Phenol degradation in a fixed‐bed bioreactor using micro‐cellular polymer‐immobilized Pseudomonas syringae

Highly porous (85% void volume) polymer beads with interconnecting micro‐pores were prepared for the immobilization of Pseudomonas syringae for the degradation of phenol in a fixed‐bed column bioreactor. The internal architecture of this support material (also known as PolyHIPE Polymer) could be controlled through processing before the polymerization stage. The transient and steady state phenol utilization rates were measured as a function of substrate solution flow rate and initial substrate concentration. The spatial concentration of the bacteria on the micro‐porous support particles as well as within them was studied using scanning electron microscopy at various time intervals during the continuous operation of the bioreactor. It was found that although bacterial penetration into the porous support was present after 20 days, bacterial viability however, was compromised after 120 days as a result of the formation of a biofilm on the support particles. The steady state phenol utilization at an initial phenol concentration of 200 mg cm^?3 was 100% provided that the flow rate was less than 7 cm³ min^?1. Substrate inhibition at a constant flow rate of 4.5 cm³ min^?1 was found to begin at 720 mg dm^?3. The critical dilution rate for bacteria washout was high as a result of the highly hydrophobic nature of the support and the reduction of pore interconnect size due to bacterial growth within the pores in the vicinity of the surface of the support. Copyright © 2004 Society of Chemical Industry     

Anaerobic biodegradation of phenol in sulfide‐rich media

In the refinery industry, the washing processes of middle‐distillates using caustic solutions generate phenol‐ and sulfide‐containing waste streams. The spent caustic liquors generated contain phenols at concentrations higher than 60 g dm^?3(638.3 mmol dm^?3). For sulfur compounds, the average sulfide concentration was 48 g dm^?3(1500 mmol dm^?3) in these streams. The goal of this study was to evaluate the specific impact of phenol and sulfide concentrations towards the phenol‐biodegradation activity of a phenol‐acclimated anaerobic granular sludge. An inhibition model was used to calculate the phenol and sulfide inhibitory concentrations that completely stopped the phenol‐biodegradation activity (IC100). A maximum phenol‐biodegradation activity of 83 µmol g^?1 VSS h^?1 was assessed and the IC100 values were 21.8 mmol dm^?3 and 13.4 mmol dm^?3 for phenol and sulfide respectively. The limitation of the phenol biodegradation flow by phenol inhibition seemed to be related to the more important sensitivity of phenol‐degrading bacteria. The up‐flow anaerobic sludge bed reactor operating in a non‐phenol‐dependent inhibition condition did not present any sensitivity to sulfide concentrations below 9.6 mmol dm^?3. At this residual concentration, the pH and bisulfide ions' concentration might be responsible for the general collapsing of the reactor activity. Copyright © 2004 Society of Chemical Industry     

Simultaneous phenol removal and biological reduction of hexavalent chromium in a packed‐bed reactor

BACKGROUND: Phenol and hexavalent chromium are considered industrial pollutants that pose severe threats to human health and the environment. The two pollutants can be found together in aquatic environments originating from mixed discharges of many industrial processes, or from a single industry discharge. The main objective of this work was to study the feasibility of using phenol as an electron donor for Cr(VI) reduction, thus achieving the simultaneous biological removal/reduction of the two pollutants in a packed‐bed reactor. RESULTS: A pilot‐scale packed‐bed reactor was used to estimate phenol removal with simultaneous Cr(VI) reduction through biological mechanisms, using a new mixed bacterial culture originated from Cr(VI)‐reducing and phenol‐degrading bacteria, operated in draw–fill mode with recirculation. Experiments were performed for feed Cr(VI) concentration of about 5.5 mg L^?1, while phenol concentration ranged from 350 to 1500 mg L^?1. The maximum reduction/removal rates achieved were 0.062 g Cr(VI) L^?1 d^?1 and 3.574 g phenol L^?1 d^?1, for a phenol concentration of 500 mg L^?1. CONCLUSION: Phenol removal with simultaneous biological Cr(VI) reduction is feasible in a packed‐bed attached growth bioreactor. Phenol was found to inhibit Cr(VI) reduction, while phenol removal was rather unaffected by Cr(VI) concentration increase. However, the recorded removal rates of phenol and Cr(VI) were found to be much lower than those obtained from previous research, where the two pollutants were examined separately. Copyright © 2008 Society of Chemical Industry     

CO2 methanation: Optimal start‐up control of a fixed‐bed reactor for power‐to‐gas applications

Utilizing volatile renewable energy sources (e.g., solar, wind) for chemical production systems requires a deeper understanding of their dynamic operation modes. Taking the example of a methanation reactor in the context of power‐to‐gas applications, a dynamic optimization approach is used to identify control trajectories for a time optimal reactor start‐up avoiding distinct hot spot formation. For the optimization, we develop a dynamic, two‐dimensional model of a fixed‐bed tube reactor for carbon dioxide methanation which is based on the reaction scheme of the underlying exothermic Sabatier reaction mechanism. While controlling dynamic hot spot formation inside the catalyst bed, we prove the applicability of our methodology and investigate the feasibility of dynamic carbon dioxide methanation. © 2016 American Institute of Chemical Engineers AIChE J, 63: 23–31, 2017     

Dynamics of a draft tube gas—liquid—solid fluidized bed bioreactor for phenol degradation

The transient response of a draft tube gas—liquid—solid fluidized bed biofilm reactor (DTFB) to a step increase in influent phenol concentration was experimentally investigated. A mathematical model, which considers the external mass transfer resistance, the simultaneous diffusion, reaction, and adsorption of phenol and oxygen inside the bioparticles, the dynamics of biofilm growth, and the time delay of microbial growth during the transient period, is proposed. The biofilm properties such as thickness and density are allowed to vary in the model with biofilm growth to simulate the real biofilm system. Simulation results predicted from the proposed model show reasonable agreement with the experimental data.     

Activated carbon‐filled cellulose acetate hollow‐fiber membrane for cell immobilization and phenol degradation

The activated carbon‐filled cellulose acetate (CA) hollow‐fiber membranes were prepared by using phase‐inverse technique and subsequently characterized by scanning electronic microscopy (SEM), atomic force microscopy (AFM), dynamic mechanical analysis (DMA), thermal mechanical analysis (TMA), and tensile analysis. The SEM observation demonstrated that the activated carbon‐filled CA hollow‐fiber membranes possess four‐layer structure, which consists of an external skin dense layer, an external void layer, a central sponge layer, and an internal skin dense layer, whereas the pure CA hollow‐fiber membranes lack the macrovoid layer. As the measurement of AFM, the roughness of both internal and external surface of activated carbon‐filled fibers is much higher than that of pure CA fiber, respectively. Higher Young's modulus and storage modulus of filled membranes indicate that the activated carbon particles were homogeneously dispersed in the polymeric matrix. To investigate the feasibility of the newly developed hollow‐fiber membranes for cell immobilization cells and to evaluate the inhibitory effect of phenol on immobilized cells, Pseudomonas putida ATCC 17484 was chosen to be immobilized on both pure CA and activated carbon‐filled hollow‐fiber membranes. Batch experiments for phenol biodegradation were carried out for both free suspension and immobilized cells at the initial concentration of 1500 mg/L phenol. In the case of free suspension, neither cell growth nor phenol degradation occurred to any measurable extent up to 35 h. We found that both pure CA fiber and activated carbon‐filled fiber immobilization systems can completely degrade the phenol. However, the biodegradation rate of activated carbon‐filled fiber system was higher than that of pure CA fiber system. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 695–707, 2000     

A preliminary evaluation of a continuous‐flow reactor for liquid–liquid–solid phase‐transfer catalyzed synthesis of n‐butyl phenyl ether

This study evaluates the feasibility of using a continuous‐flow stirred vessel reactor (CFSVR) to synthesize n‐butyl phenyl ether (ROPh) from n‐butyl bromide (RBr) and sodium phenolate (NaOPh) by liquid–liquid–solid phase‐transfer catalysis (triphase catalysis). The factors affecting the preparation of triphase catalysts, the etherification reaction in a batch reactor, and the performance in a CFSVR were investigated. The kinetic study with a batch reactor indicated that when the initial concentration of NaOPh or RBr was high, the conversion of RBr would depend on the initial concentration of both RBr and NaOPh. The reaction can be represented by a pseudo‐first‐order kinetic model when the concentration of NaOPh is in proper excess to that of RBr, and the apparent activation energy is 87.8 kJ mol^?1. When the etherification reaction was carried out in the CFSVR, the catalyst particles did not flow out of the reactor, even at a high agitation speed. The conversion of RBr in the CFSVR was, as predicted, lower than that in the batch reactor, but was higher than the theoretical value because the dispersed phase is not completely mixed. Copyright © 2004 Society of Chemical Industry     

Poly(dimethylsiloxane‐b‐styrene) diblock copolymers prepared by reversible addition‐fragmentation chain transfer polymerization: Kinetic model

Well‐defined polydimethylsiloxane‐block‐polystyrene (PDMS‐b‐PS) diblock copolymers were prepared by reversible addition‐fragmentation chain transfer (RAFT) polymerization using a functional PDMS‐macro RAFT agent. The RAFT polymerization kinetics was simulated by a mathematical model for the RAFT polymerization in a batch reactor based on the method of moments. The model described molecular weight, monomer conversion, and polydispersity index as a function of polymerization time. Good agreements in the polymerization kinetics were achieved for fitting the kinetic profiles with the developed model. In addition, the model was used to predict the effects of initiator concentration, chain transfer agent concentration, and monomer concentration on the RAFT polymerization kinetics. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Membrane‐Aerated Biofilm Reactor Behaviors for the Treatment of High‐Strength Ammonium Industrial Wastewater

A single‐tube membrane‐aerated biofilm reactor (MABR) was used to investigate the effect of the reaction time, reaction temperature, pH value, C/N ratio, and sludge concentration on the removal rates of the NO_x^–‐N and COD in high‐strength ammonium industrial water by supplying oxygen during the batch experiment. The homogeneous mathematical model is developed to predict their transient responses using Monod kinetics with dual substrate limitation. The model incorporates mass transport by convection and diffusion in the surrounding liquid contained inside the interconnected pores and channels within the biofilm. Transport and kinetic parameters are estimated from experiments and the model successfully predicts concentration measurements in some of the sets of experiments.     

Relative strength of H‐bonding groups on biodegradable polymer‐based blends in solution

The intermolecular hydrogen bonding interactions between poly(3‐hydroxybutyrate) and poly(styrene‐co‐vinyl phenol) copolymers with mutual solvent epichlorohydrin were thoroughly investigated by steady‐state fluorescence and viscosity techniques. Fluorescence spectroscopy along with viscosity technique was used to asses the intermolecular hydrogen bonding between poly‐(3‐hydroxybutyrate) and its blends with five copolymer samples of styrene–vinyl phenol, containing different proportions of vinyl phenol but similar average molecular weight and polydispersity index. In the case of very low OH contents (2–4 mol %), as expected, both components of poly(3‐hydroxybutyrate) and poly(styrene‐co‐4‐vinylphenol) chains are well separated and remain so independently of the mixed polymer ratio and overall polymer concentration as well. Conversely, when the OH content reaches 5.8 mol % or more, a significant decrease of the intrinsic fluorescence intensity emitted by the copolymer is detected upon addition of aliquots of poly(3‐hydroxybutyrate). In these cases, an average value for the interassociation equilibrium constant, K_A = 8.7, was obtained using a binding model formalism. A good agreement of these results with those obtained from complementary viscosity measurements, through the interaction parameter, Δb, was found. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 900–910, 2006     

A Nonbactericidal Zinc‐Complexing Ligand as a Biofilm Inhibitor: Structure‐Guided Contrasting Effects on Staphylococcus aureus Biofilm

Zinc‐complexing ligands are prospective anti‐biofilm agents because of the pivotal role of zinc in the formation of Staphylococcus aureus biofilm. Accordingly, the potential of a thiosemicarbazone (compound C1) and a benzothiazole‐based ligand (compound C4) in the prevention of S. aureus biofilm formation was assessed. Compound C1 displayed a bimodal activity, hindering biofilm formation only at low concentrations and promoting biofilm growth at higher concentrations. In the case of C4, a dose‐dependent inhibition of S. aureus biofilm growth was observed. Atomic force microscopy analysis suggested that at higher concentrations C1 formed globular aggregates, which perhaps formed a substratum that favored adhesion of cells and biofilm formation. In the case of C4, zinc supplementation experiments validated zinc complexation as a plausible mechanism of inhibition of S. aureus biofilm. Interestingly, C4 was nontoxic to cultured HeLa cells and thus has promise as a therapeutic anti‐biofilm agent. The essential understanding of the structure‐driven implications of zinc‐complexing ligands acquired in this study might assist future screening regimes for identification of potent anti‐biofilm agents.     

Dynamic properties of a continuous stirred tank biofilm bioreactor for aerobic processes

A dynamic analysis of a continuous stirred tank bioreactor with biofilm was performed. The existence of gas, liquid, and biofilm were taken into account. The proposed heterogeneous model of such bioreactor takes into account dynamic biofilm growth and interphase transfer of substrates and biomass for a double‐substrate aerobic process. Simulations were performed to investigate the influence of important process parameters, i.e., toxic substrate concentration in the feed stream, detachment rate coefficient, mean residence time of the liquid and aeration intensity, on dynamic properties of the bioreactor. Dynamic behavior at conditions of anoxia of microorganisms were shown. A method was proposed to reduce bioreactor start‐up time significantly. The paper presents a mathematical model of the bioreactor that uses a discrete model of biofilm growth based on the theory of cellular automata. Dynamics of the bioreactor based on the continuous and discrete biofilm model was compared. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1818–1829, 2017     

Effect of co‐contaminant phenol on performance of a laboratory‐scale RBC with algal‐bacterial biofilm treating petroleum hydrocarbon‐rich wastewater

BACKGROUND: Hydrocarbon degradation by algal‐bacterial systems has advantages over degradation by conventional heterotrophic systems. However, oily wastewaters often contain co‐contaminants that may inhibit the degradation of total petroleum hydrocarbons (TPH), leading to system failure. RESULTS: This paper reports the effect of phenol on treatment of wastewater containing petroleum hydrocarbons, i.e. diesel oil in a lab‐scale rotating biological contactor with biofilm consisting predominantly of Burkholderia cepacia and a freshwater algal culture. The effect of phenol loading from 0.11–0.69 g phenol m^?2 d^?1 on diesel degradation was studied with 21 h hydraulic retention time and TPH loading of 27.33 g TPH m^?2 d^?1. With increase in phenol loading, complete removal of phenol was observed. However, TPH removal decreased from 99% to 94% and significant decrease in TCOD removal was observed possibly due to biomass growth in suspension. Presence of algal culture in the biofilm made it feasible to operate the RBC at a high organic loading. The benefits included better immobilization of the bacterial culture, release of oxygen and generation of alkalinity. Lowering in pH due to accumulation of acidic intermediates formed during oil biodegradation was not observed in this study. CONCLUSION: This system can be recommended for treatment of industrial wastewaters containing TPH and phenols, with proper handling of biosolids. Copyright © 2010 Society of Chemical Industry     

Diallyl bisphenol A—novolac epoxy system cocured with bisphenol‐A‐bismaleimide—cure and thermal properties

Novolac epoxy (EPN)—2,2′‐diallyl bisphenol A (DABA) resin system was modified by cocuring it with bisphenol A bismaleimide (BMI). Molar concentration of BMI in the stochiometric blend of EPN and DABA was varied from 0.5 to 2.0. The cure optimization was done using DSC, IR spectroscopy, and rheological studies. The curing proceeded by phenol‐epoxy and Alder‐ene reactions. The performance of the ternary Epoxy‐Allyl phenolic‐Bismaleimide system was evaluated through their thermal and dynamic mechanical characterization. BMI improved the overall thermal stability and the modulus of the resultant composites. The increase in BMI concentration in the system resulted in enhanced glass transition temperature with a consequent improvement in high temperature performance typically estimated by their lap shear strength at high temperatures. The high temperature performance of the epoxy‐phenol‐bismaleimide (EPB) system was found to be far superior to the epoxy‐phenol (EP)system. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Dynamic Matrix Control of a Bubble‐Column Reactor for Microbial Synthesis Gas Fermentation

A spatiotemporal metabolic model of a representative syngas bubble‐column reactor was applied to design and evaluate dynamic matrix control (DMC) schemes for regulation of the desired by‐product ethanol and the undesired by‐product acetate. This model was used to develop linear step response models for controller design and also served as the process in closed‐loop simulations. A 2 × 2 DMC scheme with manipulation of the liquid and gas feed flows to the column provided a superior performance to proportional integral (PI) control due to slow process dynamics combining the multivariable and constrained nature of the control problem. Ethanol concentration control for large disturbances was further improved by adding the flow of a pure hydrogen stream as a third manipulated variable. The advantages of DMC for syngas bubble‐column reactor control are demonstrated and a design strategy for future industrial applications is provided.     

Photo‐induced birefringence phenomenon of a double azo polymer

Poly(glycidyl methacrylate) grafted with double azo bond 4[4′‐(phenylazo)phenylazo]phenol was synthesized and characterized. Photo‐induced birefringence phenomenon of this polymer was studied by static absorption and dynamic pump‐probe techniques, and was compared with that of another polymer Poly{(methyl methacrylate)‐co‐4‐[(3‐methacryloyloxy)} [P(MMA‐co‐MAZ)] containing mono azobenzene chromophore. The results showed that former polymer carrying two azo bonds, with a larger birefringence ratio, had a relatively faster optical switching response than the latter polymer under the same pump beam power. Copyright © 2003 Society of Chemical Industry     

Dynamic modeling and simulations of the behavior of a fixed‐bed reactor‐exchanger used for CO2 methanation

A multidimensional heterogeneous and dynamic model of a fixed‐bed heat exchanger reactor used for CO₂ methanation has been developed in this work that is based on mass, energy and momentum balances in the gas phase and mass and energy balances for the catalyst phase. The dynamic behavior of this reactor is simulated for transient variations in inlet gas temperature, cooling temperature, gas inlet flow rate, and outlet pressure. Simulation results showed that wrong‐way behaviors can occur for any abrupt temperature changes. Conversely, temperature ramp changes enable to attenuate and even fade the wrong‐way behavior. Traveling hot spots appear only when the change of an operating condition shifts the reactor from an ignited steady state to a non‐ignited one. Inlet gas flow rate variations reveal overshoots and undershoots of the reactor maximum temperature. © 2017 American Institute of Chemical Engineers AIChE J, 64: 468–480, 2018     

Application of chitosan‐entrapped β‐galactosidase in a packed‐bed reactor system

The model enzyme β‐galactosidase was entrapped in chitosan gel beads and tested for hydrolytic activity and its potential for application in a packed‐bed reactor. The chitosan beads had an enzyme entrapment efficiency of 59% and retained 56% of the enzyme activity of the free enzyme. The Michaelis constant (K_m) was 0.0086 and 0.011 μmol/mL for the free and immobilized enzymes, respectively. The maximum velocity of the reaction (V_max) was 285.7 and 55.25 μmol mL^?1 min^?1 for the free and immobilized enzymes, respectively. In pH stability tests, the immobilized enzyme exhibited a greater range of pH stability and shifted to include a more acidic pH optimum, compared to that of the free enzyme. A 2.54 × 16.51‐cm tubular reactor was constructed to hold 300 mL of chitosan‐immobilized enzyme. A full‐factorial test design was implemented to test the effect of substrate flow (20 and 100 mL/min), concentration (0.0015 and 0.003M), and repeated use of the test bed on efficiency of the system. Parameters were analyzed using repeated‐measures analysis of variance. Flow (p < 0.05) and concentration (p < 0.05) significantly affected substrate conversion, as did the interaction progressing from Run 1 to Run 2 on a bed (p < 0.05). Reactor stability tests indicated that the packed‐bed reactor continued to convert substrate for more than 12 h with a minimal reduction in conversion efficiency. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1294–1299, 2004     

Dynamic real‐time optimization with closed‐loop prediction

Process plants are operating in an increasingly global and dynamic environment, motivating the development of dynamic real‐time optimization (DRTO) systems to account for transient behavior in the determination of economically optimal operating policies. This article considers optimization of closed‐loop response dynamics at the DRTO level in a two‐layer architecture, with constrained model predictive control (MPC) applied at the regulatory control level. A simultaneous solution approach is applied to the multilevel DRTO optimization problem, in which the convex MPC optimization subproblems are replaced by their necessary and sufficient Karush–Kuhn–Tucker optimality conditions, resulting in a single‐level mathematical program with complementarity constraints. The performance of the closed‐loop DRTO strategy is compared to that of the open‐loop prediction counterpart through a multi‐part case study that considers linear dynamic systems with different characteristics. The performance of the proposed strategy is further demonstrated through application to a nonlinear polymerization reactor grade transition problem. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3896–3911, 2017     

Alkylation of phenol with tert‐butyl alcohol over a catalyst synthesized from coal fly ash

The alkylation of phenol with tert‐butyl alcohol was carried out in a continuous flow reactor over a catalyst synthesized from fly ash. The activity of the synthesized catalyst was compared with those of other conventional zeolite catalysts such as 13X (NaX) and Hβ. Of all the catalysts tested, zeolite Hβ showed the highest activity in phenol conversion followed by the synthesized zeolite (HZOP‐31). The activity of commercial 13X zeolite was found to be same as that of HZOP‐31. Ce‐exchanged catalyst (CeZOP‐31) showed even better performance than 13X in the alkylation of phenol. The effects of different parameters such as reactant mole ratio, temperature and space velocity on phenol conversion and tert‐butyl phenol selectivity were studied. The effect of mass transfer resistance was found to be negligible within the feed rate range and particle size range studied. The apparent activation energy for the reaction of tert‐butyl alcohol over HZOP‐31 was determined as 30.1 kJ mol^?1. Copyright © 2006 Society of Chemical Industry