Conversion of 4-Methylanisole Catalyzed by Pt/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and by Pt/SiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>: Reaction Networks and Evidence of Oxygen Removal

Abstract  

The conversion of 4-methylanisole, a prototypical bio-oil compound, was catalyzed by Pt/Al₂O₃, Pt/SiO₂-Al₂O₃, or HY zeolite at 573 K and atmospheric pressure. More than a dozen products were formed with each catalyst, the most abundant being 4-methylphenol, 2,4-dimethylphenol, and 2,4,6-trimethylphenol; toluene was also a major product when the catalyst was supported platinum with H₂ as a co-reactant. 4-Methylphenol was the only methylphenol isomer formed in significant yields, which indicates that migration of the methyl group on the aromatic ring is not significant under the selected reaction conditions. The data determine approximate reaction networks including reactions forming 4-methylphenol, 2,4-dimethylphenol, and toluene as primary products. The kinetically significant reaction classes were transalkylation, observed with all three catalysts, and hydrogenolysis (including hydrodeoxygenation) and hydrogenation, observed only with the platinum-containing catalysts operating in the presence of H₂. Data such as those reported here provide a starting point for predicting the conversion of whole bio-oils for removal of oxygen and upgrading of fuel properties.     

Characteristics and Catalytic Properties of Pd/SiO2 Synthesized by One-step Flame Spray Pyrolysis in Liquid-phase Hydrogenation of 1-Heptyne

In this study, Pd/SiO₂ catalysts with 0.5–10 wt.% Pd loadings were prepared by one-step flame spray pyrolysis (FSP) and characterized by N₂ physisorption, X-ray diffraction (XRD), transmission electron microscopy (TEM), CO chemisorption, and X-ray photoelectron spectroscopy (XPS). The average cluster/particles size of Pd as revealed by TEM were ca. 0.5–3 nm. The turnover frequencies (TOFs) of the flame-made catalysts decreased from 66.2 to 4.3 per s as Pd loading increased from 0.5 to 10 wt.%, suggesting that the catalytic activity was dependent on Pd particle/cluster size. However, there were no appreciable influences on 1-heptene selectivity. The flame-made Pd/SiO₂ showed better properties than the conventional prepared catalysts. Their advantages are not only the presence of large pores that facilitates diffusion of the reactants and products, but also the high-catalytic activity of as-synthesized catalysts so that further pretreatment is not necessary.     

Arsenic and other elements in hair, nails, and skin-scales of arsenic victims in West Bengal, India

For the first time, biological tissues (hair, nails, and skin-scales) of arsenic victims from an arsenic affected area of West Bengal (WB), India were analyzed for trace elements. Analysis was carried out by inductively coupled plasma-mass spectrometry (ICP-MS) for 10 elements (As, Se, Hg, Zn, Pb, Ni, Cd, Mn, Cu, and Fe). A microwave digester was used for digestion of the tissue samples. To validate the method, certified reference materials--human hair (GBW 07601) and bovine muscle (CRM 8414)--were analyzed for all elements. The W test was used to study the normal/log normal distribution for each element in the tissue samples. For hair (n=44) and nails (n=33), all elements show log-normal distribution. For skin-scale samples (n=11), data are not sufficient to provide the information about the trend. Geometric mean, standard error, and range for each element were presented and compared with literature values for other populations. This study reveals the higher levels of toxic elements As, Mn, Pb, and Ni in the tissue samples compared with available values in the literature. The elevated levels of these toxic metals in the tissues may be due to exposure of these elements through drinking water and food. The correlations of Mn and Ni with other essential elements, e.g. Fe, Cu, Zn, suggest that Mn and Ni may substitute for those elements in hair, nails, and skin-scales. However, correlation represents the relation between two elements only and does not take into consideration of the presence of other elements. Principle component analysis was applied to explain the behavior among the elements present in hair and nails. This study reveals that in the arsenic-affected areas of WB, the concentrations of other toxic elements in drinking water and foodstuff should be monitored to evaluate the arsenic poisoning.     

Upgrading of Lignin-Derived Compounds: Reactions of Eugenol Catalyzed by HY Zeolite and by Pt/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

Abstract  

The conversion of eugenol (4-allyl-2-methoxyphenol), a compound derived from the lignin in woody biomass, was catalyzed by HY zeolite at 573 K and atmospheric pressure. The main products were isoeugenol and guaiacol, formed by isomerization and by deallylation, respectively. Substituted guaiacols with saturated side-chains (4-methylguaiacol, 4-ethylguaiacol, and 4-propylguaiacol) were also formed, by hydrogen transfer and alkylation reactions. The pseudo-first-order rate constant for the overall disappearance of eugenol was found to be 12.4 L (g of catalyst)/h. When the catalyst was Pt/γ-Al₂O₃ used in the presence of H₂, significant hydrogenation of the propenyl side-chain took place, accompanied by isomerization, and hydrodeoxygenation. Under similar operating conditions, the reaction catalyzed by Pt/γ-Al₂O₃ in the presence of H₂ gave a higher eugenol conversion (X = 0.70) than the reaction catalyzed by HY zeolite (X = 0.11), primarily because of the dominant hydrogenation observed with the former catalyst. In the absence of H₂ as a co-reactant, the acidic γ-Al₂O₃ support in Pt/γ-Al₂O₃ evidently catalyzed all the classes of reactions catalyzed by HY zeolite.     

Catalytic Reactions of Guaiacol: Reaction Network and Evidence of Oxygen Removal in Reactions with Hydrogen

Abstract  

The conversion of guaiacol, a prototypical compound representative of lignin-derived pyrolysis bio-oils, was catalyzed by Pt/Al₂O₃ in the presence of H₂ at 573 K. The conversion took place with a high selectivity for aromatic carbon–oxygen bond cleavage relative to the accompanying methyl group transfer reactions. This oxygen removal was not observed in the absence of H₂ as a co-reactant. Products that were formed by methyl-group transfer match those produced in the conversion catalyzed by zeolite HY, which was not active for oxygen removal reactions.     

Cyclohexanone Conversion Catalyzed by Pt/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>: Evidence of Oxygen Removal and Coupling Reactions

Abstract  

The conversion of cyclohexanone, often identified as an intermediate in the conversion of lignin-derived compounds, was catalyzed by Pt/γ-Al₂O₃ in the presence of H₂ at 573 K. Dehydrogenation was a kinetically significant reaction, indicated by a high selectivity for phenol. Oxygen-removal reactions are indicated by products including benzene, cyclohexene, and cyclohexene. Bimolecular reactions involving cyclohexanone and/or products of its conversion led to the formation of bicyclic C₁₂ compounds, with 2-cyclohexylcyclohexan-1-one and 2-phenylphenol being the most abundant. Increasing the H₂ partial pressure led to increased oxygen removal and faster formation of monocyclic and bicyclic hydrocarbons. At temperatures higher than 573 K, dehydrogenation became the dominant reaction class.     

Catalytic Conversion of Anisole: Evidence of Oxygen Removal in Reactions with Hydrogen

Abstract  

The conversion of anisole, a prototypical bio-oil compound, was catalyzed by Pt/Al₂O₃ in the presence of H₂ at 573 K, with the selectivity for C–O bond breaking approximately matching that for ring hydrogenation; these reactions were accompanied by methyl group transfers matching those in the conversion catalyzed by HY zeolite.