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Tubular reactors cover a large class of processes in chemical and biochemical engineering. They are typically reactors in which the medium is not homogeneous (like fixed-bed reactors, packed-bed reactors, fluidized-bed reactors,...) and possibly involve diferent phases (liquid/solid/gas). The dynamics of nonisothermal axial dispersion or plug flow tubular reactors are described by semilinear partial differential equations (PDE's) derived from mass and energy balances. The main source of nonlinearities in such dynamics is concentrated in the kinetics terms of the model equations. Like tubular reactors many physical phenomena are modelled by partial differential equations (PDE's). Such systems are called distributed parameter systems. Control problems of these systems can be formulated in state-space form in a way analogous to those of lumped parameter systems (those described by ordinary differential equations) if one introduces a suitable infinite-dimensional state-space and suitable operators instead of the usual matrices. This thesis deals with the synthesis of optimal control laws with a view to regulate the temperature and the reactant concentration of a nonisothermal plug flow reactor model. Several tools of linear and semilinear infinite-dimensional system theory are extended and/or developed, and applied to this model. On the one hand, the concept of asymptotic stability is studied for a class of infinite-dimensional semilinear Banach state- space systems. Asymptotic stability criteria are established, which are based on the concept of strictly m-dissipative operator. This theory is applied to a nonisothermal plug flow reactor. On the other hand, the concept of optimal Linear-Quadratic (LQ) feedback is studied for class of infinite-dimensional linear systems. This theory is applied to a linearized plug flow reactor model in order to design an LQ optimal feedback controller. Then the resulting nonlinear closed-loop system performances are analyzed. Finally this control design strategy is extended to a large class of first-order hyperbolic PDE's systems.

Orientador: Teresa Massako Kakuta Ravagnani / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-17T16:55:35Z (GMT). No. of bitstreams: 1 Possani_Germano_M.pdf: 3312667 bytes, checksum: 30058f7ade4b339ee579a28950283ff8 (MD5) Previous issue date: 2011 / Resumo: Dentre os termoplásticos mais utilizados atualmente na indústria, pode-se mencionar o estireno, principal responsável pela produção de plásticos e borrachas. No processo de fabricação de estireno, a principal rota química é por meio da desidrogenação de etilbenzeno, com o hidrogênio como subproduto. A conversão de etilbenzeno nesta reação é em torno de 50,0 %, devido ao equilíbrio termodinâmico. Para deslocar esse equilíbrio e aumentar a produtividade de estireno,foram desenvolvidas novas configurações de reatores, tal como os reatores com membrana. eatores equipados com membranas de paládio fornecem uma seletividade maisalta ao estireno uando comparados com reatores equipados apenas com membranas porosas. Para explorar o otencial desse tipo de reator, modelagens matemáticas foram desenvolvidas a fim de determinar os parâmetros cruciais que regem esses processos. O objetivo deste trabalho foi modelar e simular um reator de leito fixo catalítico, envolto por uma membrana inerte permseletiva ao hidrogênio com transferência de calor e massa, sendo composta por uma camada de aço inoxidável de 1,6 mm de espessura, a qual serviu de suporte para a deposição de um filme de 20 µm de paládio. Para essa modelagem foram utilizados os métodos de Runge-Kutta-Gill para o cálculo das variáveis no sentido axial, tanto no retentato quanto no permeado, considerando no retentato um leito fixo catalítico descrito pelo modelo Pseudo-homogêneo, e para os cálculos das equações não lineares das frações molares das espécies e do fluxo mássico de hidrogênio na direção radial do reator foi utilizado o método de Newton-Raphson. Foram analisados os perfis de temperatura, pressão e concentração dos componentes da reação axialmente, considerando a transferência de massa e energia através da membrana, além dos valores para a conversão do etilbenzeno e produtividade em relação ao estireno. Como resultados das simulações foram obtidos valores para a conversão e produtividade de 50,3 % e 35,2 %, respectivamente, para o reator na condição de reator de leito fixo catalítico convencional, e 71,2 % e 60,2 %, para o reator na condição de reator de leito fixo catalítico envolto por uma membrana permseletiva ao hidrogênio, sendo estes valores 41,6 % maiores para a conversão do etilbenzeno e 71,0 % maiores para a produtividade em relação ao estireno. Concluiu-se que com a implementação da membrana no reator em estudo, considerando também a troca térmica na membrana, esta é uma boa opção como nova alternativa para o processo de fabricação do estireno / Abstract: Among the most widely used thermoplastics in the industry, styrene can be mentioned, the main responsible for the production of plastics and rubbers. In the manufacturing process of styrene, the principal chemical route is by means of dehydrogenation of ethylbenzene, with hydrogen as a byproduct. The conversion of ethylbenzene in this reaction is around 50,0 % due to thermodynamic equilibrium. To overcome this equilibrium and increase the productivity of styrene, new reactor configurations were developed such as membrane reactors. Membrane reactors equipped with a palladium membrane provide a higher selectivity compared with reactors that are equipped only with a porous membrane. To explore the potential of this type of reactor, mathematical models were developed to determine the crucial parameters governing these processes. The aim of this study was to model and simulate a fixed bed catalytic reactor, surrounded by a permselective to hydrogen inert membrane with heat and mass transfer, composed by a layer of stainless steel of 1,6 mm thickness, which served as support for deposition of a 20 µm film of palladium. For this modeling the Runge-Kutta-Gill method was used to calculate the variables in the axial direction, both in tube side and in permeate side, considering in tube side a catalytic fixed bed described by Pseudo-homogeneous model, and for the calculations of nonlinear equations of the mole fractions of species and the mass flow of hydrogen in the radial direction it was used the method of Newton-Raphson. Profiles of temperature, pressure and concentration of reaction components on axial toward were analyzed considering the heat and mass transfer across the membrane, besides the values for ethylbenzene conversion, selectivity and productivity in relation to styrene. As the simulation results, values were obtained for the conversion and productivity of 50,3 % and 35,2 %, respectively, putting the reactor on condition of conventional catalytic fixed bed reactor, and 71,2 % and 60,2 % for the reactor on condition of catalytic fixed bed reactor surrounded by a permselective membrane to hydrogen, then , the obtained values were 41,6 % higher for the conversion of ethylbenzene and 71,0 % higher for the productivity of styrene. It was concluded that with the implementation of a membrane in reactor under study, also considering the heat transfer in the membrane, this technology is a good option as new alternative to the styrene manufacturing process / Mestrado / Sistemas de Processos Quimicos e Informatica / Mestre em Engenharia Química

Research on the electrocoagulation (EC) of hexane extractable materials (HEM) has been conducted at the University of New Orleans using a proprietary bench-scale EC reactor. The original reactor configuration forced the fluid to follow a vertical upward-downward path. An alternate electrode arrangement was introduced so that the path of flow became horizontal. Both configurations were evaluated by comparing the residence time distribution (RTD) data generated in each case. These data produced indication of internal recirculation and stagnant water when the fluid followed a vertical path. These anomalies were attenuated when the fluid flowed horizontally and at a velocity higher than 0.032 m s-1 . A series of EC experiments were performed using a synthetic emulsion with a HEM concentration of approximately 700 mg l-1. It was confirmed that EC of HEM follows first-order kinetics, and kinetic constants of 0.0441 s-1 and 0.0443 s-1 were obtained from applying both the dispersion and tanks-in-series (TIS) models, respectively. In both cases R2 was 0.97. Also, the TIS model indicated that each cell of the EC behaves as an independent continuous-stirred-tank reactor.

The loss of efficiency and performance of bioprocesses on scale-up is well known, but not fully understood. This work addresses this problem, by studying the effect of some fermentation gradients (pH, glucose and oxygen) at a larger scale in a bench-scale two compartment reactor (PFR + STR) using the cadaverine-producing recombinant bacterium, Corynebacterium glutamicum DM1945 Δact3 Ptuf-ldcC_OPT. The initial scale down strategy increased the magnitude of these gradients by only increasing the mean cell residence time in the plug flow reactor (τ_PFR). The cell growth and product related rate constants were compared as the τ_PFR was increased; differences were significant in some cases, but only up to 2 min residence time. For example, losses in cadaverine productivity when compared to the control fed-batch fermentation on average for the τ_PFR of 1 min, 2 min and 5 min were 25 %, 42 % and 46 % respectively. This indicated that the increasing the τ_PFR alone does not necessarily increase the magnitude of fermentation gradients. The new scale-down strategy developed here, increased the magnitude of fermentation gradients by not only increasing the τ_PFR, but also considering the mean frequency at which the bacterial cells entered the PFR section (f_m). The f_m was kept constant by reducing the broth volume in the STR. Hence, the bacterial cells also spent shorter times in the well mixed STR, as the τ_PFR was increased (hypothesised as giving the bacterial cells less time to recover the non-ideal PFR section of the SDR). On adoption of this strategy cadaverine productivity decreases for the τ_PFR of 1 min, 2 min and 5 min were 25 %, 32 % and 53 % respectively. Thus, highlighting that loss in performance is most likely to occur as the magnitude of heterogeneity within the fermentation environment increases. However, Corynebacterium glutamicum DM1945 Δact3 Ptuf-ldcC_OPT did show some resilience in its biomass productivity. It was only marginally affected in the harshest of conditions simulated here.

Le biodiesel est un biocarburant, composé d'un mélange de mono-esters d'acide gras saturés et insaturés avec une longue chaîne carbonée. Ce travail de thèse présente les données de la littérature sur l'origine du biodiesel et son procédé de fabrication ; sont présentées aussi les performances et les émissions des moteurs diesel fonctionnant au biodiesel et la cinétique d'oxydation du biodiesel. Des efforts ont été faits pour mettre en évidence les principales différences entre les esters méthyliques et éthyliques tout en montrant que d'autres recherches sont encore à développer. Pour ces raisons, les délais d'auto-inflammation de cinq esters méthyliques et éthyliques ont été mesurés dans un tube à onde de choc : l'acrylate d'éthyle, l'acrylate de méthyle, le crotonate d'éthyle, le crotonate de méthyle et le butanoate d'éthyle. Les mécanismes cinétiques détaillés d'oxydation des cinq esters étudiés ont été générés automatiquement en utilisant le logiciel EXGAS. L'oxydation du butanoate d'éthyle, molécule modèle d'esters éthyliques d'huiles végétales (EEHV) a été étudiée dans un réacteur piston à pression atmosphérique pour une gamme de température allant de 500 à 1200 K. Les résultats représentent les profils de concentration des réactifs, les intermédiaires stables et les produits finaux. Le modèle cinétique a été validé de façon satisfaisante par une comparaison entre les résultats simulés et expérimentaux / An increasingly popular biofuel is biodiesel, composed of a mixture of saturated and unsaturated fatty acid methyl or ethyl esters, with a long aliphatic main chain. This PhD dissertation provides a literature review concerning the origin of biodiesel, its manufacturing process, performance and emissions of diesel engines fueled with biodiesel, and the kinetics of oxidation of biodiesel. Efforts were made to highlight the main differences between methyl and ethyl esters while showing where further research needs to be developed or pursued. For these reasons, the autoignition of five esters were measured behind reflected shock tube: ethyl acrylate, methyl acrylate, ethyl crotonate, methyl crotonate, and ethyl butanoate. Detailed mechanisms for the oxidation of the five studied esters were automatically generated using the version of EXGAS software. In addition, the oxidation of ethyl butanoate as a model compound for Fatty Acid Ethyl Esters (FAEE) has been investigated in tubular plug flow reactor at atmospheric pressure over wide range of temperature (500-1200 K). The results consist of concentration profiles of the reactants, stable intermediates, and final products. The model was again validated satisfactorily by comparison between computed results and the generated experimental data

Användningen av kommunalt avfall för att producera förnybar energi, huvudsaklig biogas, uppfyller 8 av Sveriges 16 miljökvalitetsmål. Två typer av rötningsprocesser som används är kontinuerligt omrörda tankreaktorer (CSTR) och pluggflödesreaktorer (PFR). Rapportens syfte är att direkt jämföra de två reaktorkonfigurationerna, PFR och CSTR, med samma substratblandning. Båda reaktortyperna drevs med samma belastning (5,2 g VS/L dag), hydraulisk retentionstid (30 dagar) och driftstemperatur (520C). Två PFR-reaktorer drevs med återcirkulation av rötrester. Under projektets gång mättes olika parametrar, vilka var: pH, total gasvolym och gassammansättning, FOS/TAC (organiska syror/alkalinitet), flyktiga fettsyror (VFA), ammonium-kvävekoncentration och TS (torrsubstanshalt) och VS (organiska ämnen). Studieresultatet var uppdelat i två sektioner. Avsnitt 1 sammanfattar uppstartsperioden, där alla tre CSTR (D1-R, D2-NR och C1-NR) kördes i icke-återcirkulerande läge. Uppstartsperioden gjordes för att säkerställa reaktorernas stabilitet och det gällde att uppnå en liknande baslinje för detektion. Inom studien accepterades avvikelser för baslinjen inom intervallet 0-5%. För uppstartsperioden varierade den specifika metanproduktionen med 2 % mellan D1-NR och D2-R, D1-R och C1-NR med 6 %, och D2-NR och C1-NR med 8 %. För ammoniak-koncentrationen var skillnaden mellan D1-R och D2-NR 2 % och mellan D1-R och C1-NR 9 %, mellan D2-NR och C1-NR, 7%. Med dessa variationer togs beslutet att utesluta reaktor C1-NR från den experimentella perioden för projektet. Avsnitt 2 jämför PFR och CSTR återcirkulerat/icke återcirkulerat läge. En CSTR drevs med 30 % återcirkulation av rötrest och en CSTR drevs i icke-återcirkulationsläge. Att jämföra PFR och CSTR återcirkulerat/icke återcirkulerat läge visade att PFR:erna övervann båda CSTR:erna när det gäller den specifika metanproduktionen. Där PFR producerade 395±93 NL/KgVS och 372±42 (N)L/KgVS CSTR med återcirkulation 280±10 (N)L/KgVS och den icke-återcirkulerade CSTR producerade 250±7 (N)L/KgVS. NH4+-N-nivåerna mellan PFR och CSTR visade en skillnad på 1 g/L, där PFR var den med högre NH4+-N (2,53±0,39 g/L för PFR-A och 2,73±0,43 g/L för PFR-T). En av skillnaderna mellan de återcirkulerade och de icke-återcirkulerade CSTR:erna var VFA-koncentrationen. VFA-koncentrationen i de återcirkulerade var 1,05±0,90 g/L och 0,43±0,25 g/L i de icke-återcirkulerade. VFA-koncentrationen för PFR var i genomsnitt 0,28±0,12 g/L och 0,40 ±0,16 g/L. Graden av nedbrytning i CSTRs var 90-91%, och 63-65% i PFR. Den är möjligen felberäknad och visar en inkonsekvens mellan reaktorernas prestanda och specifik metanproduktion. / The use of municipal waste to produce renewable energy, in the form of biogas, fulfils eight of Sweden's sixteen environmental quality objectives. The most common technology to produce biogas is anaerobic digestion (AD). Two common types of AD processes are continuously stirred reactors (CSTR) and plug flow reactors (PFR). The thesis aims at directly comparing the two reactor configurations using the same substrate mix. For this, two PFRs (PFR-T and PFR-A) and three CSTRs (D1-R, D2-NR and C1-NR) were setup. All reactors were operated at the same organic loading rate (5.2 g VS/L-day), hydraulic retention time (30 days) and operational temperature (52°C). During the project, various parameters were measured to evaluate the reactor performance, such as pH, total gas volume and gas composition, FOS/TAC (organic acids/alkalinity), volatile fatty acids (VFA), ammonium-nitrogen concentration, and solid and volatile solid of digestate.   The study result was divided into two sections. Section 1 summarises the start-up period (42 days), where the CSTRs and the PFRs were operated under non-recirculation mode. The start-up period was done to ensure the stability of the reactors and was concerned with achieving a similar baseline for performance. For the start-up period, the specific methane production between D1-R and D2-NR varied by 2% while the variation between C1-NR and D2-NR was 8%. Likewise, for the ammonia concentration, the difference between D1-R and D2-NR was 2%, while C1-NR differed by 9% from D2-NR. Based on these findings, the decision was taken to exclude reactor C1-NR from the experimental period of the project.  Section 2 compares the PFR and CSTR. One CSTR was operated with 30% recirculation of digest, while the other CSTR was operated in non-recirculation mode. The two PFRs were operated with recirculation of digestate. The experiments showed that the PFRs outperformed both CSTRs regarding the specific methane production. The PFRs produced 395±93 (N)L/kg-VS and 372±42 (N)L/kg-VS. In contrast, the CSTR with recirculation reached 280±10 (N)L/kg-VS and the non-recirculated CSTR produced 250±7 (N)L/kg-VS. The NH4+-N levels for the PFRs and CSTRs showed a 1 g/L difference, with a higher value for the PFRs (2.53±0.39 g/L for PFR-A, and 2.73±0.43 g/L for PFR-T). One of the significant differences between the recirculated and the non-recirculated CSTRs was the VFA concentration. The VFA concentration in the recirculated and non-recirculated reactor was 1.05±0.90 g/L and 0.43±0.25 g/L, respectively. The VFA concentration for the two PFRs was on average 0.28±0.12 g/L and 0.40 ±0.16 g/L. The degree of degradation in the CSTRs was 90-91% compared to 63-65% in the PFRs. The degree of degradation is possibly miscalculated and shows an inconsistency between the reactor performance in terms of specific methane production.