anthracene, and fluoranthene under oxidation and reduction conditions were investigated in this study. This project looks at catalytic and green approaches of converting PAHs to less toxic and/or less stable derivatives that are amenable to further degradation. Hydrothermal reactions have been performed at 300°C with pure H₂O and Nafion-SiO₂ catalyst for oxidation, and pure H₂O, HCOOH, Pd-C, and Nafion-SiO₂ catalysts for reductive hydrogenation. Time series has been performed for both the oxidation and hydrogenation systems. The products of the reaction were identified and quantified by the use of Gas Chromatography-Mass Spectrometry and the NIST Library. The reaction products include oxidized products of anthracene and fluorene; and hydrogenated derivatives of anthracene and fluoranthene. Fluoranthene did not undergo oxidation, and fluorene did not undergo hydrogenation under the conditions of this research.     

Effects of temperature,reaction time,atmosphere, and catalyst on hydrothermal liquefaction of Chlorella

Hydrothermal liquefaction (HTL) is the direct conversion of wet biomass into bio-oil at high temperature (200–400°C) and high pressure (10–25 MPa). In this work, we investigated HTL with 4.5 g of Chlorella and 45 ml of water/ethanol (1:1 vol. ratio) in a 100 ml reactor. Bio-oils produced are characterized via elemental analysis, thermogravimetric analysis, and gas chromatography–mass spectrometry (GC–MS). HTL of Chlorella was investigated at 240 and 250°C for 0 and 15 min under an air or H₂ atmosphere and with and without 5% zeolite Y. Temperature increased the bio-oil yield from 38.75% at 240°C to 43.04% at 250°C for 15 min reaction time. Longer reaction time increased the bio-oil yield at 250°C from 39.14% for 0 min to 43.04% for 15 min. The H₂ atmosphere had a significant effect for HTL at 240°C. Zeolite Y increased the bio-oil yield significantly from 32.03% to 43.06% at 250°C for 0 min. The carbon content of bio-oil increased with the temperature while the oxygen content decreased. The boiling point distribution of bio-oils in the range of 110–300°C varies with temperature, and atmosphere. At 240°C for 15 min, the 110–300°C range increased from 31.19% in air (240-15-air) to 39.25% in H₂ (240-15-H₂). The H₂ atmosphere increased the content of hydrocarbons, alcohols, and esters from 69.61% in air (240-0-air) to 82.83% in H₂ (240-0-H₂). Overall, temperature, reaction time, atmosphere, and catalyst all significantly influenced the yield and/or quality of bio-oils from HTL of Chlorella.     

Thermal decomposition of trichloroethylene under a reducing atmosphere of hydrogen

The thermal reaction of trichloroethylene (TCE: C₂HCl₃) has been conducted in an isothermal tubular flow reactor at 1 atm total pressure in order to investigate characteristics of chlorinated hydrocarbons decomposition and pyrolytic reaction pathways for formation of product under excess hydrogen reaction environment. The reactions were studied over the temperature range 650 to 900 °C with reaction times of 0.3–2.0 s. A constant feed molar ratio C₂HCl₃: H₂ of 4: 96 was maintained through the whole experiments. Complete decay (99%) of the parent reagent, C₂HCl₃ was observed at temperature near 800 °C with 1 s reaction time. The maximum concentration (28%) of C₂H₂Cl₂ as the primary intermediate product was found at temperature 700 °C where up to 68% decay of C₂HCl₃ occurred. The C₂H₃Cl as highest concentration (19%) of secondary products was detected at 750 °C. The one less chlorinated methane than parent increased with temperature rise subsequently. The number of qualitative and qualitative chlorinated products decreased with increasing temperature. HCl and dechlorinated hydrocarbons such as C₂H₄, C₂H₆, CH₄ and C₂H₂ were the final products at above 800 °C. The almost 95% carbon material balance was given over a wide range of temperatures, and trace amounts of C₆H₆, C₄H₆ and C₂HCl were observed above 800 °C. The decay of reactant, C₂HCl₃ and the hydrodechlorination of intermediate products, resulted from H atom cyclic chain reaction via abstraction and addition replacement reactions. The important pyrolytic reaction pathways to describe the important features of reagent decay, intermediate product distributions and carbon mass balances, based upon thermochemical and kinetic principles, were suggested. The main reaction pathways for formation of major products along with preliminary activation energies and rate constants were given.     

Differences in catalytic liquefaction kinetics of corn stalk fractions

Biomass-based polyol obtained by chemical liquefaction technology is a potential substitute for polyether or polyester polyol in preparation of degradable polymers. To obtain the favorable biomass-based polyol products, one important emphasis is to reveal the liquefaction kinetics. The liquefaction kinetics of different corn stalk (CS) fractions, i.e. whole CS, ear husk and leaf blade, were investigated in this work. The liquefactions were catalyzed with sulfuric acid at 120–180 °C for 15–90 min. The results indicated that the apparent reaction rate constant (k), apparent activation energy (E), ΔG′, and ΔH′ of liquefaction reactions differed remarkably with different CS fractions. The highest k of 1.8 × 10^?4 s^?1 was obtained from ear husk liquefaction at 120 °C, which was twofold and 2.7-fold higher than those of whole CS and leaf blade, respectively. However, k is not correlated with the stalk heterogeneity at temperature over 120 °C. The calculated E _{ear husk}, E _{whole CS} and E _{leaf blade} were 65.88, 81.64 and 85.23 kJ mol^?1, respectively. ΔG′ and ΔH′ values of ear husk liquefaction reactions were lower than those of the other two fractions. This work was the first comparison of kinetics with different biomass fractions, casting light on the effect of heterogeneity on liquefaction, and suggesting that CS fractions should be given themselves optimum applications in future.