Oxygen Enhanced Oxygen Enhanced Reforming: Reforming: A Low Capital Cost Retrofit Solution A Low Capital Cost Retrofit Solution to Debottleneck Hto Debottleneck H22 Plant Production Plant Production CapacityCapacity

Making Our Planet More Productive

Gregory J. Panuccio, Troy M. Raybold, Gregory J. Panuccio, Troy M. Raybold, James P. Meagher, Raymond F. James P. Meagher, Raymond F. Drnevich, and V. JanarthananDrnevich, and V. Janarthanan

AIChE 2010 Annual MeetingAIChE 2010 Annual MeetingSan Antonio, TXSan Antonio, TXMarch 24March 24thth, 2010, 2010 Copyright © 2010 Praxair, Inc. All rights reserved.

Hydrogen Demand in the Refining IndustryHydrogen Demand in the Refining Industry

•• Heavier and more sour crudeHeavier and more sour crude

•• Stringent sulfur specifications for Stringent sulfur specifications for transportation fuelstransportation fuels

•• HH22 processing intensity increasingprocessing intensity increasing– Hydrotreating

– Hydrocracking

•• Additional HAdditional H22 supply requiredsupply required

1 Joanne Shore (2002), “Refining Challenges: Changing Crude Oil Quality and Product Specifications,” World Fuels Conference, Washington, D.C.

2 Oil & Gas Journal, Industry Reports

30.0

30.5

31.0

31.5

32.0

32.5

33.0

33.5

34.0

34.5

35.0

1980 1985 1990 1995 2000 20050.85

0.97

1.09

1.21

1.33

1.45

AP

I Gra

vity

, Deg

rees

Su

lfu

r C

on

ten

t, w

t%

North America Refinery Input1

5

7

9

11

13

15

17

19

21

2004 2006 2008 2010 2012 2014 2016400

450

500

550

600

650

700

750

800

Ref

iner

y H

2D

eman

d, B

scfd

H2

Pro

cess

ing

Inte

nsi

ty, s

cf/b

bl

North America Refinery H22

Solutions for Increasing HSolutions for Increasing H22 Supply CapacitySupply Capacity

•• Increase HIncrease H22 recovery from byproduct sourcesrecovery from byproduct sources

•• New dedicated supplyNew dedicated supply– Liquid H2

– Build additional SMR

•• Increase production capacity in existing SMRIncrease production capacity in existing SMR33

Method H2 Rate CapEx

Modify WGS Reactor + 3-5% Medium

Upgrade Reformer + 5-15% Medium to High

Install Pre-reformer + 8-10% Medium

Install OER + 10-15% Low

Install Post-reformer + 20-30% High

3 S. Ratan and C.F. Vales (2002), “Improve Your Hydrogen Potential,” Hydrocarbon Processing, 81(3), pp. 57-64.

Oxygen Enhanced ReformingOxygen Enhanced Reforming

•• Enrich combustion air with oxygenEnrich combustion air with oxygen44

•• Two OTwo O22 enrichment methodsenrichment methods– Pre-mix O2 with sparger– Lance O2 directly into combustion zone

•• Increase fired duty without increasing flue Increase fired duty without increasing flue gas flowgas flow

•• Additional heat available to increase HAdditional heat available to increase H22throughputthroughput

•• Little to no effect on steam export rateLittle to no effect on steam export rate

•• Works with any style reformer (cylindrical, Works with any style reformer (cylindrical, box, terrace wall, etc.)box, terrace wall, etc.)

•• Continuation of PraxairContinuation of Praxair’’s proven Os proven O22enhancement technologies (e.g. FCCs, enhancement technologies (e.g. FCCs, SRUs, and process heaters)SRUs, and process heaters)

Sparged O2

Syngas to Back-end

Reformer Tubes

Lanced O2

Flue Gas to

Heat Recovery

Process Feed

Combustion

Air

Fired

Reformer

Burner Fuel

4 R.F. Drnevich et. al. (2006), “Production Enhancement for a Reactor,” US Patent 6,981,994.

Oxygen Enhanced ReformingOxygen Enhanced Reforming

•• Heat flux and tube wall temperatures (TWTs) Heat flux and tube wall temperatures (TWTs) increase in cold endincrease in cold end

•• Little to no increase in Max TWTLittle to no increase in Max TWT

•• Incremental efficiency higher than baselineIncremental efficiency higher than baseline

•• 1010--15% incremental H15% incremental H22 possiblepossible

•• 1515--20 tons O20 tons O22 required per 1 mmscf of required per 1 mmscf of incremental Hincremental H22

•• Operational flexibilityOperational flexibility– Tunable incremental output or – Turn O2 completely off

•• Low CapEx, simple equipment, simple Low CapEx, simple equipment, simple installationinstallation

Hea

t F

lux

OER

Base

Tube Length

TW

Ts

OER

Base

Tube Length

Max.

OER: Sparger v. Lance(s)OER: Sparger v. Lance(s)

•• Custom designed for each SMRCustom designed for each SMR

•• SpargerSparger– Combustion air enrichment

○ Single penetration

○ One pipe

○ Moderate flame temperature rise

•• LanceLance– Combustion zone O2 management

○ Multiple penetrations

○ Adjustable nozzle orientation and O2 flow distribution

○ Staged O2 combustion

○ Increased cool flue gas recirculation within the furnace

OER EquipmentOER Equipment

•• Flow Control SkidFlow Control Skid •• Oxygen Generation/StorageOxygen Generation/Storage– Liquid Storage

– On-site generation (VPSA, Cryo ASU)

– Pipeline

•• Oxygen Injection DeviceOxygen Injection Device

Sparger

Lance

OER Field TestingOER Field Testing

•• Tested at Praxair SMRTested at Praxair SMR

•• Cylindrical, upCylindrical, up--fired/upfired/up--flow flow reformerreformer

•• PSA for purificationPSA for purification

•• PrePre--mixed (sparger) and mixed (sparger) and lancing Olancing O22 enrichment enrichment techniques testedtechniques tested

OER Field TestingOER Field Testing

•• OO22 supply and control supply and control equipment installed equipment installed while SMR in operationwhile SMR in operation

•• Single day outage for Single day outage for installation of sparger installation of sparger and lancesand lances

•• Simple to uninstall or Simple to uninstall or idle (operational idle (operational flexibility)flexibility)

Lance Penetration

Field Test ResultsField Test Results

•• Stable SMR operation observed Stable SMR operation observed –– 20 to 60 minute transitions20 to 60 minute transitions

Operating Condition Base OER OER

O2 Injection Device None Lances Sparger

H2 Production Rate 100% 111% 110%

O2 in Air[1] 20.8% 21.9% 22.1%

O2/H2[2], ton/mmscf N/A 22 20

Natural Gas Feed + Fuel 100% 109% 108%

∆Maximum TWT[3], °F Base -1 +2

∆Reformer Outlet Temp, °F Base +1 +4

PSA Feed CH4 4.9% 5.6% 5.4%

NOx Emissions[3], lb/mmbtu 100% 88% 120%

[1] Equivalent O2 enrichment level for OER cases with lances[2] Corrected for equivalent flue gas flowrate and flue gas O2 concentration[3] Calculated (not measured)

50

60

70

80

90

100

110

120

Base SMR OER Pre-reformer New SMR

Cost of Incremental HCost of Incremental H22

•• OER incremental HOER incremental H22 production cost is competitiveproduction cost is competitive

•• OER installed cost range: $0.5 MM to $1.5 MM dependent onOER installed cost range: $0.5 MM to $1.5 MM dependent on– SMR Size

– Distance between O2 supply and SMR– O2 injection method

•• Low CapEx leads to short payback timesLow CapEx leads to short payback times

No

rmal

ized

H2

Co

st

100 95 108 227

OER Implementation ProcessOER Implementation Process

•• Detailed analysis of SMRDetailed analysis of SMR– Collect design and operating data– Assess current operation and OER retrofit via reconciled process model

•• Installation and StartInstallation and Start--upup– Praxair responsibilities

○ Provide equipment (O2 supply system, flow skid, injection device)○ Manpower for training and support of installation and start-up

– Customer responsibilities○ Conduct safety reviews

○ Prepare equipment sites, pour foundations○ Install equipment, piping and controls

○ Start-up and commission the equipment

•• Liquid or pipeline OLiquid or pipeline O22 supply project startsupply project start--up 6 to 12 months after contractup 6 to 12 months after contract

SummarySummary

•• Refinery HRefinery H22 demand will continue to growdemand will continue to grow

•• Retrofitting existing SMRs to increase capacity is favorableRetrofitting existing SMRs to increase capacity is favorable

•• Oxygen Enhanced Reforming is a good retrofit solutionOxygen Enhanced Reforming is a good retrofit solution– 10 to 15% incremental H2 production capacity

– Low CapEx exposure– Minimal effect on export steam

– Competitive incremental production cost

– High incremental efficiency– Simple equipment, easy to install and operate

– Operational flexibility: tunable incremental rate that can be turned off