CHARACTERIZATION OF FLUIDIZED BED REACTORS WITH GAS TRACER MEASUREMENTS

In a steady state bench scale fluidized bed the decomposition reaction of NaHCO₃ was carried out. The residence times distributions, DRT, of carbon dioxide (the gaseous product) and non adsorbing argon (the reference tracer) were mass spectroscopically measured as a function of the bed temperature. By means of single-, two- and three-phase dispersion models as well as by a cell model, the DRT's were evaluated on line by a computer.

The steady state transverse and longitudinal concentration profiles of these tracers upstream from the plane source were also measured and evaluated by a dispersion model as well as by a counter current back mixing model. Comparison of the steady state and nonsteady state dispersion coefficient measurements indicate that the longitudinal gas mixing is only partially due to backmixing. The experimentally determined wake fractions agree well with those published in the literature. Since the adsorption rate of CO₂ on the pore surface area of the particles in the dense phase is high no interphase transfer from the interstitial gas of the dense phase into the bubble phase takes place.

The desorption of CO₂ and its return into the interstitial gas and than into the gas phase occurs only slowly and with an initial time lag. The on-line DRT can be used as a diagnostical technique for investigation of the reactor during its operation, if operation disturbances or breakdowns occur.     

Phenolic wastewater treatment in a three‐phase fluidised bed bioreactor containing low density particles

The treatment of phenolic wastewater was investigated in a gas–liquid–solid fluidised bed bioreactor containing polypropylene particles of density 910 kg m^?3. Measurements of chemical oxygen demand (COD) versus residence time (t) were performed for various ratios of settled bed volume to bioreactor volume (V_b/V_R) and air velocities (u) to determine the values of (V_b/V_R) and u for which the largest reduction in COD occurred. Optimal operation, corresponding to the largest COD removal, was attained when the bioreactor was controlled at the ratio (V_b/V_R) = 0.55 and an air velocity u = 0.036 m s^?1. Under these conditions, the value of COD was practically at steady state for times greater than 50 h. At this steady state, only about 50% COD removal was achieved in the treatment of a ‘raw’ wastewater (no mineral salts added), whereas in the operation with wastewater enriched in nutrient salts approximately 90% COD removal was attained. The following amount of mineral salts (mg dm^?3): (NH₄)₂SO₄—500; KH₂PO₄—200; MgCl₂—30; NaCl—30; CaCl₂—20; and FeCl₃—7, when added to wastewater before treatment, was sufficient for biomass growth. The application of low density particles (used as biomass support) in a bioreactor allowed the control of biomass loading in the apparatus. In the cultures conducted after change in (V_b/V_R) at a set u, the steady state mass of cells grown on the particles was achieved after approximately 6 days of operation. With change in u at a set (V_b/V_R), the new steady state biomass loading occurred after culturing for about 2 days. Phenolic wastewater was successfully treated in a bioreactor. In the operation conducted in a bioreactor optimally controlled at (V_b/V_R) = 0.55, u = 0.036 m s^?1 and t = 50 h, conversions greater than 99% were achieved for all phenolic constituents of the wastewater. Conversions of about 90% were attained for other hydrocarbons. Copyright © 2005 Society of Chemical Industry     

Direct evidence for ArO-S bond cleavage upon inactivation of Pseudomonas aeruginosa arylsulfatase by aryl sulfamates

Pseudomonas aeruginosa arylsulfatase catalyses the cleavage of aryl sulfates and is an excellent model for human estrone sulfatase, which is implicated in hormone‐dependent breast cancer. Aryl sulfamates are inactivators of sulfatases; however, little is known about their mechanism. We studied the inactivation of Pseudomonas aeruginosa arylsulfatase A by a range of aryl sulfamates, including the clinical agent 667COUMATE (STX64) used to inactivate estrone sulfatase. Inactivation was time dependent, irreversible, and active‐site directed, consistent with a covalent modification at the active site. In terms of the kinetic parameters of inactivation k_inact and K_i, K_i values are in the micromolar to nanomolar range, and the inactivation half‐life is less than 30 s. A Brønsted plot of k_inact/K_i has a steep slope (β_lg=?1.1), which implies that the transition state for the first irreversible chemical step of inactivation involves a high degree of charge transfer and cleavage of the ArO? S bond. Detection of the released phenol and titration of the residual activity showed the stoichiometry of inactivation to be in the range 3–6, with the greatest values found for the most effective inactivators. Thus, multiple sulfamoylation events appear to occur during the inactivation process. These data provide valuable insight into the mechanism of sulfatase inactivation by sulfamates.     

Catalysis by Dihydrofolate Reductase from the Psychropiezophile Moritella profunda

The influence of temperature and pH on the stability and catalytic activity of dihydrofolate reductase (MpDHFR) from the cold‐adapted deep‐sea bacterium Moritella profunda was studied. The thermal melting temperature was found to be ～38 °C and was not affected by pH, while activity measurements demonstrated that its stability was maximal at pH 7 and was reduced dramatically below pH 6 or above pH 8. The steady‐state rate constant (k_cat) was maximal at neutral pH and higher temperatures, while the Michaelis constants (K_M) for both substrate and cofactor were optimal at lower temperatures and at elevated or reduced pH. For both temperature and pH, any change in k_cat was therefore offset by a similar change in K_M. Both the activation enthalpy and entropy of the MpDHFR‐catalysed reaction were lower than those of DHFR from E. coli leading overall to a very small difference in activation free energy and therefore similar steady‐state rate constants at the same temperature. The chemical step of the reaction is not rate limiting at pH 7, but becomes progressively more rate limiting as the pH increases. These results demonstrate adaptation of MpDHFR to its environment and show compromises between enthalpic and entropic contributions to the reaction, and between k_cat and K_M.     

Intensification of the biocatalytic oxidation of phenol with the use of activators of interface oxygen transfer

The transport of oxygen from the gas to the aqueous phase determines the rate of the biocatalytic oxidation of phenol. In this work, activators of the interphase transfer of O₂ are used to intensify the process, thus raising considerably the rate of gas entering the reaction space without additional power consumption, in contrast to the widely used methods of mixing and bubbling. We present the results from studies of the effect a number of substances on the value of K _L a at various mixing speeds of 100 to 1200 rpm. The solid-liquid phase and its activators are compared in terms of effectiveness. The maximum K _L a increase under different hydrodynamic conditions was achieved for activated carbon (3.7 times), aerosol (1.5 times), n-dodecane (3.1 times). These results are explained by a shuttle mechanism of O₂ phase transfer. It is shown that when K _L a is increased from 2.8 to 18.5 h^T-1, the biocatalytic oxidation of phenol is accelerated by a factor of 2.4. Using activated carbon as an activator of O₂ phase transfer allows us to increase the rate of the biocatalytic oxidation of phenol by ∼20%.     

Modelling Oxygen Transfer and Aerobic Growth in Shake Flasks and Well‐Mixed Bioreactors

Oxygen transfer is an important aspect of aerobic metabolism. In this work, microbial growth on glucose (fast metabolism) and phenol (slow metabolism) have been studied using Pseudomonas putida in shake flasks and a mixed bioreactor considering both substrate and oxygen depletion. Under typical operating conditions, the highest mass transfer coefficient (K_La) for the aerated well‐mixed bioreactor was found to be 50.8 h^?1, while the maximum non‐aerated shake flask K_La was 21.1 h^?1. The presence of media and/or dead cells did not have significant effect on measured values of K_La. A new equation for prediction of K_La in shake flasks with an absolute average deviation of 11.1% is introduced, and a combined model for oxygen mass transfer and microbial growth is shown to fit experimental data during growth on glucose and phenol in both shake flasks and the mixed bioreactor with an absolute average deviation of 19.3%.     

Biodegradation of phenol-polluted air using an external loop airlift bioreactor

Biological air treatment methods are an alternative to conventional treatment methods such as activated carbon adsorption and chemical scrubbing. An external loop airlift bioreactor has been utilized to treat phenol-contaminated air using Pseudomonas putida. Saturated air was found to be cleansed of phenol below the detectable limit because of the high mass transfer rate of the pollutant from the air and the high growth rate of Pseudomonas putida. The bioreactor was found to degrade over 99% of the inlet phenol at rates from 21·5 to 194 mg h^?1 at concentrations between 650 and 850 mg m^?3 of air. A model of the system is developed based on an initial transient period followed by a pseudo-steady state period. The simulations compared well with the experimental data.     

Effect of multiple extrusions on the impact properties of polypropylene/clay nanocomposites

Polypropylene (PP)‐based polymer nanocomposites containing organically modified montmorillonite (OMMT) with and without maleic anhydride grafted PP, were compounded by twin‐screw extrusion. The extrusion process was repeated various numbers of times to increase the extruder residence time (T_R) and, through that, the particle dispersion. Rheological measurements fitted to a modified Carreau–Yasuda model defining a melt yield stress were used to indicate changes in the particle dispersion with regard to T_R. This analysis showed a monotonically increased dispersion of clay particles in the PP matrix with increasing extruder T_R. The small‐strain tensile properties were tested at both ambient (20°C) and elevated (90°C) temperatures, and no significant changes were observed in the tensile strength or modulus as a function of T_R. Instrumented Izod impact tests showed that the nanocomposite impact strength (σ_i) increased monotonically with increased T_R by 70% from least dispersed to best dispersed, which was still 20% below the level for neat PP. Both the fracture initiation energy and propagation energy increased with T_R, but the primary effect on σ_i came from the fracture propagation energy, which delivered 80% of the improvement. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Lag phase model for transient growth of pseudomonas putida on phenol

The successful design of large‐scale bioreactors requires the ability to predict both steady‐state and dynamic operating conditions. At the same time, mathematical models should not be too complex in order to reduce experimental work required to determine kinetic parameters. A simple model which predicts the behaviour of batch and transient continuous culture operations is presented and experimentally verified. The model is based on two regions of metabolic activity: the lag phase and the active phase. Pseudomonas putida growing on phenol as a substrate in a well‐mixed bioreactor was tested in three modes of operation: batch, continuous start‐up and continuous step‐change. The model is demonstrated to predict all the qualitative aspects of the dynamic phases of growth and is quantitatively accurate.     

Are the Catalytic Properties of Enzymes from Piezophilic Organisms Pressure Adapted?

We report the crystal structure of dihydrofolate reductase (DHFR) from the psychropiezophilic bacterium Moritella profunda, which was isolated from the deep ocean at 2 °C and 280 bar. The structure is typical of a chromosomal DHFR and we were unable to identify any obvious structural features that would suggest pressure adaptation. In particular, the core regions of the enzyme are virtually identical to those of the DHFR from the mesophile Escherichia coli. The steady‐state rate at pH 9, which is limited by hydride transfer at atmospheric pressure, is roughly constant between 1 and 750 bar, falling at higher pressures. However, the value of K_M increases with increasing pressure, and as a result k_cat/K_M decreases over the entire pressure range studied. Isotope effect studies showed that increasing the pressure causes a change in the rate‐limiting step of the reaction. We therefore see no evidence of pressure adaptation in either the structure or the activity of this enzyme.     

Investigations on hydrodynamics of radial flow moving bed reactors

Distributions of pressure and velocity in the main channels were studied in a radial flow cold model of a moving bed reactor, 500 mm in diameter, in four different gas flow modes, inward Z gas flow, inward Π gas flow, outward Z gas flow, outward Π gas flow. It has been found that, in outward Π gas flow mode, the axial non-uniformity of the gas is at a minimum. The following correlations are proposed for the momentum recovery factors K_a and K_b: K_a = 0.684 + 0.0128 (du/dx)/u, K_b = 1.135 + 0.0158 (du/dx)/u. Pressure distributions in the main channels can be accurately predicted using K_a and K_b.     

Continuous bioremediation of phenol‐polluted air in an external loop airlift bioreactor with a packed bed

An external loop airlift bioreactor with a small amount (99% porosity) of stainless steel mesh packing inserted in the riser section was used for bioremediation of a phenol‐polluted air stream. The packing enhanced volatile organic chemical and oxygen mass transfer rates and provided a large surface area for cell immobilization. Using a pure strain of Pseudomonas putida, fed‐batch and continuous runs at three different dilution rates were completed with phenol in the polluted air as the only source of growth substrate. 100% phenol removal was achieved at phenol loading rates up to 33 120 mg h^?1 m^?3 using only one‐third of the column, superior to any previously reported biodegradation rates of phenol‐polluted air with 100% efficiency. A mathematical model has been developed and is shown to accurately predict the transient and steady‐state data. Copyright © 2006 Society of Chemical Industry     

Mass Transfer and Bioremediation of Naphthalene and Methyl Naphthalenes in Baffled and Bead Mill Bioreactors

Mass transfer and bioremediation of naphthalene, 2‐methylnaphthalene and 1,5‐dimethylnaphthalene have been studied in a rotating bioreactor modified with the addition of baffles and beads. Mass transfer rates of these low solubility organic particles dissolving in water (based on the working volume of the bioreactor) were highest in the bioreactor that combined beads and baffles, with the overall mass transfer coefficient (K_La) reaching up to 25 h^?1. Based on its capacity to hold the largest volume of polluted media, the simple baffled bioreactor was considered to be the optimum roller bioreactor design. Using Pseudomonas putida, the bioremediation rate of naphthalene reached 61 mg/l‐h in this vessel and using mixed substrates, the bioremediation rate of 2‐methylnaphthalene reached 30 mg/l‐h. The dissolution rates for hydrophobic particles into the culture media during the bioremediation process were up to four times higher compared to mass transfer rates into abiotic controls, which was likely due to the production of biosurfactants by P. putida.     

Temperature dependency of granule characteristics and kinetic behavior in UASB reactors

When an inhibitory substrate, phenol, was treated under mesophilic conditions (25, 30, 35, and 40 °C), the upflow anaerobic sludge bed (UASB) reactors at 30 °C resulted in the greatest amount of biomass and the largest granule size, while the UASB reactors at 25 °C resulted in the smallest granule size and the greatest amount of wash‐out of sludge. The granule size tended to be negatively correlated with the amount of wash‐out of sludge. With an increase in temperature, the kinetic constant k for anaerobic phenol degradation increased and the half saturation constant (K_s) decreased. The mass fraction of methanogens (f) increased with increasing operational temperature in the UASB reactors and the activation energy (E_a) for acetate methanogenesis was larger than that for phenol acidogenesis in the batch reactors, indicating that the operational temperature imposes a more influential effect on methanogens than on acidogens. From the results of the activity of acidogens and methanogens (expressed in specific COD utilization rate), the rate‐limiting step is phenol acidogenesis. Copyright © 2004 Society of Chemical Industry     

Dimensional Analysis of Crossflow Microfiltration Data

Abstract

A new approach to correlating crossflow microfiltration (CFMF) data based on dimensional analysis is presented. The steady state flux was assumed to be a function of the trans‐membrane pressure (ΔP), the crossflow velocity (u), the particle concentration (c), filtrate viscosity (μ), and membrane resistance (R _m). Correlations of the form J/u=K(ΔP/cu ²) ^a (ΔP/μuR _m) ^b were tested on three sets of published data: one for CFMF of dried yeast suspensions in a laminar flow hollow fiber module, one for dried yeast suspensions in a turbulent flow tubular module and one for suspensions of latex particles in a laminar flow flat sheet module. The R ² values for the fits of the correlations to the data were 0.98, 0.94, and 0.91 respectively.     

Measurement of O2-N2 binary sorption on 5A zeolite by isotope tracer and perturbation chromatography

Isotope tracer chromatography allows to extract simply and quickly multi component adsorption data and is demonstrated for single component and binary adsorption equilibria for O₂ and N₂ on 5A zeolite as an example. In this modification of conventional tracer chromatography, a small pulse of an isotope tracer is injected in an adsorbable carrier gas (pure or multicomponent mixture) flowing through a column filled with adsorbent and is designed to operate at almost uniform pressure. Isotherm parameters are readily extracted by fitting measurements of residence times at various pressures and carrier composition. The isotherms were in excellent agreement with volumetric measurements. Isotope tracer chromatography is shown to be superior to perturbation chromatography since the influence of the injection volume on the carrier gas composition is substantially smaller for tracer experiments. Unfortunately, this new improved gas chromatographic technique requires rather expensive isotopes. The strength of this new approach lies in the advantage of working with small adsorbent samples (1 g) making a rapid screening of newly developed materials possible.Nomenclature K _exp,tr,i experimental tracer adsorption constant (mol/kg pure adsorbent/Pa) - K _i Henry adsorption equilibrium constant (mol/kg pure adsorbent/Pa) - K _i,part partition coefficient - K _pert composite Henry constant (mol/kg pure adsorbent/Pa) - L column length (m) - L _i Langmuir adsorption constant (1/Pa) - n _i amount adsorbed on the solid (mol/kg adsorbent) - N _i adsorbent loading (Pa) - p total pressure (Pa) - p _i partial pressure of component i (Pa) - p _in column inlet pressure (Pa) - p _out column outlet pressure (Pa) - q _i amount of component i in the micropores (Pa) - R gas constant (J/mol/K) - t time (s) - T temperature (K) - v _f superficial velocity in adsorbent column (m/s) - v _out velocity at the outlet of the column (m/s) - V _inlet volumetric flow rate at inlet conditions (ml/s) - x molar fraction of tracer - y molar fraction of component i in the carrier gas - z axial coordinate (m) Greek letters _ext bed voidage, external porosity - _macr macropore porosity [_macr= _p (1–_ext)] - _micr micropore porosity - _tot total porosity - _p pellet porosity - volume fraction of binder material - _d dead time (s) - _tracer tracer residence time (s) - _pert perturbation residence time (s) - _crys crystal density (kg/m³)     

Continuous Application of Polyglycerol‐Supported Salen in a Membrane Reactor: Asymmetric Epoxidation of 6‐Cyano‐2,2‐dimethylchromene

In the current work, suitability of hyperbranched polyglycerol as a high loading catalyst support is demonstrated. A polyglycerol‐supported manganese‐salen complex (chemzyme) is applied as a homogeneous catalyst in the epoxidation of 6‐cyano‐2,2‐dimethylchromene. The recyclability of the corresponding catalyst was investigated in repetitive batch experiments as well as a continuous operation of the reaction in an ultrafiltration membrane reactor. An enhanced stability of the catalyst in repetitive batches was observed as a result of immobilization whereby the total turnover number increased from 23 in a single batch to 80 in four repetitive batches. To enable continuous operation, a continuously operated, stirred tanked reactor (CSTR) was equipped with an ultrafiltration membrane (MPF‐50) and a retention of 98% was determined. The continuous chemzyme membrane reactor was operated over the course of 20 residence times. After approximately 12 residence times, the steady state was reached yielding 70% conversion as well as an enantiomeric excess up to 92%. A space‐time yield (sty) of 458 g L ⁻¹ d⁻¹ and a turnover frequency (TOF_reaction) of up to 18 h⁻¹ was reached in the steady state. It was determined that the total turnover number (TTN) was enhanced by a factor of 10 from 24 (batch) up to 240 for 20 residence times in CSTR operation.     

Catalytic depolymerisation and conversion of Kraft lignin into liquid products using near-critical water

A high-pressure pilot plant was developed to study the conversion of LignoBoost Kraft lignin into bio-oil and chemicals in near-critical water (350 °C, 25 MPa). The conversion takes place in a continuous fixed-bed catalytic reactor (500 cm³) filled with ZrO₂ pellets. Lignin (mass fraction of approximately 5.5%) is dispersed in an aqueous solution containing K₂CO₃ (from 0.4% to 2.2%) and phenol (approximately 4.1%). The feed flow rate is 1 kg/h (reactor residence time 11 min) and the reaction mixture is recirculated internally at a rate of approximately 10 kg/h. The products consist of an aqueous phase, containing phenolic chemicals, and a bio-oil, showing an increased heat value (32 MJ/kg) with respect to the lignin feed. The 1-ring aromatic compounds produced in the process are mainly anisoles, alkylphenols, guaiacols and catechols: their overall yield increases from 17% to 27% (dry lignin basis) as K₂CO₃ is increased.     

Disruption of ergosterol biosynthesis,growth, and the morphological transition in <Emphasis Type="Italic">Candida albicans</Emphasis> by sterol methyltransferase inhibitors containing sulfur at C-25 in the sterol side chain

The sterol substrate analog 25-thialanosterol and its corresponding sulfonium salt were evaluated for their ability to serve as antifungal agents and to inhibit sterol methyltransferase (SMT) activity in Candida albicans. Both compounds inhibited cell proliferation, were fungistatic, interrupted the yeastlike-form to germ-tube-form transition, and resulted in the accumulation of zymosterol and related Δ²⁴-sterols concurrent with a decrease in ergosterol, as was expected for the specific inhibition of SMT activity. Feedback on sterol synthesis was evidenced by elevated levels of cellular sterols in treated vs. control cultures. However, neither farnesol nor squalene accumulated in significant amounts in treated cultures, suggesting that carbon flux is channeled from the isoprenoid pathway to the sterol pathway with minor interruption or redirection until blockage at the C-methylation step. Activity assays using solubilized C. albicans SMT confirmed the inhibitors impair SMT action. Kinetic analysis indicated that 25-thialanosterol inhibited SMT with the properties of a time-dependent mechanismbased inactivator K _i of 5 =gmM and apparent k _inact of 0.013 min⁻¹, whereas the corresponding sulfonium salt was a reversible-type transition state analog exhibiting a K _i of 20 nM. The results are interpreted to imply changes in ergosterol homeostasis as influenced by SMT activity can control growth and the morphological transition in C. albicans, possibly affecting disease development.     

Fatigue Crack Growth Behavior of Silicon Nitride: Roles of Grain Aspect Ratio and Intergranular Film Composition

The role of microstructure in affecting the fatigue crack growth resistance of grain bridging silicon nitride ceramics doped with rare earth (RE = Y, La, Lu) oxide sintering additives was investigated. Three silicon nitride ceramics were prepared using MgO‐RE₂O₃ and results were compared with a commercial Al₂O₃‐Y₂O₃‐doped material. Decreasing stress intensity range (ΔK) fatigue tests were conducted using compact‐tension specimens to measure steady‐state fatigue crack growth rates. Specimens doped with MgO‐RE₂O₃ additives showed a significantly higher resistance to crack growth than those with Al₂O₃‐Y₂O₃ additives and this difference was attributed to the much higher grain aspect ratio for the MgO‐RE₂O₃‐doped ceramics. When the crack growth data were normalized with respect to the total contribution of toughening by bridging determined from the monotonically loaded R‐curves, the differences in fatigue resistance were greatly reduced with the data overlapping considerably. Finally, all of the MgO‐RE₂O₃‐doped silicon nitrides displayed similar steady‐state fatigue crack growth behavior suggesting that they are relatively insensitive to the intergranular film.