®

Synthesis Gas Purification in Gasification to Ammonia/Urea Plants

Synthesis Gas Purification in Synthesis Gas Purification in Gasification to Ammonia/Urea PlantsGasification to Ammonia/Urea Plants

GASIFICATION TECHNOLOGIES CONFERENCE

October 4-6, 2004Washington D.C

Dave Heaven, John Mak Fluor Enterprises, Inc., Aliso Viejo, California,

Dan Kubek, Mike Clark,Curtis SharpUOP LLC, Des Plaines, Illinois

®

OutlineOutline

Conversion of low valued refinery residue and coke to syngas using gasification is proven and viable for ammonia productionCase studies were conducted to evaluate today’s syngas purification technologies for ammonia and urea productionCompare the process differences between Selexol + PSA to Rectisol + N2 Wash process. Compare their capital and operating costsThe process configuration was adopted in the Coffeyville Resources Ammonia Fertilizer Complex. Operating data of the gas purification unit are reviewed

®

Gas Purification TechnologiesGas Purification Technologies

Technology 1

Rectisol

Methanol solvent operates at very low temperatures. Methanol solvent is H2S selective.

N2 Wash

Fractionation process operates at cryogenic temperatures

Technology 2

Selexol

DMPEG solvent operates at mildly refrigerated or ambient temperatures. Selexol is H2S selective

PSA

Adsorption process operates at ambient temperatures

®

Case StudiesCase Studies

Case 1 - Selexol/ PSA

Case 2 - Selexol/PSA + CO2 production

Case 3 - Rectisol/N2 Wash

Case 4 - Rectisol/N2 Wash + CO2 production

®

SELEXOL/PSA PROCESSSELEXOL/PSA PROCESS

COALGRINDING/

SLURRYPREP

COAL

AIRSEPARATION

PLANT

QUENCHGASIFIERS

CO SHIFT /HEAT

RECOVERY

SULFURPLANT

SYNGASSCRUBBING

AMMONIAPLANT

SULFUR

PSA

SELEXOL

AMMONIA

RAW WATER

CW

HP O2

LP N2

HP N2

TREATEDGAS

STEAM

2000 MTD

2590 MTD

WASTE GAS

AC

ID G

AS

TAIL

GA

S R

ECYC

LE

H2

®

SELEXOL DESIGN WITH CO2 PRODUCTIONSELEXOL DESIGN WITH CO2 PRODUCTION

430 PSIG

900PSIG

170 PSIG

®

CO2 PURIFICATIONCO2 PURIFICATION

®

RECTISOL / N2 WASH PROCESSRECTISOL / N2 WASH PROCESS

COALGRINDING/

SLURRYPREP

COAL

AIRSEPARATION

PLANT

QUENCHGASIFIERS

CO SHIFT /HEAT

RECOVERY

SULFURPLANT

SYNGASSCRUBBING

AMMONIAPLANT

SULFUR

N2 WASH

RECTISOL

AMMONIA

RAW WATER

CW

HP O2

LP N2

HP N2

TREA

TED G

AS

STEAM

2000 MTD

2450 MTD

WASTE GAS

AC

ID G

AS

TAIL

GA

S R

ECYC

LE

H2

CO

2 PUR

GE

REC

YCLE

®

Selexol/PSA Selexol/PSA vsvs Rectisol/N2 WashRectisol/N2 Wash

Rectisol/ NRectisol/ N22 WashWash

Removes all CO2

-80°F (SS Material)

Regen by N2 stripping

Very pure syngas product

CO2 product at low pressure

Selexol/ PSASelexol/ PSA

Partially remove CO2

0° to 40°F (CS Material)

Regen by Steam

Syngas contains ppmlevels of inerts

CO2 product at high pressure

®

Capital Cost ComparisonCapital Cost Comparison

No CO2 Production With CO2 Production

Cost ($1,000) Case 1 Case 3 Case 2 Case 4 Selexol/PSA Rectisol/N2

WashSelexol/PSA Rectisol/N2

WashSelexol Unit 22,862 N / A 22,862 N / APSA Unit 34,342 N / A 34,342 N / ARectisol /N2 Wash Units N / A 100,800 N / A 100,800Balance of Plant (BOP*) 430,080 412,020 434,014 416,990Incremental Capital Costs Base 43,596 0 43,596Incremental BOP Costs Base (18,060) 3,934 (13,090)Incremental Overall Plant Capital Costs

Base 25,536 3,934 30,506

*BOP Cost exclude ammonia synthesis

®

Operating Cost ComparisonOperating Cost Comparison

No CO2 Production With CO2 Production

Cost ($1,000) Case 1 Case 3 Case 2 Case 4 Selexol/PSA Rectisol/N2

WashSelexol/PSA Rectisol/N2

WashGas Purification & BOPFixed Operating Costs 19,430 19,900 19,512 20,174Utility & Feed & Chemicals 52,980 54,360 56,625 59,118Total Annual Oper. Cost 72,410 74,260 76,137 79,292Incremental Oper. Cost:Fixed Operating Costs Base 470 82 744Utility & Feed & Chemicals Base 1,380 3,645 6,138Annual Operating Cost Base 1,850 3,727 6,882

®

Study ResultsStudy Results

Selexol + PSA syngas is more economical than Rectisol + N2

Wash in syngas purification, both in capital and operating costs

Same conclusions apply to different gasification technologies, plant capacities and types of feedstocks

The Selexol + PSA design were applied in the syngas purification process of Coffeyville Resources Coffeyville, Gasification Ammonia Complex for ammonia and urea production

®

Coffeyville ResourcesCoffeyville, Kansas, USAGasification Ammonia Complex

Coffeyville ResourcesCoffeyville, Kansas, USAGasification Ammonia Complex

UOP 2004.05-20

®

Coffeyville Resources Ammonia Fertilizer ComplexCoffeyville Resources Ammonia Fertilizer Complex

Feedstock: 45 MT/H petroleum cokeCommercial Operation: July 2000Process LicensorsGasification: ChevronTexacoGas Purification Block:

- Acid Gas Removal: Selexol- H2 Purification: Polybed PSA

Sulfur: Black & Veatch PritchardAir Separation: BOCAmmonia / UAN: Ammonia Casale / Weatherly

UOP 2004.05-21

®

Coffeyville Block Flow DiagramAirAir

Air SeparationUnit

AmmoniaSynthesis

PolybedPSA

UAN Plant

NHNH3 3 ProductProduct

NN22 UANUANProductProduct

High Purity HydrogenHigh Purity HydrogenOO2 Purified COPurified CO22 2

CO2Purification

Raw HRaw H22 COCO22 VentVent

Raw CORaw CO22Tail GasTail Gas

QuenchGasification

SyngasScrubbing

CO Shift & Gas Cooling

Selexol2-stage

Claus Plant

Acid GasAcid GasPetroleum Petroleum

Coke UOP TechnologiesClausUnit

Coke

UOP 2004.05-24

®

Coffeyville Resources Gasification Ammonia / UAN ComplexCoffeyville Resources Gasification Ammonia / UAN Complex

UOP 2004.05-23

®

Coffeyville Resources SELEXOL and POLYBED PSA UnitsCoffeyville Resources SELEXOL and POLYBED PSA Units

UOP 2004.05-23

®

Coffeyville Resources SELEXOL UnitCoffeyville Resources SELEXOL Unit

UOP 2004.05-23

®

Coffeyville Resources POLYBED PSA UnitCoffeyville Resources POLYBED PSA Unit

UOP 2004.05-23

®

Coffeyville Operations SummaryCoffeyville Operations Summary

Operated since July 2000Operated since July 2000-- Convert pet coke to urea and ammonia using UOP Gas Convert pet coke to urea and ammonia using UOP Gas Purification BlockPurification Block

•• SELEXOL + PSASELEXOL + PSA

SELEXOL ProductsSELEXOL Products PSA ProductPSA Product>90 MM SCFD of raw H>90 MM SCFD of raw H22 HH22 Purity >99.3%Purity >99.3%

< 1 < 1 ppmppm HH22S S < 5 < 5 ppmppm COCO< 1 < 1 ppmppm COSCOS COCO22 below below DetDet. Limits. Limits

>10.6 MM SCFD of CO>10.6 MM SCFD of CO22>93% of CO>93% of CO22 RemovedRemoved

Acid Gas >44 mole % HAcid Gas >44 mole % H22SS

UOP 2004.05-27

®

Coffeyville Operations SummaryCoffeyville Operations Summary

Operated since July 2000Operated since July 2000

•• Highly ReliableHighly Reliable•• No SolventNo Solvent--Related IssuesRelated Issues

•• No reclaimingNo reclaiming•• Minimal Solvent LossesMinimal Solvent Losses

•• Meets All Product SpecificationsMeets All Product Specifications•• HH22 Purity to PSA Purity to PSA •• COCO22 Purity for Urea ProductionPurity for Urea Production•• HH22S in Acid GasS in Acid Gas

UOP 2004.05-27

®

ConclusionsConclusions

Due to high natural gas prices, production of fertilizer products from refinery residue and coal is economically attractive

Coffeyville Resources has proven that UOP SELEXOL plus POLYBED PSA processes are viable for fertilizer production

Fluor and UOP have proven Gas Purification Portfolio for:

– Separation of H2S and CO2

– Separation of CO2 and H2

– Purification of H2

UOP 2004.05-21

®

Synthesis Gas Purification In Gasification Based Ammonia/Urea PlantsSynthesis Gas Purification In Gasification Synthesis Gas Purification In Gasification Based Ammonia/Urea PlantsBased Ammonia/Urea Plants