Oxygen Enhanced Reforming:

A Low Capital Cost Retrofit Solution to Debottleneck H2 Plant Production Capacity

Gregory J. Panuccio, Troy M. Raybold, James P. Meagher, Raymond F. Drnevich, and V. Janarthanan
Making Our Planet More Productive

AIChE 2010 Annual Meeting San Antonio, TX March 24th, 2010

Copyright 2010 Praxair, Inc. All rights reserved.

Hydrogen Demand in the Refining Industry

North America Refinery Input1
35.0 34.5 1.45

Sulfur Content, wt%

H2 processing intensity increasing

Hydrotreating Hydrocracking

API Gravity, Degrees

34.0 33.5 33.0 32.5 32.0 31.5 31.0 30.5

1.33

1.21

Additional H2 supply required North America Refinery H2

21

1.09

2
800 750 700 650 600 550 500 450 400 2016

0.97

1985

1990

1995

2000

Refinery H2 Demand, Bscfd

30.0 1980

0.85 2005

19 17 15 13 11 9 7 5 2004

Heavier and more sour crude Stringent sulfur specifications for transportation fuels

Joanne Shore (2002), Refining Challenges: Changing Crude Oil Quality and Product Specifications, World Fuels Conference, Washington, D.C. 2 Oil & Gas Journal, Industry Reports

2006

2008

2010

2012

2014

H2 Processing Intensity, scf/bbl

Solutions for Increasing H2 Supply Capacity

Increase H2 recovery from byproduct sources New dedicated supply
Liquid H2 Build additional SMR

Increase production capacity in existing SMR3

Method Modify WGS Reactor Upgrade Reformer Install Pre-reformer Install OER Install Post-reformer H2 Rate + 3-5% + 5-15% + 8-10% + 10-15% + 20-30% CapEx Medium Medium to High Medium Low High

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

Oxygen Enhanced Reforming

Enrich combustion air with oxygen Two O2 enrichment methods
Pre-mix O2 with sparger Lance O2 directly into combustion zone
4
Syngas to Back-end

Flue Gas to Heat Recovery

Increase fired duty without increasing flue gas flow Additional heat available to increase H2 throughput Little to no effect on steam export rate Works with any style reformer (cylindrical, box, terrace wall, etc.) Continuation of Praxairs proven O2 enhancement technologies (e.g. FCCs, SRUs, and process heaters)
4

Fired Reformer

Reformer Tubes

Burner Fuel Process Feed Lanced O2 Sparged O2 Combustion Air

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

Oxygen Enhanced Reforming

Heat Flux

Heat flux and tube wall temperatures (TWTs) increase in cold end Little to no increase in Max TWT Incremental efficiency higher than baseline 10-15% incremental H2 possible 15-20 tons O2 required per 1 mmscf of incremental H2 Operational flexibility
Tunable incremental output or Turn O2 completely off

OER

Base

Tube Length
Max. OER

TWTs
Base

Low CapEx, simple equipment, simple installation

Tube Length

OER: Sparger v. Lance(s)

Custom designed for each SMR Sparger
Combustion air enrichment
Single penetration One pipe Moderate flame temperature rise

Lance
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 Equipment
Flow Control Skid Oxygen Generation/Storage
Liquid Storage On-site generation (VPSA, Cryo ASU) Pipeline

Oxygen Injection Device

Sparger

Lance

OER Field Testing

Tested at Praxair SMR Cylindrical, up-fired/up-flow reformer PSA for purification Pre-mixed (sparger) and lancing O2 enrichment techniques tested

OER Field Testing

O2 supply and control equipment installed while SMR in operation Single day outage for installation of sparger and lances Simple to uninstall or idle (operational flexibility)

Lance Penetration

Field Test Results

Operating Condition O2 Injection Device H2 Production Rate O2 in Air[1] O2/H2[2], ton/mmscf Natural Gas Feed + Fuel Maximum TWT[3], F Reformer Outlet Temp, F PSA Feed CH4 NOx Emissions[3], lb/mmbtu Base None 100% 20.8% N/A 100% Base Base 4.9% 100% OER Lances 111% 21.9% 22 109% -1 +1 5.6% 88% OER Sparger 110% 22.1% 20 108% +2 +4 5.4% 120%

Stable SMR operation observed 20 to 60 minute transitions

[1] [2]

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

Cost of Incremental H2
OER incremental H2 production cost is competitive
120

100
110

95

108

227

Normalized H2 Cost

100 90 80 70 60 50 Base SMR OER Pre-reformer New SMR

OER 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 times

OER Implementation Process

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

Installation and Start-up

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 O2 supply project start-up 6 to 12 months after contract

Summary
Refinery H2 demand will continue to grow Retrofitting existing SMRs to increase capacity is favorable Oxygen 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