Supercritical water gasification of RDF and its components over RuO2/γ-Al2O3 catalyst:new insights into RuO2 catalytic reaction mechanisms

Five samples including a composite refuse derived fuel (RDF) and four combustible components of municipal solid wastes (MSW) have been reacted under supercritical water conditions in a batch reactor. The reactions have been carried out at 450 °C for 60 min reaction time, with or without 20 wt% RuO2/gamma-alumina catalyst. The reactivities of the samples depended on their compositions; with the plastic-rich samples, RDF and mixed waste plastics (MWP), giving similar product yields and compositions, while the biogenic samples including mixed waste wood (MWW) and textile waste (TXT) also gave similar reaction products. The use of the heterogeneous ruthenium-based catalyst gave carbon gasification efficiencies (CGE) of up to 99 wt%, which was up by at least 83% compared to the non-catalytic tests. In the presence of RuO2 catalyst, methane, hydrogen and carbon dioxide became the dominant gas products for all five samples. The higher heating values (HHV) of the gas products increased at least two-fold in the presence of the catalyst compared to non-catalytic tests. Results show that the ruthenium-based catalyst was active in feedstock steam reforming, methanation and possible direct hydrogenolysis of C-C bonds. This work provides new insights into the catalytic mechanisms of RuO2 during SCWG of carbonaceous materials, along with the possibility of producing high yields of methane from MSW fractions.

Coke formation in the oxidative dehydrogenation of ethylbenzene to styrene by TEOM

A packed bed microbalance reactor setup (TEOM-GC) is used to investigate the formation of coke as a function of time-on-stream on γ-Al2O3 and 3P/SiO2 catalyst samples under different conditions for the ODH reaction of ethylbenzene to styrene. All samples show a linear correlation of the styrene selectivity and yield with the initial coverage of coke. The COX production increases with the coverage of coke. On the 3 wt% P/SiO2 sample, the initial coke build-up is slow and the coke deposition rate increases with time. On alumina-based catalyst samples, a fast initial coke build-up takes place, decreasing with time-on-stream, but the amount of coke does not stabilize. A higher O2 : EB feed ratio results in more coke, and a higher temperature results in less coke. This coking behaviour of Al2O3 can be described by existing "monolayer-multilayer" models. Further, the coverage of coke on the catalyst varies with the position in the bed. For maximal styrene selectivity, the optimal coverage of coke should be sufficient to convert all O2, but as low as possible to prevent selectivity loss by COX production. This is in favour of high temperature and low O2 : EB feed ratios. The optimal coke coverage depends in a complex way on all the parameters: temperature, the O2 : EB feed ratio, reactant concentrations, and the type of starting material. This journal is

Oxidation and stabilisation chemistry of metallocene-based polyolefins during melt processing

Metallocene catalyzed linear low density polyethylene (m-LLDPE) is a new generation of olefin copolymer. Based on the more recently developed metallocene-type catalysts, m-LLDPE can be synthesized with exactly controlled short chain branches and stereo-regular microstructure. The unique properties of these polymers have led to their applications in many areas. As a result, it is important to have a good understanding of the oxidation mechanism of m-LLDPE during melt processing in order to develop more effective stabilisation systems and continue to increase the performance of the material. The primary objectives of this work were, firstly, to investigate the oxidative degradation mechanisms of m-LLDPE polymers having different comonomer (I-octene) content during melt processing. Secondly, to examine the effectiveness of some commercial antioxidants on the stabilisation of m-LLDPE melt. A Ziegler-polymerized LLDPE (z-LLDPE) based on the same comonomer was chosen and processed under the same conditions for comparison with the metallocene polymers. The LLDPE polymers were processed using an internal mixer (torque rheometer, TR) and a co-rotating twin-screw extruder (TSE). The effects of processing variables (time, temperature) on the rheological (MI, MWD, rheometry) and molecular (unsaturation type and content, carbonyl compounds, chain branching) characteristics of the processed polymers were examined. It was found that the catalyst type (metallocene or Ziegler) and comonomer content of the polymers have great impact on their oxidative degradation behavior (crosslinking or chain scission) during melt processing. The metallocene polymers mainly underwent chain scission at lower temperature (<220°C) but crosslinking became predominant at higher temperature for both TR and TSE processed polymers. Generally, the more comonomers the m-LLDPE contains, a larger extent of chain scission can be expected. In contrast, crosslinking reactions were shown to be always dominant in the case of the Ziegler LLDPE. Furthermore, it is clear that the molecular weight distribution (MWD) of all LLDPE became broader after processing and tended generally to be broader at elevated temperatures and more extrusion passes. So, it can be concluded that crosslinking and chain scission are temperature dependent and occur simultaneously as competing reactions during melt processing. Vinyl is considered to be the most important unsaturated group leading to polymer crosslinking as its concentration in all the LLDPE decreased after processing. Carbonyl compounds were produced during LLDPE melt processing and ketones were shown to be the most imp0l1ant carbonyl-containing products in all processed polymers. The carbonyl concentration generally increased with temperature and extrusion passes, and the higher carbonyl content fonned in processed z-LLDPE and m-LLDPE polymers having higher comonomer content indicates their higher susceptibility of oxidative degradation. Hindered phenol and lactone antioxidants were shown to be effective in the stabilization of m-LLDPE melt when they were singly used in TSE extrusion. The combination of hindered phenol and phosphite has synergistic effect on m-LLDPE stabilization and the phenol-phosphite-Iactone mixture imparted the polymers with good stability during extrusion, especially for m-LLDPE with higher comonomer content.

Zirconia and alumina based catalysts for steam reforming of naphthalene

The present paper deals with experimentation of ZrO2 and Al2O3-supported catalysts for conversion of naphthalene, chosen as tar model compound of pyrolysis or gasification syngas. In particular, the reforming capacity of active metals and promoters such as Co, Ni, Fe, Cr, Ce and Pt was tested in a fixed bed reactor at temperature from 400 to 900 °C. As regards ZrO2-supported catalysts, the best results were achieved by the Ni/Fe/Pt catalyst with 96% naphthalene conversion, 78% and 280% as CO and H2 production yield at 800 °C. Regarding Al2O3-supported catalysts, they were more active on average than the zirconia ones, achieving a very good performance even at 500 °C (90–100% naphthalene conversion, 30–40% CO yield and 300–350% H2 yield at 550 °C). Influence of different amounts of alumina, montmorillonite and carbon on carrier composition as well as pellets’ size were also studied. Both zirconia and alumina catalysts showed deactivation at higher temperatures due to coke deposition, resulting in a strong H2 production drop. Regeneration of catalysts by O2 and steam as well as activation by H2 were also studied. The activated catalyst was able to convert more than 99% naphthalene at 450 °C with a CO and H2 production yield of 26% and 420%, respectively.

An ultra-sensitive localised surface plasmon resonance fibre device for environmental sensing based upon a structured bi-metal coating

We demonstrate a bi-metal coating (platinum and gold or silver) localised surface plasmon resonance fibre device that produces an index spectral sensitivity of over 11,000 nm/RIU, yielding an index resolution of 5×10-6in the aqueous index regime, consisting of a structured multi-layered thin film on D-shaped fibre. © 2014 SPIE.

NOx storage-reduction characteristics of Ba-based lean NOx trap catalysts subjected to simulated road aging

In order to study the effect of washcoat composition on lean NOx trap (LNT) aging characteristics, fully formulated monolithic LNT catalysts containing varying amounts of La-stabilized CeO2 (5 wt% La2O3) or CeO2-ZrO2 (Ce:Zr = 70:30) were subjected to accelerated aging on a bench reactor. Subsequent catalyst evaluation revealed that aging resulted in deterioration of the NOx storage, NOx release and NOx reduction functions, whereas the observation of lean phase NO2 slip for all of the aged catalysts indicated that LNT performance was not limited by the kinetics of NO oxidation. After aging, all of the catalysts showed increased selectivity to NH3 in the temperature range 250–450 °C. TEM, H2 chemisorption, XPS and elemental analysis data revealed two main changes which can explain the degradation in LNT performance. First, residual sulfur in the catalysts, present as BaSO4, decreased catalyst NOx storage capacity. Second, sintering of the precious metals in the washcoat was observed, which can be expected to decrease the rate of NOx reduction. Additionally, sintering is hypothesized to result in segregation of the precious metal and Ba phases, resulting in less efficient NOx spillover from Pt to Ba during NOx adsorption, as well as decreased rates of reductant spillover from Pt to Ba and reverse NOx spillover during catalyst regeneration. Spectacular improvement in LNT durability was observed for catalysts containing CeO2 or CeO2-ZrO2 relative to their non-ceria containing analog. This was attributed to (i) the ability of ceria to participate in NOx storage/reduction as a supplement to the main Ba NOx storage component; (ii) the fact that Pt and CeO2(-ZrO2) are not subject to phase segregation; and (iii) the ability of ceria to trap sulfur, resulting in decreased sulfur accumulation on the Ba component.

Carbon nanotube-supported metal catalysts for NOx reduction using hydrocarbon reductants. Part 1:catalyst preparation, characterization and NOx reduction characteristics

A dual catalyst system for the Selective Catalytic Reduction of NOx with hydrocarbons (HC-SCR), including distinct low and high temperature formulations, is proposed as a means to abate NOx emissions from diesel engines. Given that satisfactory high temperature HC-SCR catalysts are already available, this work focuses on the development of an improved low temperature formulation. Pt supported on multiwalled carbon nantubes (MWCNTs) was found to exhibit superior NOx reduction activity in comparison with Pt/Al2O3, while the MWCNT support displayed a higher resistance to oxidation than activated carbon. Refluxing the MWCNT support in a 1:1 mixture of H2SO4 and HNO3 prior to the metal deposition step proved to be beneficial for the metal dispersion and the NOx reduction performance of the resulting catalysts. This support effect is ascribed to the increased Brønsted acidity of the acid-treated MWCNTs, which in turn enhances the partial oxidation of the hydrocarbon reductant. Further improvements in the HC-SCR performance of MWCNT-based formulations were achieved using a 3:1 Pt–Rh alloy as the supported phase.

Catalytic systems based on carbon fiber materials for the low-temperature oxidation of carbon monoxide

New heterogenized catalytic systems for the low-temperature oxidation of CO were synthesized by supporting solutions of Pd, Cu, and Fe salts on carbon fibrous materials (carbopon and busofit). The carbon supports were studied by elemental analysis, SEM, TGA, and TPD. The effects of the nature of the support, the concentration and composition of the active component, and the conditions of preparation on the efficiency of the catalytic system were studied. It was ascertained that attenuation of hydrophilic properties of the support led to the decrease in system activity. The investigation of the catalysts by XPS showed that sample treatment in the reaction medium results in redistribution of the components of the active phase in the near-surface layer of the catalyst. The catalytic system based on carbon fibrous material carbopon prepared by supporting active components (Pd, Cu, and Fe salts) in three stages with intermediate activation in the reaction medium ensures 95% conversion of CO under respiratory conditions, and is promising for the design of the main element of breathing masks on its basis.

Propene combustion over a model Pt/Al2O3/NiAl{110} catalyst

The genesis of a catalytically active model Pt/Al2O3/NiAl{110} oxidation catalyst is described. An ultrathin, crystalline γ-Al2O3 film was prepared via direct oxidation of a NiAl{110} single-crystal substrate. The room-temperature deposition of Pt clusters over the γ-Al2O3 film was characterised by LEED, AES and CO titration and follows a Stranski–Krastanov growth mode. Surface sulfation was attempted via SO2/O2 adsorption and thermal processing over bare and Pt promoted Al2O3/NiAl{110}. Platinum greatly enhances the saturation SOx coverage over that of bare alumina. Over clean Pt/γ-Al2O3 surfaces some adsorbed propene desorbs molecularly [similar]250 K while the remainder decomposes liberating hydrogen. Coadsorbed oxygen or sulfate promote propene combustion, with adsorbed sulfoxy species the most efficient oxidant. The chemistry of these alumina-supported Pt clusters shows a general evolution from small polycrystalline clusters to larger clusters with properties akin to low-index, Pt single-crystal surfaces.

Highly sensitive, localized surface plasmon resonance fiber device for environmental sensing, based upon a structured bi-metal array of nano-wires

We demonstrate a bi-metal coated (platinum and gold or silver), localized surface plasmon resonance fiber sensor with an index sensitivity exceeding 11,900 nm/RIU, yielding an index resolution of 2 × 10-5 in the aqueous index regime. This is one of the highest index sensitivities achieved with an optical fiber sensor. The coatings consist of arrays of bi-metal nano-wires (typically 36 nm in radius and 20 μm in length), supported by a silicon dioxide thin film on a thin substrate of germanium, the nano-wires being perpendicular to the longitudinal axis of the D-shaped fiber.

Bio-based chemicals from biorefining:carbohydrate conversion and utilisation

The quest for sustainable sources of fuels and chemicals to meet the demands of a rapidly rising global population represents one of this century's grand challenges. Biomass offers the most readily implemented, and low cost, solution for transportation fuels, and the only non-petroleum route to organic molecules for the manufacture of bulk, fine and speciality chemicals and polymers. Chemical processing of such biomass-derived building blocks requires catalysts compatible with hydrophilic, bulky substrates to facilitate the selective deoxygenation of highly functional bio-molecules to their target products. This chapter addresses the challenges associated with carbohydrate utilisation as a sustainable feedstock, highlighting innovations in catalyst and process design that are needed to deliver high-value chemicals from biomass-derived building blocks. © 2014 Woodhead Publishing Limited. All rights reserved.

Platinum-catalysed cinnamaldehyde hydrogenation in continuous flow

Platinum is one of the most widely used hydrogenation catalysts. Here we describe the translation of batch reactions to continuous flow, affording tunable C=O versus C=C hydrogenation over a Pt/SiO2 catalyst, resulting in high steady state activity and single-pass yields in the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol under mild conditions. Negligible catalyst deactivation occurs under extended flow operation due to removal of reactively-formed poisons from the reaction zone. Process intensification imparts a four-fold enhancement in cinnamyl alcohol productivity.

Catalyst design for biorefining

The quest for sustainable resources to meet the demands of a rapidly rising global population while mitigating the risks of rising CO2 emissions and associated climate change, represents a grand challenge for humanity. Biomass offers the most readily implemented and low-cost solution for sustainable transportation fuels, and the only non-petroleum route to organic molecules for the manufacture of bulk, fine and speciality chemicals and polymers. To be considered truly sustainable, biomass must be derived fromresources which do not compete with agricultural land use for food production, or compromise the environment (e.g. via deforestation). Potential feedstocks include waste lignocellulosic or oil-based materials derived from plant or aquatic sources, with the so-called biorefinery concept offering the co-production of biofuels, platform chemicals and energy; analogous to today's petroleum refineries which deliver both high-volume/low-value (e.g. fuels and commodity chemicals) and lowvolume/ high-value (e.g. fine/speciality chemicals) products, thereby maximizing biomass valorization. This article addresses the challenges to catalytic biomass processing and highlights recent successes in the rational design of heterogeneous catalysts facilitated by advances in nanotechnology and the synthesis of templated porous materials, as well as the use of tailored catalyst surfaces to generate bifunctional solid acid/base materials or tune hydrophobicity.

Pd/C catalysts based on synthetic carbons with bi- and tri-modal pore-size distribution:applications in flow chemistry

Two new types of phenolic resin-derived synthetic carbons with bi-modal and tri-modal pore-size distributions were used as supports for Pd catalysts. The catalysts were tested in chemoselective hydrogenation and hydrodehalogenation reactions in a compact multichannel flow reactor. Bi-modal and tri-modal micro-mesoporous structures of the synthetic carbons were characterised by N2 adsorption. HR-TEM, PXRD and XPS analyses were performed for characterising the synthesised catalysts. N2 adsorption revealed that tri-modal synthetic carbon possesses a well-developed hierarchical mesoporous structure (with 6.5 nm and 42 nm pores), contributing to a larger mesopore volume than the bi-modal carbon (1.57 cm3 g-1versus 1.23 cm3 g-1). It was found that the tri-modal carbon promotes a better size distribution of Pd nanoparticles than the bi-modal carbon due to presence of hierarchical mesopore limitting the growth of Pd nanoparticles. For all the model reactions investigated, the Pd catalyst based on tri-modal synthetic carbon (Pd/triC) show high activity as well as high stability and reproducibility. The trend in reactivities of different functional groups over the Pd/triC catalyst follows a general order alkyne ≫ nitro > bromo ≫ aldehyde.

Fenton chemistry-based detemplation of an industrially relevant microcrystalline beta zeolite. Optimization and scaling-up studies

A mild template removal of microcrystalline beta zeolite, based on Fenton chemistry, was optimized. Fenton detemplation was studied in terms of applicability conditions window, reaction rate and scale up. TGA and CHN elemental analysis were used to evaluate the detemplation effectiveness, while ICP, XRD, LPHR-Ar physisorption, and 27Al MAS NMR were applied to characterize the structure and texture of the resulting materials. The material properties were compared to calcination. By understanding the interplay of relevant parameters of the Fenton chemistry, the process can be optimized in order to make it industrially attractive for scale-up. The H2O2 utilization can be minimized down to 15 mL H2O2/g (88 °C, 30 ppm Fe), implying a high solid concentration and low consumption of H2O2. When Fe concentration must be minimized, values as low as 5 ppm Fe can be applied (88 °C, 30 mL H2O2/g), to achieve full detemplation. The reaction time to completeness can be reduced to 5 h when combining a Fe-oxalate catalyst with UV radiation. The protocol was scaled up to 100 times larger its original recipe. In terms of the material's properties, the scaled material is structurally comparable to the calcined counterpart (comparable Si/Al and XRD patterns), while it displays benefits in terms of texture and Al-coordination, the latter with full preservation of the tetrahedral Al