Recent Selexol Recent Selexol TM TM , PolySep , PolySep TM TM and PolyBed and PolyBed TM TM Operating Experience with Operating Experience with Gasification Gasification for Power and Hydrogen for Power and Hydrogen Daniel J. Kubek, Curtis R. Sharp, & Douglas E. Kuper Daniel J. Kubek, Curtis R. Sharp, & Douglas E. Kuper UOP LLC, Des Plaines, Illinois, USA UOP LLC, Des Plaines, Illinois, USA Michael E. Clark Michael E. Clark UOP LLC, Houston, Texas, USA UOP LLC, Houston, Texas, USA Maurizio Di Dio & Michael Whysall Maurizio Di Dio & Michael Whysall UOP NV, Antwerp, Belgium UOP NV, Antwerp, Belgium Gasification Technologies 2002 Gasification Technologies 2002 27 27 - - 30 October 2002 30 October 2002 San Francisco, California, USA San Francisco, California, USA UOP GTC-01
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Operating Experience with Operating Experience with GasificationGasificationfor Power and Hydrogenfor Power and Hydrogen
Daniel J. Kubek, Curtis R. Sharp, & Douglas E. KuperDaniel J. Kubek, Curtis R. Sharp, & Douglas E. KuperUOP LLC, Des Plaines, Illinois, USAUOP LLC, Des Plaines, Illinois, USA
Michael E. ClarkMichael E. ClarkUOP LLC, Houston, Texas, USAUOP LLC, Houston, Texas, USA
Maurizio Di Dio & Michael WhysallMaurizio Di Dio & Michael WhysallUOP NV, Antwerp, BelgiumUOP NV, Antwerp, Belgium
Gasification Technologies 2002Gasification Technologies 200227 27 -- 30 October 2002 30 October 2002 San Francisco, California, USASan Francisco, California, USA
UOP GTC-01
Technologies for Synthesis Gas TreatmentTechnologies for Synthesis Gas Treatment–– SELEXOL ProcessSELEXOL Process -- Acid Gas RemovalAcid Gas Removal
–– POLYSEP Membrane SystemPOLYSEP Membrane System -- HH22 Recovery and HRecovery and H22/CO /CO AdjustmentAdjustment
–– POLYBED PSA SystemPOLYBED PSA System -- HH22 PurificationPurification
Case Study:Case Study:Refinery Hydrogen & Power ProductionRefinery Hydrogen & Power Production–– Gasification of Refinery ResiduesGasification of Refinery Residues
for Hydrogen and Powerfor Hydrogen and Power–– Benefits of High Purity HydrogenBenefits of High Purity Hydrogen
for Hydrotreaters & Hydrocrackersfor Hydrotreaters & Hydrocrackers•• Existing unitsExisting units•• Grass root unitsGrass root units
ConclusionsConclusionsUOP GTC-03
Selexol ProcessSelexol Process
Cyclic absorption/regeneration process for Cyclic absorption/regeneration process for selective removal of Hselective removal of H22S, COS, & COS, COS, & CO22
Uses a physical solventUses a physical solvent{Chemical formula CH{Chemical formula CH33O(CO(C22HH44O)O)nnCHCH33 where n is between 3 & 9}where n is between 3 & 9}
55 operating units in syngas and natural gas 55 operating units in syngas and natural gas serviceservice
UOP GTC-04
PolySep Membrane SystemPolySep Membrane SystemGasGas--permeable hollow fiber polymer membranespermeable hollow fiber polymer membranesConcentration (or Recovery) of HConcentration (or Recovery) of H22 and adjustment of and adjustment of syngas Hsyngas H22/CO ratio/CO ratioSeparation based on difference in permeation rates Separation based on difference in permeation rates between Hbetween H22 and impurities (Hand impurities (H22 is fast)is fast)Partial pressure difference Partial pressure difference across membrane provides across membrane provides driving forcedriving forceSupplied as a skidSupplied as a skid--mounted mounted systemsystem~ 40 operating units~ 40 operating units
Multiple vessels containing adsorbentMultiple vessels containing adsorbentImpurities adsorbed at high partial pressureImpurities adsorbed at high partial pressureImpurities desorbed at low partial pressure to Impurities desorbed at low partial pressure to regenerate bedregenerate bedHH22 recovered at high purity (typically 99 to recovered at high purity (typically 99 to 99.9999 vol%)99.9999 vol%)Supplied as a skidSupplied as a skid--mounted systemmounted system~ 700 operating units~ 700 operating units
Farmland Gas Purification BlockFarmland Gas Purification Block
Operating ResultsOperating ResultsRaw HRaw H22 from Selexol unit to PSA unitfrom Selexol unit to PSA unit–– > 93 mole % H> 93 mole % H22–– < 5 mole % CO< 5 mole % CO22–– < 1 ppm H< 1 ppm H22S & < 1 ppm COSS & < 1 ppm COS
High Purity HHigh Purity H22 product from PSA to ammonia syngas loopproduct from PSA to ammonia syngas loop–– 90 MM SCFD High Purity H2 (> 99.9%)90 MM SCFD High Purity H2 (> 99.9%)–– 90 % hydrogen recovery90 % hydrogen recovery
Raw CORaw CO22 from Selexol unit to COfrom Selexol unit to CO22 purification reactorpurification reactor–– 10.6 MM SCFD Raw CO2 (> 95 mole %)10.6 MM SCFD Raw CO2 (> 95 mole %)–– < 1 ppm H< 1 ppm H22S & < 10 ppm COSS & < 10 ppm COS
UOP GTC-17
Case StudyCase StudyRefinery Gasification Complex for Refinery Gasification Complex for
Hydrogen & Power ProductionHydrogen & Power Production
UOP GTC-18
Case Study: Refinery Gasification ComplexCase Study: Refinery Gasification Complexfor Hydrogen & Power Productionfor Hydrogen & Power Production
ScopeScopeGasification complex converts Petroleum Coke to SyngasGasification complex converts Petroleum Coke to SyngasUses low value (or negative value) feedUses low value (or negative value) feedPower, steam, and hydrogen produced for export back to Power, steam, and hydrogen produced for export back to the refinerythe refinery–– Production of ultra high purity hydrogen ( > 99.9 mole % Production of ultra high purity hydrogen ( > 99.9 mole %
HH22) for hydroprocessing units) for hydroprocessing units–– Removal of CORemoval of CO22 stream for sequestration and dilution of gas stream for sequestration and dilution of gas
turbine feed (> 98 mole % COturbine feed (> 98 mole % CO22))–– Removal of concentrated HRemoval of concentrated H22S stream to Claus (35 to 65 mole S stream to Claus (35 to 65 mole
% H% H22S)S)
UOP GTC-19
Case Study: Refinery Gasification ComplexCase Study: Refinery Gasification Complexfor Hydrogen & Power Productionfor Hydrogen & Power Production
ProductsProducts–– 500 MW electricity500 MW electricity–– 80 MM SCFD Ultra High Purity H80 MM SCFD Ultra High Purity H22
–– SteamSteam–– COCO22
UOP GTC-20
Process TechnologiesProcess TechnologiesGasificationGasificationCOS HydrolysisCOS Hydrolysis** on unshifted Syngas to Gas Turbineon unshifted Syngas to Gas TurbineCO Shift on Syngas to HCO Shift on Syngas to H22 PurificationPurificationGas Purification BlockGas Purification Block–– Acid Gas RemovalAcid Gas Removal UOP Selexol (2UOP Selexol (2--stage)stage)–– HH22 Purification: Purification: 99.9 % H99.9 % H22 with PSAwith PSA
95.0 % H95.0 % H22 with Methanatorwith Methanator
Claus UnitClaus Unit* requirement depends on split between power & H* requirement depends on split between power & H22 productionproduction
Case Study: Refinery Gasification ComplexCase Study: Refinery Gasification Complexfor Hydrogen & Power Productionfor Hydrogen & Power Production
oror
UOP GTC-21
Case Study: Refinery Gasification ComplexCase Study: Refinery Gasification Complexfor Hydrogen & Power Productionfor Hydrogen & Power Production
Study of HStudy of H22 Purity Purity -- Options ConsideredOptions ConsideredOption 1:Option 1:–– Single stage of CO shift with “partial” COSingle stage of CO shift with “partial” CO22
removalremoval–– PSA with 99.9 mol% HPSA with 99.9 mol% H22 puritypurity
Option 2:Option 2:–– Two stages of CO shift with “complete” COTwo stages of CO shift with “complete” CO22
removalremoval–– Methanation with 95 mol% HMethanation with 95 mol% H22 puritypurity
UOP GTC-22
Case Study: Option 1 Case Study: Option 1 -- PSA SystemPSA System
RawRawHH22 PolyBed
PSA
High High Purity HPurity H22
NN22 / CO/ CO22DiluentDiluent
PSAPSATail GasTail Gas
1-Stage CO Shift & Gas
Cooling
Treated Treated UnshiftedUnshifted
SyngasSyngas
Air Separation Unit
COS Hydrolysis & Gas CoolingGasifier with
Quench & Scrubbing
NN22
OO22
Steam for ExportSteam for Export
FeedFeed
AirAir
Acid GasAcid Gas
Tail GasTail Gas
Combined Cycle Power
Plant
Claus Plant
ElementalElementalSulfurSulfur
Electric PowerElectric Power
NN22
SELEXOL2-stage
UOP GTC-23
Case Study: Option 2 Case Study: Option 2 -- MethanatorMethanator
Low Low Purity HPurity H22
Methanator
RawRawHH222-Stage CO
Shift & Gas Cooling
Treated Treated UnshiftedUnshifted
SyngasSyngas
Air Separation Unit
COS Hydrolysis & Gas CoolingGasifier with
Quench & Scrubbing
NN22
OO22
Steam for ExportSteam for Export
SELEXOL2-stage
FeedFeed
AirAir
Acid GasAcid Gas
Tail GasTail Gas
Combined Cycle Power
Plant
Claus Plant
ElementalElementalSulfurSulfur
Electric PowerElectric Power
NN22
UOP GTC-24
Advantages of High Purity HAdvantages of High Purity H22 in in Refinery HydrotreatingRefinery Hydrotreating
Advantages of 99.9 % HAdvantages of 99.9 % H22 over 95 % Hover 95 % H22
Minimize capital cost of new hydroprocessing Minimize capital cost of new hydroprocessing unitsunitsMinimize operating costs by extending catalyst Minimize operating costs by extending catalyst life life -- by as much as 100%by as much as 100%Increase throughput of existing unitsIncrease throughput of existing units
UOP GTC-25
Advantages of High Purity HAdvantages of High Purity H22 in in Refinery HydrotreatingRefinery Hydrotreating
Advantages of PSA over MethanationAdvantages of PSA over MethanationPSA removes CO and COPSA removes CO and CO22 to ppm levelsto ppm levelsCO ShiftCO Shift–– 11--stage required for PSAstage required for PSA–– 2 to 3 stages required for Methanation2 to 3 stages required for Methanation
COCO22 Slip in Selexol UnitSlip in Selexol Unit–– PSA allows higher slip (%) since it is not sensitive to CO + PSA allows higher slip (%) since it is not sensitive to CO +
COCO22 levels in feedlevels in feed–– Methanation requires low slip (ppm level) since CO + COMethanation requires low slip (ppm level) since CO + CO22
levels levels >> 1.5 % cause excessive temperature exotherm1.5 % cause excessive temperature exothermPSA can remove NPSA can remove N22 and Ar and Ar -- thus Othus O22 purity is not criticalpurity is not critical
UOP GTC-26
Benefits of 99.9% PSA HBenefits of 99.9% PSA H22 vs. 95% vs. 95% Methanator HMethanator H22 for Existing Unitsfor Existing Units
Existing Hydrotreater #1Existing Hydrotreater #1Basis:Basis: 40,000 BPD operating with 95% makeup H40,000 BPD operating with 95% makeup H22
Benefit:Benefit: 30 vs. 17 month cycle resulting in $500,000/yr30 vs. 17 month cycle resulting in $500,000/yrlower annualized turnaround costlower annualized turnaround cost
Existing Hydrotreater #2Existing Hydrotreater #2Basis:Basis: 16,500 BPD operating with 95% makeup H16,500 BPD operating with 95% makeup H22
Benefit:Benefit: 5 vs. 3.5 year cycle resulting in $100,000/yr5 vs. 3.5 year cycle resulting in $100,000/yrlower annualized turnaround costlower annualized turnaround cost
UOP GTC-27
Benefits of 99.9% PSA HBenefits of 99.9% PSA H22 vs. 95% vs. 95% Methanator HMethanator H22 for Existing Unitsfor Existing Units
Existing HydrocrackerExisting HydrocrackerBasis:Basis: 44,500 BPD operating with 90% makeup H44,500 BPD operating with 90% makeup H22
from Methanator and Platforming net gasfrom Methanator and Platforming net gas
Benefit:Benefit: 4 vs. 3 year cycle resulting in $1.2 million/yr4 vs. 3 year cycle resulting in $1.2 million/yrlower annualized turnaround costlower annualized turnaround cost
oror
Equivalent cycle length and 8% more feedEquivalent cycle length and 8% more feedresulting in $3 million/yr higher profitresulting in $3 million/yr higher profit
UOP GTC-28
Benefits of 99.9% PSA HBenefits of 99.9% PSA H22 vs. 95% vs. 95% Methanator HMethanator H22 for Grass Roots Unitsfor Grass Roots Units
Grass Roots HydrotreaterGrass Roots HydrotreaterBasis:Basis: Hydrotreater for UltraHydrotreater for Ultra--Low Sulfur DieselLow Sulfur Diesel
Production Production -- 5 ppm Sulfur Product,5 ppm Sulfur Product,50,000 BPD capacity designed for 95%50,000 BPD capacity designed for 95%makeup Hmakeup H22
Benefit:Benefit: Equivalent cycle length with 160 psi lowerEquivalent cycle length with 160 psi lowerdesign pressure resulting in 13% lowerdesign pressure resulting in 13% lowercapital cost capital cost -- an $8 million savingsan $8 million savings
UOP GTC-29
UOP Gas Purification Block ConclusionsUOP Gas Purification Block ConclusionsSarlux & Farmland Units DemonstrateSarlux & Farmland Units Demonstrate
UOP Gas Purification Block optimizes acid gas UOP Gas Purification Block optimizes acid gas removal and hydrogen purificationremoval and hydrogen purificationSelexol, PolySep Membrane, & PolyBed PSA are well Selexol, PolySep Membrane, & PolyBed PSA are well suited for gasification servicesuited for gasification serviceHigh overall sulfur recovery (> 99.75%)High overall sulfur recovery (> 99.75%)High HHigh H22S concentration in acid gas to Claus unitS concentration in acid gas to Claus unitBulk COBulk CO22 removal if necessaryremoval if necessaryVery stable operationVery stable operationMinimal operator attention requiredMinimal operator attention required
UOP GTC-30
CoCo--production of Power & High Purity Hproduction of Power & High Purity H22using PolySep Membrane and PolyBed PSAusing PolySep Membrane and PolyBed PSA
in a Refinery Gasification Complexin a Refinery Gasification ComplexHigh Purity HHigh Purity H22 for Existing Hydroprocessing Unitsfor Existing Hydroprocessing Units–– Extension of cycle time to reduce OPEX for HydrotreaterExtension of cycle time to reduce OPEX for Hydrotreater–– Extension of cycle time or increase in capacity for Extension of cycle time or increase in capacity for
HydrocrackerHydrocracker
High Purity HHigh Purity H22 for Grass Roots Hydroprocessing Unitsfor Grass Roots Hydroprocessing Units–– Reduction in CAPEX & OPEX for HydrotreatersReduction in CAPEX & OPEX for Hydrotreaters–– Similar benefit for HydrocrackersSimilar benefit for Hydrocrackers
UOP Gas Purification Block ConclusionsUOP Gas Purification Block Conclusions