Reductions in ozone concentrations due to controls on variability in industrial flare emissions in Houston, Texas

High concentrations of ozone in the Houston/Galveston area are associated with industrial plumes of highly reactive hydrocarbons, mixed with NOx. The emissions leading to these plumes can have significant temporal variability, and photochemical modeling indicates that the emissions variability can lead to increases and decreases of 10-50 ppb, or more, in ozone concentrations. Therefore, in regions with extensive industrial emissions, accounting for emission variability can be important in accurately predicting peak ozone concentrations, and in assessing the effectiveness of emission control strategies. This work compares the changes in ozone concentrations associated with two strategies for reducing flare emissions in Houston, Texas. One strategy eliminates the highest emission flow rates, that occur relatively infrequently, and a second strategy reduces emissions that occur at a nearly constant level. If emission variability is accounted for in air quality modeling, these control scenarios are predicted to be much more effective in reducing the expected value of daily maximum ozone concentrations than if similar reductions in the mass of emissions are made and constant emissions are assumed. The change in the expected value of daily maximum ozone concentration per ton of emissions reduced, when emissions variability is accounted for, is 5-10 times the change predicted when constant (deterministic) inventories are used. Keywords: Photochemical Grid Model, highly reactive volatile organic compounds (HRVOC), ozone, uncertainty analysis

HAZOP: Our Primary Guide in the Land of Process Risks: How can we improve it and do more with its results?

PresentationAll risk management starts in determining what can happen. Reliable predictive analysis is key. So, we perform process hazard analysis, which should result in scenario identification and definition. Apart from material/substance properties, thereby, process conditions and possible deviations and mishaps form inputs. Over the years HAZOP has been the most important tool to identify potential process risks by systematically considering deviations in observables, by determining possible causes and consequences, and, if necessary, suggesting improvements. Drawbacks of HAZOP are known; it is effort-intensive while the results are used only once. The exercise must be repeated at several stages of process build-up, and when the process is operational, it must be re-conducted periodically. There have been many past attempts to semi- automate the HazOp procedure to ease the effort of conducting it, but lately new promising developments have been realized enabling also the use of the results for facilitating operational fault diagnosis. This paper will review the directions in which improved automation of HazOp is progressing and how the results, besides for risk analysis and design of preventive and protective measures, also can be used during operations for early warning of upcoming abnormal process situations

Crude oil to chemicals: light olefins from crude oil

[EN] The possibility to fulfill the increasing market demand and producers' needs in processing crude oil, a cheap and universally available feedstock, to produce petrochemicals appears to be a very attractive strategy. Indeed, many petrochemicals are produced as side streams during crude oil refining, which primary goal remains transportation fuel production. Availability of some critical feedstocks may then depend on local refining policy. In order to improve flexibility, it has been proposed to directly crack crude oil to produce petrochemicals, in particular light olefins (ethylene, propylene, butenes), using technologies derived from fluid catalytic cracking. This paper attempts to review the main research works done on the topic in the literature in the last five decades, focussing on process as well as catalyst technology, with a special interest for fluid catalytic cracking (FCC) based technology that can be used towards maximizing chemicals from crude oil. Factors investigated include use of severe cracking conditions, on-purpose additives (from ZSM5 to more exotic, metal doped additives), recycle streams and multiple riser systems.The authors thank Saudi Aramco for material and financial support. Financial support by the Spanish Government-MINECO through program "Severo Ochoa" (SEV 2012-0267), Consolider Ingenio (2010-Multicat, CSD-2009-0050), MAT2012-31657, CTQ2015-70126-R (MINECO/FEDER), by the European Union through ERC-AdG-2014-671093-SynCatMatch and by the Generalitat Valenciana through the Prometeo program (PROMETEOII/2013/011) is also acknowledged.Corma Canós, A.; Corresa Mateu, E.; Mathieu ., Y.; Sauvanaud ., LL.; Al-Bogami, S.; Al-Ghrami, M.; Bourane, A. (2017). Crude oil to chemicals: light olefins from crude oil. Catalysis Science & Technology. 7(1):12-46. https://doi.org/10.1039/c6cy01886fS12467

The effect of variability in industrial emissions on ozone formation in Houston, Texas

Ambient observations have indicated that high concentrations of ozone observed in the Houston/Galveston area are associated with plumes of highly reactive hydrocarbons, mixed with NOx, from industrial facilities. Ambient observations and industrial process data, such as mass flow rates for industrial flares, indicate that the VOCs associated with these industrial emissions can have significant temporal variability. To characterize the effect of this variability in emissions on ozone formation in Houston, data were collected on the temporal variability of industrial emissions or emission surrogates (e.g., mass flow rates to flares). The observed emissions variability was then used to construct region-wide emission inventories with variable industrial emissions, and the impacts of the variability on ozone formation were examined for two types of meteorological conditions, both of which lead to high ozone concentrations in Houston. The air quality simulations indicate that variability in industrial emissions has the potential to cause increases and decreases of 10-52 ppb (13-316%), or more, in ozone concentration. The largest of these differences are restricted to regions of 10-20 km2, but the variability also has the potential to increase region wide maxima in ozone concentrations by up to 12 ppb. Keywords: Photochemical Grid Model, highly reactive volatile organic compounds (HRVOC), ozone, uncertainty analysis, Monte Carlo simulation

Vanadium interaction with FCC catalysts

Fluidised cracking catalysts, which contain a form of zeolite-Y as the main catalytically active component, are widply used commercially for the conversion of crude oil into more profitable product streams. During the cracking reaction, these catalysts are contaminated with vanadium which has a marked effect on the crystallinity of the zeolite-Y component and, as a consequence, activity and selectivity for hydrocarbon processing is degraded. The purpose of this work has been to carry out a detailed investigation, on the laboratory scale, of the effect of vanadium contaminatioil on both commercial and model rare earth ion-exchanged zeolite-Y catalysts. Vanadium contamination was achieved using a standard (Mitchell) method and catalysts were subject to treatment conditions similar to those found in the regenerator part of a fluidised catalytic cracking unit using a specially constructed furnace. Investigations of the solid state chemical reactions between vanadium and rare earth compounds, both in the presence and absence of silica and alumina support materials typical of those found in commercial catalysts, extend the study. Extensive use is made of magic-angle-spinning nuclear magnetic resonance spectroscopy (51V and 27Al), X-ray powder diffraction and surface area measurements for sample characterisation. The apparatus for surface area measurements was constructed during the course of the work. It is suggested that the reduction in crystallinity of rare earth ion-exchanged zeolite-Y in the presence of vanadium is associated with the removal of rare earth ions from the cage structure of the zeolite. The extent of this process depends upon the details of the treatment conditions and important factors are identified. The observation of the formation of LaVO4 in a range of hydrothermally treated lanthanum ion-exchanged zeolite-Y samples supports the proposed model

Pattern recognition approaches to state identification in chemical plants

Ph.DDOCTOR OF PHILOSOPH

Implementation and performance assessment of a real-time optimization system on a virtual fluidized-bed catalytic-cracking plant

This thesis develops and evaluates RTO implementation in a FCCU virtual plant, taking into account each RTO stage (noise elimination, steady-state detection, data validation, parameter estimation, and optimization). The dynamic data to carry out this analysis were obtained from an FCCU virtual plant based on a dynamic deterministic model developed in Matlab®. The model output data were contaminated with Gaussian and gross errors to simulate measurements from a real plant. For denoising, steady-state detection, data reconciliation, parameter estimation, and optimization, different strategies and algorithms were studied and assessed, while a decentralized PID was proposed for the control system. Finally, the most appropriate strategies for the case study were implemented and their performance was fully evaluated.Resumen: Esta tesis desarrolla y evalúa la implementación de la RTO en una planta virtual de FCCU, teniendo en cuenta cada etapa de una RTO (eliminación de ruido, detección de estado estable, validación de datos, estimación de parámetros y optimización). Los datos dinámicos para llevar a cabo este análisis se obtuvieron de una planta virtual de FCCU basada en un modelo determinista dinámico desarrollado en Matlab®. Los datos de salida del modelo se contaminaron con error de Gauss y error grueso para simular mediciones de una planta real. Para la eliminación de ruido, la detección de estado estable, la reconciliación de datos, la estimación de parámetros y la optimización, se estudiaron y evaluaron diferentes estrategias y algoritmos, mientras que para el sistema de control se propuso un PID descentralizado. Finalmente, se implementaron las estrategias más apropiadas para el estudio de caso y se evaluó su desempeño en conjunto.Maestrí

Model-based approach for the plant-wide economic control of fluid catalytic cracking unit

Fluid catalytic cracking (FCC) is one of the most important processes in the petroleum refining industry for the conversion of heavy gasoil to gasoline and diesel. Furthermore, valuable gases such as ethylene, propylene and isobutylene are produced. The performance of the FCC units plays a major role on the overall economics of refinery plants. Any improvement in operation or control of FCC units will result in dramatic economic benefits. Present studies are concerned with the general behaviour of the industrial FCC plant, and have dealt with the modelling of the FCC units, which are very useful in elucidating the main characteristics of these systems for better design, operation, and control. Traditional control theory is no longer suitable for the increasingly sophisticated operating conditions and product specifications of the FCC unit. Due to the large economic benefits, these trends make the process control more challenging. There is now strong demand for advanced control strategies with higher quality to meet the challenges imposed by the growing technological and market competition. According to these highlights, the thesis objectives were to develop a new mathematical model for the FCC process, which was used to study the dynamic behaviour of the process and to demonstrate the benefits of the advanced control (particularly Model Predictive Control based on the nonlinear process model) for the FCC unit. The model describes the seven main sections of the entire FCC unit: (1) the feed and preheating system, (2) reactor, (3) regenerator, (4) air blower, (5) wet gas compressor, (6) catalyst circulation lines and (7) main fractionators. The novelty of the developed model consists in that besides the complex dynamics of the reactorregenerator system, it includes the dynamic model of the fractionator, as well as a new five lump kinetic model for the riser, which incorporates the temperature effect on the reaction kinetics; hence, it is able to predict the final production rate of the main products (gasoline and diesel), and can be used to analyze the effect of changing process conditions on the product distribution. The FCC unit model has been developed incorporating the temperature effect on reactor kinetics reference construction and operation data from an industrial unit. The resulting global model of the FCC unit is described by a complex system of partial-differential-equations, which was solved by discretising the kinetic models in the riser and regenerator on a fixed grid along the height of the units, using finite differences. The resulting model is a high order DAE, with 942 ODEs (142 from material and energy balances and 800 resulting from the discretisation of the kinetic models). The model offers the possibility of investigating the way that advanced control strategies can be implemented, while also ensuring that the operation of the unit is environmentally safe. All the investigated disturbances showed considerable influence on the products composition. Taking into account the very high volume production of an industrial FCC unit, these disturbances can have a significant economic impact. The fresh feed coke formation factor is one of the most important disturbances analysed. It shows significant effect on the process variables. The objective regarding the control of the unit has to consider not only to improve productivity by increasing the reaction temperature, but also to assure that the operation of the unit is environmentally safe, by keeping the concentration of CO in the stack gas below a certain limit. The model was used to investigate different control input-output pairing using classical controllability analysis based on relative gain array (RGA). Several multi-loop control schemes were first investigated by implementing advanced PID control using anti-windup. A tuning approach for the simultaneous tuning of multiple interacting PID controllers was proposed using a genetic algorithm based nonlinear optimisation approach. Linear model predictive control (LMPC) was investigated as a potential multi-variate control scheme applicable for the FCCU, using classical square as well as novel non-square control structures. The analysis of the LMPC control performance highlighted that although the multivariate nature of the MPC approach using manipulated and controlled outputs which satisfy controllability criteria based on RGA analysis can enhance the control performance, by decreasing the coupling between the individual low level control loops operated by the higher level MPC. However the limitations of using the linear model in the MPC scheme were also highlighted and hence a nonlinear model based predictive control scheme was developed and evaluated.EThOS - Electronic Theses Online ServiceGBUnited Kingdo

Factors And Preventive Measures Relative To The High Temperature Corrosion Of Blade/Disk Components In FCC Power Recovery Turbine.

LecturePg. 11-26Power recovery expander turbines in the Fluid Catalytic Cracking Unit (FCCU) process operate under certain conditions that can adversely affect their performance and operational capability or integrity. For instance, erosion of the rotor blade tips by the spent catalyst can significantly reduce their efficiency and power output. Perhaps more significantly, the high temperature gaseous/catalyst environments that a power recovery turbine operates can, under certain conditions, lead to corrosive attack. This corrosive attack can cause blade failure in the location of the blade/disk root attachment where the stress intensity at the corrosive attack location exceeds the critical stress intensity necessary for fracture to occur. The fracture mechanism of Waspaloy turbine blades and how the various factors such as corrosion product morphology, depth of penetration into the alloy and a reduction in fracture toughness of the material, influence the fracture mechanism are addressed. Since the corrosive attack is the main contributor that leads to failure, the characterization and identification of the various corrosion product phases that can form under certain gaseous/ catalyst conditions will be examined. As a result of both the ability to accurately predict the susceptibility of corrosive attack and an understanding of the failure mechanism, certain protective measures can be taken. The preventive measures that have been developed by the senior author's company, such as a steam barrier system and a protective coating of the blade, are highlighted