The UOP Selexol™Selexol™ Process: Efficient Removal in Gasification Value Chain Henry Traylor UOP LLC, A Honeywell Company

2013 Instituto Petroquímico Argentino (IPA) Conference 09 October 2013 Buenos Aires, Argentina

© 2013 UOP LLC. All rights reserved. UOP 6196-1 Honeywell’s Businesses

• $37.6 billion in revenues in 2012, 50% outside of U.S. • Nearly 125,000 employees operating in 100 countries • 19,000 engineers and scientists • Morristown, NJ global corporate headquarters

Performance Automation & Materials & Transportation Aerospace Control Solutions Technologies Systems

UOP 6196-2 UOP Company Profile Serving the Gas Processing, Refining & Petrochemical Industries

Profile — Significant Technology Position Sales: Breakdown Business Units: • Gas Processing and Hydrogen (GP&H) • Process Technology & Equipment (PT&E) Equipment Products • Cataly sts, Adsorbents & Specialties (CA&S) 35% • Renewable Energy and Chemicals (RE&C) Products Equipment Offering: Services 45% • Technology, catalyst & services to the refining, Services Licensing 13% petrochildhemical and gas process iidiing industries Licensing • Supplier of molecular sieve adsorbents to process 7% and manufacturing industries

UOP Facilities — Global Footprint Sal es: Geogr aphi c

Worldwide Headquarters Des Plaines, Illinois (suburban Chicago) Middle East 3,500+ Employees China Asia Pacific 9% 19% 12%

Global South Customers America North 9% America 32% E&A 9% • 20 Offices • 17 Countries India CIS 5% • 12 Manufacturing Facilities UOP Offices UOP Manufacturing Sites 5% • 5 Engineering Centers UOP 6195-3 3 UOP’s Solution in Cleanup

Acid Gas Removal PSA Recovery

Our techn ol ogi es an d pr oducts ar e desi gn ed to deliv er superi or perf orm an ce, safety and value when combined in an integrated system: . High availability and reliability of processes and products . Lower capital expenditure and operating costs resulting in lower cost of production of hydrogen

UOP 6196-4 Syngas Treating with Selexol Process

Sulfur Recovery UOP Tail Power Polysep Gas Membrane Treating

Hydrogen COS UOP Hydrolysis UOP MTO CO Shift Selexol Chemi cal s Synthesis Gas Process

UOP Methanation Substitute Polybed Natural Gas PSA

FT UOP Synthesis Liquids Liquid Upgrading Fuels

UOP 6196-5 Commercial Excellence & Experience

Acquired by Over 110 Invented by Transferred to Union Carbide units in AlliedSignal in ‘50s Dow in ‘01 in ‘90 operations

 Global presence in syngas & natural gas applications  Unique characteristics for syngas applications: ‒ Power (IGCC) ‒ SNG ‒ Chemicals ‒ Hydrogen ‒ Synfuels  Natural gas applications: ‒ Hydrocarbon Gas Dewpoint Control

‒ EOR – High CO2 Content Gas ‒ LNG Peak Shaving – CO2 Removal ‒ Landfill Gas Treating ‒ Biogas

Selexol process… growing footprint in gas cleanup UOP 6196-6 Selexol Process Applications Worldwide

Recent Selexol Applications in Operation

 Sarlux: IGCC power and H2  API: IGCC power

 Coffeyville Energy Resources: H2 and CO2 capture

 SdRidSandRidge: NtNatura l gas CO2 removalfl for EOR

 Nexen: H2, fuel and future CO2 capture

Projects in Construction

 Duke Energy: IGCC power and future CO2 capture

 Southern Company: IGCC power and CO2 capture

UOP 6196-7 Commercial Experience in Gasification

Selexol Syngas Plant StartStart--upup Application Production Unit Duty Flow Feedstock 404 Sarlux IGCC Power 550 MW net MMSCFD Visbreaker 2000 Sulfur Italy H2 Production 40000 Nm³/h @420 Residue psia 169 API IGCC MMSCFD Visbreaker 1999 Power 250 MW net Sulfur Italy @744 Residue psia 151 Coffeyville Ammonia 21 T/h Sulfur & MMSCFD Resources 2000 Petcoke Urea 62 T/h CO @535 USA 2 psia 320 Nexen H Production 337,000 MMSCFD Asphaltene 2008 2 Sulfur Canada & Fuel Gas Nm³/h syngas @ 550 Residue psia

UOP 6196-8 Key Characteristics of Selexol Process

Feature Benefit

• Low Vapor Pressure • Low solvent loss

• Non -fouling • Clean service

• High on-stream efficiency • High availability

• Low equipment count • Lower CAPEX

• Low cooling requirements • Lower OPEX

• Low power requirements • Lower OPEX

• Non-toxic • Safe Operation

Selexol Process… cost effective solution for H2S & CO2 removal UOP 6196-9 Selexol Process Overview

 Absorption/regeneration process for selective removal of H2S, COS, RSH & CO2 – Uses SELEXOLTM physical solvent from Dow Chemical – Uses a typical solvent-extraction flow scheme – Loading directly proportional to partial pressure  Has unique selectivity characteristics that make it attractive for syngas and natural gas applications  Product Quality – Can be essentially sulfur free

– Project specific CO2 capture and quality

– Projjpect specific acid gas H2S concentration

UOP 6196-10 Selexol Process in Syngas Applications Typical Gasification Complex

Typical Raw Syngas

 H2 30 - 50%  CO 30 - 50%  Ar 0.5 - 1%  N2 0.7 - 1.5%

 CO2 5 - 19%  H2S 0.5 - 2%  COS 200-1000 ppmv  Ni & Fe Carbonyls

 HCN, NH3 ... No Shift, CO2 Full Shift or Partial Shift

Coal or PetCoke, Raw Treated Biomass Syngas Selexol Syngas Sour Applications: Gasifier Shift Unit  Power  SNG  Chemicals O2 Tail H2S Gas  Hydrogen  Liquid Fuels Sulfur Air Sulfur  etc Separation Recovery

UOP 6196-11 What is the SELEXOL Process?

 Absorption/regeneration process for selective removal of H2S, COS, & CO2 – Uses a physical solvent – Uses a typical solvent-extraction flow-scheme – Loading directly proportional to partial pressure

Physical vs Chemical Acid Gas gg Chemical Solvent Treated Typical Gas Physical Solvent Gasification Application t Loadin nn

Feed Gas Solve Partial Pressure High Pressure is advantageous

UOP 6196-12 What is the SELEXOL Process?

 A physical solvent – Polyethylene Glycol – Chemical formula: CH3O(C2H4O)nCH3 where n has a specific distribution – A clear fluid that looks like tinted water  RtdbhiRegenerated by changing pressure, t ttemperature or applying a stripping gas  Unique selectivity characteristics desirable for gasification syngas ttitreating:

– H2 ~ 1 :Relative Solubility Data – CO ~ 2.2

– CO2 ~ 76 – COS ~ 175

– H2S ~ 680 Selexol = Selective

UOP 6196-13 Flow-scheme Applications

Two Basic Flow-schemes • Sulfur removal only ‒ Typically for power applications ‒ Can reduce treated gas any desired sulfur level ‒ One sol ven t ab sor ber w ith so lven t regenera tion

• Sulfur removal with separate CO2 removal ‒ Typically for applications producing hydrogen, chemicals, SNG or coal-to-liquids ‒ TilliTypically invo lves more s titringen t pro dtduct specifications ‒ Independent solvent absorbers with integrated soltlvent regenera tion

UOP 6196-14 Two Basic Flow Schemes 1. Selexol for Sulfur Removal Only

 Power applications typically require sulfur removal only to 10 to 20 ppmv. Less than 1 ppmv can be achieved  One solvent absorber with solvent regeneration

Treated Acid Gas H2S Gas Stripper Lean Solution Reflux Filter Accumulator

Sulfur Makeup Water Absorber Reflux Pump H2S Export Feed Concentrator Water Gas

Stripper Reboiler Packinox Exchanger

UOP 6196-15 Two Basic Flow Schemes 2. Sulfur Removal & CO2 Capture Treated Gas Tailored Design  Sulfur in treated gas as low as 0.1 ppmv CO2  Sulfur in CO as low as 2 ppmv Absorber 2  CO2 purity as high as 99.7 mol%  Tuned acid gas composition Acid CO2 H2S Gas Stripper Lean Solution Reflux Filter Accumulator

Sulfur Makeup Water Absorber Reflux Pump Shifted H2S Export Feed Concentrator Water Gas

Stripper Reboiler Packinox Exchanger

UOP 6196-16 Reliability / Availability/ Maintainability

  Scheduled Outage Hrs  Forced Outage Hrs     Availability%  1  100   Period Hours 

 On stream availability >99%  No scheduled maintenance requirement  Reliability is >99%  Failure rate ~1.97 failures/year  Overall Plant availability dependent on gasification block ~80-90%  Outage to on-line  within 2-3 hours  Selexol plant can still be operated with loss of refrigeration at ~50% reduced capacity

UOP 6196-17 Experience with RRfiefinery Feed dtstock

UOP 6196-18 Sarlux S.r.l Italy … Visbreaker Tar

High Purity H2 to Hydrocracker

Steam PolybedTM Electric for PSA Air Power Export

Raw H2 Air O2 Combined PolysepTM Separation Cycle Power Membrane Unit Plant

Purified Syngas

Elemental Feed GifiGasifier GCliGas Cooling Sulfur with Quench & COS Selexol Claus Plant & Scrubbing Hydrolysis

Tail Gas

UOP Technologies UOP 6196-19 API Energia … Asphalt

Electric Power

Combined Steam for Cycle Power Export Plant

Air

O2 N2 Air S eparati on Syngas Unit Expander

Feed- Elemental stock Gasifier Gas Cooling Sulfur with Quench & COS Selexol Claus Plant & Scrubbing Hydrolysis

Tail Gas Treatment & Incinerator

UOP Technologies UOP 6196-20 Coffeyville, US … Petcoke

Air

NH3 Product

N Air Separation 2 Ammonia UAN Plan t UAN Unit Synthesis Product

O2 High Purity H2 Purified CO2 Raw H CO Vent Polybed 2 CO2 2 PSA Purification Raw CO Tail Gas 2

Quench Syngas CO Shift & Selexol Gasification Scrubbing Gas Cooling 22--stagestage

Acid Gas Petroleum Coke Claus Plant

UOP Technologies UOP 6196-21 Summary

 Proven technology, enhanced reliability and availability  Efficient and high overall sulfur recovery  Simple flow schemes & limited number of equipment  Enhanced safety and reduced maintenance  Selexol unit designed to operate even with loss of refrigeration at reduced capacity  Treat gases that other technologies cannot tolerate  Low CAPEX and OPEX  Customizable units

 Facilitates high pressure CO 2 capture  System Integration (CO Shift/COS hydrolysis, synthesis/ Methanation etc.,)  World-Class Technical Support from UOP and Dow Chemical

LiLower cost option for gasification UOP 6196-22 UOP 6196-23