PACT™ Light Alkanes upgrade to Octane and Aromatics Jens Michael Poulsen Anthony Baldridge 1 NGL production is rapidly increasing million barrels per day 70-75% of Natural Gasoline/C5+ supply historically used as gasoline blendstock Traditional C5+ Use Gasoline Petchem Exports Ethanol denaturing US natural gas plant liquids production, EIA Can traditional outlets absorb the increased C5+ Supply? 2 Excess C5+/Natural Gasoline/Gas Condensate C5+ oversupply forces exports and depress prices U.S. EIA estimates: 60% increase in C5+/natural gasoline supply within the US from 2018 to 2022 with supply continuing to outpace demand Largest Outlets: 1. Gasoline blending. Losing volume and value due to Low Octane (≈70 RON) High RVP (>12 PSIG) Sulfur (100-200 ppmw) 2. Steam cracking. Eroding market for Natural Gasoline due to low (negative) margin vs C2 Saturated markets require export of excess hydrocarbon gas liquids, at depressed prices Traditional outlets are unable to absorb the increased C5+ Supply! 3 A partnership of complementary competences World-class Refiner World-class Catalysts • 14,000 Employees • Research • 65 Countries • Development • No. 23 on Fortune 500 • Manufacturing 4 Joint Development Partnership Iterative Catalyst Design Goal Setting • Well-defined Partnership roles (P66 & HT) and existing strong relations Identify • Frequent iterative feedback loops Catalyst Design Opportunities on all organizational levels (HT) (P66 & HT) • 50 catalyst iterations tested thousands of hours in laboratory and pilot unit (≈1 barrel/day) Data Sharing Catalyst Testing (P66) (P66) Consistent feedback loop by both sides provides improved performance 5 Balancing for Optimal Results Aromatics Light Olefins Fuel Gas Controlling Factors Products • Feed Composition • Conditions • Recycle Streams • Process Design • Catalyst Choice Optimal point(s) depends on specific case (feedstock, product preferences) 6 Catalyst Development & Improvements Desired Product Selectivity Catalyst Deactivation wt% % Conversion Loss/hr. % Conversion MYR-15 MYR-21 MYR-26 MYR-39 MYR-15 MYR-21 MYR-26 MYR-39 Almost 50 catalysts developed and tested. Dramatic catalyst performance improvement from starting point 7 Catalyst Development & Performance Improvements cont’d Conversion wt% Fual Gas Selectivity Target: max. 20% MYR-44 Stacked Bed Conversion (wt%)Conversion 5 C MYR-26 Stacked Bed 12 24 36 48 60 72 84 96 hours Temp. Conversion and selectivity stability achieved 8 P66 and Topsoe jointly developed solution PACT™ Paraffin Activation and Conversion Technology PACT™ BTX ≈ 80 wt% Premium Arom. Octane Gasoline ≈0 100 Octane Reformate Natural Gasoline 70 blendstock Light Naphtha RVP 12 BTX RVP Aromatics Sulfur 4 PSIG +50 ppm Sulfur Diluents 1 ppm PACT™ aromatizes, improves Octane, RVP, and removes Sulfur 9 Not many good options for upgrading Natural Gasoline Steam Catalytic Ref. PACT™ Cracker Aromatization C5/C5+ Feedstock ( ) Feed Flexibility Product Tunability ( ) Fuels Product Low Capital PACT is the most effective and versatile upgrade for Natural Gasoline 10 Development targets set and achieved PACT™ parameter Target Result Single pass conversion >50% 74% Product selectivity >70% 73% Fuel Gas Selectivity ≤20% 14% LPG Selectivity Min. 13% All performance targets are achieved 11 A simple and robust process PACT™ is a simple and robust process using proven process components. Decision at project start. • Conventional process components (heaters, chillers, coolers, separators, exchangers) • Fixed-bed adiabatic Reactors • Standard Compressor Recycle • Standard PSA (for hydrogen recovery) • Regeneration system known from MTG and other coke-forming processes • Easily scalable Process advantages realized through differentiated approach 12 Innovative and patented 2-stage catalyst system C5+/Natural Olefin catalyst Gasoline Feed • Light Olefin Generation • Low Coking Rate Olefin Catalyst Utilizing the adiabatic temperature profile => Aromatics Catalysts MYR high per-pass conversion Catalysts • Olefin conversion • Aromatics Generation • Low Coking Rate Significantly increased pre-pass conversion, reduced coking, longer catalyst life 13 Flexibility of technology to fit Business Cases Feedstock Main Activation step Post-treatment Final product Gasoline No fractionation 87-93 RON RVP 7-9 PSIG Blendstock Once-through Fractionation >100 RON RVP 2-4 PSIG BTX Aromatics >80 wt% Split, select fraction, Pipeline bypass or Recycle Alkylation Diluent reject rest Process tailormade to specific feedstock and product 14 Per-pass conversion % C3 nC4 iC4 C5 C6 30 50 70 80 90 Heavier alkanes have high per-pass conversion and are therefore more likely to be feasible in a once-through process than lighter alkanes which typically require recycle of unconverted feed. High per-pass conversion 15 Product composition (Natural Gasoline, once-through process) Example BTX stream composition wt% Other 11% Paraffins ✓ Rich in methyl-groups: 23% C9 Aro >2 methyl groups/Benzene ring 7% => Value in transalkylation ✓ Toluene + Xylene ≈ 50 wt% Eb 4% ✓ 67 wt% mono-aromatics in liquid product Benzene ✓ 99 wt% of aromatics are mono- Xylenes 6% aromatics 20 wt% ✓ Good diluent for crude oil (bitumen) Toluene 29 wt% 16 BTX product composition (Natural Gasoline, recycle process) Example BTX stream composition wt% Other Hexane 5% 2% Recycle process: C9 Aro Benzene ✓ Unconverted alkanes are recycled 7% 12% and converted Eb 4% ✓ Olefins and naphthenes are recycled and converted Product is: ✓ Rich in methyl-groups: >2 methyl groups/Benzene ring => Value in transalkylation. Xylenes Toluene ✓ Toluene + Xylene ≈ 70 wt% 30 wt% 40 wt% ✓ 90 wt% mono-aromatics in liquid product ✓ 99 wt% of aromatics are mono-aro. ✓ Excellent feedstock for aromatics purification/separation units 17 Recycle vs once-through product composition Natural Gasoline feed example wt% 45 40 Recycle 35 Once-through 30 Recycle process converts 25 more paraffins and olefins to valuable aromatics. 20 15 10 5 0 Toluene Xylenes Benzene C9 Aro Other Eb Hexane Paraffins 18 Product yields Example: Flow Flow Unit Flow Unit Stream % Feed C5+ 100 100,000 kg/h 24,300 bbl/day Products BTX mix/Reformate 66 66,000 kg/h 12,017 bbl/day Hydrogen 6 6,000 kg/h 60 MMSCFD LPG (C3-C4 mix) 8 8,000 kg/h 2,464 bbl/day Fuel gas 20 20,000 kg/h 11.2 MMSCFD *24,300 bbl/day = 100 mt/hour = 840 kmt/yr @ 350 days Minimum 2/3 of product is BTX mix/Reformate 19 Economics of PACT™ BTX Aromatics Example: Investment Example: LPG Fuel gas • Total Investment BTX case 6% 4% Heat Power Catalysts ≈ $180 MM USD* 1% 3% Maintena… 1% • Unit size H2 24,300 bbl/day = 100 mt/h 16% Profitability BTX C5+ Example: 74% 94% • Gross Margin $123 MM/year • Avg. Annual Rate of Return AARR Revenue Expenses ≈ 50% $570 MM $447 MM • Return of investment ≈ 2 years *CAPEX accuracy ±40% Capacity: C5+ feed 24,300 bbl/day = 100 mt/hour = 840,000 mt/yr PACT™ is a profitable solution in many cases 20 Conclusion: PACT™ creates more value from C5+ PACT™ BTX ✓ A simple, robust, flexible, and cost-effective process to ≈ 80 wt% convert C5+ into higher-value, higher-octane aromatic Arom. Octane and sulfur-free products ≈0 100 ✓ High selectivity and yield Octane 70 ✓ Flexible design maximizes options RVP ✓ Integration into existing refinery structure 12 ✓ Downstream processing for octane maximization ✓ Separations for purified streams RVP Sulfur 4 PSIG +50 ppm PACT homepage https://info.topsoe.com/pact Sulfur 1 ppm For more information contact Topsoe, Jens Michael Poulsen, [email protected], phone +45 41 39 03 59 21.