The UOP The UOP SelexolSelexol™ Process: ™ Process: Efficient Acid Gas Removal Efficient Acid Gas Removal in Gasification Value Chainin Gasification Value Chain

The UOP The UOP SelexolSelexol™ Process: ™ Process: Efficient Acid Gas Removal Efficient Acid Gas Removal in Gasification Value Chainin Gasification Value ChainHenry Henry TraylorTraylorUOP LLC, A Honeywell CompanyUOP LLC, A Honeywell Company

in Gasification Value Chainin Gasification Value Chainin Gasification Value Chainin Gasification Value Chain

2013 Instituto Petroquímico Argentino (IPA) Conference

© 2013 UOP LLC. All rights reserved. UOP 6196-1

09 October 2013Buenos Aires, Argentina

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

AerospaceAerospaceAutomation & Automation &

Control SolutionsControl Solutions

Performance Performance Materials & Materials &

TechnologiesTechnologiesTransportation Transportation

SystemsSystemsAerospaceAerospace Control SolutionsControl Solutions TechnologiesTechnologies SystemsSystems

UOP 6196-2

UOP Company ProfileServing the Gas Processing, Refining & Petrochemical Industries

Profile Significant Technology Position Sales: BreakdownProfile — Significant Technology Position

Business Units:• Gas Processing and Hydrogen (GP&H)• Process Technology & Equipment (PT&E)

Catal sts Adsorbents & Specialties (CA&S)

Sales: Breakdown

Products

35%Equipment

• Catalysts, Adsorbents & Specialties (CA&S)• Renewable Energy and Chemicals (RE&C)

Offering: • Technology, catalyst & services to the refining,

h i l d i i d i

Equipment

45%Services

13%

35%Products

Services

Licensingpetrochemical and gas processing industries• Supplier of molecular sieve adsorbents to process

and manufacturing industries

UOP Facilities — Global Footprint Sales: Geographic

Licensing

7%

13%Licensing

UOP Facilities Global Footprint Sa es Geog ap c

Asia Pacific19%

China12%

Middle East9%

Worldwide HeadquartersDes Plaines, Illinois (suburban Chicago)3,500+ Employees

North America

32%

SouthAmerica

9%

E&A 9%

GlobalCustomers

E&A 9%

CIS 5%India5%

UOP OfficesUOP Manufacturing Sites

• 20 Offices• 17 Countries• 12 Manufacturing Facilities• 5 Engineering Centers

3UOP 6195-3

UOP’s Solution in Syngas Cleanup

Our technologies and products are designed to deliver superior performance,

Acid Gas RemovalAcid Gas Removal PSAPSA Sulfur RecoverySulfur Recovery

Ou tec o og es a d p oducts a e des g ed to de e supe o pe o a 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 inLower capital expenditure and operating costs resulting inlower cost of production of hydrogen

UOP 6196-4

Syngas Treating with Selexol Process

SulfurRecovery Tail

GasTreating

PowerPowerUOPPolysep

Membrane

UOPSelexol

COSHydrolysisCO Shift

HydrogenHydrogenUOPMTO

Ch i lCh i lSynthesis Gas

SelexolProcess

CO Shift

UOPPolybed

ChemicalsChemicals

Methanation SubstituteSubstituteNatural GasNatural GasPSA

UOPLiquids

Upgrading

FTSynthesis LiquidLiquid

FuelsFuels

Natural GasNatural Gas

UOP 6196-5

Commercial Excellence & Experience

Invented by Invented by AlliedSignal in ‘50sAlliedSignal in ‘50s

Acquired by Acquired by Union Carbide Union Carbide

in ‘90in ‘90Transferred to Transferred to

Dow in ‘01Dow in ‘01Over 110 Over 110 units in units in

operations operations

Global presence in syngas & natural gas applications Unique characteristics for syngas Unique characteristics for syngas

applications:‒ Power (IGCC)‒ SNG‒ ChemicalsChemicals‒ Hydrogen‒ Synfuels

Natural gas applications:Hydrocarbon Gas Dewpoint Control‒ 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

S dRid N t l CO l f EOR SandRidge: Natural gas CO2 removal for EOR

Nexen: H2, fuel and future CO2 capture

Projects in Construction

Duke Energy: IGCC power and future CO2 captureDuke Energy: IGCC power and future CO2 capture

Southern Company: IGCC power and CO2 capture

UOP 6196-7

Commercial Experience in Gasification

PlantPlant StartStart--upup ApplicationApplication ProductionProductionSelexol Selexol

Unit DutyUnit DutySyngas Syngas

FlowFlow FeedstockFeedstock404

Sarlux IGCCItaly 2000 Power

H2 Production550 MW net40000 Nm³/h Sulfur

404 MMSCFD

@420 psia

Visbreaker Residue

169API IGCC

Italy 1999 Power 250 MW net Sulfur

169 MMSCFD

@744 psia

Visbreaker Residue

151CoffeyvilleResources

USA2000 Ammonia

Urea21 T/h62 T/h

Sulfur & CO2

151 MMSCFD

@535 psia

Petcoke

NexenCanada 2008 H2 Production

& Fuel Gas337,000

Nm³/h syngas Sulfur

320 MMSCFD

@ 550 psia

Asphaltene Residue

UOP 6196-8

Key Characteristics of Selexol Process

• Low solvent loss• Low Vapor Pressure

Feature Benefit

• Clean service

• High availability

• Non -fouling

• High on-stream efficiency High availability

• Lower CAPEX

High on-stream efficiency

• Low equipment count

• Lower OPEX

• Lower OPEX

• Low cooling requirements

• Low power requirements

• Safe Operation• Non-toxic

Selexol Process… cost effective solution for H2S & CO2 removalUOP 6196-9

Selexol Process Overview

Absorption/regeneration process for selective removal of H2S, COS, RSH & CO2

– Uses SELEXOLTM physical solvent from Dow ChemicalUses SELEXOL 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 syngasand natural gas applicationsProduct Quality

– Can be essentially sulfur free

– Project specific CO2 capture and quality

– Project specific acid gas H2S j p g 2concentration

UOP 6196-10

Selexol Process in Syngas ApplicationsTypical Gasification ComplexTypical Raw Syngas H2 30 - 50% CO 30 - 50%

Typical Gasification Complex

Ar 0.5 - 1% N2 0.7 - 1.5% CO2 5 - 19% H2S 0.5 - 2%

COS

CO2No Shift, Full Shift or Partial Shift

COS 200-1000 ppmv Ni & Fe Carbonyls HCN, NH3 ...

Coal or PetCoke,Biomass

Treated Syngas

Raw Syngas

Gasifier SourShift

Selexol Unit

Partial Shift

Applications:

O2 H2S

Shift

Tail Gas

Unit Power SNG Chemicals Hydrogen Liquid Fuels

SulfurAir Separation

Sulfur Recovery

Liquid Fuels etc

UOP 6196-11

What is the SELEXOL Process?

Absorption/regeneration process for selective removal of H2S, COS, & CO2

– Uses a physical solventUses a physical solvent– Uses a typical solvent-extraction flow-scheme– Loading directly proportional to partial pressure

Physical vs Chemical

g

AcidGas

nt L

oadi

ng Chemical SolventPhysical Solvent

GasTreatedGas Typical

Gasification Application

Partial Pressure

Solv

en

FeedGas

Partial Pressure

High Pressure is advantageousUOP 6196-12

What is the SELEXOL Process?

A physical solvent– Polyethylene Glycol Dimethyl Ether

Chemical formula:– Chemical formula: CH3O(C2H4O)nCH3 where n has a specific distribution

– A clear fluid that looks like tinted waterR t d b h i t tRegenerated by changing pressure, temperature or applying a stripping gasUnique selectivity characteristics desirable for gasification

t tisyngas treating:– H2 ~ 1 :Relative Solubility Data– CO ~ 2.2– CO2 ~ 76– COS ~ 175

H S 680– H2S ~ 680Selexol = 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

O l t b b ith l t ti‒ One solvent absorber with solvent regeneration

• Sulfur removal with separate CO2 removalSulfur removal with separate CO2 removal‒ Typically for applications producing hydrogen,

chemicals, SNG or coal-to-liquidsT i ll i l t i t d t‒ Typically involves more stringent product specifications

‒ Independent solvent absorbers with integrated l t tisolvent regeneration

UOP 6196-14

Two Basic Flow Schemes1. Selexol for Sulfur Removal Only

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

regeneration

H SAcidTreated

Lean SolutionFilter

H2SStripper

RefluxAccumulator

GasTreated

Gas

SulfurAbsorber Reflux

PumpH2SConcentrator

ExportWaterFeed

MakeupWater

StripperReboiler

Concentrator

PackinoxExchanger

WaterFeedGas

Exchanger

UOP 6196-15

Treated

Two Basic Flow Schemes2. Sulfur Removal & CO2 Capture

CO2

TreatedGas Tailored Design

Sulfur in treated gas as low as 0.1 ppmv Sulfur in CO as low as 2 ppmv

H SAcid

2Absorber

CO

Sulfur in CO2 as low as 2 ppmv CO2 purity as high as 99.7 mol% Tuned acid gas composition

Lean SolutionFilter

H2SStripper

RefluxAccumulator

GasCO2

SulfurAbsorber Reflux

PumpH2SConcentrator

ExportWater

MakeupWater

ShiftedFeed

StripperReboiler

Concentrator

PackinoxExchanger

WaterFeedGas

Exchanger

UOP 6196-16

Reliability / Availability/ Maintainability

1001%

HoursPeriodHrsOutageForcedHrsOutageScheduledtyAvailabili

On stream availability >99% No scheduled maintenance 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

hhours Selexol plant can still be operated

with loss of refrigeration at ~50% reduced capacityreduced capacity

UOP 6196-17

Experience with Experience with R fi F d t kR fi F d t kRefinery FeedstockRefinery Feedstock

UOP 6196-18

Sarlux S.r.l Italy … Visbreaker Tar

Steam

High Purity H2to Hydrocracker

PolybedPolybedTMTM

ElectricPower

Raw H2

Steamfor

ExportAir

PolybedPolybedPSAPSA

PolysepPolysepTMTM

MembraneMembraneO2 Air

Separation Unit

Air Separation

Unit

Combined Cycle Power

Plant

Combined Cycle Power

Plant

G C liG C liElemental

G ifiG ifi

Purified Syngas

Gas Cooling& COS

Hydrolysis

Gas Cooling& COS

HydrolysisSulfurFeed

Claus PlantClaus PlantGasifier

with Quench& Scrubbing

Gasifierwith Quench& Scrubbing

SelexolSelexol

Tail GasTail Gas

UOP 6196-19UOP TechnologiesUOP Technologies

API Energia … Asphalt

CombinedCombinedCycle Power Cycle Power

Pl tPl t

Electric Power

Steam for Export

Ai S tiAi S ti

PlantPlantp

O2 SyngasSyngasN2

Air

Air Separation Air Separation UnitUnit

Feed Elemental

Syngas Syngas ExpanderExpander

GasifierGasifierwith Quenchwith Quench& Scrubbing& Scrubbing

Feed-stock Gas CoolingGas Cooling

& COS& COSHydrolysisHydrolysis

SelexolSelexol Claus PlantClaus Plant

ElementalSulfur

Tail GasTail GasTreatment &Treatment &IncineratorIncinerator

UOP TechnologiesUOP TechnologiesUOP 6196-20

Coffeyville, US … Petcoke

Air SeparationAir Separation AmmoniaAmmoniaN2UAN Pl tUAN Pl t

NH3 Product

UAN

Air

Air SeparationAir SeparationUnitUnit SynthesisSynthesis UAN PlantUAN Plant UAN

Product

O2 High Purity H2 Purified CO2Raw

PolybedPolybedPSAPSA

Tail GasRaw CO2

COCO22PurificationPurification

CO2 VentH2

QuenchQuenchGasificationGasification

SyngasSyngasScrubbingScrubbing CO Shift & CO Shift &

Gas CoolingGas CoolingSelexolSelexol22--stagestage

Tail Gas

Petroleum Coke Claus PlantClaus Plant

Acid Gas

UOP 6196-21UOP TechnologiesUOP Technologies

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 Treat gases that other technologies cannot tolerate Low CAPEX and OPEX

Customizable units Facilitates high pressure CO capture Facilitates high pressure CO2 capture System Integration (CO Shift/COS

hydrolysis, Methanol synthesis/ Methanation etc.,))

World-Class Technical Support from UOP and Dow Chemical

L iLower cost option for gasification

UOP 6196-22

UOP 6196-23