ADVANCES in FLUID CATALYTIC CRACKING (November 2005)
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Abstract Process Economics Program Report 195A ADVANCES IN FLUID CATALYTIC CRACKING (November 2005) Recent emphasis in fluid catalytic cracking is on maximum light olefins production, gasoline sulfur reduction and compliance with FCCU NOx and SOx emissions requirements. New cracking catalysts and additives for the reduction of NOx, SOx and gasoline sulfur continue to significantly improve FCCU operation. New hardware designs offer improved unit operation and efficiency. Areas of recent new hardware design improvements include the standpipe inlet, third stage cyclones, spent catalyst distributor and catalyst stripping. Wet gas scrubbers or selective catalytic reduction may now be required in some cases to meet emissions requirements. This report provides an overview of FCC developments in catalyst, process and hardware technologies since PEP Report 195, Advances in Fluid Catalytic Cracking, issued in 1991. The report then develops process economics for cracking the most common type of FCC feedstock, vacuum gas oil. PEP Report 228, Refinery Residue Upgrading, issued in 2000 reviews the special issues and technology of Residual Fluid Catalytic Cracking (RFCC) and develops process economics for cracking a residual feedstock. Since the refinery production of light olefins such as propylene offers refiners in some regions, especially Asia and Western Europe, an opportunity for profit, the process economics of maximum light olefins FCC from VGO are developed. Air emissions (SOX, NOX) from FCCUs and the reduction of FCC gasoline sulfur are major environmental issues discussed. Professionals and managers involved in the energy industry who manage, research, develop, plan, operate, design plants or manage investments in the petroleum refining and allied industries could benefit from the information contained in this report. PEP’05 RHN R eport No. 195A ADVANC E S IN FL UID C ATAL YTIC C R AC K ING by R ichard H. Niels en November 2005 A private report by the P R OC E S S E C ONOMIC S P R OG R AM S R I Menlo P ark, C alifornia 94025 SRIC agrees to assign professionally qualified personnel to the preparation of the Process Economics Program’s reports and will perform the work in conformance with generally accepted professional standards. No other warranties expressed or implied are made. Because the reports are of an advisory nature, neither SRIC nor its employees will assume any liability for the special or consequential damages arising from the Client’s use of the results contained in the reports. The Client agrees to indemnify, defend, and hold SRIC, its officers, and employees harmless from any liability to any third party resulting directly or indirectly from the Client’s use of the reports or other deliverables produced by SRIC pursuant to this agreement For detailed marketing data and information, the reader is referred to one of the SRI Consulting programs specializing in marketing research. THE CHEMICAL ECONOMICS HANDBOOK Program covers most major chemicals and chemical products produced in the United States and the WORLD PETROCHEMICALS PROGRAM covers major hydrocarbons and their derivatives on a worldwide basis. In addition the SRIC DIRECTORY OF CHEMICAL PRODUCERS services provide detailed lists of chemical producers by company, product, and plant for the United States, Western Europe, Canada, and East Asia, South America and Mexico. CONTENTS 1 INTRODUCTION ........................................................................................................ 1-1 2 CONCLUSIONS ......................................................................................................... 2-1 3 SUMMARY ................................................................................................................. 3-1 COMMERCIAL ASPECTS ......................................................................................... 3-1 TECHNICAL ASPECTS ............................................................................................. 3-2 ECONOMICS ASPECTS............................................................................................ 3-4 4 INDUSTRY STATUS.................................................................................................. 4-1 ROLE OF CATALYTIC CRACKING........................................................................... 4-2 FIXED SOURCE EMMISIONS REGULATIONS........................................................ 4-3 Particulates................................................................................................................. 4-4 SOx ................................................................................................................................................................................................. 4-5 NOx ................................................................................................................................................................................................. 4-5 CO .............................................................................................................................. 4-5 PRODUCT SPECIFICATIONS................................................................................... 4-6 Gasoline...................................................................................................................... 4-6 Diesel.......................................................................................................................... 4-9 Propylene, Propane, Ethylene and Ethane ................................................................ 4-11 SUPPLY AND DEMAND ............................................................................................ 4-15 Motor Fuels................................................................................................................. 4-15 Propylene.................................................................................................................... 4-19 INSTALLED CATALYTIC CRACKING CAPACITY.................................................... 4-21 NEW CONSTRUCTION ............................................................................................. 4-44 5 GENERAL PROCESS REVIEW ................................................................................ 5-1 FEEDSTOCK.............................................................................................................. 5-1 PRODUCTS................................................................................................................ 5-8 iii CONTENTS (Continued) Gasoline...................................................................................................................... 5-9 CHEMISTRY............................................................................................................... 5-12 Cracking Mechanisms ................................................................................................ 5-13 Alkene Cracking Mechanism................................................................................ 5-13 Alkane Cracking Mechanism................................................................................ 5-15 Carbenium Ion Mechanisms............................................................................ 5-15 Coke and Catalyst Decay..................................................................................... 5-19 Carbonium Ion Mechanisms............................................................................ 5-23 Dichotomies.......................................................................................................... 5-23 Sulfur Compound Cracking Mechanism............................................................... 5-25 Coke Combustion................................................................................................. 5-29 NOx Formation Mechanism .................................................................................. 5-30 Cracking Kinetics........................................................................................................ 5-33 FCC GASOLINE SULFUR REDUCTION................................................................... 5-36 Feedstock Hydrodesulfurization ................................................................................. 5-37 Gasoline End Point Reduction ................................................................................... 5-38 Co-processing C5-C6s................................................................................................. 5-38 Post Treatment ........................................................................................................... 5-39 CATALYSIS ................................................................................................................ 5-40 Adsorption and Diffusion ............................................................................................ 5-41 Catalyst Attrition.......................................................................................................... 5-42 Commercial FCC Catalysts ........................................................................................ 5-43 Gasoline Sulfur Reduction.................................................................................... 5-46 Maximum Light Olefins ......................................................................................... 5-46 Maximum Middle Distillates.................................................................................. 5-47 Catalyst Additives ......................................................................................................