Refining/Petrochemical Integration A New Paradigm Anil Khatri, GTC Technology Coking and CatCracking Conference New Delhi - October 2013
Presentation Themes Present integration schemes focus on propylene, and miss the potential to capture added value from aromatics Valuable components exist in FCC gasoline heavy olefins & aromatics Patented GTC purification and conversion technology can upgrade traditional fuel components to high value petrochemicals Component Value Relative to Unleaded Gasoline Naphtha 0.87 Unleaded Gasoline 1.00 Toluene 1.13 Benzene 1.15 Ethylene 1.24 Mixed Xylenes 1.26 Paraxylene 1.43 Propylene 1.55 Styrene 1.63 CH 3 CH 3 CH 3 Benzene Toluene Mixed Xylenes Propylene Page 2
Presentation Overview Gasoline demand and clean fuel regulations around the world Process for recovering aromatics from FCC Gasoline - GT-BTX-PluS Processes for utilization of FCC olefins Case study No gasoline, only p-xylene and benzene Page 3
World Gasoline Demand Stagnant or Decreasing Major Regions Gasoline Supply/Demand Unit: 1,000 B/D 2006 2008 2010 2012* US Gasoline Demand 10,929 11,120 11,340 10,850 Gasoline Surplus (Deficit) (1,135) (1,100) (870) (200) EUROPE Gasoline Demand 2,546 2,430 2,334 2,250 Gasoline Surplus (Deficit) 902 1,000 1,200 1,150 MIDEAST GULF Gasoline Demand 1,193 1,368 1,545 1,750 Gasoline Surplus (Deficit) (250) (120) (200) (300) ASIA PACIFIC Gasoline Demand 3,966 4,210 4,505 4,800 Gasoline Surplus (Deficit) 150 250 300 200 Source: Asian Pacific Energy Consulting * Estimated Page 4
Gasoline Specification Limitation Imposed on Aromatics Vehicle Emission Standard Equivalent 1993/1995 2000 2005 CURRENT Euro II Euro III Euro IV Euro V U.S. Sulfur, ppm, max 1,000/500 150 50 (10) 10 30 Aromatics, vol%, max - 42 35 35 25 Olefins, vol%, max - 18 18 18 8.5 Benzene, vol%, max 5.0 1.0 1.0 1.0 0.62 Page 5
Aromatics Trends Aromatics demand for petrochemicals is growing Sources: CMAI Page 6
FCC Gasoline Desulfurization Conventional Three-Stage Process LCN C5-iC6 - (optional) Caustic Extraction Mild HDS FCC Naphtha MCN 70-150 o C Medium HDS ULS Gasoline Blending C 6 -C 9 Olefins Saturation (unavoidable) Sulfur Desulfurization (needed) HCN 150 o C-EP Severe HDS Page 7
Aromatics Extraction with GT-BTX PluS LCN C 5 -ic 6 - (optional) Caustic Extraction Mild HDS ULS Gasoline Blending Raffinate: Paraffins + Olefins FCC Naphtha MCN 70-150 o C Extract: Sulfur + Aromatics HDS Aromatics Solvent H 2 H 2 S GT-BTX PluS HCN 150 o C-EP Severe HDS ULS Gasoline Blending Page 8
Aromatics Extraction Alternatives Liquid-liquid Extraction Extractive Distillation H 2 O Raffinate Extract Raffinate Extract Feed Feed Solvent Solvent Page 9
Different Solvent Systems for Aromatics Recovery Solvent S/F Relative volatility (α) n-c 7 /benzene Techtiv (GT-BTX ) 3.0 2.44 Sulfolane 3.0 2.00 N-methyl pyrrolidone 3.0 1.95 N-formyl morpholine 3.0 1.89 Tri-ethylene glycol 3.0 1.44 Tetra-ethylene glycol 3.0 1.39 Glycol blends (CAROM) 3.0 1.35 No solvent 0 0.57 (α) R.V. = (y A /x A )/(y B /x B ) Page 10
GT-BTX PluS - General Flow Scheme Lean solvent Raffinate Aromatics to downstream fractionation Hydrocarbon Feed Extractive Distillation Column (EDC) Solvent Recovery Column (SRC) Aromatics-rich solvent Page 11
Typical Refinery Configuration with GT-BTX PluS - Products to Gasoline Wide Naphtha Range Hydrotreating Isomerization Gasoline Crude Oil Crude Distillation Kerosene Naphtha Reforming Desulfurization Gasoline Fuel Gasoil FCCU FCC Naphtha GT-BTX PluS Olefinic Raffinate to Gasoline Gasoline Zero Δ in octane value Low benzene Low sulfur Page 12
Typical Refinery Integrated with Aromatics using GT-BTX PluS Wide Naphtha Range Hydrotreating Isomerization Benzene Crude Oil Crude Distillation Kerosene Gasoil Naphtha Reforming Desulfurization Fuel Fuel Aromatics Plant Toluene Xylenes Heavy Aromatics FCCU FCC Naphtha GT-BTX PluS Much preferred to recycling FCC naphtha to catalytic reforming Page 13
Options for FCC C 4 + Olefins Gasoline blending zero change in octane value desulfurized de-benzenized Aromatization BTX, PX Re-cracking C3 = Page 14
Aromatization: Generate BTX from Low Value Streams FCC C4/C5 FCC C6 C8, non-aromatic cut Steam Cracker heavy olefins Dry Gas LPG Aromatics Page 15
Additional Aromatics from FCC C 4 C 8 Olefin Fraction Crude Oil Crude Distillation Wide Naphtha Range Kerosene Gasoil Hydrotreating Naphtha Reforming Desulfurization Isomerization Fuel Fuel Aromatics Plant Benzen e Toluene Xylenes Heavy Aromatics C4-C5 Aromatization C6-C8 FCCU FCC Naphtha GT-BTX PluS More Aromatics from Non-Traditional Feedstock Page 16
Refinery configuration with GT-BTX PluS to facilitate increased Propylene Wide Naphtha Range Hydrotreating Isomerization Fuel Crude Oil Crude Distillation Kerosene Gasoil Naphtha Reforming Desulfurization Fuel Fuel Additional Propylene Olefinic Raffinate FCCU FCC Naphtha GT-BTX PluS Aromatics Extends Range of FCC Naphtha Recycle Page 17
GT-BTX PluS - Enabling Technology Technically advanced extraction process enables Desulfurized gasoline to < 15 ppm sulfur with zero octane loss Reduced benzene in cracked gasoline to < 0.5% benzene FCC olefins preserved for conversion to aromatics or propylene Patented process available through GTC Technology Page 18
Case Study GT-BTX PluS & GT-Aromatization Part of a recent project implemented for Rafinerie Onesti C 4 -C 5 Cut Aromatization Unit Liquid Product LPG + Off Gas Olefinic Raffinate H 2 Off Gas High-severity FCC feed Primary Fractionation C 6- C 8 Cut C 9 -C 10 GT-BTX PluS H 2 Off Gas HDS C 6 -C 10 Aromatics* Heavies Pygas Pygas Selective HDT Pygas C 11 + *Stream is sent to Aromatics Complex for Benzene and Paraxylene recovery Page 19
Incremental Aromatics from Gasoline Source C 6 -C 9 AROMATICS KG/HR TPA INDIGENOUS FCC 11,427 97,126 PYGAS 8,029 68,245 AROMATIZATION 26,525 225,471 TOTAL 45,981 390,842 Total incremental BTX = 320 KTA Page 20
Conclusions Refinery/Petrochemical integration involves more than simple propylene recovery Recycling FCC gasoline to naphtha reforming is not true integration, and misses the main point of process efficiency GT-BTX PluS is the enabling technology which permits the best use of molecules to their highest value Page 21