Fixed bed reactor performance of invertase immobilized on montmorillonite

Invertase was immobilized on acid activated montmorillonite via two independent procedures, adsorption and covalent binding. The immobilized enzymes were characterized by XRD, NMR and N2 adsorption measurements and their activity was tested in a fixed bed reactor. XRD revealed that the enzyme was situated on the periphery of the clay and the side chains of different amino acid residues were involved in intercalation with the clay matrix. NMR demonstrated that tetrahedral Al was linked to the enzyme during adsorption and the octahedral Al was involved during covalent binding. Secondary interaction of the enzyme with Al was also observed. N2 adsorption studies showed that covalent binding of enzymes caused pore blockage since the highly polymeric species were located at the pore entrance. The fixed bed reactor proved to be efficient for the immobilized invertase. The optimum pH and pH stability improved upon immobilization. The kinetic parameters calculated also showed an enhanced efficiency of the immobilized systems. They could be used continuously for long period. Covalently bound invertase demonstrated greater operational stability.

Glucoamylase immobilized on montmorillonite: Synthesis, characterization and starch hydrolysis activity in a fixed bed reactor

Glucoamylase from Aspergillus Niger was immobilized on montmorillonite clay (K-10) by two procedures, adsorption and covalent binding. The immobilized enzymes were characterized using XRD, surface area measurements and 27Al MAS NMR and the activity of the immobilized enzymes for starch hydrolysis was tested in a fixed bed reactor (FBR). XRD shows that enzyme intercalates into the inter-lamellar space of the clay matrix with a layer expansion up to 2.25 nm. Covalently bound glucoamylase demonstrates a sharp decrease in surface area and pore volume that suggests binding of the enzyme at the pore entrance. NMR studies reveal the involvement of octahedral and tetrahedral Al during immobilization. The performance characteristics in FBR were evaluated. Effectiveness factor (η) for FBR is greater than unity demonstrating that activity of enzyme is more than that of the free enzyme. The Michaelis constant (Km) for covalently bound glucoamylase was lower than that for free enzyme, i.e., the affinity for substrate improves upon immobilization. This shows that diffusional effects are completely eliminated in the FBR. Both immobilized systems showed almost 100% initial activity after 96 h of continuous operation. Covalent binding demonstrated better operational stability.

Zur Adsorption und Reaktion von Stickstoffmonoxid an Aktivkohle

Die Verwendung von Aktivkohlen und -koksen stellt eine Alternative zu herkömmlichen Prozessen zur Verminderung der NOx-Emissionen in Rauchgasen dar. An diesen Materialien wird Stickstoffmonoxid adsorbiert und katalytisch zu N2 reduziert. Eine einheitliche Erklärung über die ablaufenden Vorgänge und die Reaktionsmechanismen gibt es noch nicht. Die Ergebnisse der bisher veröffentlichten wissenschaftlichen Arbeiten sind sehr unterschiedlich, wenn nicht sogar widersprüchlich. In dieser Arbeit wird, anhand der Messung von NO-Durchbruchskurven und thermischen Desorptionsspektren, die Adsorption und Reaktion von Stickstoffmonoxid an Aktivkohlen und -koksen in Anwesenheit von Sauerstoff und Wasserdampf untersucht. Zur Durchführung der experimentellen Untersuchungen wird eine Versuchsanlage, bestehend aus einer Vorrichtung zur Gasgemischaufbereitung, einem Festbettreaktor und einer Gasanalytik, konzipiert und aufgebaut. Die Untersuchungen erfolgen bei Temperaturen zwischen 100 und 150 °C. Die NO-, O2- und H2O-Konzentrationen werden anhand der Rauchgaszusammensetzung kohlegefeuerter Kraftwerke gewählt. Die experimentellen Untersuchungen konzentrieren sich auf die Verwendung einer Aktivkohle aus Ölpalmschalen, die in einem Drehrohrreaktor am Institut für Thermische Energietechnik der Universität Kassel hergestellt wurde. Die experimentellen Ergebnisse zeigen, dass während des Prozesses NO-Adsorption, -Reduktion und -Oxidation, NO2-Bildung, -Adsorption und -reduktive Desorption, H2O-Adsorption sowie O2-Vergasung gleichzeitig stattfinden. Bei niedrigen Temperaturen werden die NO2-Bildung und die Adsorption bevorzugt. Die NO-Reduktion läuft über adsorbiertes NO mit CO2- und CO-Bildung. Durch O2-Vergasung werden aktive freie Cf-Plätzen für die NO-Reaktion und -Adsorption gebildet. Wasserdampf wird an der Aktivkohle adsorbiert und belegt aktive Plätze für diese Prozesse. Aus den experimentellen Ergebnissen werden kinetische und Gleichgewichtsparameter der NO-Sorption bestimmt. Ein vereinfachtes mathematisches Modell des Festbettreaktors, das zur Berechnung der NO-Durchbruchskurven bei unterschiedlichen Temperaturen dient, wird aufgestellt.

Influence of Osteopenia in Autogenous Bone Graft Healing With or Without Expanded Polytetrafluoroethylene Membranes: Histologic and Histomorphometric Study in Rats

Purpose: The aim of this study was to quantitatively evaluate and qualitatively describe autogenous bone graft healing with or without an expanded polytetrafluoroethylene (e-PTFE) membrane in ovariectornized rats. Materials and Methods: Eighty Wistar rats, weighing approximately 300 g each, were used. A graft was obtained from the parietal bone and fixed to the sidewall of each animal's left mandibular ramus. The animals were randomly divided into four experimental groups (n = 20 in each group): group 1, sham operated and autogenous bone graft only- group 2, sham operated and autogenous bone graft covered by e-PTFE membrane; group 3, ovariectornized (OVX) and autogenous bone graft only- group 4, OVX and autogenous bone graft covered by e-PTFE membrane. The animals were sacrificed at five different time points: immediately after grafting or at 7, 21, 45, or 60 days after grafting. Histologic examination and morphometric measurement of the sections were performed, and values were submitted to statistical analyses. Results: Both groups (sham and OVX) experienced loss of the original graft volume when it was not covered by the membrane, whereas use of the membrane resulted in additional bone formation beyond the edges of the graft and under the membrane. Histologic analysis showed integration of the grafts in all animals, although a larger number of marrow spaces was found in OVX groups. Conclusions: Association of bone graft with an e-PTFE membrane resulted in maintenance of its original volume as well as formation of new bone that filled the space under the membrane. Osteopenia did not influence bone graft repair, regardless of whether or not it was associated with e-PTFE membrane, but descriptive histologic analysis showed larger numbers of marrow spaces in the bone graft and receptor bed and formation of new bone in the OVX animals. INT J ORAL MAXILLOFAC IMPLANTS 2009;24:1074-1082

Effect of drying method on the adsorption isotherms and isosteric heat of passion fruit pulp powder

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Immobilization of lipases and assay in continuous fixed bed reactor

Lipases are versatile enzymes regarding the range of reactions they catalyse and substrates on which they act. They are as well important as catalyst in organic synthesis. Their immobilization on appropriate supports confer them greater stability besides the possibility of operating in continuous reactors. In order to explore these abilities, the reactions involving hydrolysis of p-nitrophenyl acetate (PNPA) and transesterification of PNPA with n-butanol were chosen. Lipases from two different sources were assayed, namely: microbial (Candida rugosa, CRL, Sigma Type VII) and pancreatic (PPL, Sigma, Type 11). Two immobilization methods were also used, namely: 1) adsorption, using as support the following silica derivatives (150-300μm e 450μ): phenyl, epoxy, amino and without derivation, and 2) covalent binding, using glutaraldehyde as binding agent and silica amino as support. This later method led to better results. Hydrolytic activity was 6.1 U/gsupport for CRL and 0.97U/gsupport for PPL, and of transesterification, 2,8U/gsupport for CRL and 1,9U/gsupport for PPL. Stability of the immobilized enzyme as a function of temperature was evaluated for CRL at 40°C and 50°C and for PPL at 32°C and 40°C. The assays were initially carried out batchwise, both for soluble and immobilized enzymes, aiming to the obtention of parameters for the continues reactor. Lipases immobilized by covalent binding were used in the assays of operacional stability in continuos reactors. For PPL in aqueous medium, at 32°C, and CRL in organic medium at 40°C, both operating continuously, no significant loss of activity was detected along the analysis period of 17 days. In the case of CRL in aqueous medium at 40°C there was a loss of activity around 40% after 18 days. For PPL in organic medium at 40°C the loss was 33% after 20 days. Compairing both sources with each other, very different results were obtained. Higher activitiy was found for CRL, both for hydrolysis and for transesterification reactions, with higher stability in organic medium. PPL showed lower activity as well as higher stability in aqueous medium. The immobilization method by covalent binding showed to be the most appropriate. Immobilized lipases are therefore relatively stable both in aqueous and organic medium.

The effect of biomass immobilization support material and bed porosity on hydrogen production in an upflow anaerobic packed-bed bioreactor

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Performance and composition of bacterial communiies in anaerobic fluidized bed reactors for hydrogen production: Effects of organic loading rate and alkalinity

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Performance and composition of bacterial communities in anaerobic fluidized bed reactors for hydrogen production: Effects of organic loading rate and alkalinity

This study evaluated the effects of the organic loading rate (OLR) and pH buffer addition on hydrogen production in two anaerobic fluidized bed reactors (AFBRs) operated simultaneously. The AFBRs were fed with glucose, and expanded clay was used as support material. The reactors were operated at a temperature of 30 degrees C, without the addition of a buffer (AFBR1) and with the addition of a pH buffer (AFBR2, sodium bicarbonate) for OLRs ranging from 19.0 to 140.6 kg COD m(-3) d(-1) (COD: chemical oxygen demand). The maximum hydrogen yields for AFBR1 and AFBR2 were 2.45 and 1.90 mol H-2 mol(-1) glucose (OLR of 84.3 kg COD m(-3) d(-1)), respectively. The highest hydrogen production rates were 0.95 and 0.76 L h(-1) L-1 for AFBR1 and AFBR2 (OLR of 140.6 kg COD m(-3) d(-1)), respectively. The operating conditions in AFBR1 favored the presence of such bacteria as Clostridium, while the bacteria in AFBR2 included Clostridium, Enterobacter, Klebsiella, Veillonellaceae, Chryseobacterium, Sporolactobacillus, and Burkholderiaceae. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Assessment of CO2 adsorption capacity on activated carbons by a combination of batch and dynamic tests

In this work, batch and dynamic adsorption tests are coupled for an accurate evaluation of CO2 adsorption performance for three different activated carbons obtained from olives stones by chemical activation followed by physical activation with CO2 at varying times, i.e. 20, 40 and 60 h. Kinetic and thermodynamic CO2 adsorption tests from simulated flue-gas at different temperature and CO2 pressure are carried out both in batch (a manometric equipment operating with pure CO2) and dynamic (a lab-scale fixed-bed column operating with CO2/N2 mixture) conditions. The textural characterization of the activated carbon samples shows a direct dependence of both micropore and ultramicropore volume on the activation time, hence AC60 has the higher contribution. The adsorption tests conducted at 273 and 293 K showed that, when CO2 pressure is lower than 0.3 bar, the lower the activation time the higher CO2 adsorption capacity and a ranking ωeq(AC20)>ωeq(AC40)>ωeq(AC60) can be exactly defined when T= 293 K. This result can be likely ascribed to a narrower pore size distribution of the AC20 sample, whose smaller pores are more effective for CO2 capture at higher temperature and lower CO2 pressure, the latter representing operating conditions of major interest for decarbonation of a flue-gas effluent. Moreover, the experimental results obtained from dynamic tests confirm the results derived from the batch tests in terms of CO2 adsorption capacity. It is important to highlight that the adsorption of N2 on the synthesized AC samples can be considered negligible. Finally, the importance of a proper analysis of characterization data and adsorption experimental results is highlighted for a correct assessment of CO2 removal performances of activated carbons at different CO2 pressure and operating temperature.

Activation of a spherical carbon for toluene adsorption at low concentration

This paper complements a previous one [1] about toluene adsorption on a commercial spherical activated carbon and on samples obtained from it by CO2 or steam activation. The present paper deals with the activation of a commercial spherical carbon (SC) having low porosity and high bed density (0.85 g/cm3) using the same procedure. Our results show that SC can be well activated with CO2 or steam. The increase in the burn-off percentage leads to an increase in the gravimetric adsorption capacity (more intensively for CO2) and a decrease in bed density (more intensively for CO2). However, for similar porosity developments similar bed densities are achieved for CO2 and steam. Especial attention is paid to differences between both activating agents, comparing samples having similar or different activation rates, showing that CO2 generates more narrow porosity and penetrates more inside the spherical particles than steam. Steam activates more from the outside to the interior of the spheres and hence produces larger spheres size reductions. With both activation agents and with a suitable combination of porosity development and bed density, quite high volumetric adsorption values of toluene (up to 236 g toluene/L) can be obtained even using a low toluene concentration (200 ppmv).

Local liquid holdups and hysteresis in a 2-D packed bed using X-ray radiography

An X-ray visualization technique has been used for the quantitative determination of local liquid holdups distribution and liquid holdup hysteresis in a nonwetting two-dimensional (2-D) packed bed. A medical diagnostic X-ray unit has been used to image the local holdups in a 2-D cold model having a random packing of expanded polystyrene beads. An aqueous barium chloride solution was used as a fluid to achieve good contrast on X-ray images. To quantify the local liquid holdup, a simple calibration technique has been developed that can be used for most of the radiological methods such as gamma ray and neutron radiography. The global value of total liquid holdup, obtained by X-ray method, has been compared with two conventional methods: drainage and tracer response. The X-ray technique, after validation, has been used to visualize and quantify, the liquid hysteresis phenomena in a packed bed. The liquid flows in preferred paths or channels that carry droplets/rivulets of increasing size and number as the liquid flow rate is increased. When the flow is reduced, these paths are retained and the higher liquid holdup that persists in these regions leads to the holdup hysteresis effect. Holdup in some regions of the packed bed may be an order of magnitude higher than average at a particular flow rate. (c) 2005 American Institute of Chemical Engineers

Simulation of binary mixture adsorption of methane and CO2 at supercritical conditions in carbons

Knowledge of the adsorption behavior of coal-bed gases, mainly under supercritical high-pressure conditions, is important for optimum design of production processes to recover coal-bed methane and to sequester CO2 in coal-beds. Here, we compare the two most rigorous adsorption methods based on the statistical mechanics approach, which are Density Functional Theory (DFT) and Grand Canonical Monte Carlo (GCMC) simulation, for single and binary mixtures of methane and carbon dioxide in slit-shaped pores ranging from around 0.75 to 7.5 nm in width, for pressure up to 300 bar, and temperature range of 308-348 K, as a preliminary study for the CO2 sequestration problem. For single component adsorption, the isotherms generated by DFT, especially for CO2, do not match well with GCMC calculation, and simulation is subsequently pursued here to investigate the binary mixture adsorption. For binary adsorption, upon increase of pressure, the selectivity of carbon dioxide relative to methane in a binary mixture initially increases to a maximum value, and subsequently drops before attaining a constant value at pressures higher than 300 bar. While the selectivity increases with temperature in the initial pressure-sensitive region, the constant high-pressure value is also temperature independent. Optimum selectivity at any temperature is attained at a pressure of 90-100 bar at low bulk mole fraction of CO2, decreasing to approximately 35 bar at high bulk mole fractions. (c) 2005 American Institute of Chemical Engineers.

Treatment of naphthalene-2-sulfonic acid from tannery wastewater by a granular activated carbon fixed bed inoculated with bacterial isolates Arthrobacter globiformis and Comamonas testosteroni

The kinetics of naphthalene-2-sulfonic acid (2-NSA) adsorption by granular activated carbon (GAC) were measured and the relationships between adsorption, desorption, bioavailability and biodegradation assessed. The conventional Langmuir model fitted the experimental sorption isotherm data and introduced 2-NSA degrading bacteria, established on the surface of the GAC, did not interfere with adsorption. The potential value of GAC as a microbial support in the aerobic degradation of 2-NSA by Arthrobacter globiformis and Comamonas testosteroni was investigated. Using both virgin and microbially colonised GAC, adsorption removed 2-NSA from the liquid phase up to its saturation capacity of 140 mg/g GAC within 48 h. However, between 83.2% and 93.3% of the adsorbed 2-NSA was bioavailable to both bacterial species as a source of carbon for growth. In comparison to the non-inoculated GAC, the combination of rapid adsorption and biodegradation increased the amount (by 70–93%) of 2-NSA removal from the influent phase as well as the bed-life of the GAC (from 40 to >120 d). A microbially conditioned GAC fixed-bed reactor containing 15 g GAC removed 100% 2-NSA (100 mg/l) from tannery wastewater at an empty bed contact time of 22 min for a minimum of 120 d without the need for GAC reconditioning or replacement. This suggests that small volume GAC bioreactors could be used for tannery wastewater recycling.

Separation of n-paraffins by selective adsorption

A study has been undertaken of the vapor-phase adsorptive separation of n-alkanes from Kuwait kerosene (Kuwait National Petroleum Company, heavy kerosene) using zeolite molecular sieves. Due to the shortage of information on the adsorption of multicomponent systems in the open literature, the present investigation was initiated to study the effect of feed flowrate, temperature, and zeolite particle size on the height of mass transfer zone (MTZ) and the dynamic capacity of the adsorbent for multicomponent n-alkanes adsorption on a fixed-bed of zeolite type-5A. The optimum operating conditions for separation of the n-alkanes has been identified so that the effluent would also be of marketable quality. The effect of multicycle adsorption-desorption stages on the dynamic behaviour of zeolite using steam as a desorbing agent has been studied and compared with n-pentane and n-hexane as desorbing agents. The separation process comprised one cycle of adsorption using a fixed-bed of zeolite type-5A. The bed was fed with vaporized kerosene until saturation had been achieved whereby the n-alkanes were adsorbed and the denormalized material eluted. The process of adsorption-desorption was carried out isobarically at one atmosphere. A mathematical model has been developed to predict the breakthrough time using the method of characteristics. The results were in a reasonable agreement with the experimental values. This model has also been utilized to develop the equilibrium isotherm. Optimum operating conditions were achieved at a feed flowrate of 33.33 x 10-9 m3/s, a temperature of 643 K, and a particle size of (1.0 - 2.0) x 10-3 m. This yielded an HMTZ value and a dynamic capacity of 0.206 m and 9.6S3 x 10-2 kg n-alkanes/kg of zeolite respectively. These data will serve as a basis for design of a commercial plant. The purity of liquid-paraffin product desorbed using steam was 83.24 wt%. The dynamic capacity was noticed to decrease sharply with the cycle number, without intermediate reactivation of zeolite, while it was kept unchanged by intermediate reactivation. Normal hexane was found to be the best desorbing agent, the efficiency of which was mounted to 88.2%.