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CC process modelling has been one of the key elements of Shells FCC R&D programme over many decades because of its importance for unit optimisation and refinery economics. The Shell Advanced and Rigorous Cat Cracking Model (SHARC) is the result of this effort. SHARC is an advanced computer model that helps FCCU operators in three vital ways: it accurately predicts the economic impact of changes in feedstock, catalyst and operating conditions; it can be used to optimise the performance of the unit on a continuous (on-line) or regular (off-line) basis; and it can generate LP vectors for refinery planning and scheduling models to perform refinery-wide optimisation. SHARC has been applied to many (Resid-) FCCUs, and refineries have benefited greatly from this development. SHARC was developed initially for Shell refineries; it is now available for commercial licensing. This paper provides an overview of SHARC model development within Shell. It goes on to discuss Shells feed characterisation technology and yield model, developed on the basis of an extensive research programme, highly consistent pilot plant- and commercial data; Shells recent R&D in low sulphur fuels management; and
a new FCCU process model: the Shell FCC Process Model [11]. This model converted the kinetic network model into an integrated form by introducing selectivity relationships, and a robust and simplified feedstock characterisation technology was developed. The Shell FCC Process Model was then successfully implemented in Shells on-line optimisation systems in 1985. In 1994 Shell further improved its FCC Process Model with the aid of extensive data newly obtained from its Riser Pilot Plant units and commercial Precision Test Run (PTR) programs. The resulting model, SHARC, was released in 1995. Since then, more than seven new SHARC releases have been issued. SHARC is an open-equation based model with a very friendly graphical (Windows type) user interface. With its proprietary robust feedstock characterisation, riser/reactor and regenerator kinetics, and selectivity relationships based on extensive and consistent pilot plant- and PTR data, SHARC is capable of accurately estimating yields and product properties, even when widely different feedstocks, catalysts and operating conditions are employed. FCC process modelling (or SHARC development) has always been an integrated program within Shell. It is
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cial applications). Customer needs are the main driving force for ongoing SHARC development, which takes place in order to meet the foreseeable future needs of the oil refining industry. SHARC can also be integrated vertically with on-line optimisation (e.g., SPOT), refinery simulation tools (e.g., RefSim) and refinery planning and scheduling models (e.g., Impress, PIMS and RPMS).
Experimental capabilities
Shells Research and Technology (Westhollow Technology Centre in Houston and Shell Research and Technology Centre Amsterdam) has extensive FCC experimental facilities. The lab scale reactors used have included fixed-bed reactors (in the 1940s and 1950s), fixed fluidised bed reactors (1960s) and, since the 1970s, Riser Pilot Plants. The experimental facilities have provided extensive information for understanding the FCC reaction kinetics and for developing the SHARC model. Over the last 30 years, Shell has carried out extensive Riser Pilot Plant- and PTR programmes. More than 50,000 high quality and consistent data sets were generated, providing in-depth understanding of FCC process fundamentals. Shells FCC experimental facilities now comprise the following equipment: L-85, Riser Pilot Plant (small riser); Residue Riser Pilot Plant (large riser); CDU, Cyclic Deactivation Unit
(metalated catalyst preparation); L-87, steamers (metals free catalyst preparation); L-87C, steamer (catalyst deactivation studies with metals); MAT 5000, micro-reactor for special studies. Over the last several years, the Residue Riser Pilot Plant has been used to generate experimental data to develop the FCC product property model for clean fuel management. Key features of this test facility are: capability to process a wide range of (heavy) feedstocks relatively high throughput (~5 kg/ hr) wide range of cracking temperatures and cat/oil ratios continuous regeneration highly automated, high productivity The Residue Riser Pilot Plant is being used to generate high quality yield and product property data, for a very wide range of feedstocks and operating conditions. These data are used for further development and enhancement of SHARC.
Analytical support
Analytical support plays an important role in SHARC model development. Feedstock characterisation, catalyst characterisation and FCC product property analyses are all essential for FCCU optimisation. Shells process researchers and analytical chemists have worked very closely to utilise advanced analytical technologies in its FCC R&D programs. In the early 1960s, Shell used gas chromatography (GC) and mass spectrometry (MS) techniques to detail the FCC feedstock composition, which, in conjunction with study of FCC reaction kinetics, enabled the development of Shells FCC kinetic network model. Since then, Shell has applied and further developed GC/MS, NMR, HPLC and
supported by four key elements: Experimental (Riser Pilot Plant facilities and capabilities); Analytical support (feedstock, catalyst and product characterisation); Precision Test Run program (high quality data from commercial FCCUs); Commercial FCCU experience (model validation/improvement through feedback from commer-
Highly automated test facilities L85 Riser Pilot Plant control panel
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consistent yield- and product property data from commercial units. It can also be used to identify/diagnose mechanical problems and to quantify the impact of hardware modifications. Over the past 30 years, a very extensive database has been generated from the PTR program. Precision tests are always conducted under wellcontrolled operating conditions. Yields are measured on the basis of reactor overhead samples, thereby eliminating the impact of fractionation, external product streams and other uncertainties. The feedstock, catalyst, and product samples are all collected at the same time to ensure high consistency of the data. Shell has been using PTR data to validate its model concepts and calibrate the model. This validation has proved that SHARC can be applied to a very wide range of feedstocks and provides high accuracy: the standard deviations between measurement and model prediction for yields are normally within the measurement error range of gas chromatography.
FCC process modelling program. Shells experience of FCC operation often helps to define the requirements of the FCC process model, allowing Shell researchers to understand what aspects are most important to FCC and refinery operation now and in the foreseeable future. Shells knowledge of FCC operation and design has allowed SHARC to be developed and structured on the basis of very robust process fundamentals and practical aspects.
other advanced analytical techniques to characterise residual and other feedstocks. Shell has also developed proprietary techniques to quantify the activity of zeolitic FCC catalysts and has advanced the compositional analysis of FCC products (e.g. PIONA). Advances have recently been made in the analyses of gasoline composition [14] and sulphur distribution as a function of boiling points, as these analyses are increasingly important for clean fuel management.
SHARC has been developed to reflect the actual behaviour of an FCCU. As a major FCC operator, Shell can use its FCCUs to validate the model concepts. Validation via commercial data is one of the key steps of Shells
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to be employed in describing observed FCCU behaviour. This approach helps to ensure that the engineering principles are correct, and that the integrity of the first derivatives is not compromised. In-depth understanding of FCC reactions and kinetics allows a complex kinetic model to be appropriately simplified by developing governing selectivity relationships and ratios. SHARC has been designed to respond to changes in operating variables in the same way that an actual FCCU would respond. For example, the principal factors dictating the operational performance of an FCCU are total coke make and overall FCCU heat balance: these, above all else, command the constant attention of FCCU operators. The model calculations therefore focus firstly on establishing the FCCU carbon- and heat balance, before proceeding to estimate the detailed product yield structure.
NVC than by CCR. SHARC feedstock properties can be obtained through simple analyses, most of which are ASTM methods. Only a few analyses require the use of Shell analytical techniques. However, these are simple and can be run in a refinery laboratory. Shell has also developed an analytical technique to measure SHARC feed properties with a very short turnaround time. Several refineries are using this feedstock characterisation for their on-line FCC optimisers.
(model) representation of cat crackers. The quality and consistency of the data are very critical. The pilot plant units used for SHARC development respond to changes in feedstock and operating variables in the same way as commercial FCCUs. Comparisons of yields and product properties obtained in Shells Riser Pilot Plants and in commercial units have resulted in a series of parallel curves, suggesting the Shell pilot plants can be used as a means of identifying what feedstock, catalyst and operating variables are likely to be significant, and what basic chemical engineering principles need to be employed in describing observed FCCU behaviour. Shells pilot plant data provides high repeatability and is produced under strictly controlled conditions.
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Estimating the effects on yields and product properties resulting from changes
SHARC capabilities
The model is in essence a procedure for estimating the impacts of changes in design, feedstock, catalyst and operating variables away from a known operating point. It can be used stand-alone (off-line), or in integration with FCCU on-line optimisation systems and with refinery planning and scheduling tools. Shells experience of SHARC applications in refineries indicates that the model can perform quite well in the areas listed below. Estimating the effects on yields and product properties resulting from changes in feedstock, catalyst addition rate and operating conditions. This capability has been most often applied by refiners to improve their FCCU performance via feedstock selection and optimisation, catalyst evaluation and management, and unit optimisation (off-line and/or online). Performing marginal feed evaluations hence benefiting from the ability to select the right additional feed at the right price. Many refineries use SHARC as a tool in conjunction with a refinery LP
model to determine the value of each available FCC marginal stream, enabling them to make economically justifiable decisions about feedstock purchases or sales. Helping to select the best catalyst for use in a given FCCU, under its operating constraints, and given the refinerys particular economic goals. Monitoring, evaluating and optimising the performance of FCCU on a continuous basis. SHARC pro-
vides a complete and automated unit monitoring system. SHARC analyses the unit performance and tracks the yield selectivity parameters, normalised yields (i.e. normalising the effects of feedstock and operating conditions), and important hardware performance parameters. The unit monitoring system is able to distinguish the impacts of feedstock, catalyst, unit hardware, and operating conditions. Refinery
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scheduling tools to enhance overall hydrocarbon management capability. SHARC provides complete integration with refinery planning and scheduling models, and can automatically generate the LP model vectors based on the pre-defined matrix.
plete distribution of gasoline properties (olefins, aromatics, sulphur and nitrogen) and sulphur distribution in the 221oC+ fractions as a function of boiling point, feedstock, catalyst, and operating conditions have been developed and implemented in SHARC. Therefore, SHARC is becoming a very useful tool for refineries in managing low sulphur fuel specifications and optimising FCC and hydroprocessing units.
Reduction of gasoline and diesel fuel emissions is well under way in most regions around the world SHARC is used to perform FCC unit optimisation, both off-line and on-line
engineers can thereby monitor and evaluate unit hardware and catalyst performance on a continuous basis, and quickly identify any deterioration. The unit monitoring data also helps the refineries to identify unit improvement opportunities and carry out unit T/A planning.
Identifying opportunities to improve unit performance, or as an investment decision support tool to assess the effects of unit revamps. SHARC can also be used to evaluate proposed design modifications or vendors design proposals. Helping refineries to achieve clean fuels management. SHARC provides accurate estimations of product properties (density, gasoline octane, sulphur, hydrogen content, gasoline benzene and olefins, LCO cetane number and viscosity, etc.). The com-
first started in the U.S. with the introduction of reformulated gasoline (RFG) and oxygenated gasoline. Now, the reduction of gasoline and diesel fuel emissions is well under way in most regions around the world.
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the 1990 refinery baseline. The Simple Model, which was used until the end of 1997, allowed a 15% reduction in VOCs (Volatile Organic Compounds) and toxics emissions with no increase in NOx emissions. Since 1 January 1998, refiners have been required to use a Complex Model for certification. The Complex Model is a set of equations for calculating percent reductions for three types of vehicle emissions for RFG and conventional gasoline relative to specified baseline gasoline: Volatile organic compounds (VOCs) Nitrogen oxides (NOx) Toxic air pollutants (toxics) The Complex Model expresses emissions as complex functions of eight measurable gasoline properties: RVP; oxygen; sulphur; aromatics; olefins; benzene; percentage of fuel evaporated at 93oC (200oF, E200) and at 149oC (300oF, E300). In Europe, EU Directive 98/70EC (dated 13 October 1998) sets out new stringent specifications for automotive fuels. The first phase was introduced on 1 January 2000 and indicative specifications for 2005 were outlined. Asian countries and Australia have also set specifications for gasoline and diesel fuel.
on emission reductions are: VOCs : RVP, aromatics, sulphur, NOx : sulphur, aromatics, olefins; and Toxics : benzene, aromatics, oxygen. Therefore, FCC gasoline significantly contributes towards VOCs, NOx and toxic emissions, because of its high levels of olefins, sulphur and heavy aromatics. Accurately predicting sulphur, olefins, benzene and aromatics content in the FCC gasoline; and sulphur, nitrogen, and aromatics in FCC light cycle oil (LCO) has become extremely important for refiners to manage and meet clean fuel specifications.
Database and FCC product properties model for clean fuel management
Since 1993, Shell has been committed to developing an FCC product property model to accurately describe detailed gasoline compositional properties. Dedicated experimental programs have been conducted to generate an extensive database [13] for clean fuel management. The database and the knowledge developed from the programmes have been used for clean fuel (or low sulphur fuel) management studies in many Shell advised refineries. The experimental programmes have been performed in the Shells Residue Riser Pilot Plant. The experimental programmes emphasise the feedstock effect because this has a significant impact on gasoline composition, all the relevant physical properties of gasoline, and LCO/HCO properties. A very wide range of feedstocks, in terms of feed origin,
composition, and upstream treatment, has been used for the experiments. Some feedstocks are listed in Table-1. Catalyst type (and contents of zeolite, matrix, rare earth and additives) also affects the gasoline composition, bromine number, octane, and density. Shell has performed many catalyst evaluation studies in its Riser Pilot Plants, using equilibrium catalysts obtained from several FCCUs (processing significantly different feedstocks) Tests are done over a range of cracking temperatures and cat/oil ratios, covering a commercially realistic range of conversions. As a result of this test programme, a detailed product property model has been developed and is being implemented in SHARC now. It is able to predict the following product properties: The effect on gasoline sulphur distribution from changes in FCC feedstock quality (including feedstock origin and upstream treatment), fractionator cut points, and operating conditions. The effect on gasoline benzene, olefins and aromatics from changes in FCC feedstock quality, fractionator cut points, operating conditions, and catalyst properties. The effect on gasoline octane from changes in FCC feedstock quality, fractionator cut points, operating conditions, and catalyst properties. The effect on LCO, HCO, and slurry properties (aromatics, NVC, basic nitrogen, and total nitrogen) from changes in FCC feedstock quality, fractionator cut points, operating conditions, and catalyst properties.
Table-1 Some Feedstocks used in Shells FCC Product Properties Programmes 2900 2924 2952 2960 2974 3005 3008 3442 3463 3476 0.917 0.946 0.989 0.897 12.2 11.75 8.45 12.52 0.94 700 221 0.80 0.53 0.35 1.47 1500 4300 600 386 0.81 1398 76 0.25 0.15 0.894 12.4 0.10 60 5.4 0.50 0.986 11.15 1.08 5100 1426 5.60 0.961 10.62 1.18 4200 822 2.80 0.900 12.23 1.66 600 162 0.25 0.921 12.33 0.45 1100 303 3.85 0.899 12.85 0.78 1100 351 3.50
Sulphur, %wt Total Nitrogen, ppmw Basic Nitrogen, ppmw Con. Carbon %wt
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Shell is utilising the detailed product property model to evaluate options for clean fuel management in Shell advised refineries and to help the refineries in making the most effective investment decisions. The detailed product property model is becoming an essential tool for refineries in effectively managing and optimising refining processes in order to meet clean fuel specifications.
of using SHARC. In an average unit this can equate to an annual margin increase of $23 million. SHARC is an extremely valuable tool as pressure continues to grow on refinery margins and the ability to react quickly, and with confidence, becomes vital for success. Shell is also committed to the future improvement of FCC process modelling. The continuous development of SHARC is essential for the Shell advised refineries to meet new challenges and requirements in the future.
Enquiry Number 10-03
HA
SHARC is currently used in more than 35 refineries LRCC complex in Port Dickson, Malaysia
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ENQUIRY NO 168
References
1. J. W. Wilson, Fluid Catalytic Cracking Technology and Operation, PennWell Publishing Company, 1997. 2. F. H. H. Khouw, G. V.Tonks, et al, The Shell Residue Fluid Catalytic Cracking Process, Akzo Catalysts Symposium (Fluid Catalytic Cracking), 1991. 3. B. S. Greensfelder and H. H. Voge, Catalytic Cracking of Pure Hydrocarbons Cracking of Paraffins, Industrial and Engineering Chemistry, Vol. 37, No. 6 (1945). 4. B. S. Greensfelder and H. H. Voge, Catalytic Cracking of Pure Hydrocarbons Cracking of Olefins, Industrial and Engineering Chemistry, Vol. 37, No. 10 (1945). 5. B. S. Greensfelder, H. H. Voge and G. M. Good, Catalytic Cracking of Pure Hydrocarbons Cracking of Naphthenes, Industrial and Engineering Chemistry, Vol. 37, No. 11 (1945). 6. B. S. Greensfelder, H. H. Voge and G. M. Good, Catalytic Cracking of Pure Hydrocarbons Aromatics and Comparison of Hydrocarbon Classes, Industrial and Engineering Chemistry, Vol. 37, No. 12 (1945). 7. B. S. Greensfelder, H. H. Voge and G. M. Good, Catalytic Cracking of Pure Hydrocarbons Secondary Reactions of Olefins, Industrial and Engineering Chemistry, Vol. 38, No. 10 (1946). 8. G. M. Good, H. H. Voge and B. S. Greensfelder, Catalytic Cracking of Pure Hydrocarbons Cracking of Structural Isomers, Industrial and Engineering Chemistry, Vol. 39, No. 8 (1947). 9. B. S. Greensfelder, H. H. Voge and G. M. Good, Catalytic Cracking of Pure Hydrocarbons Mechanisms of Reaction, Industrial and Engineering Chemistry, Vol. 41, No. 11 (1949). 10. O. M. Shultz and R. D. Jaquay, A Kinetic Model for Catalytic Cracking, Shell Oil Technical Progress Report, TPR H67-009, 1967. 11. W. M. Edwards and H. van der Eijk, A Simplified Kinetic Yield Model for Catalytic Cracking Background and Development, Shell Cat. Cracking and Alkylation Meeting, 1984. 12. W. J. Mo and J. M. H. Dirkx, Shell Advanced and Rigorous Cat Cracking Model (SHARC), Model User Manual, 1995. 13. W. A. Parker, W. J. Mo and G. R. Harper, Database for FCC Product Properties, Shell WTC Report, TPR-WTC 28-93, 1993. 14. A. Evans and W. J. Mo, A New Analytical Technique for Gasoline Composition as A Function of Boiling Point, WTC Technical Progress Report, Shell Chemicals, 2000. 15. R. P. van der Werf, FCC Monitoring Through Precision Testing, Petroleum and Coal 2, V. 42, July 2000 (presented at the 39th International Petroleum Conference, Bratislava, Sep-20, 1999).
Hydrocarbon Asia wishes to thank Weijian Mo, George Hadjigeorge and Frank Khouw of Shell Global Solutions, US, Houston, Texas, USA, and Renie van der Werf and Fred Muller of Shell Global Solutions International, Amsterdam, the Netherlands for contributing this paper.
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