Catalytic Reforming for Aromatics Production Topsoe Catalysis Forum Munkerupgaard, Denmark August 27 28, 2015 Greg Marshall GAM Engineering LLC GAM Engineering LLC 1
REFINERY CONFIURATION LPG NAPHTHA HYDROTREATING ICN ISOMERISATION CATALYTIC REFORMING GASOLINE BLENDING MOTOR GASOLINE ALKYLATION CRUDE DISTILLATION (APS/VPS) JET HYDROTREATING DISTILLATE HYDROTREATING AVIATION FUEL ic4= LUBES AROMATICS SEPARATION EXTRACTION/ FRACTIONATION DISTILLATE BLENDING BENZENE TOLUENE XYLENES ADO HEATING OIL VGO HYDROCRACKING/ GOFINING CATALYTIC CRACKING (FCCU) FCCU DISTILLATE HYDROTREATING RESIDUUM PROCESSING FUEL OIL/ ASPHALT GAM Engineering LLC 2
Role of Catalytic Reforming MAIN PROCESS FOR UPGRADING LOW OCTANE NAPHTHAS TO HIGH OCTANE GASOLINE BLENDING COMPONENTS OR CHEMICALS INTERMEDIATES (BENZENE/TOLUENE/XYLENES) NUMBER OF IMPORTANT BYPRODUCTS H 2 FOR HYDROTREATING C 1 C 2 FOR FUEL GAS C 3 C 4 FOR LPG C 4 ' S TO MOGAS OR ALKYLATION (IC 4= ) AROMATICS FOR CHEMICALS MODERN CATALYTIC REFORMING DEVELOPED IN THE EARLY 1950'S WITH DEMAND FOR INCREASED GASOLINE OCTANE SIGNIFICANT IMPROVEMENTS OVER THERMAL REFORMING HIGHER OCTANE AND YIELD BETTER QUALITY (SULPHUR, DIOLEFINS) GAM Engineering LLC 3
Process Description Naphtha feedstock Typical C 6 to C 10 Feed tailored to the desired product C 6 to C 8 is better Fractionated to remove heavy ends Hydrotreated to remove Sulfur Nitrogen Olefins Oxygenates Metals Paraffins, naphthenes and aromatics Combined with hydrogen rich recycle gas Vaporized in feed effluent heat exchangers Necessary to be all vapor before heater GAM Engineering LLC 4
Process Description Continued Feed and recycle gas Heated to reaction temperature in furnace Introduced to first reactor Desired reactions are endothermic Strong endotherm in first reactor reaching a reaction quench temperature Followed by 2 to 4 additional reactor heater combinations Entire reaction train in vapor phase GAM Engineering LLC 5
Simplified Semi Regen Reformer GAM Engineering LLC 6
Cyclic Reforming UPPER REACTION HEADER UPPER REGEN HEADER TO/FROM REGEN CIRCUIT REACTORS A - S A B C D S FIRST REHEAT FURNACE SECOND REHEAT FURNACE THIRD REHEAT FURNACE PREHEAT FURNACE LOWER REACTION HEADER HYDROFINED NAPHTHA FEED LOWER REGEN HEADER TO EFFLUENT EXCHANGERS, SEPARATOR DRUM, ETC. GAM Engineering LLC 7
UOP CCR Reformer Regenerator #1 Cat Flow #2 Regenerated Catalyst #3 Hydrogen Spent Catalyst Start Hydrotreated Naphtha Charge GAM Engineering LLC 8
Unit Revamps Most done to stretch existing unit capacity Heater preplacement due to creep Lowering pressure to increase yields Changing feed effluent exchangers Purge from compressor discharge Switching from mono metallic catalyst to bi metallic catalyst GAM Engineering LLC 9
Catalyst Dual Function Acid : Alumina with chloride Metal : Pt with or without promoter metals ( Re, Ir, Sn) Re provides coke stability and additional run length Sulfiding required Ir additional activity Sulfiding required Sn promotes yield at low coke levels no sulfiding required Supported on gamma alumina High surface area 200 m 2 /gm fresh catalyst 120 m 2 /gm aged catalyst Surface area decline with exposure to high temperature and steam Heart of reforming process Promotes good reactions GAM Engineering LLC 10
Products SAME HYDROCARBON TYPES AS FEED BUT PRIMARILY AROMATIC AND C 7 PARAFFINS AROMATICS ARE THE PRINCIPAL SOURCE OF HIGH OCTANE NAPHTHENES AND C 8 + PARAFFINS ESSENTIALLY ABSENT AT 98 + RON LIGHTER PARAFFINS ARE MORE BRANCHED THAN IN FEED BUT ARE STILL PREDOMINATELY SINGLE METHYL SUBSTITUTED WITH LOW RON RON % Aromatics Vs RON 100 98 96 94 92 90 88 86 84 0,0% 20,0% 40,0% 60,0% 80,0% GAM Engineering LLC 11 % Aromatics
Unit Optimization Low pressure and low H2 / HC ratio favor Higher liquid yields Higher aromatic yields Coke High temperatures favor Dehydrogenation Dehydrocyclization Hydrocracking Coke GAM Engineering LLC 12
Feed Selection High yield Easy feed Naphthenic feeds Example Sleipner Condensate ~70% naphthenes Require large reheat furnaces high endotherms High hydrogen and aromatics yields Lower Yield More difficult feed Paraffinic feeds Example Lt Arab Naphtha ~ 70% paraffins Reactor endotherms decreased Higher Lt ends yields GAM Engineering LLC 13
Mogas Vs Aromatics Operation Mogas operation Targets C5+ RON needed for gasoline blending Target can and will change based on gasoline grade blended Typical RON 92 to 95 with short excursions to 98 as needed Aromatics operation Target maximum aromatics concentration in reformate Typical RON of reformate > 98 with some units operating up to 102 Feed and unit type dependent Semi regen units require frequent regeneration Cyclic and CCR better suited for aromatics operation Minimize C9 non aromatics GAM Engineering LLC 14
Yield versus Severity 88 Typical yield with a feed Watson K of 11.8 87 86 85 C5+ Yield 84 83 82 81 80 79 90 91 92 93 94 95 96 97 98 99 100 RON GAM Engineering LLC 15
Expected Yields Reformer Types and Yields 95 90 C5+ Yield 85 80 Semi Regen Cyclic Semi Regen 2 CCR 75 70 0 2 4 6 8 10 12 14 Months
Aromatics Recovery Remove light ends Depentanize via distillation Remove heavy ends C8 overhead in distillation tower Can separate A8 from A9 by distillation Cannot separate A8 from P9 by distillation Azeotrope formed Mogas and / or aromatic solvents C6 to C8 stream sent to solvent extraction Raffinate to mogas or specialty solvents GAM Engineering LLC 17
BTX Recovery Clay Treater Fractionation BZ product O/H Tower bottoms to another fractionator Toluene product overhead Tower bottoms to another fractionator Tower overhead concentrated Para Xylene Sent to Parex for production of pure Px Parex reject stream sent to Para Xylene Isomerazation Tower bottoms sent to another fractionator Produces Ortho Xylene from tower overhead Tower bottoms sent to mogas GAM Engineering LLC 18
Additional Px Product Toluene is divided between sales and STDP Flow rates determined by economics STDP Feeds Toluene Major product are Benzene Para xylene GAM Engineering LLC 19