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Praxair’s Modular Syngas Generator

Energy Frontiers International

Gas-to-Market and Energy Conversion Forum

Omni William Penn Hotel, Pittsburgh, PA

October 21 – 23, 2014

OTM

Outline

Background

Oxygen Transport Membrane (OTM) based Syngas Generation

OTM Panel Arrays

Demonstration System

Scale-up

Greenfield Methanol

Gas to Liquids

Next Steps

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1995

2005

2014

Praxair Ceramic Membranes History

Several breakthroughs in the last two years

Syngas Alliance Formed / Dissolved

BP In-License For O2/N2

Robust new materials developed

Fundamental reliability

improvement demonstrated

OTM Combined Reforming

Demonstrated

StarGenTM commercialized

3

Reactively Driven Oxygen Transport Membranes

Oxyfuel combustion at high pressure without ASU and air compression

50-400 psi

typical

Oxygen

Flux

Fuel Air

Tube cross-section

Ceramic Membrane Function Ceramic Membrane Structure

Porous support Active layers

Porous support Active layers

4 4

Praxair’s OTM Syngas Technology

Robust materials avoid “killer

problems” from 2003 program

Pressure inside tubes avoids

expensive vessels and internals

Conventional reforming requires

– Separate SMR and/or ATR & ASU

OTM Combined Reforming

– SMR + ATR + ASU in a single package

Optimized OTM configuration for GTL

O2-

Heat OTM

(with catalyst)

Low

Pressure

Air

Steam + NG Syngas

Partially

Reformed

Feed

Depleted Air

Reformer

Reforming

Catalyst

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Recent Membrane Progress

• Improved substrate • Stable chemistry • Better thermal match • Improved manufacturing process

Gen.1 Gen.2 • 2X increase in O2 flux • 4X increase in creep life • 10X reduction in degradation Membrane Membrane

Membranes achieve early commercialization targets

6 6

Test Systems Developed

Successful integration of membranes into systems

Successful multi-module syngas

production

■ Operating with 3 panel arrays (108

OTM tubes)

■ Representative commercial process

elements

■ Multiple successful heating / cooling

cycles

■ Capacity up to 190 Nm3/hr syngas

Modules have shown excellent

operational flexibility

■ 13 Modules tested (>200 OTM

tubes)

■ More than 4,700 hrs of flux testing

■ >25 module thermal cycles

■ Ceramics robust to thermal and

chemical cycling

Single Tube Testing Module Testing System Testing

Membranes can deliver

requirements of the process

■ Flux and fuel conversion

demonstrated

■ >20,000 hrs over 25 tubes

■ Focus on Gen 2 membrane

characterization at high

pressure

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Combined Reforming with OTM Panel Array

OTMs

Reformers

NG + Steam

to reformers

Product

Syngas

Successful transition to improved process and hardware configuration

membranes

reformer

panel array

structured catalyst

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Panel Array Operation

Combined Reforming Demonstrated at Panel Level

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Demonstration Reactor

Successful transition to panel array modules with combined reforming

Panel Array Modules:

– Successful integration and operation in

NG/steam/secondary reformer mode

– 3 panel arrays (108 OTM tubes)

– Approximately 17,500 scfd syngas (4200 scfd

NG) produced at 100 psig

Development System Operation

Hot Standby Light-Off Controlled Run

No O2/C

control

Building

Pressure

Controlled

Run

Transition to

standby

R-07 R-08 R-09 R-10 R-11 R-12

R-14

PI-2125

FI-695

8:00 AM 9:00 AM 10:00 AM 11:00 AM 12:00 PM 1:00 PM 2:00 PM 3:00 PM 4:00 PM 5:00 PM

Time

Demonstration System Startup 10-14-14

NG

/Ste

am

0 t

o 4

50

scf

h

Syst

em P

ress

ure

0

– 1

10

psi

g

Tub

es

85

0 –

10

00

C

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Panel Array Scale-Up

Single Array

(Development)

Double Array

(Small-scale syngas)

Quad Array

(Medium-scale syngas)

Capacity: 4X 4X

5,000 scfd NG 20,000 scfd NG 80,000 scfd NG Feed per panel

Furnace Design and Scale-up

Scale up simplified by replication of standard elements, modules

Panel Array

Modular Furnace Design

Furnace “Pack”

Furnace “Train”

Ceramic and Reformer

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Saint-Gobain Ceramics Manufacturing

Focus on high-volume ceramics meeting cost targets

Experienced world class ceramic

manufacturer

Competencies in critical areas:

– Ceramic powder manufacturing

– Industrial ceramic component

manufacturing

– SOFC development experience

Development Subcontract

– Currently supplying membranes,

seals, and ceramic subassemblies

Saint-Gobain Furnace Investment

Sealed OTM assemblies

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Greenfield Methanol Economics

Joint evaluation with multiple third parties

Plant capacities: 1000 – 3000 metric tons/day

Benefits of OTM versus current alternatives

– OTM vs SMR

• 11% reduction in NG consumption

• 40% reduction in CO2 emissions

• 11% reduction in capital investment

– OTM vs combined reformer (SMR + ATR)

• Comparable NG consumption

• No ASU required

– Compelling economic advantage

• 20% increase in net income

• 4% increase in project returns

Efficiency of a combined reformer without need for an O2 plant

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Gas-to-Liquids (GTL) Segmentation

OTM could significantly improve economics of small GTL

Project Size Large Small Micro

Liquids Production, bpd 5,000-150,000 500 – 5,000 50 – 500

Financial drivers Monetize Remote

gas NG / Oil Spread

Waste / Problem

Gas

NG Feed From: Large / Remote

Gas field

Pipeline or multiple

wells Associated Gas

NG Feed Rate, MMSCFD >50 5 – 50 0.5 – 5

Project Viability Making money,

Huge investment

Capex challenge,

Case by case

Not economical

with current tech

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Benefits of OTM for GTL

Liquid

Synthesis

FT Liquids ATR, POx

or SMR

ASU

NG

Off-Sites*

■ Syngas is a bottleneck

– 60% of project capex

– Poor scaling below 1500 BBL/d

– Extensive site work

– Requires syngas conditioning

With Current Technology

Liquid

Synthesis

FT Liquids

OTM

ASU

NG

Off-Sites*

With OTM

Better yield, lower capital & power by 1 step reforming & air separation

■ OTM Benefits

– No ASU

– Process and equipment simplification

– Modular design, shop construction

– Minimal site work

– Repeatable elements, modules

– Higher quality syngas

– 30% lower capex at 1000 BBL/d vs ATR +

ASU

Praxair Business Confidential 17

Modular Concept for GTL

OTM Syngas Train -100 double panels

-Air preheater

-Burner

-Mixed Feed PH

-Steam superheater

Cooling Train -PG Boiler

-Steam Drum

-NG Preheater

-Prereformer / Desulfurizer

-BFW heater

-ID/FD fan package

OTM Syngas Pack

(10 Panels)

Skid Modules: 8 ft (W) x 9.5 ft (H) x 53 ft (L)

North American Intermodal

-Train

-Truck

-Ship

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Next Steps

Demonstration System

– Continue testing of prototype commercial-scale OTM panels

– Demonstrate safe, reliable and robust operation

– Optimize control schemes

Commercialization

– Develop supply chain for panel and pack fabrication

– Execute DOE sponsored 750,000 scfd OTM system at National Carbon

Capture Center

• Start-up scheduled for early 2016

– Evaluate opportunities to demonstrate OTM based GTL

• Discussions underway with third parties

• Tentative on-stream 2017

Building momentum for commercialization

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More work is needed, but future looks promising

Natural Gas OTM

• Diesel

• Methanol

• Synthetic Crude

• Gasoline

Step change improvements in syngas technology are on the way

Acknowledgements

This material is based upon work supported by the Department of Energy under Award Number DE-FE26-07NT43088. Neither the United States Government nor any agency thereof, nor any of their employees, makes any warranty, express or implied, or assumes any legal liability or responsibility for the accuracy, completeness, or usefulness of any information, apparatus, product, or process disclosed, or represents that its use would not infringe privately owned rights. Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States Government or any agency thereof. The views and options of authors expressed herein do not necessarily state or reflect those of the United States government or any Agency thereof.

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