Cracking Of Petroleum Residues By Reactive Molecular Distillation

It is known that the Brazilian oils are more heavy - super heavy - viscous, its operation is difficult, especially its production, including all stages - elevation, runoff and primary processing - in addition to their transfer, and refining itself. Studies indicate the existence of oil fields as heavy lifting and that the simple flow of the base of the pit to the surface seems impossible at first sight, especially in off-shore fields, compromising both technically and economically a project to produce a new field. Therefore, efforts are needed to develop alternatives aimed at reducing the API gravity, viscosity and sulfur content of extra-heavy oil, adding a higher commercial value for these oils. This work aims to study, propose and develop enhanced hybrid process that transforms the extra-heavy oil, or part thereof, in lighter crude oil to generate a mixture: lower sulfur content, lower density, lower viscosity, lower content of volatile (aromatics and asphaltenes), greater resistance to the processes of purification. The process studied is the Reactive molecular distillation with the addition of tetralin that suffer from high temperature cracking of molecules, providing protons that help the breakdown of asphaltenes and residues will suffer as a consequence physicochemical changes, such as those mentioned above. This way you can improve the problems associated with the deposition of asphaltenes at high temperatures. The conversion of light with immediate reduction of API gravity and sulfur content promoted a better use of extra-heavy oil and the DMR is a product of high-value oil and very interesting for the oil industry and the environment. The experimental work proposed in this study was conducted to cracking and separation of fractions and petroleum. The evaluation and characterization of the cracking results were obtained after analysis of properties such as density, viscosity, sulfur content, molar mass and mass balance of the currents. © 2012 Published by Elsevier Ltd.42329334Erciyes, A.T., Ishikawa, H., Inuzuka, M., Hiraoka, S., Mori, H.E., Yamada, I., Vaporization of binary liquid mixtures from surface at reduced pressure (1987) Chem Eng Symp Series, 1, pp. A359-A371Moraes, E.B., Batistella, C.B., Torres Alvarez, M.E., Maciel Filho, R., Wolf Maciel, M.R., Evaluation of tocopherol recovery through simulation of molecular distillation process (2004) Appl Biochem Biotech, 114, pp. 689-711Noeres, C., Kenig, E.Y., Górak, A., Modelling of reactive separation processes (2003) Reactive Absorption and Reactive Distillation. Chem Eng Process, 42, pp. 157-178Duarte, F.A., Mello, P.A., Bizzi, C.A., Nunes, M.A.G., Moreira, E.M., Alencar, M.S., Motta, H.N., Flores, E.M.M., Sulfur removal from hydrotreated petroleum fractions using ultrasound-assisted oxidative desulfurization process (2001) Fuel, 90, pp. 2158-216

Proposal Of A Process Intensification And Green Technology On Ethyl Acetate Production

Although reactive distillation column is not a new concept, it has gained renewed interest in recent years as an effective way to pursue intensification of conventional chemical processes. Reactive distillation operations were first used by the chemical and petrochemical industry in esterification processes to separate reaction products from the reactants to increase product yields. Reactive distillation technology combines chemical synthesis steps with separations by distillation. This combination can lead to intensified, high-efficiency process systems with significant green engineering attributes. Among several approaches to process intensification are hybrid combinations of separation and reaction for chemical synthesis. These combinations offer new process alternatives that may have greatly improved efficiencies (e.g., in reduced energy requirements, lower solvent use, reduced equipment investment, and greater selectivity). Many of these potential advantages are intimately linked to the principles and challenges for green engineering. This work presents a study of establishment of a complete reactive distillation system for production of ethyl acetate via esterification of acetic acid with ethanol using ASPEN PLUS. Ethyl acetate is an important organic solvent widely used in the production of varnishes, ink, synthetic resins, and adhesive agents. Ethyl acetate is normally produced via reversible reaction of acetic acid with ethanol. There are only a few papers in the literature on the subject of the production of ethyl acetate via reactive distillation. A suitable NRTL (nonrandom two-liquid) model parameter set for calculating of liquid activity coefficients has been established with excellent prediction of the compositions and temperatures for the four azeotropes in the system. The predicted four azeotropes in this system include three homogeneous azeotropes of ethanol/ethyl acetate, ethanol/water and ethanol/ethyl acetate/water and also one heterogeneous azeotrope of ethyl acetate/water. A reactive distillation column with an overhead decanter can be designed to achieve over 93 wt% of ethyl acetate composition at organic phase top product stream while the bottom product stream is designed to be rich in acetic acid so that it can be recycled and mixed with fresh acid makeup stream to serve as acid feed to reactive distillation column. Since the purity of the optimum top organic product specification in industry, an additional column is designed to purify the ethyl acetate product of the reactive distillation column to over 99.5 wt%. The top draw of the second column will be recycled back to the decanter. Concluding, the process intensification of ethyl acetate production by reactive distillation was composed by two columns, including the reactive distillation column and the second column, one decanter, and two recycle streams. The optimum operating condition of the overall system will also be studied to minimize the total operating cost and the size of the plant wide of the overall system while meeting product specifications

A New Methodology For Mixture Characterization And Solvent Screening For Separation Process Application

Great significance is attached to phase equilibria in the design and optimisation of separation processes since it provides quantitative information on compositions in vapor and liquid phases The objective of this work is to develop a methodology for studying the vapor-(liquid)-liquid phase behavior of ternary systems and for rapidly determining the presences of partial miscibility and ternary azeotrope by using the commercial simulator PROII (Simulation Sciences. 1992). for the phase equilibrium calculation and generation of multiple data. The methodology uses flash simulation to do liquid-(liquid)-vapor equilibrium calculations: simulation results are used to generate equilibrium surfaces, which enable the thermodynamic characterization of ternary systems. Every system has three equilibrium surfaces . y1,y2 and y3. In the equilibrium surfaces one can observe if the system presents a gap of miscibility by observing a flat line formation. The number and extent of the flat lines give the dimensions of partial miscibility region of the system. It is possible also to identify, from the equilibrium surfaces, points for which x1 = y1, x2 = y2 and x3=y3 Lines formed by these points are designated non-ideality lines (x1=y1 and x3=y3) and inversion line (x2=y2). and they are used to verify if there exist ternary azeotropes. In this work we are establishing a relationship between the characteristic shape of the inversion line and the choice of the best solvent or entrainer to separate mixtures by extractive or azeotropic distillation. The developed methodology still can determine three phase equilibrium compositions.20SUPPL.1S219S224Andrade, M.H.C., (1991), MSc Thesis. DPQ/FEQ/UNICAMPDluzniewski, J.H., Adler, S.B., Ozkardesh, H., Barner, H.E., Aid to Correlation of Complex Equilibria (1973) Chemical Engineering Progress, 69 (11), pp. 79-80Gautam, R., Seider, W.D., Computation of Phase and Chemical Equilibrium, Part I Local and Constrained Minima in Gibbs Free Energy (1979) AIChE Journal, 25 (6), pp. 991-999Gmehling, J., Oken, U., Arlt, W., Vapor - Liquid Equilibrium Data Collection - Aqueous - Organic Systems (Supplement 1) (1981) Chemistry Data Series, 1 (PART 1A). , DECHEMAHenley, E.J., Rosen, E.M., (1969) Material and Energy Balance Computation, , New York, WileyHenriques, R.C.F., (1995), MSc Thesis, DPQ/FEQ/UNICAMPHorsley, L.H., (1973) Azeotropic Data - III. Advances in Chemistry Series 116, , American Chemical Society Washington, D.CMaciel, M.R.W., (1989), PhD Thesis. Department of Chemical Engineering, University of Leeds, England. UKMaciel, M.R.W., D'Avila, S.G., Sbaite, C.A., Stinghen, A.O., Desidratação do Etanol por Destilação Azeotrópica (1992) COBEQ, pp. 152-161. , 9° Congresso Brasileiro de Engenharia QuimicaMaciel, M.R.W., Prestes, J.M., (1994) Modelagem de Colunas de Destilação Azeotropica Em Batelada para Minimização de Poluentes Industriais, pp. 54-58. , Encuentro Latinoamericano de Ingenieria Quimica. Antofagasta. Chile. MayoMartini, R.F., (1995), Msc Thesis. DPQ/FEQ/UNICAMPMcGreavy, C., Maciel, M.R.W., Presentation of Multicomponent Phase Equilibria for Analysis od Distillation Process International Chem. Eng. Conference (1989) CHEMPOR'89, pp. 7C1-7CA. , LisbonPham, H.N., Doherty, M.F., Design and Synthesis of Heterogeneous AZeotropic Distillations - I.Heterogeneous Phase Diagrams (1990) Chemical Engineering Science, 45 (7), pp. 1823-1836Pham, H.N., Doherty, M.F., Design and Synthesis of Heterogeneous Azeotropic Distillations - II.Residue Curve Maps (1990) Chemical Engineering Science, 45 (7), pp. 1837-1843Pham, H.N., Doherty, M.F., Design and Synthesis of Heterogeneous Azeotropic Distillations - III.Column Sequences (1990) Chemical Engineering Science, 45 (7), pp. 1845-1854Prokopakis, G.J., Seider, W.D., Feasible Specifications in Azeotropic Distillation (1983) AIChF Journal, 29 (1), pp. 49-60(1992) PROII. Versão 3.02, , In

Kinetic And Reactor Models For Hdt Of Middle Distillates

Hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) of middle distillates over a commercial Ni-Mo/γ-Al 2O 3) have been studied under wide operating conditions (340 to 380°C and 38 to 98 atm), A Power Law model was presented to each one of those reactions. The parameters of kinetic equations were estimated solving the ordinary differential equations by the 4 th order Runge-Kutta-Gill algorithm and Marquardt method for searching the set of kinetic parameters (kinetic constants as well as the order of the reactions). An adiabatic diesel hydrotreating tricklebed reactor packed with the same catalyst was simulated numerically in order to check up the behavior of this reaction system. One dimensional pseudo-homogeneous model was used in this work. For each feed, the mass and energy balance equations were integrated along the length of the catalytic bed using the 4 th Runge-Kutta-Gill method. The performances oftwo industrial reactors were checked. © 1999 Elsevier Science Ltd.23SUPPL. 1S791S794Girgis, M.J., Gates, B.C., Reviews Reactivities, Reaction Networks, and Kinetics in High-Pressure Catalytic Hydroprocessing (1991) Ind. Eng. Chern. Res., 30, pp. 2021-2058Marquardt, D.M., An Algorithm for Least Squares Estimation ofNonlinear Parameters (1963) J. Soc Indust. AppJ. Math., 11 (2), pp. 431-441Tarhan, M.O., (1983) Catalytic Reactor Design, , McGraw-Hili, Inc. New YorkSatterfield, C.N., Pelosof, A.A., Sherwoord, T.K., Mass Tranfer Limitations in a Trickle Bed Reactor (1969) AIChe, 1 (15), pp. 226-23

Pinch analysis of evaporation systems

Evaporation systems are separation processes widely used in chemical industries. Some guidelines can be found in the literature for the process integration of multiple effect evaporators. In the published methodologies some aspects are neglected as boiling point rise, effect of pressure on latent heat of water, sensible heat of liquid streams, heat of mixing, effects configuration and inclusion of accessories. In this work, a new graphical representation for the integration of multiple effect evaporators was developed, using rigorous physical properties. From this representation, an algorithm for optimization of bleed streams was conceived using the concepts of Pinch Analysis. As a case study, a crystal glucose plant was optimized using this new methodology. The optimization of bleed streams showed as result a steam consumption 16% smaller than a similar previous study. From energy and capital costs, it is shown that the integrated evaporator exhibits a total cost 14% smaller than the non-integrated configuration.52553

Development Of A Methodology To Reproduce And To Optimize The Operating Conditions Of A Natural Gas Processing Unit

The objective of this work is to make a simulation to be possible to reproduce and to optimize the operating conditions of the Natural Gas Processing Unit, which belongs to PETROBRAS (Brazilian Petroleum Limited Company). The unit process is the refrigerated absorption and it has been studied its energetic optimization and the reduction of absorption oil molecular weight. The simulation has been built in a unique computer file. To bring near the column internal flows and temperatures to the real values, column stage efficiencies have been incorporated using a method, developed in this work, beginning with O'Connell global efficiency. For optimization, two aspects have been studied. Firstly, it is proposed to reduce the molecular weight of the oil, until the molecular weight of the natural gasoline (C5+). This has resulted in a possible reduction of the fuel gas in 30.7% and 5.8% in the total absorved power. Secondly, the application of PINCH technology has shown that it is possible to economize until 16.4% of the fuel gas, making a new lay-out of the process.20SUPPL.2S1511S1516Gomes, L.G., (1982) HYSIM User's Guide, , MSc Thesis, LDPS, DPQ, FEQ/UNICAMP, Hyprotech Ltd, Hyprotech Ltd, HYSIM User's Guide, 1991King, C.J., (1980) Separation Processes, , Mc-Graw-Hill New Work, Second editionLinnhoff, B., Hindmarsh, E., The Pinch Design Method for Heat Exghanger Networks (1983) Chemical Eng. Science, 38, p. 745Linnhoff, B., Townsend, D.W., Boland, D., Hewitt, G.F., Thomas, B.E.A., Guy, A.R., Efficient Use of Energy (1982) The Institution of Chemical Engineer

Simulation Of A Sieve Plate Column With Ethanol/water System Using The Nonequilibrium Stage Model

An experimental evaluation was made of a distillation column which shows the behavior of temperature and composition profiles along the equipment and the validation of the nonequilibrium stage model. A stainless steel column with eight sieve plates was built and was operated at total reflux. After reaching steady state, the liquid samples and the temperature were taken at each stage in the column and the samples were analyzed using GC. With the data in each stage and with the data obtained from simulations, it was possible to corroborate the model. The results showed that the nonequilibrium stage model reproduces the real conditions of the process.73672

Evaluation Of The Pid Performance For Fcc Units

Catalytic cracking reactions are high mass carbon chain molecules breaking of heavy oils such as gasoil and petroleum refining residues. This process is extremely important because derived products of petroleum of high molecular weight are transformed in products of higher commercial values. This work objective is the implementation of a deterministic mathematical model using the mass and energy balances that describe a FCC conversor, and the development of a FORTRAN language simulator. It is intended, also, to study cases in order to explore the potential of the model to simulate the process control strategy. It is considered an evaluation of PID controllers under disturbances in some controlled variables important for operation. Good performance results have been achieved through simulations carried out in two distinct cases: at first, perturbations on the air temperature for the regenerator and, at second, on the feedstock, considering the PID action in some meshes of the process catalytic cracking.ABADIE, E., (1997) Craqueamento Catalítico. Relatório SEREC/CEN-SUD, , Rio de JaneiroMORO, L.F., ODLOAK, D., Constrained multivariable control of fluid catalytic cracking converters (1995) J. Proc. Control, 5 (1), pp. 29-39MORO, L.F., (1992) Desenvolvimento de um Controlador Preditivo Multivariável para um Conversor Industrial de Craqueamento Catalítico, , Dados. Dissertação (Tese de Mestrado) USP-SP, 77 pSPANDRI, R., Sintonia de Controladores Regulatórios (2003) Boletim Técnico Petrobras, , RJVIEIRA, W.G., (2002) FCC: Controle Preditivo e Identificação Via Redes Neurais, , Dados. Dissertação Tese de Doutorado, UNICAMP-S

Computer Aided Design Of Acetaldehyde Plant With Zero Avoidable Pollution

Appreciable efforts have been expended in the manufacture of chemical products in such a way that pollution may be minimized and, if possible, even avoided. The conceptual design of such production plants involves an interplay between design and operational requirements, which attempt to balance non-commensurable objectives such as economics, safety health and environmental impact. If the environmental impact problem is not considered in the conceptual phase of the process development, there is a need to extensive end-of-pipe treatment of wastes which is always an expensive activity with negative economic effect. In this sense, in this work, a conceptual design of an acetaldehyde plant with zero avoidable pollution is presented. The proposed process is based on the oxidation of ethyl alcohol over Fe-Mo catalyst. In order to obtain high performance operation (high conversion and complete selectivity) a non-conventional reactor design is proposed. The computer aided design involves the experimental conversion of ethanol to acetaldehyde, the reactor analysis through extensive simulation using specific computer simulation code. The separating problem and the whole plant analysis is made using the HYSIM commercial simulator. It is shown the great potential of the proposed process which permits very high conversion and complete selectivity leading to zero waste emission. The process methodology considered in this work involves since the experimental conversion of ethanol to acetaldehyde up to the proposition of a new reactor design, a set of separation units and the whole acetaldehyde plant simulation.20SUPPL.2S1389S1393Domingues, A., (1992) Modelagem do Processo de Oxidação do Etanol a Acetaldeído, , Msc Thesis, UNICAMP,FEQ/DPQ/LOPCA, Campinas, São Paulo, BrasilHan, C., Douglas, J.M., Stephanopoulos, G., Agent-Based Approach to a Design Support System for the Synthesis of Continuous Chemical Process (1995) Computer Chem. Engng, 19 (SUPPL.), pp. S63-S69Froment, G.F., Bischoff, K.B., (1990) Chemical Reactor Analysis and Design, 2nd Edition, , John Wiley & SonsMaciel Filho, R., Domingues, A., A Multitubular Reactor for Obtention of Acetaldehyde by Oxidation of Ethyl Alcohol (1992) Chemical Engineering Science, 47 (9-11), pp. 2571-2576Maciel Filho, R., McGreavy, C., The Influence of Configurations on Controller Design of Multitubular Reactors (1993) Computers Chem. Engng., 17 (5-6), pp. 569-583. , (a)Maciel Filho, R., McGreavy, C., Mutiltubular Reactor Design for Waste Minimization (1993) Trans Ichem E, 71 (PART B). , (b), AugustStefanis, S.K., Livingston, A.G., Pistikopoulos, E.N., Minimizing the Environmental Impact of Process Plants. A Process Systems Methodology (1995) Computers Chem. Engng, 19 (SUPPL.), pp. S39-S4