Aqueous two-phasemicellar systems in an oscillatory flowmicro-reactor: study of perspectives and experimental performance

BACKGROUND: Aqueous two-phase micellar systems (ATPMS) are micellar surfactant solutions with physical properties that make them very efficient for the extraction/concentration of biological products. In this work the main proposal that has been discussed is the possible applicability and importance of a novel oscillatory flow micro-reactor (micro-OFR) envisaged for parallel screening and/or development of industrial bioprocesses in ATPMS. Based on the technology of oscillatory flow mixing (OFM), this batch or continuous micro-reactor has been presented as a new small-scale alternative for biological or physical-chemical applications. RESULTS: ATPMS experiments were carried out in different OFM conditions (times, temperatures, oscillation frequencies and amplitudes) for the extraction of glucose-6-phosphate dehydrogenase (G6PD) in Triton X-114/buffer with Cibacron Blue as affinity ligand. CONCLUSION: The results suggest the potential use of OFR, considering this process a promising and new alternative for the purification or pre-concentration of bioproducts. Despite the applied homogenization and extraction conditions have presented no improvements in the partitioning selectivity of the target enzyme, when at rest temperature they have influenced the partitioning behavior in Triton X-114 ATPMS. (C) 2011 Society of Chemical Industry

Paste Residence Time in a Spouted Bed Dryer. IV: Effect of the Inert Particle Size Distribution

The residence time distribution and mean residence time of a 10% sodium bicarbonate solution that is dried in a conventional spouted bed with inert bodies were measured with the stimulus-response method. Methylene blue was used as a chemical tracer, and the effects of the paste feed mode, size distribution of the inert bodies, and mean particle size on the residence times and dried powder properties were investigated. The results showed that the residence time distributions could be best reproduced with the perfect mixing cell model or N = 1 for the continuous stirred tank reactor in a series model. The mean residence times ranged from 6.04 to 12.90 min and were significantly affected by the factors studied. Analysis of variance on the experimental data showed that mean residence times were affected by the mean diameter of the inert bodies at a significance level of 1% and by the size distribution at a level of 5%. Moreover, altering the paste feed from dripping to pneumatic atomization affected mean residence time at a 5% significance level. The dried powder characteristics proved to be adequate for further industrial manipulation, as demonstrated by the low moisture content, narrow range of particle size, and good flow properties. The results of this research are significant in the study of the drying of heat-sensitive materials because it shows that by simultaneously changing the size distribution and average size of the inert bodies, the mean residence times of a paste can be reduced by half, thus decreasing losses due to degradation.

Residence time distributions of gas flowing through rotating drum bioreactors

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

Design analysis for refolding monomeric protein

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

Hydrogen production from cassava processing wastewater in an anaerobic fixed bed reactor with bamboo as a support material

Attempting to associate waste treatment to the production of clean and renewable energy, this research sought to evaluate the biological production of hydrogen using wastewater from the cassava starch treatment industry, generated during the processes of extraction and purification of starch. This experiment was carried out in a continuous anaerobic reactor with a working volume of 3L, with bamboo stems as the support medium. The system was operated at a temperature of 36°C, an initial pH of 6.0 and under variations of organic load. The highest rate of hydrogen production, of 1.1 L.d-1.L-1, was obtained with application of an organic loading rate of 35 g.L-1.d-1, in terms of total sugar content and hydraulic retention time of 3h, with a prevalence of butyric and acetic acids as final products of the fermentation process. Low C/N ratios contributed to the excessive growth of the biomass, causing a reduction of up to 35% in hydrogen production, low percentages of H2 and high concentrations of CO2in the biogas.

Computationally reliable approaches of contractive MPC for discrete-time systems

La tesis pretende explorar acercamientos computacionalmente confiables y eficientes de contractivo MPC para sistemas de tiempo discreto. Dos tipos de contractivo MPC han sido estudiados: MPC con coacción contractiva obligatoria y MPC con una secuencia contractiva de conjuntos controlables. Las técnicas basadas en optimización convexa y análisis de intervalos son aplicadas para tratar MPC contractivo lineal y no lineal, respectivamente. El análisis de intervalos clásicos es ampliado a zonotopes en la geometría para diseñar un conjunto invariante de control terminal para el modo dual de MPC. También es ampliado a intervalos modales para tener en cuenta la modalidad al calcula de conjuntos controlables robustos con una interpretación semántica clara. Los instrumentos de optimización convexa y análisis de intervalos han sido combinados para mejorar la eficacia de contractive MPC para varias clases de sistemas de tiempo discreto inciertos no lineales limitados. Finalmente, los dos tipos dirigidos de contractivo MPC han sido aplicados para controlar un Torneo de Fútbol de Copa Mundial de Micro Robot (MiroSot) y un Tanque-Reactor de Mezcla Continua (CSTR), respectivamente.

A stable one-step-ahead predictive control of non-linear systems

In this paper stability of one-step ahead predictive controllers based on non-linear models is established. It is shown that, under conditions which can be fulfilled by most industrial plants, the closed-loop system is robustly stable in the presence of plant uncertainties and input–output constraints. There is no requirement that the plant should be open-loop stable and the analysis is valid for general forms of non-linear system representation including the case out when the problem is constraint-free. The effectiveness of controllers designed according to the algorithm analyzed in this paper is demonstrated on a recognized benchmark problem and on a simulation of a continuous-stirred tank reactor (CSTR). In both examples a radial basis function neural network is employed as the non-linear system model.

A comparative study of multilayered and single layered neural network based predictive controllers

The authors compare the performance of two types of controllers one based on the multilayered network and the other based on the single layered CMAC network (cerebellar model articulator controller). The neurons (information processing units) in the multi-layered network use Gaussian activation functions. The control scheme which is considered is a predictive control algorithm, along the lines used by Willis et al. (1991), Kambhampati and Warwick (1991). The process selected as a test bed is a continuous stirred tank reactor. The reaction taking place is an irreversible exothermic reaction in a constant volume reactor cooled by a single coolant stream. This reactor is a simplified version of the first tank in the two tank system given by Henson and Seborg (1989).

Avaliação da influência da agitação no tratamento anaeróbio por leito fixo de manipueira

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Catalytic liquid- and gas-phase oxidations for the synthesis of intermediates and specialty chemicals: some examples of industrial relevance

Nowadays, it is clear that the target of creating a sustainable future for the next generations requires to re-think the industrial application of chemistry. It is also evident that more sustainable chemical processes may be economically convenient, in comparison with the conventional ones, because fewer by-products means lower costs for raw materials, for separation and for disposal treatments; but also it implies an increase of productivity and, as a consequence, smaller reactors can be used. In addition, an indirect gain could derive from the better public image of the company, marketing sustainable products or processes. In this context, oxidation reactions play a major role, being the tool for the production of huge quantities of chemical intermediates and specialties. Potentially, the impact of these productions on the environment could have been much worse than it is, if a continuous efforts hadn’t been spent to improve the technologies employed. Substantial technological innovations have driven the development of new catalytic systems, the improvement of reactions and process technologies, contributing to move the chemical industry in the direction of a more sustainable and ecological approach. The roadmap for the application of these concepts includes new synthetic strategies, alternative reactants, catalysts heterogenisation and innovative reactor configurations and process design. Actually, in order to implement all these ideas into real projects, the development of more efficient reactions is one primary target. Yield, selectivity and space-time yield are the right metrics for evaluating the reaction efficiency. In the case of catalytic selective oxidation, the control of selectivity has always been the principal issue, because the formation of total oxidation products (carbon oxides) is thermodynamically more favoured than the formation of the desired, partially oxidized compound. As a matter of fact, only in few oxidation reactions a total, or close to total, conversion is achieved, and usually the selectivity is limited by the formation of by-products or co-products, that often implies unfavourable process economics; moreover, sometimes the cost of the oxidant further penalizes the process. During my PhD work, I have investigated four reactions that are emblematic of the new approaches used in the chemical industry. In the Part A of my thesis, a new process aimed at a more sustainable production of menadione (vitamin K3) is described. The “greener” approach includes the use of hydrogen peroxide in place of chromate (from a stoichiometric oxidation to a catalytic oxidation), also avoiding the production of dangerous waste. Moreover, I have studied the possibility of using an heterogeneous catalytic system, able to efficiently activate hydrogen peroxide. Indeed, the overall process would be carried out in two different steps: the first is the methylation of 1-naphthol with methanol to yield 2-methyl-1-naphthol, the second one is the oxidation of the latter compound to menadione. The catalyst for this latter step, the reaction object of my investigation, consists of Nb2O5-SiO2 prepared with the sol-gel technique. The catalytic tests were first carried out under conditions that simulate the in-situ generation of hydrogen peroxide, that means using a low concentration of the oxidant. Then, experiments were carried out using higher hydrogen peroxide concentration. The study of the reaction mechanism was fundamental to get indications about the best operative conditions, and improve the selectivity to menadione. In the Part B, I explored the direct oxidation of benzene to phenol with hydrogen peroxide. The industrial process for phenol is the oxidation of cumene with oxygen, that also co-produces acetone. This can be considered a case of how economics could drive the sustainability issue; in fact, the new process allowing to obtain directly phenol, besides avoiding the co-production of acetone (a burden for phenol, because the market requirements for the two products are quite different), might be economically convenient with respect to the conventional process, if a high selectivity to phenol were obtained. Titanium silicalite-1 (TS-1) is the catalyst chosen for this reaction. Comparing the reactivity results obtained with some TS-1 samples having different chemical-physical properties, and analyzing in detail the effect of the more important reaction parameters, we could formulate some hypothesis concerning the reaction network and mechanism. Part C of my thesis deals with the hydroxylation of phenol to hydroquinone and catechol. This reaction is already industrially applied but, for economical reason, an improvement of the selectivity to the para di-hydroxilated compound and a decrease of the selectivity to the ortho isomer would be desirable. Also in this case, the catalyst used was the TS-1. The aim of my research was to find out a method to control the selectivity ratio between the two isomers, and finally to make the industrial process more flexible, in order to adapt the process performance in function of fluctuations of the market requirements. The reaction was carried out in both a batch stirred reactor and in a re-circulating fixed-bed reactor. In the first system, the effect of various reaction parameters on catalytic behaviour was investigated: type of solvent or co-solvent, and particle size. With the second reactor type, I investigated the possibility to use a continuous system, and the catalyst shaped in extrudates (instead of powder), in order to avoid the catalyst filtration step. Finally, part D deals with the study of a new process for the valorisation of glycerol, by means of transformation into valuable chemicals. This molecule is nowadays produced in big amount, being a co-product in biodiesel synthesis; therefore, it is considered a raw material from renewable resources (a bio-platform molecule). Initially, we tested the oxidation of glycerol in the liquid-phase, with hydrogen peroxide and TS-1. However, results achieved were not satisfactory. Then we investigated the gas-phase transformation of glycerol into acrylic acid, with the intermediate formation of acrolein; the latter can be obtained by dehydration of glycerol, and then can be oxidized into acrylic acid. Actually, the oxidation step from acrolein to acrylic acid is already optimized at an industrial level; therefore, we decided to investigate in depth the first step of the process. I studied the reactivity of heterogeneous acid catalysts based on sulphated zirconia. Tests were carried out both in aerobic and anaerobic conditions, in order to investigate the effect of oxygen on the catalyst deactivation rate (one main problem usually met in glycerol dehydration). Finally, I studied the reactivity of bifunctional systems, made of Keggin-type polyoxometalates, either alone or supported over sulphated zirconia, in this way combining the acid functionality (necessary for the dehydrative step) with the redox one (necessary for the oxidative step). In conclusion, during my PhD work I investigated reactions that apply the “green chemistry” rules and strategies; in particular, I studied new greener approaches for the synthesis of chemicals (Part A and Part B), the optimisation of reaction parameters to make the oxidation process more flexible (Part C), and the use of a bioplatform molecule for the synthesis of a chemical intermediate (Part D).

Studio fluidodinamico di un reattore continuo agitato meccanicamente tramite tecniche PIV e PLIF

The study and understanding of the motion of the fluid phases in a mechanically stirred reactor has always been, and still are, an open problem which absorbs the study and the work of many researchers. In recent decades, thanks to the growing opportunities offered by the development of technology, we have made great strides in the understanding of mixing, one of the major unit operations at the base of many industrial processes. A complete understanding of this process and its optimization for industrial applications is a challenging task due to the complex interactions between the many factors at play that include physical, chemical and biological. The purpose of this thesis is the study of a fluid-mechanically-agitated continuous reactor through the use of optical diagnostic techniques, which allowed to determine the range of motion and the time of perfect homogenization in a reactor of standard geometry in different operating conditions.

Biogas and bio-hydrogen: production and uses. A review

The first part of this essay aims at investigating the already available and promising technologies for the biogas and bio-hydrogen production from anaerobic digestion of different organic substrates. One strives to show all the peculiarities of this complicate process, such as continuity, number of stages, moisture, biomass preservation and rate of feeding. The main outcome of this part is the awareness of the huge amount of reactor configurations, each of which suitable for a few types of substrate and circumstance. Among the most remarkable results, one may consider first of all the wet continuous stirred tank reactors (CSTR), right to face the high waste production rate in urbanised and industrialised areas. Then, there is the up-flow anaerobic sludge blanket reactor (UASB), aimed at the biomass preservation in case of highly heterogeneous feedstock, which can also be treated in a wise co-digestion scheme. On the other hand, smaller and scattered rural realities can be served by either wet low-rate digesters for homogeneous agricultural by-products (e.g. fixed-dome) or the cheap dry batch reactors for lignocellulose waste and energy crops (e.g. hybrid batch-UASB). The biological and technical aspects raised during the first chapters are later supported with bibliographic research on the important and multifarious large-scale applications the products of the anaerobic digestion may have. After the upgrading techniques, particular care was devoted to their importance as biofuels, highlighting a further and more flexible solution consisting in the reforming to syngas. Then, one shows the electricity generation and the associated heat conversion, stressing on the high potential of fuel cells (FC) as electricity converters. Last but not least, both the use as vehicle fuel and the injection into the gas pipes are considered as promising applications. The consideration of the still important issues of the bio-hydrogen management (e.g. storage and delivery) may lead to the conclusion that it would be far more challenging to implement than bio-methane, which can potentially “inherit” the assets of the similar fossil natural gas. Thanks to the gathered knowledge, one devotes a chapter to the energetic and financial study of a hybrid power system supplied by biogas and made of different pieces of equipment (natural gas thermocatalitic unit, molten carbonate fuel cell and combined-cycle gas turbine structure). A parallel analysis on a bio-methane-fed CCGT system is carried out in order to compare the two solutions. Both studies show that the apparent inconvenience of the hybrid system actually emphasises the importance of extending the computations to a broader reality, i.e. the upstream processes for the biofuel production and the environmental/social drawbacks due to fossil-derived emissions. Thanks to this “boundary widening”, one can realise the hidden benefits of the hybrid over the CCGT system.

Flow regime, hydrodynamics, floc size distribution and sludge properties in activated sludge bubble column, air-lift and aerated stirred reactors

This paper presents a comparative study how reactor configuration, sludge loading and air flowrate affect flow regimes, hydrodynamics, floc size distribution and sludge solids-liquid separation properties. Three reactor configurations were studied in bench scale activated sludge bubble column reactor (BCR), air-lift reactor (ALR) and aerated stirred reactor (ASR). The ASR demonstrated the highest capacity of gas holdup and resistance, and homogeneity in flow regimes and shearing forces, resulting in producing large numbers of small and compact floes. The fluid dynamics in the ALR created regularly directed recirculation forces to enhance the gas holdup and sludge flocculation. The BCR distributed a high turbulent flow regime and non-homogeneity in gas holdup and mixing, and generated large numbers of larger and looser floes. The sludge size distributions, compressibility and settleability were significantly influenced by the reactor configurations associated with the flow regimes and hydrodynamics.

Hydrometallurgical process modeling using advanced mathematical tools

Hydrometallurgical process modeling is the main objective of this Master’s thesis work. Three different leaching processes namely, high pressure pyrite oxidation, direct oxidation zinc concentrate (sphalerite) leaching and gold chloride leaching using rotating disc electrode (RDE) are modeled and simulated using gPROMS process simulation program in order to evaluate its model building capabilities. The leaching mechanism in each case is described in terms of a shrinking core model. The mathematical modeling carried out included process model development based on available literature, estimation of reaction kinetic parameters and assessment of the model reliability by checking the goodness fit and checking the cross correlation between the estimated parameters through the use of correlation matrices. The estimated parameter values in each case were compared with those obtained using the Modest simulation program. Further, based on the estimated reaction kinetic parameters, reactor simulation and modeling for direct oxidation zinc concentrate (sphalerite) leaching is carried out in Aspen Plus V8.6. The zinc leaching autoclave is based on Cominco reactor configuration and is modeled as a series of continuous stirred reactors (CSTRs). The sphalerite conversion is calculated and a sensitivity analysis is carried out so to determine the optimum reactor operation temperature and optimum oxygen mass flow rate. In this way, the implementation of reaction kinetic models into the process flowsheet simulation environment has been demonstrated.

Chemical treatment of Escherichia coli: 3. Selective extraction of a recombinant protein from cytoplasmic inclusion bodies in intact cells

In previous parts of this study we developed procedures for the high-efficiency chemical extraction of soluble and insoluble protein from intact Escherichia coli cells. Although high yields were obtained, extraction of recombinant protein directly from cytoplasmic inclusion bodies led to low product purity due to coextraction of soluble contaminants. In this work, a two-stage procedure for the selective extraction of recombinant protein at high efficiency and high purity is reported. In the first stage, inclusion-body stability is promoted by the addition of 15 mM 2-hydroxyethyldisulfide (2-HEDS), also known as oxidized P-mercaptoethanol, to the permeabil ization buffer (6 M urea + 3 mM ethylenediaminetetra-acetate [EDTA]). 2-HEDS is an oxidizing agent believed to promote disulfide bond formation, rendering the inclusion body resistant to solubilization in 6 M urea. Contaminating proteins are separated from the inclusion-body fraction by centrifugation. in the second stage, disulfide bonds are readily eliminated by including reducing agent (20 mM dithiothreitol [DTT]) into the permeabilization buffer. Extraction using this selective two-stage process yielded an 81% (w/w) recovery of the recombinant protein Long-R-3-IGF-I from inclusion bodies located in the cytoplasm of intact E. coli, at a purity of 46% (w/w). This was comparable to that achieved by conventional extraction (mechanical disruption followed by centrifugation and solubilization). A pilot-scale procedure was also demonstrated using a stirred reactor and diafiltration. This is the first reported study that achieves both high extraction efficiency and selectivity by the chemical treatment of cytoplasmic inclusion bodies in intact bacterial cells. (C) 1999 John Wiley & Sons, Inc.