Applied Petrochemical Research (v.2, #1-2)

The First KACST-Oxford Petrochemical Forum, 2011 by Peter P. Edwards; Hamid A. Almegren; Tiancun Xiao (1-2).

The energy challenge by Chris Llewellyn Smith (3-6).
This paper provides an overview of the enormous challenge of meeting future energy demand in an environmentally responsible manner. A portfolio approach is required, which must include more solar, wind, hydro, bio and marine energy wherever sensible, and demand reduction (through better planning, especially in the world’s expanding cities), increased efficiency, more nuclear power, and (if feasible, safe and economically competitive) carbon capture and storage. In the longer term, the world will need much more solar power, advanced nuclear fission, and fusion power—if it can be made to work reliably and competitively. The policy priority is to put a (high) price on carbon in the context of a global agreement (through a tax, or cap and trade with a floor price to provide certainty for investors), which is easily said, but very hard to do.
Keywords: Energy demand; Energy supply; Energy efficiency; Fossil fuels; Renewable energy; Nuclear energy

Gold catalysis: helping create a sustainable future by Nikolaos Dimitratos; Jennifer K. Edwards; Christopher J. Kiely; Graham J. Hutchings (7-14).
In recent years there has been a general realisation that supported gold and gold bimetallic nanoparticles can be very effective for a broad range of redox reactions. In this paper we review the preparation of gold palladium nanoparticles using a sol-immobilisation methodology and show their effectiveness for the oxidation of benzyl alcohol and the direct synthesis of hydrogen peroxide.
Keywords: Gold catalysis; Alcohol oxidation; Hydrogen peroxide synthesis

Electron microscopic studies of growth of nanoscale catalysts and soot particles in a candle flame by Wu Zong Zhou; Feng Jiao Yu; Heather F. Greer; Zheng Jiang; Peter P. Edwards (15-21).
Scanning electron microscopy and high-resolution transmission electron microscopy have been used to investigate non-classic crystal growth of catalytic nanoparticles, such as zeolites, perovskites, metal and alloy particles. Growth mechanisms of some crystals with novel morphologies, for example, BiOBr flower-like particles and ZnO twin-crystals, have also been studied. A development of sampling method for soot particles inside a candle flame allows us to reveal all four well-known carbon forms, amorphous, graphitic, fullerenic and nanodiamond particles. This article demonstrates that electron microscopy is a powerful tool to study the microstructures of small particles, giving us more freedom to develop new materials.
Keywords: Crystal growth; ZnO; BiOBr; CaCO3Electron microscopy

Syn-gas-based mono ethylene glycol synthesis in Pujing Chemical by Nianjun Luo; Yang Ji; Yanpeng Mao; Bo Zhang (23-26).
Mono ethylene glycol (MEG) is a kind of important fundamental chemical, mainly used in polyester synthesis. Traditional MEG production is based on petroleum resources. This study reports about a new kind of MEG technology to synthesize CO and hydrogen, developed by Pujing Chemical. Laboratorial researches were performed well by developing both carbonylation catalyst and hydrogenation catalyst. Later, a 300 t/a hydrogenation pilot plant was employed to verify the hydrogenation catalyst, and another 1000 t/a pilot plant was set up to validate the whole flow process, catalysts and purification technology in Anhui Province, China.
Keywords: Mono ethylene glycol; Carbonylation; Hydrogenation; Pilot plant

Role of metal substitution in lanthanum zirconate pyrochlores (La2Zr2O7) for dry (CO2) reforming of methane (DRM) by Devendra Pakhare; Daniel Haynes; Dushyant Shekhawat; James Spivey (27-35).
Dry (CO2) reforming of methane (DRM) produces syngas with H2/CO ratio of ≤1. In this work, we report the use of pyrochlores (A2B2O7) as catalysts for this reaction. Here, we examine lanthanum zirconate pyrochlores, LZ, with lanthanum and zirconium occupying the A and B sites, respectively. Three catalysts are tested: LZ and two pyrochlores in which the B-site has been isomorphically substituted with (a) Ru (2 wt%) (designated LRuZ) and (b) Pt (3.78 wt%) (designated LPtZ). These levels of substitution by weight correspond to identical atomic levels of substitution at the B-site. The effect of isomorphic substitution of Ru and Pt on the structure and activity of the pyrochlores in DRM is studied in this work. ICP-OES, XRD, H2 and CH4 TPR were used to characterize the structure of the catalysts. XRD results confirmed the formation of the La2Zr2O7 phase in the bulk of the pyrochlores. H2 TPR showed higher reduction temperatures for LPtZ compared to LRuZ, suggesting a less reducible, stable Pt in the pyrochlore structure compared to Ru. Quantitative analysis showed that LRuZ consumed 0.534 mg H2/gcat, whereas LPtZ consumed only 0.161 mg H2/gcat corresponding to much greater extent of reduction for LRuZ compared to LPtZ. CO formation during CH4 TPR showed that both materials have reactive lattice oxygen which helps in reducing carbon formation during DRM. Temperature programmed oxidation studies of the catalyst immediately after CH4 TPR showed greater carbon formation over LPtZ (1.67 gc/gcat) compared to LRuZ (1.17 gc/gcat) suggesting that Pt activates CH4 to a greater extent compared to Ru. Temperature programmed DRM surface reaction showed that the light off temperature for LRuZ was about 45 °C lower than that of LPtZ. These are novel results and constitute the first report of which we are aware for Pt and Ru substituted pyrochlores for DRM.
Keywords: Dry reforming; Lanthanum zirconate; Pyrochlores; Lattice oxygen; Isomorphic substitution; Perovskite

Microwave treatment in oil refining by Adrian Porch; Dan Slocombe; Jan Beutler; Peter Edwards; Afrah Aldawsari; Tiancun Xiao; Vladimir Kuznetsov; Hamid Almegren; Saud Aldrees; Naif Almaqati (37-44).
In this paper, we discuss the potential of using microwave techniques in the refinement of heavy fraction of petroleums such as bunker oil. After discussing the fundamental issues associated with conversion of microwave energy into heat, we present measurements of the dielectric properties of heavy oils at 2.45 GHz using a highly sensitive resonant cavity method, and also over a broader frequency range (100 MHz to 8 GHz) using a coaxial probe technique. We find that the dielectric loss is very small even in these heavy oils, but still may be sufficiently large to provide efficient conversion of microwave energy into heat on untreated samples, and could be massively enhanced by means of a microwave-absorbing additive (e.g., carbon black). We conclude by discussing the design of a suitable microwave actuator for heavy oil cracking within a flow process.
Keywords: Microwave; Dielectric; Petroleum

Oxidation of benzylic alcohols over Cr (MCM-41/ZSM-5) assisted by microwaves by Zoubida Lounis; Naouel Boumesla; A. E. K. Bengueddach (45-50).
The oxidation of benzylic alcohols in the machine of microwave (Discover, CEM-SP1245 model, USA) by the composite material type Cr-(MCM41/ZSM5) with high crystallinity, exchanged at low content of chromium has dramatically reduced the reaction times and have high conversion rates and high yields compared to conventional heating. Ketones were obtained for only 10 min of reaction. The composite materials used containing both micropore and mesopore structures are stable for this type of reaction. The method uses composite materials Cr (50-MCM41/ZSM5) as the catalyst system and t-BuOOH as the stoichiometric terminal oxidant. The reactions carried out by the microwave and made without the use of an organic solvent, because, the substrates are mixed directly or, in our case, the subtract is mixed with silica which is inactive in the reaction.
Keywords: Benzylic oxidation; Microwaves; Composite materials; Catalyse; Chromium exchange

Removing of hydrocarbon contaminated soil via air flushing enhanced by surfactant by Th. Abdel-Moghny; Ramadan S. A. Mohamed; E. El-Sayed; Shoukry Mohammed Aly; Moustafa Gamal Snousy (51-59).
Surfactants enhanced air sparging actually acts to displace the organic contaminant entrapped in soil pores. In this work, a comparison study was carried out between two air-flushing modes, namely, continuous air flushing and pulsed air flushing, which was conducted to remediate soil contaminated with waste-lubricant oil. Therefore, coarse sand was artificially polluted and mixed well with waste-lubricant oil at different concentrations of 10, 25 and 50 wt% to give the soil an oil blend. Then a laboratory glass column was established and backed with contaminated soil to study the effect of flow rate, pollutant and surfactant concentrations on the removal of waste-lubricant oil from soil. The contaminated soil was washed with pure water and flushed with both air-flushing modes at a pressure of 2 kPa and flow rate of 6 L min−1. After that fixed 300 mL nonionic surfactant solutions (NPEO9.3) at concentrations of 3, 5 and 7 wt%, were poured individually along with air injection at the same pressure and flow rate. The treated soil was washed several times with pure water to eliminate the residual surfactant solutions. It was found that water washing and air injection remove 27 % of oil; however, air injection along with surfactant solutions increased the oil removal efficiency up to 90 %. Moreover, both air-flushing modes succeeded in removing the pollutant with majority to pulsed air mode over continuous mode; therefore, pulsed air flushing was applied for 25 and 50 wt% waste lubricant oils in presence of 3 wt% nonionic surfactant.
Keywords: Air injection; Soil washing; Surfactant flushing; Waste-lubricant oils