High-pressure gasification reactivity of biomass chars produced at different temperatures

The knowledge of biomass char gasification kinetics is of considerable importance in the design of advanced biomass gasifiers, some of which operate at high pressures. In the present work the effects of pyrolysis temperature, total pressure and CO₂ concentration on the gasification of biomass chars have been studied using the thermogravimetric approach. The chars were obtained by pyrolysis in a drop tube furnace reactor at temperatures of 1000 and 1400 °C. The gasification tests were carried out in a pressurized thermogravimetric analyser (PTGA) at different temperatures, pressures and CO₂ concentrations. The reactivity measurements were conducted under the kinetically controlled regime, and three nth-order kinetic models as well as the Langmuir–Hinshelwood model were applied to determine the kinetic parameters.     

Sorption of ofloxacin and chrysoidine by grape stalk. A representative case of biomass removal of emerging pollutants from wastewater

Emerging pollutants, as antibiotics or dyes, in aquatic ecosystems are a crucial concern and numerous techniques have been developed for their removal. Efficiency, cost effectiveness, and biodegradability reveal biomass sorption as one of the most appealing methods. This study aims to evaluate the effectiveness of grape stalk as a sorbent for ofloxacin (a fluoroquinolone antibiotic) and chrysoidine (an azo-dye). The kinetic and the thermodynamic aspects of the sorption were studied. A pseudo first-order kinetic behavior is shown by both substances, though the kinetic constants of ofloxacin are almost double than those of chrysoidine. The sorption isotherms, which strictly follow the Langmuir model, show remarkable differences as a function of pH and of biomass size. The trend of Langmuir parameters, Q_max and K, as a function of pH and size, is discussed, and different binding mechanisms are proposed. Kinetic and thermodynamic parameters prefigure grape stalk as a potential biomass for scavenging toxic substances from wastewater.     

Mercury exchange between diphenylmercury and bis(p-chlorophenyl)mercury

Experimental methods for investigating mercury exchange between diphenyl mercury and bis(p-chlorophenyl)mercury have been evaluated and kinetic parameters determined using a novel partition technique. An octahedral transition state has been proposed. The investigation was complicated by a relatively fast reaction rate, and the kinetic interference of impurities or hydrolysis products.     

Biomass pyrolysis kinetics: A comparative critical review with relevant agricultural residue case studies

Biomass pyrolysis is a fundamental thermochemical conversion process that is of both industrial and ecological importance. From designing and operating industrial biomass conversion systems to modeling the spread of wildfires, an understanding of solid state pyrolysis kinetics is imperative. A critical review of kinetic models and mathematical approximations currently employed in solid state thermal analysis is provided. Isoconversional and model-fitting methods for estimating kinetic parameters are comparatively evaluated. The thermal decomposition of biomass proceeds via a very complex set of competitive and concurrent reactions and thus the exact mechanism for biomass pyrolysis remains a mystery. The pernicious persistence of substantial variations in kinetic rate data for solids irrespective of the kinetic model employed has exposed serious divisions within the thermal analysis community and also caused the broader scientific and industrial community to question the relevancy and applicability of all kinetic data obtained from heterogeneous reactions. Many factors can influence the kinetic parameters, including process conditions, heat and mass transfer limitations, physical and chemical heterogeneity of the sample, and systematic errors. An analysis of thermal decomposition data obtained from two agricultural residues, nutshells and sugarcane bagasse, reveals the inherent difficulty and risks involved in modeling heterogeneous reaction systems.     

Performance of anaerobic sequencing batch biofilm reactor submitted to different influent volume feeds and cycle time periods maintaining organic loading

The stability and efficiency of an anaerobic reactor containing biomass immobilized on polyurethane foam were assessed. The reactor with mechanical stirring of 500 rpm and maintained at 30+/-1 degrees C treated synthetic wastewater with a concentration of approx 500 mg of chemical oxygen demand/L and was fed with different influent volumes and cycle times maintaining organic load. Operation was in batch mode with renewal of only part of the volume of wastewater to be treated; that is reactor discharge was not complete, but partial. The main operational characteristic investigated was the ratio of the volume of wastewater fed per cycle (VA) to the volume of wastewater in the reactor (VA) maintaining the same volumetric organic load. This way, operating flexibility could be verified in relation to the volume of treated wastewater at each cycle and the cycle time for the same organic load. The results indicated that the reactor was able to operate with different VA/Vu ratios with no significant loss in performance, thus allowing increased operational flexibility. For conditions in which VA was >or=50% of VA, removal efficiencies of filtered and nonfiltered organic matter were about 84 and 79%, respectively, whereas at conditions of higher initial influent dilution, these efficiencies were slightly lower, about 80 and 74%, respectively. At higher initial influent dilutions, it became difficult to maintain a constant reactor medium volume, owing to a high formation rate of viscous polymer-like material, likely of microbiologic origin.     

Shrinking-bed model for percolation process applied to dilute-acid pretreatment/hydrolysis of cellulosic biomass

For many lignocellulosic substrates, hemicellulose is biphasic upon dilute-acid hydrolysis, which led to a modified percolation process employing simulated two-stage reverse-flow. This process has been proven to attain substantially higher sugar yields and concentrations over the conventional single-stage percolation process. The dilute-acid pretreatment of biomass solubilizes the hemicellulose fraction in the solid biomass, leaving less solid biomass in the reactor and reducing the bed. Therefore, a bed-shrinking mathematic kinetic model was developed to describe the two-stage reverse-flow reactor operated for hydrolyzing biphasic substrates, including hemicellulose, in corn cob/stover mixture (CCSM). The simulation indicates that the shrinking-bed operation increases the sugar yield by about 5%, compared to the nonshrinking bed operation in which 1 reactor volume of liquid passes through the reactor (i.e.,t = 1.0). A simulated optimal run further reveals that the fast portion of hemicellulose is almost completely hydrolyzed in the first stage, and the slow portion of hemicellulose is hydrolyzed in the second stage. Under optimal conditions, the bed shrank 27% (a near-maximum value), and a sugar yield over 95% was attained.     

Assembly of a Multiphase Bioreactor for Laboratory Demonstrations: Study of the Oxygen-Transfer Efficiency in Activated Sludge

A simple experimental device has been assembled with the aim of increasing students understanding of multiphase reactors and to highlight the importance of economic considerations in real chemical engineering problems. The multiphase reactor studied is an activated sludge reactor. In this type of reactor, organic matter and nitrogen substrates, which are contained in wastewater, are oxidized by solid bacterial groups that employ oxygen. Gas dispersion is a factor of critical importance in the operating performance and cost of every multiphase reactor. In the work covered here, students determine the influence of this factor on the assembly while considering that energy consumption (economic cost) depends on both the type of aerator used and the operational conditions for a given aerator. A theoretical model is proposed that allows the interpretation of the results based on the assumptions that gas absorption and biochemical reactions are the limiting steps. Experimental data are fitted to this model, and the parameters obtained allow comparison of the behavior of each type of aerator and also provide an understanding of the process.     

Estimation of Fundamental Kinetic Parameters of Polyhydroxybutyrate Fermentation Process of Azohydromonas australica Using Statistical Approach of Media Optimization

Polyhydroxybutyrate or PHB is a biodegradable and biocompatible thermoplastic with many interesting applications in medicine, food packaging, and tissue engineering materials. The present study deals with the enhanced production of PHB by Azohydromonas australica using sucrose and the estimation of fundamental kinetic parameters of PHB fermentation process. The preliminary culture growth inhibition studies were followed by statistical optimization of medium recipe using response surface methodology to increase the PHB production. Later on batch cultivation in a 7-L bioreactor was attempted using optimum concentration of medium components (process variables) obtained from statistical design to identify the batch growth and product kinetics parameters of PHB fermentation. A. australica exhibited a maximum biomass and PHB concentration of 8.71 and 6.24?g/L, respectively in bioreactor with an overall PHB production rate of 0.75?g/h. Bioreactor cultivation studies demonstrated that the specific biomass and PHB yield on sucrose was 0.37 and 0.29?g/g, respectively. The kinetic parameters obtained in the present investigation would be used in the development of a batch kinetic mathematical model for PHB production which will serve as launching pad for further process optimization studies, e.g., design of several bioreactor cultivation strategies to further enhance the biopolymer production.     

Biosorption of uranium by immobilized cells of Rhodotorula glutinis

Biosorption of uranium ions from diluted solution (≤40 mg L^?1) onto immobilized cells of Rhodotorula glutinis was investigated in a batch system. Equilibrium, kinetic and thermodynamic studies were conducted by considering the effect of initial uranium concentration, contact time and temperature. Non-linear forms of Langmuir, Freundlich and Sips isotherm models were used to fit the equilibrium data, Sips model was designated as the best one. Kinetic data were simulated by non-linear pseudo-first-order, pseudo-second-order and intra-particle diffusion equations. Pseudo-first-order kinetic equation described the experimental data better than pseudo-second-order equation and intra-particle diffusion equation can fit the kinetic data with two independent curves. Thermodynamic parameters, including ?H ⁰, ?G ⁰ and ?S ⁰, were evaluated, the sorption process was determined to be spontaneous and endothermic. Uranium sorption from pure uranium solutions and uranium pit wastewater by immobilized biomass and blank beads, as well as the regeneration results indicated that immobilized R. glutinis can be use to recovery uranium from uranium pit wastewater.     

Radiotracer investigation in a rotary fluidized bioreactor

A rotary fluidized bioreactor (RFBR) designed for treatment of wastewater was required to be investigated for its hydrodynamic behaviour and validation of design. A radiotracer investigation was carried out to measure residence time distribution (RTD) of wastewater in the RFBR using ⁸²Br as a radiotracer. The radiotracer was instantaneously injected into the inlet feed line and monitored at the inlet and outlet of the reactor using collimated scintillation detectors connected to a data acquisition system. The measured RTD data was treated and simulated using a tanks-in-series model and model parameters i.e. number of tanks describing the degree of mixing was obtained. The results of the investigation showed no flow abnormalities and the reactor behaved as an ideal continuously stirred-tank reactor at all the operating conditions. Based on the results, the design of the reactor was validated.     

AnSBBR Applied to the Treatment of Metalworking Fluid Wastewater: Effect of Organic and Shock Load

An investigation was performed regarding the application of a mechanically stirred anaerobic sequencing batch biofilm reactor containing immobilized biomass on inert polyurethane foam (AnSBBR) to the treatment of soluble metalworking fluids to remove organic matter and produce methane. The effect of increasing organic matter and reactor fill time, as well as shock load, on reactor stability and efficiency have been analyzed. The 5-L AnSBBR was operated at 30?°C in 8-h cycles, agitation of 400 rpm, and treated 2.0 L effluent per cycle. Organic matter was increased by increasing the influent concentration (500, 1,000, 2,000, and 3,000 mg chemical oxygen demand (COD)/L). Fill times investigated were in the batch mode (fill time 10 min) and fed-batch followed by batch (fill time 4 h). In the batch mode, organic matter removal efficiencies were 87%, 86%, and 80% for influent concentrations of 500, 1,000, and 2,000 mgCOD/L (1.50, 3.12, and 6.08 gCOD/L.d), respectively. At 3,000 mgCOD/L (9.38 gCOD/L.d), operational stability could not be achieved. The reactor managed to maintain stability when a shock load twice as high the feed concentration was applied, evidencing the robustness of the reactor to potential concentration variations in the wastewater being treated. Increasing the fill time to 4 h did not improve removal efficiency, which was 72% for 2,000 mgCOD/L. Thus, gradual feeding did not improve organic matter removal. The concentration of methane formed at 6.08 gCOD/L was 5.20 mmolCH₄, which corresponded to 78% of the biogas composition. The behavior of the reactor during batch and fed-batch feeding could be explained by a kinetic model that considers organic matter consumption, production, and consumption of total volatile acids and methane production.     

Biomass pyrolysis: Kinetic modelling and experimental validation under high temperature and flash heating rate conditions

This work analyzes and discusses the general features of biomass pyrolysis, both on the basis of a new set of experiments and by using a detailed kinetic model of biomass devolatilization that includes also successive gas phase reactions of the released species and is therefore able to predict the main gases composition. Experiments are performed in a lab-scale Entrained Flow Reactor (EFR) to investigate biomass pyrolysis under high temperatures (1073–1273 K) and high heating fluxes (10–100 kW m⁻²). The influence of particle dimensions and temperature has been tested versus solid residence time in the reactor. The particle size appeared as the most crucial parameter. The pyrolysis of 0.4 mm particles is nearly finished under this range of temperatures after a reactor length of 0.3 m, with more than 75 wt% of gas release, whereas the conversion is still under evolution until the end of the reactor for larger particles up to 1.1 mm, due to internal heat transfer limitations. The preliminary comparisons between the model and the experimental data are encouraging and show the ability of this model to contribute to a better design and understanding of biomass pyrolysis process under severe conditions of temperature and heating fluxes typically found in industrial gasifiers.     

Feasibility of treating swine manure in an anaerobic sequencing batch biofilm reactor with mechanical stirring

Anaerobic sequencing batch reactors containing granular or flocculent biomass have been employed successfully in the treatment of piggery wastewater. However, the studies in which these reactors were employed did not focus specifically on accelerating the hydrolysis step, even though the degradation of this chemical oxygen demand (COD) fraction is likely to be the limiting step in many investigations of this type of wastewater. The mechanically stirred anaerobic sequencing batch biofilm reactor offers an alternative for hastening the hydrolysis step, because mechanical agitation can help to speed up the reduction of particle sizes in the fraction of particulate organic matter. In the present study, a 4.5-L reactor was operated at 30°C, with biomass immobilized on cubic polyurethane foam matrices (1 cm of side) and mechanical stirring provided by three flat-blade turbines (6 cm) at agitation rates varying from 0 to 500 rpm. The reactor was operated to treat diluted swine waste, and mechanical stirring efficiently improved degradation of the suspended COD. The operational data indicate that the reactor remained stable during the testing period. After 2 h of operation at 500 rpm, the suspended COD decreased by about 65% (from 1500 to 380 mg/L). Apparent kinetic constants were also calculated by modified first-order expressions.     

Direct Red 28 Adsorption on Amosil and <Emphasis Type="Italic">Avena sativa </Emphasis> L.: Mass Transfer and Kinetics Modelling on the Solid/Solution Interface

Adsorption kinetics is a key issue for successful sorbent selection and the proper design of batch and fixed-bed adsorption systems. The aim of the present study was to determine the kinetics, mass transfer and diffusion coefficients and to establish the rate-controlling mechanism/s during Direct Red 28 adsorption on Amosil and Avena sativa L. biomass. Five kinetic models (pseudo-second order, Blanchard, Avrami, Ritchie and power function) and and four mass transfer (external diffusion, film diffusion, particle diffusion, intraparticle diffusion) mathematical models were applied to the experimental data. To confirm the best-fitting model(s), error analyses were conducted. The integrative comparative analyses of the values of the predicted model parameters, coefficients and error functions established that the intraparticle diffusion model best represented the experimental results of the dye sorption on dried A. sativa L. biomass, while for the Direct Red 28/Amosil system, the kinetic behavior is the best described by either the pseudo-second or Blanchard’s model. Boyd’s effective intraparticle diffusion coefficient (D _i ), characterizing the dye sorption on Amosil, is significantly lower than that for the system Direct Red 28/A. sativa L. biomass. The low values of the Bi number (Bi < 0.5) suggests that the mass transfer resistance, for both systems, is concentrated at the fluid/solid phase surface.     

A study of nicotinic acid synthesis on a pilot installation and its simulation

Technological process parameters of the nicotinic acid synthesis by oxidation of β-picoline on a vanadium-titanium catalyst in a unit tube of a pilot installation were determined: conversion of β-picoline, yield and selectivity for products, and parametric sensitivity of the "hot point" temperature to variation of parameters at the reactor inlet. A mathematical simulation of the process was carried using the model of heat-and-mass transfer in a bed of a tubular reactor and the kinetic model of oxidation of β-picoline.     

Kinetic models comparison for steam gasification of different nature fuel chars

The reactivity in steam of five different types of solid fuels (two coals, two types of biomass and a petcoke) has been studied. The fuel chars were obtained by pyrolysis in a fixed-bed reactor at a temperature of 1373 K for 30 min. The gasification tests were carried out by thermogravimetric analysis (TG) at different temperatures and steam concentrations. The reactivity study was conducted in the kinetically controlled regime and three representative gas-solid models, volumetric model (VM), grain model (GM) and random pore model (RPM), were applied in order to describe the reactive behaviour of the chars during steam gasification. The kinetic parameters of these models were derived and the ability of the models to predict conversion and char reactivity during gasification was assessed. The best model for describing the behaviour of the samples was the RPM. The effect of the partial pressure of steam in gasification was studied, and the reaction order with respect to steam was determined. The reactivity of the chars was compared by means of a reactivity index. Biomass exhibited a higher reactivity than coals and petcoke. However, significant differences in reactivity were observed between the two types of biomass used, which could be due to catalytic effects.     

Modeling of biomass-based hydrogen production via catalytic sorption-enhanced reformer integrated with a gasifier

The sorption enhanced reformer concept breaks the thermodynamic limits of steam methane reforming and water-gas shift reactions with selective CO₂ removal to produce more H₂. In this paper, we propose a dynamic kinetic model for sorption-enhanced steam reformers (SERs) integrated with biomass gasifiers. An analysis of operating conditions was conducted to examine high purity hydrogen production. The kinetic model was validated with published literature results at different reactor pressures (5-20 bar), steam/carbon ratios (2-5), and reactor temperatures (673K–1023K). This study shows that biomass gasifiers can be integrated with SER reactors to produce high purity H₂.     

Kinetic Model of Photoautotrophic Growth of Chlorella sp. Microalga,Isolated from the Setúbal Lagoon

In this work, a kinetic expression relating light availability in the culture medium with the rate of microalgal growth is obtained. This expression, which is valid for low illumination conditions, was derived from the reactions that take part in the light‐dependent stage of photosynthesis. The kinetic expression obtained is a function of the biomass concentration in the culture, as well as of the local volumetric rate of absorption of photons, and only includes two adjustable parameters. To determine the value of these parameters and to test the validity of the hypotheses made, autotrophic cultures of the Chlorella sp. strain were carried out in a modified BBM medium at three CO₂ concentrations in the gas stream, namely 0.034%, 0.34% and 3.4%. Moreover, the local volumetric rate of photon absorption was predicted based on a physical model of the interaction of the radiant energy with the suspended biomass, together with a Monte Carlo simulation algorithm. The proposed intrinsic expression of the biomass growth rate, together with the Monte Carlo radiation field simulator, are key to scale up photobioreactors when operating under low irradiation conditions, independently of the configuration of the reactor and of its light source.     

Toxicity assessment of raw and ozonated benzothiazole synthetic wastewater

Ozonation experiments were performed with model wastewater containing 100 g m^?3 benzothiazole concentration. Ozonation was carried out in jet-loop reactor with external recirculation of the reaction mixture. Benzothiazole removal efficiency was 87%. Benzothiazole residual concentration and concentration of its degradation products after ozonation were expressed as COD and TOC values. In terms of biodegradability, respirometric measurements with activated sludge microorganisms were performed on samples of ozonated model wastewater. Increase in oxygen uptake rate compared to the endogenous phase was recorded in all measurements. Experimental data were fitted by Monod and Haldane equations. The best match of experimental and calculated data was achieved by Haldane kinetic model due to substrate and degradation products inhibition. The results of respirometric measurements indicate that ozonation improves the biodegradability of model wastewater and increases the oxygen uptake rate of activated sludge. However, substrate inhibition was observed with higher COD content. Toxicity test was performed on three organisms (Sinapis alba, Daphnia magna and Vibrio fischeri), and has shown that each studied organism responds differently on ozonated wastewater. Inhibition of S. alba decreases with ozonation time. Inhibition of V. fischeri reached maximum at 10 min of ozonation and inhibition of D. magna has minimum at the same ozonation time.