Effects of promoters on catalytic activity and carbon deposition of Ni/gamma-Al2O3 catalysts in CO2 reforming of CH4

Catalytic reforming of methane with carbon dioxide was studied in a fixed-bed reactor using unpromoted and promoted Ni/gamma-Al2O3 catalysts. The effects of promoters, such as alkali metal oxide (Na2O), alkaline-earth metal oxides (MgO, CaO) and rare-earth metal oxides (La2O3, CeO2), on the catalytic activity and stability in terms of coking resistance and coke reactivity were systematically examined. CaO-, La2O3- and CeO2-promoted Ni/gamma-Al2O3 catalysts exhibited higher stability whereas MgO- and Na2O-promoted catalysts demonstrated lower activity and significant deactivation. Metal-oxide promoters (Na2O, MgO, La2O3, and CeO2) suppressed the carbon deposition, primarily due to the enhanced basicities of the supports and highly reactive carbon species formed during the reaction. In contrast, CaO increased the carbon deposition; however, it promoted the carbon reactivity. (C) 2000 Society of Chemical Industry.

Novel silica gel supported TiO2 photocatalyst synthesized by CVD method

TiO2 in anatase crystal phase is a very effective catalyst in the photocatalytic oxidation of organic compounds in water. To improve the recovery rate of TiO2 photocatalysts, which in most cases are in fine powder form, the chemical vapor deposition (CVD) method was used to load TiO2 onto a bigger particle support, silica gel. The amount of titania coating was found to depend strongly on the synthesis parameters of carrier gas flow rate and coating time. XPS and nitrogen ads/desorption results showed that most of the TiO2 particles generated from CVD were distributed on the external surface of the support and the coating was stable. The photocatalytic activities of TiO2/silica gel with different amounts of titania were evaluated for the oxidation of phenol aqueous solution and compared with that of Degussa P25. The optimum titania loading rate was found around 6 wt % of the TiO2 bulk concentration. Although the activity of the best TiO2/silica gel sample was still lower than that of P25, the synthesized TiO2/silica gel catalyst can be easily separated from the treated water and was found to maintain its TiO2 content and catalytic activity.

Residence time distributions of gas flowing through rotating drum bioreactors

Residence time distribution studies of gas through a rotating drum bioreactor for solid-state fermentation were performed using carbon monoxide as a tracer gas. The exit concentration as a function of time differed considerably from profiles expected for plug flow, plug flow with axial dispersion, and continuous stirred tank reactor (CSTR) models. The data were then fitted by least-squares analysis to mathematical models describing a central plug flow region surrounded by either one dead region (a three-parameter model) or two dead regions (a five-parameter model). Model parameters were the dispersion coefficient in the central plug flow region, the volumes of the dead regions, and the exchange rates between the different regions. The superficial velocity of the gas through the reactor has a large effect on parameter values. Increased superficial velocity tends to decrease dead region volumes, interregion transfer rates, and axial dispersion. The significant deviation from CSTR, plug flow, and plug flow with axial dispersion of the residence time distribution of gas within small-scale reactors can lead to underestimation of the calculation of mass and heat transfer coefficients and hence has implications for reactor design and scaleup. (C) 2001 John Wiley & Sons, Inc.

Oxidation of toluene in waste gas streams using mesoporous Ti-hexagonal mesoporous silica

Various mesoporous catalysts with titanium loadings between 0.5 and 4 Ti wt. % and surface areas between 600 and 1,600 m(2)/g were synthesized using the molecular designed dispersion technique. These catalysts were tested using toluene oxidation in a fixed bed reactor at temperatures between 300 and 550degreesC. The reaction products were found to be CO2 and CO with selectivity towards CO2 above 80% for all catalysts. The catalytic activity of the catalysts increases with titanium loading. The total conversion at 550degreesC was not affected by the textural porosity, but increased textural porosity did significantly reduce the ignition temperature by up to 50degreesC. The Thiele modulus was calculated to be much less than one for all these materials indicating that the reaction rate is not diffusion, limited.

Fermentative production of hydrogen from cassava processing wastewater by Clostridium acetobutylicum

This work reports on the effect of initial substrate concentration on COD consumption, pH, and H(2) production during cassava processing wastewater fermentation by Clostridium acetobutylicum ATCC 824. Five initial COD wastewater concentrations, namely 5.0, 7.5, 10.7, 15.0, and 30.0 g/L, were used. The results showed that higher substrate concentrations (30.0 and 15.0 COD/L) led to lower H(2) yield as well as less efficient substrate conversion into H(2). On the other hand, initial COD concentrations of 10.7, 7.5 and 5 g/L furnished 1.34, 1.2 and 2.41 mol H(2)/mol glucose, with efficiency of glucose conversion into H(2) of 34, 30, and 60% (mol/mol), respectively. These results demonstrate that cassava processing wastewater, a highly polluting effluent, can be successfully employed as substrate for H(2) production by C acetobutylicum at lower COD concentrations. (C) 2011 Elsevier Ltd. All rights reserved.

Design analysis for refolding monomeric protein

Renaturation of protein expressed as inclusion bodies within Escherichia coli is a key step in many bioprocesses. Operating conditions for the refolding step dramatically affect the amount of protein product recovered, and hence profoundly influence the process economics. The first systematic comparison of refolding conducted in batch, fed-batch and continuous stirred-tank reactors is provided Refolding is modeled as kinetic competition between first-order refolding (equilibrium reaction) and irreversible aggregation (second-order). Simulations presented allow direct comparison between different flowsheets and refolding schemes using a dimensionless economic objective. As expected from examination of the reaction kinetics, batch operation is the most inefficient merle. For the base process considered, the overall cost of fed-batch and continuous refolding is virtually identical (less than half that of the batch process). Reactor selection and optimization of refolding using overall economics are demonstrated to be vitally important.

Microbiology and application of the anaerobic ammonium oxidation ('anammox') process

Ten years ago, an anaerobic ammonium oxidation ('anammox') process was discovered in a denitrifying pilot plant reactor. From this system, a highly enriched microbial community was obtained, dominated by a single deep-branching planctomycete, Candidatus Brocadia anammoxidans. Phylogenetic inventories of different wastewater treatment plants with anammox activity have suggested that at least two genera in Planctomycetales can catalyse the anammox process. Electron microscopy of the ultrastructure of B. anammoxidans has shown that several membrane-bounded compartments are present inside the cytoplasm. Hydroxylamine oxidoreductase, a key anammox enzyme, is found exclusively inside one of these compartments, tentatively named the 'anammoxosome'.

Characterization of pore structure and coordination of titanium in TiO2 and SiO2-TiO2 sol-pillared clays

Titania sol-pillared clay (TiO2 PILC) and silica-titania sol-pillared clay (SiO2-TiO2 PILC) were synthesized by the sol-gel method. Supercritical drying (SCD) and treatment with quaternary ammonium surfactants were used to tailor the pore structure of the resulting clay. It was found that SCD approach increased the external surface area of the PILCs dramatically and that treatment with surfactants could be used to tailor pore size because the mesopore formation in the galleries between the clay layers follows the templating mechanism as observed in the synthesis of MCM-41 materials. Highly mesoporous solids were thus obtained. In calcined TiO2 PILC, ultrafine crystallites in anatase phase, which are active for photocatalytic oxidation of organics, were observed. In SiO2-TiO2 PILCs and their derivatives, titanium was highly dispersed in the matrix of silica and no crystal phase was observed. The highly dispersed titanium sites are good catalytic centers for selective oxidation of organic compounds. (C) 2001 Academic Press.

Biodegradation of high strength phenolic wastewater using SBR

This investigation demonstrates the capability of a bench-scale sequencing batch reactor (SBR) to biodegrade an inhibitory substrate at a high loading rate. A SBR loading rate of 3.12 kg phenol.m(-3)d(-1) (2.1 g COD.g(-1) MLVSS d(-1)) with a COD removal efficiency of 97% at a SRT of 4 days and a HRT of 10 hours was achieved; this rate was not reached before. The SBR was operated at 4 hours cycle, including 3 hours react phase. The synthetic wastewater of 1300 mg/L phenol was the sole carbon source. Oxygen uptake rates (OUR) were monitored in-situ at various stages of the SBR. The oxygen mass transfer coefficient, K(L)a, of 12.6 h(-1) was derived from respirometry. Use of respirometry in SBR aided the tracking of the soluble substrate through OUR.

The IWA Anaerobic Digestion Model No 1 (ADM1)

The IWA Anaerobic Digestion Modelling Task Group was established in 1997 at the 8th World Congress on,Anaerobic Digestion (Sendai, Japan) with the goal of developing a generalised anaerobic digestion model. The structured model includes multiple steps describing biochemical as well as physicochemical processes. The biochemical steps include disintegration from homogeneous particulates to carbohydrates, proteins and lipids; extracellular hydrolysis of these particulate substrates to sugars, amino acids, and long chain fatty acids (LCFA), respectively; acidogenesis from sugars and amino acids to volatile fatty acids (VFAs) and hydrogen; acetogenesis of LCFA and VFAs to acetate; and separate methanogenesis steps from acetate and hydrogen/CO2. The physico-chemical equations describe ion association and dissociation, and gas-liquid transfer. Implemented as a differential and algebraic equation (DAE) set, there are 26 dynamic state concentration variables, and 8 implicit algebraic variables per reactor vessel or element. Implemented as differential equations (DE) only, there are 32 dynamic concentration state variables.

The influence of calcium on granular sludge in a full-scale UASB treating paper mill wastewater

Calcium precipitation can have a number of effects on the performance of high-rate anaerobic performance including cementing of the sludge bed, limiting diffusion, and diluting the active biomass. The aim of this study was to observe the influence of precipitation in a stable full-scale system fed with high-calcium paper factory wastewater. Granules were examined from an upflow anaerobic sludge blanket reactor (volume 1,805 m(3)) at a recycled paper mill with a loading rate of 5.7-6.6 kgCOD.m(-3).d(-1) and influent calcium concentration of 400-700 gCa(.)m(-3). The granules were relatively small (1 mm), with a 200-400 mum core of calcium precipitate as observed with energy dispersive X-ray spectroscopy. Compared to other granules, Methanomicrobiales not Methanobacteriales were the dominant hydrogen or formate utilisers, and putative acidogens were filamentous. The strength of the paper mill fed granules was very high when compared to granules from other full-scale reactors, and a partial linear correlation between granule strength and calcium concentration was identified.

Quantification of sulfur and sulfur-containing compounds in wastewaters by means of a combination of liquid chromatographic methods

Low-micromolar concentrations of sulfite, thiosulfate and sulfide, present in synthetic wastewater or anaerobic digester effluent, were quantified by means of derivatization with monobromobimane, followed by HPLC separation with fluorescence detection. The concentration of elemental sulfur was determined, after its extraction with chloroform from the derivatized sample, by HPLC with UV detection. Recoveries of sulfide (both matrices), and of thiosulfate and sulfite (synthetic wastewater) were between 98 and 103%. The in-run RSDs on separate derivatizations were 13 and 19% for sulfite (two tests), between 1.5 and 6.6% for thiosulfate (two tests) and between 4.1 and 7.7% for sulfide (three tests). Response factors for derivatives of sulfide and thiosulfate, but not sulfite, were steady over a 13-month period during which 730 samples were analysed. Dithionate and tetrathionate did not seem to be detectable with this method. The distinctness of the elemental sulfur and the derivatizing-agent peaks was improved considerably by detecting elution at 297 instead of 263 nm. (C) 2002 Elsevier Science B.V. All rights reserved.

Enrichment of autotrophic anaerobic ammonium-oxidizing consortia from various wastewaters

The option for biological nitrogen removal has recently been broadened with the description of simultaneous nitrification/denitrification, anaerobic ammonium oxidation (ANAMMOX) and the concept of CANON (completely autotrophic nitrogen removal over nitrite). An autotrophic anaerobic ammonium oxidation (AAAO) consortium was successfully selected and enriched from municipal treatment plant sludges in Sydney, Australia, but not from industrial coke-oven wastewater sludges. Chemolithoautotrophic basic salt (CLABS) medium was used in the selection of AAAO organisms and chloramphenicol was added to the initial stage of selection to eliminate denitrifiers. Two different temperatures, 37degreesC and 55degreesC, were used in the selection of mesophilic and thermophilic consortia, respectively. Thermophilic AAAO organisms were not selected at 55degreesC. Mesophilic AAAO activities, however, were evident in both batch and continuous cultures, whereby ammonium was consumed concurrently with a decrease of nitrite, giving a ratio of 1:1-1:1.3 in ammonium removal rate over nitrite consumption rate. A continuous-mode mesophilic fixed-bed reactor was established to enrich the AAAO consortium. After 1 year, biofilms, pinkish in color, had developed on the support media and side wall of the feed-line tubing. Ammonium and nitrite consumption increased from similar to15 mg to 60 mg d(-1) L-1 over a period of 243 days. Later, transmission electron microscopy (TEM) and fluorescence in situ hybridization (FISH) techniques revealed that the dominant cell type in the AAAO consortium had a similar morphology and 16S rDNA sequence homology to that of the recently described ANAMMOX organism, Brocadia anammoxidans.

The anammox case - A new experimental manifesto for microbiological eco-physiology

The anaerobic ammonium oxidation process is a new process for ammonia removal from wastewater. It is also a new microbial physiology that was previously believed to be impossible. The identification of Candidatus Brocadia anammoxidans and its relatives as the responsible bacteria was only possible with the development of a new experimental approach. That approach is the focus of this paper. The approach is a modernisation of the Winogradsky/Beyerinck strategy of selective enrichment and is based on the introduction of the molecular toolbox and modern bioreactor engineering to microbial ecology. It consists of five steps: (1) postulation of an ecological niche based on thermodynamic considerations and macro-ecological field data; (2) engineering of this niche into a laboratory bioreactor for enrichment culture; (3) black-box physiological characterisation of the enrichment culture as a whole; (4) phylogenetic characterisation of the enriched community using molecular tools; (5) physical separation of the dominant members of the enrichment culture using gradient centrifugation and the identification of the species of interest in accordance with Koch's postulates; (6) verification of the in situ importance of these species in the actual ecosystems. The power of this approach is illustrated with a case study: the identification of the planctomycetes responsible for anaerobic ammonium oxidation. We argue that this was impossible using molecular ecology or conventional 'cultivation based techniques' alone. We suggest that the approach might also be used for the microbiological study of many interesting microbes such as anaerobic methane oxidisers.

Combined hydraulic and biological modelling and full-scale validation of SBR process

The biological reactions during the settling and decant periods of Sequencing Batch Reactors (SBRs) are generally ignored as they are not easily measured or described by modelling approaches. However, important processes are taking place, and in particular when the influent is fed into the bottom of the reactor at the same time (one of the main features of the UniFed process), the inclusion of these stages is crucial for accurate process predictions. Due to the vertical stratification of both liquid and solid components, a one-dimensional hydraulic model is combined with a modified ASM2d biological model to allow the prediction of settling velocity, sludge concentration, soluble components and biological processes during the non-mixed periods of the SBR. The model is calibrated on a full-scale UniFed SBR system with tracer breakthrough tests, depth profiles of particulate and soluble compounds and measurements of the key components during the mixed aerobic period. This model is then validated against results from an independent experimental period with considerably different operating parameters. In both cases, the model is able to accurately predict the stratification and most of the biological reactions occurring in the sludge blanket and the supernatant during the non-mixed periods. Together with a correct description of the mixed aerobic period, a good prediction of the overall SBR performance can be achieved.