Real time optimization in chemical process: evaluation of strategies, improvements and industrial application.

The increasing economic competition drives the industry to implement tools that improve their processes efficiencies. The process automation is one of these tools, and the Real Time Optimization (RTO) is an automation methodology that considers economic aspects to update the process control in accordance with market prices and disturbances. Basically, RTO uses a steady-state phenomenological model to predict the process behavior, and then, optimizes an economic objective function subject to this model. Although largely implemented in industry, there is not a general agreement about the benefits of implementing RTO due to some limitations discussed in the present work: structural plant/model mismatch, identifiability issues and low frequency of set points update. Some alternative RTO approaches have been proposed in literature to handle the problem of structural plant/model mismatch. However, there is not a sensible comparison evaluating the scope and limitations of these RTO approaches under different aspects. For this reason, the classical two-step method is compared to more recently derivative-based methods (Modifier Adaptation, Integrated System Optimization and Parameter estimation, and Sufficient Conditions of Feasibility and Optimality) using a Monte Carlo methodology. The results of this comparison show that the classical RTO method is consistent, providing a model flexible enough to represent the process topology, a parameter estimation method appropriate to handle measurement noise characteristics and a method to improve the sample information quality. At each iteration, the RTO methodology updates some key parameter of the model, where it is possible to observe identifiability issues caused by lack of measurements and measurement noise, resulting in bad prediction ability. Therefore, four different parameter estimation approaches (Rotational Discrimination, Automatic Selection and Parameter estimation, Reparametrization via Differential Geometry and classical nonlinear Least Square) are evaluated with respect to their prediction accuracy, robustness and speed. The results show that the Rotational Discrimination method is the most suitable to be implemented in a RTO framework, since it requires less a priori information, it is simple to be implemented and avoid the overfitting caused by the Least Square method. The third RTO drawback discussed in the present thesis is the low frequency of set points update, this problem increases the period in which the process operates at suboptimum conditions. An alternative to handle this problem is proposed in this thesis, by integrating the classic RTO and Self-Optimizing control (SOC) using a new Model Predictive Control strategy. The new approach demonstrates that it is possible to reduce the problem of low frequency of set points updates, improving the economic performance. Finally, the practical aspects of the RTO implementation are carried out in an industrial case study, a Vapor Recompression Distillation (VRD) process located in Paulínea refinery from Petrobras. The conclusions of this study suggest that the model parameters are successfully estimated by the Rotational Discrimination method; the RTO is able to improve the process profit in about 3%, equivalent to 2 million dollars per year; and the integration of SOC and RTO may be an interesting control alternative for the VRD process.

Multi-Element Analysis of Spanish Date Palm (Phoenix dactylifera L.) by Inductively Coupled Plasma-Based Techniques. Discrimination Using Multivariate Statistical Analysis

The elemental analysis of Spanish palm dates by inductively coupled plasma atomic emission spectrometry and inductively coupled plasma mass spectrometry is reported for the first time. To complete the information about the mineral composition of the samples, C, H, and N are determined by elemental analysis. Dates from Israel, Tunisia, Saudi Arabia, Algeria and Iran have also been analyzed. The elemental composition have been used in multivariate statistical analysis to discriminate the dates according to its geographical origin. A total of 23 elements (As, Ba, C, Ca, Cd, Co, Cr, Cu, Fe, H, In, K, Li, Mg, Mn, N, Na, Ni, Pb, Se, Sr, V, and Zn) at concentrations from major to ultra-trace levels have been determined in 13 date samples (flesh and seeds). A careful inspection of the results indicate that Spanish samples show higher concentrations of Cd, Co, Cr, and Ni than the remaining ones. Multivariate statistical analysis of the obtained results, both in flesh and seed, indicate that the proposed approach can be successfully applied to discriminate the Spanish date samples from the rest of the samples tested.

Central & Eastern Africa, 1635 (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: Aethiopia superior vel interior, vulgo Abissinorum sive Presbiteri Ioannis imperium. It was published by Guiljelmum et Johannem Blaeu in 1635. Scale [ca. 1:12,600,000]. Covers Central and Eastern Africa. Map in Latin.The image inside the map neatline is georeferenced to the surface of the earth and fit to the Africa Sinusoidal projected coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as drainage, cities and other human settlements, territorial boundaries, shoreline features, and more. Relief shown pictorially. Includes notes, illustrations of animals, and ornamental cartouche. This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of originators, ground condition dates, scales, and map purposes.

Central & Eastern Africa, 1655 (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: Haute Ethiopie, ou sont L'Empire des Abissins, La Nubie, et le Zanguebar : subdivisés en leurs principales parties, tirés de Sanut de Mercator &c. par le Sr. Sanson d'Abbeville. It was published by P. Mariette in 1655. Covers Central and Eastern Africa. Scale [ca. 1:12,000,000]. Map in French.The image inside the map neatline is georeferenced to the surface of the earth and fit to the Africa Sinusoidal projected coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as drainage, cities and other human settlements, territorial boundaries, shoreline features, and more. Relief shown pictorially.This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of originators, ground condition dates, scales, and map purposes.

Red Sea Region, North Africa, ca. 1730 (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: Carte de l'Egypte, de la Nubie, de l'Abyssinie &c., par Guillaume de l'Isle, de l'Academie Royal a Paris. It was published by Chez Henri de Leth, a l'enseigne du Pecheur ca. 1730. Scale [ca. 1:9,250,000]. Covers the Red Sea region, North Africa including portions of the Middle East and Europe. Map in French.The image inside the map neatline is georeferenced to the surface of the earth and fit to the Africa Sinusoidal projected coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as drainage, major roads, cities and other human settlements, territorial boundaries, shoreline features, and more. Relief shown pictorially. This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of originators, ground condition dates, scales, and map purposes.

Mediterranean Sea Region, East, 1690-1699 (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: Accuratissima orientalioris districtus maris Mediterranei tabula, authore Iusto Danckerts. It was published by Iusto Danckerts, between 1690 and 1699. Scale [ca. 1:5,300,000]. Covers the eastern Mediterranean Sea region. Map in Latin. The image inside the map neatline is georeferenced to the surface of the earth and fit to the World Miller Cylindrical projected coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as drainage, cities and other human settlements, roads, shoreline features, and more. Relief shown pictorially.This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of originators, ground condition dates, scales, and map purposes.

Mediterranean Sea Region, 1690-1699 (Raster Image)

This layer is a georeferenced raster image of the untitled historic paper map: [Mediterranean sea], authore Iusto Danckerts. It was published by Iusto Danckerts, between 1690 and 1699. Scale [ca. 1:5,300,000]. Covers the Mediterranean Sea region. Map in Latin. Source map issued on two sheets, now pasted together. The image inside the map neatline is georeferenced to the surface of the earth and fit to the World Miller Cylindrical projected coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as drainage, cities and other human settlements, roads, territorial features, shoreline features, and more. Relief shown pictorially.This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of originators, ground condition dates, scales, and map purposes.

Mediterranean Sea Region, 1700-1710 (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: Carte nouvelle de la mer Mediterranée : divisée en mer de Levant et de Ponant, subdivisés en leurs principales parties ou mers : avec les observations des Mrs. de l'Académie, dressée par ... Sanson. It was published by chez Pierre Mortier, between 1700 and 1710. Scale [ca. 1:4,375,000]. Covers the Mediterranean Sea and Black Sea regions. Map in French. The image inside the map neatline is georeferenced to the surface of the earth and fit to the World Miller Cylindrical projected coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as drainage, cities and other human settlements, roads, territorial boundaries, shoreline features, and more. Relief shown pictorially.This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of originators, ground condition dates, scales, and map purposes.

Europe & Mediterranean Sea Region, 1705 (Image 2 of 2) (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: Toonneel des oorlogs in't zuider deel van Europa, door Carel Allard = Theatre de la guerre dans l'Europe meridionale, par Charles Allard. It was published by C. Allard in 1705. Scale [ca. 1:6,800,000]. Covers a portion of Europe and the Mediterranean Sea region. This layer is image 2 of 2 total images of the two sheet source map, representing the eastern portion of the map. Map in Dutch and French. The image inside the map neatline is georeferenced to the surface of the earth and fit to the World Miller Cylindrical projected coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as drainage, cities and other human settlements, territorial boundaries, shoreline features, and more. Relief shown pictorially.This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of originators, ground condition dates, scales, and map purposes.

Indian Ocean Region, ca. 1690 (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: Nova tabula Indiae Orientalis. It was published by Carolus Allard excudit, between 1690 and 1710. Scale [ca. 1:5,500,000]. Covers the Indian Ocean Region. Map in Latin. The image inside the map neatline is georeferenced to the surface of the earth and fit to the World Miller Cylindrical projected coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as drainage, roads, cities and other human settlements, territorial boundaries, shoreline features, and more. Relief shown pictorially.This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of originators, ground condition dates, scales, and map purposes.

Middle East and South Asia, 1903 (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: A map of the countries between Constantinople and Calcutta : including Turkey in Asia, Persia, Afghanistan and Turkestan. It was published by Edward Stanford in 1903. Scale 1:6,969,600. The image inside the map neatline is georeferenced to the surface of the earth and fit to the Asia North Lambert Conformal Conic coordinate system. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as drainage, cities and other human settlements, territorial boundaries, roads, railroads, ferry routes, shoreline features, and more. Relief shown by hachures and spot heights. This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection. These maps typically portray both natural and manmade features. The selection represents a range of originators, ground condition dates, scales, and map purposes.

Turkey, Middle East, and the South Caucasus, 1771 (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: Turcia Asiatica : exhibens Natoliam modernam, in suos beglirbegatus divisam, itemque reliquos beglirbegatus, sive gubernationes et Prfecturas generales, in regionibus Georgiæ, Armeniæ, Mespotamiæ, Syriæ et Arabiæ sitos, una cum Mari Nigro, Mari Azowiensi, Mari di Marmora, et Mari Ægeo, atque adiacentibus Insulis : C. P. S. C. M. = Carte de la Turquie asiatique contenant la Natolie moderne divisée en les beglerbeys &c., ex novissimis subsidiis ac relationibus ad normam legitimae proiectionis in usum belli praesentis delineata impensis homannianorum heredum. It was published by Homannianorum Heredum in 1771. Scale [ca. 1:4,800,000]. Covers Turkey and portions of the Middle East and the South Caucasus. Map in Latin with title in French. The image inside the map neatline is georeferenced to the surface of the earth and fit to the World Miller Cylindrical projection. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as drainage, cities and other human settlements, territorial and provincial boundaries, shoreline features, and more. Relief shown pictorially. This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection as part of the Open Collections Program at Harvard University project: Islamic Heritage Project. Maps selected for the project represent a range of regions, originators, ground condition dates, scales, and purposes. The Islamic Heritage Project consists of over 100,000 digitized pages from Harvard's collections of Islamic manuscripts and published materials. Supported by Prince Alwaleed Bin Talal and developed in association with the Prince Alwaleed Bin Talal Islamic Studies Program at Harvard University.

Middle East, 1853 (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: Syria, by W. Hughes. It was published by George Cox, Jan. 1st, 1853. Scale [ca. 1:2,200,000]. Covers a portion of the Middle East including all or portions of Syria, Lebanon, Israel, Gaza Strip, West Bank, Jordan, Turkey, Iraq, Saudi Arabia, and Egypt. The image inside the map neatline is georeferenced to the surface of the earth and fit to a modified 'Europe Lambert Conformal Conic' projection with a central meridian of 38 degrees East projection. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as drainage, cities and other human settlements, territorial boundaries, shoreline features, and more. Relief shown by hachures. Includes note and inset: Continuation from the Dead Sea top Mount Sinai (Scale [ca. 1:2,200,000]). This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection as part of the Open Collections Program at Harvard University project: Islamic Heritage Project. Maps selected for the project represent a range of regions, originators, ground condition dates, scales, and purposes. The Islamic Heritage Project consists of over 100,000 digitized pages from Harvard's collections of Islamic manuscripts and published materials. Supported by Prince Alwaleed Bin Talal and developed in association with the Prince Alwaleed Bin Talal Islamic Studies Program at Harvard University.

Arabian Peninsula and Middle East, 1654 (Raster Image)

This layer is a georeferenced raster image of the historic paper map entitled: Carte des trois Arabies : tirée en partie de l'Arabe de Nubie, en partie de diuers autres autheurs, par le S. N. Sanson d'Abbeville Geographe ordinaire du Roy ; J. Somer sculp. It was published by Chez Pierre Mariette in 1654. Scale [ca. 1:7,500,000]. Map in French and Latin. Covers the Arabian Peninsula. The image inside the map neatline is georeferenced to the surface of the earth and fit to the World Miller Cylindrical projection. All map collar and inset information is also available as part of the raster image, including any inset maps, profiles, statistical tables, directories, text, illustrations, index maps, legends, or other information associated with the principal map. This map shows features such as drainage, cities and other human settlements, territorial boundaries, shoreline features, and more. Relief shown pictorially. This layer is part of a selection of digitally scanned and georeferenced historic maps from the Harvard Map Collection as part of the Open Collections Program at Harvard University project: Islamic Heritage Project. Maps selected for the project represent a range of regions, originators, ground condition dates, scales, and purposes. The Islamic Heritage Project consists of over 100,000 digitized pages from Harvard's collections of Islamic manuscripts and published materials. Supported by Prince Alwaleed Bin Talal and developed in association with the Prince Alwaleed Bin Talal Islamic Studies Program at Harvard University.