Effect of alkyl chain length on the electrochemical perfluorination of n-alkane (C6–C10) carboxylic acid chlorides

Electrochemical perfluorination (ECPF) of n-hexanoyl, n-heptanoyl, n-octanoyl, n-nonanoyl and n-decanoyl chlorides was carried out under identical experimental conditions in liquid HF. The product distribution among perfluorinated carboxylic acids, perfluoro ethers, perfluoroalkanes, isomerised and fragmented products containing less number of carbon atoms was identified using ¹⁹F NMR. The selectivity of C₆–C₁₀ perfluoro carboxylic acid varied between 29 and 36%. The alkali insoluble perfluoro cyclic ether and perfluoro alkane fractions increased with increasing chain length. The increase of perfluoroalkane fractions is mainly due to decarboxylation. Cyclic ether fractions also decreased slightly with increase in chain length. Among the cyclic ethers α substituted oxolanes were the predominant products. Six membered cyclic ethers were always found to contain β substitution. The possible pathways for these products are also indicated. An erratum to this article can be found at     

Synthesis and characterization of acidic properties of Al-SBA-15 materials with varying Si/Al ratios

Al-SBA-15 of varying Si/Al ratios in the range 11.4–78.4 was synthesized using tri-block copolymer P123. The calcined materials were examined by XRD, pore size distribution, surface area, ²⁷Al NMR spectroscopy. The acidity and acid strength distribution were studied using microcalorimetric adsorption of NH₃. The acidic properties were also examined by cumene cracking reaction as a function of Si/Al ratios. Systematic variation of acidity and activity was observed as a function of Si/Al ratio. The initial heats of NH₃ adsorption correlated well with activity indicate that acid sites with ΔH > 100 kJ/mole is responsible for cumene cracking activity. Linear correlations were obtained with total acidity and cumene cracking activities. The tetrahedral aluminum was found to be responsible for the observed acidities and catalytic activities.     

Studies of substrate specificities of lipases from different sources

Although lipases are widely applied in a wide variety of reactions, available information on the factors that are responsible for the substrate specificities of lipases from different sources is scarce. In this paper, nine lipase‐producing microorganism strains were isolated from oil‐containing samples. The properties of these enzymes, including pH optima, temperature optima, thermal stability, and pH stability, vary significantly with the different sources from which these lipases were isolated. The substrate specificities of the nine lipases, including fatty acid and positional specificities, were also studied. The fatty acid specificities of the nine lipases were observably different toward 15 substrates with different carbon chain lengths, different saturation degrees and different side chains. The lipases from S₃ Penicillium citrinum (PCL), MJ₁ Aspergillus niger (ANL), MJ₂ Aspergillus oryzae (AOL), YM Bacillus coughing (BCL), S₉ Geotrichum candidum (GCL), and S₁₁ Candida lypolytica (CLL) showed the strongest specificities to short‐chain esters, and the other lipases showed strong selectivity for medium‐ or long‐chain and branched esters. The positional specificities were examined by analyzing the hydrolytic products of triolein catalyzed by the nine lipases, using TLC. The lipases can be mainly classified into two groups by their specificities for the ester bond at position 2 of triglycerides; one group can selectively hydrolyze the ester bond at position 2 of the triglycerides, the other group cannot. All these nine lipases were divided into four groups by hierarchical clustering analysis on the basis of the results of fatty acid and positional specificities.     

A study of synthesizing benzaldehydes from propenylbenzenes and cinnamic acid derivatives

Propenylbenzenes and cinnamic acid derivatives yield correspondingly substituted benzaldehydes when oxidized by lead-ruthenium pyrochlore oxide in the presence of sodium hydrochlorite as a co-oxidant at pH 11 under heterogeneous conditions. The reaction of terminal and internal aliphatic alkenes under similar conditions affords no aldehydes.     

Effect of Ammonia on the Gas-Phase Hydration of the Common Atmospheric Ion HSO4?

Hydration directly affects the mobility, thermodynamic properties, lifetime and nucleation rates of atmospheric ions. In the present study, the role of ammonia on the formation of hydrogen bonded complexes of the common atmospheric hydrogensulfate (HSO₄⁻) ion with water has been investigated using the Density Functional Theory (DFT). Our findings rule out the stabilizing effect of ammonia on the formation of negatively charged cluster hydrates and show clearly that the conventional (classical) treatment of ionic clusters as presumably more stable compared to neutrals may not be applicable to pre-nucleation clusters. These considerations lead us to conclude that not only quantitative but also qualitative assessment of the relative thermodynamic stability of atmospheric clusters requires a quantum-chemical treatment.     

The effect of aromatics on paraffin mild hydrocracking reactions (WNiPd/CeY–Al2O3)

The conversion of heavy paraffin and aromatics into a high-quality diesel fraction was performed in a microplant using a WNiPd/CeY-alumina catalyst. The effects of aromatics and naphtheno-aromatics on mild hydrocracking of hexadecane were studied at different concentrations. Two catalysts, with and without Pd and thermal treatment, were characterized by FTIR, XPS, and TPD of ammonia and ammonia plus naphthalene to complement previous study about the surface composition. The hydrocracking activity and selectivity were tested using different amounts and types of aromatics. This study demonstrated the presence of two acid strengths that contribute in different ways to paraffin and aromatics isomerization, ring opening, and cracking reactions. The product distribution obtained by mild hydrocracking of n-C₁₆ is between amorphous (SiO₂Al₂O₃) and Y-zeolite type of support. The aromatic adsorption on acid sites reduces the cracking rate and improves the survival of di- and tri-branched paraffin. A model for the path of reaction is discussed to explain the results.     

Laboratory simulated slipstream testing of novel sulfur removal processes for gasification application

The Wabash River Integrated Methanol and Power Production from Clean Coal Technologies (IMPPCCT) project is investigating an Early Entrance Coproduction Plant (EECP) concept to evaluate integrated electrical power generation and methanol production from coal and other carbonaceous feedstocks. Research, development and testing (RD&T) that is currently being conducted under the project is evaluating cost effective process systems for removing contaminants, particularly sulfur species, from the generated gas which contains mainly synthesis gas (syngas), CO₂ and steam at concentrations acceptable for the methanol synthesis catalyst. The RD&T includes laboratory testing followed by bench-scale and field testing at the SG Solutions Gasification Plant located in West Terre Haute, Indiana. Actual synthesis gas produced by the plant was utilized at system pressure and temperature for bench-scale field testing.     

Hydrogen production from methane in a dielectric barrier discharge using oxide zinc and chromium as catalyst

The hydrogen fuel cell is a promising option as a future energy resource; however, the nature of the gas is such that the conversion process of other fuels to hydrogen on board is necessary. Among the raw fuel resources, methane could be the best candidate as it is plentiful. In this experiment, the possibility of producing hydrogen with less carbon formation from methane by a dielectric barrier discharge (DBD) was investigated. Without the addition of a catalyst, the formation of hydrogen reached between 30% and 35% at methane residence time of 0.22 min and supplied powers in the range of 60-130 W. The hydrogen selectivity increased at higher supplied power, but the process efficiency, defined as a ratio of the produced hydrogen to the supplied power, decreased slightly. In order to boost the hydrogen production with less carbon formation, a mixed oxide catalyst of zinc and chromium was added to the reactor. It was shown that the production of hydrogen was ca. 40% higher than the non-catalytic plasma process.     

Enzymatic biodiesel production: Technical and economical considerations

It is well documented in the literature that enzymatic processing of oils and fats for biodiesel is technically feasible. However, with very few exceptions, enzyme technology is not currently used in commercial‐scale biodiesel production. This is mainly due to non‐optimized process design and a lack of available cost‐effective enzymes. The technology to re‐use enzymes has typically proven insufficient for the processes to be competitive. However, literature data documenting the productivity of enzymatic biodiesel together with the development of new immobilization technology indicates that enzyme catalysts can become cost effective compared to chemical processing. This work reviews the enzymatic processing of oils and fats into biodiesel with focus on process design and economy.