Refractory DevelopmentsDevelopments for Gasification

Patrick StephanJune 8, 2015

TABLE OF CONTENTS

Saint-Gobain Background

Refractories Background

Refractories for Gasification

Refractory Developments

The Future of Refractories for Gasification

2

KEY FIGURES

Present inSales

countriesbn€

More than

employeesProduction sites

employees

Almost

sales outletsof saleson the habitat market

One of the world’s

most innovative companies*

*Source: Thomson Reuters3

REFRACTORIES BACKGROUND

4

REFRACTORY CHEMISTRY

Al2O3- high melting T, chemically inert2 3 g g ySiO2- cheap and abundant, structurally goodMgO basic steel ind strMgO- basic, steel industryCaO- good low T properties, usually mixedZrO2- high melting T, good insulatorCr O corrosion / abrasion resistantCr2O3- corrosion / abrasion resistantSiC- high heat transfer, abrasion resistant

Sourced from mined clays and minerals, or chemically derived

REFRACTORY MANUFACTURING

Pressing

Casting

Fusion Casting

ExtrusionExtrusion

processing may be similar after forming… processing may be similar after forming

REFRACTORY TYPES

Bricks and Special Shapes

Castables (Cements & Mortars)

Plastics (Ramming)

Fib (Bl k t t ) Fibers (Blankets, etc.)

Ramming Mixes and Loose Fill Powders

Chromia-Alumina Brick Shapesp

Castables & Monolithics

BRICKS & SHAPES V. CASTABLES

Bricks & Shapes CastablesShaping limits - +Shaping limits - +Size limits - +D iDensity + -Erosion ++ -Volume Stability + -Manuf. Quality + -yInstall Quality + --Drying & Curing ++ --Drying & Curing ++ --Cost - +

Process RisksFrom a refractory standpoint:

High temperature excursions High temperature excursions

Rapid thermal cycles

Chemical instability, contamination

Slagging parameters Slagging parameters

Expansion stresses

Water / steam leaks

Improper curingp p g

… can lead to forced shutdowns, expensive maintenance hot spotsexpensive maintenance, hot spots, and worse…

DEFINITION

Refractories are ceramic materials that are able to contain high temperature processes by providing thermal, structural, chemical, and corrosion barriers for a variety of industrial applications.

REFRACTORIES FOR GASIFICATION

13

TECHNICAL DESIGN

PROPERTY TRADE-OFFS

C O

AlAl22OO33 -- CrCr22OO33 -- ZrOZrO2 2 systemsystemCr2O3

Corrosion resistance ZC900

(slag, glass)

ZC60

ZC750

ZC60

ZC400

ZrO2Al2 O3

CC12

ZC400

ZrO2Thermal shock

resistanceHot

mechanical

Al2 O3

strength

THERMAL CYCLING

Rapid changes in operating t t ( 100 d Ctemperature (>100 degC per hour) cause increased mechanical stresses crackmechanical stresses, crack growth, and spalling.

Care must be taken when heating and cooling aheating and cooling a refractory lining. A controlled schedule must be followed.

(Source: DOE ARC presentation GTC 2002)presentation, GTC 2002)

ACCURATE PREDICTIONS

MICROPROBE MAPPING – INFILTRATED HOT ZONE

Selective penetration of the elementselements

Deep penetration of Ca, Si, MgConcentration of V, Fe, Mg in

surface layer ~ 1 2 mmsurface layer ~ 1-2 mm

18

DENSE LAYEROPTICAL & ELECTRONIC SlagOPTICAL & ELECTRONIC MICROSCOPY

g

Dense Cr-V-Mg-O

SEM/EDS: dense layer/refractory interface

Dense Cr-V-Mg-O

Refractory

Optical microscopy: slag/dense layer/Refractory

Dense Cr V Mg O

Optical microscopy: slag/dense layer/Refractory

R f t

No sign of microcracks in the dense layer or hot face

No spallingRefractory p g

19

PETCOKE SLAG ANALYSES

REFRACTORY DEVELOPMENTS

21

REFRACTORY ASSESSMENT PROGRAM –PRODUCT DEVELOPMENT

Lab performance tests II• Infiltration kinetics• Structural stability

Pilot Production • Industrial feasibility• Mix validation

(compared to lab

Test panel withcustomer• Performance in

operations

Performance evaluation• Corrosion

resistance prod

uct

mer

cial

s• Structural stability (compared to lab

results!)operations

• Several monthsresistance

• Thermal shockresistance

alua

ted

pfo

r com

mpe

ratio

ns

Fina

l eva

Rea

dyf op

F

RESEARCH & DEVELOPMENT OF NEW MATERIALS

Initial Performance Improvement

RunHours

5000

6000

7000

8000

9000

35%

1000

2000

3000

4000

5000

0

1000

1 2Old New

C.R.E.E. R&D CenterCavaillon, France

Northboro R&D Center Massachusetts, USA

,

EXAMPLES OF REFRACTORY DEVELOPMENTS

Transition from alumina monolithics to fired shapes

Saint-Gobain patents related to addition of zirconia

DOE ARC NETL development of phosphate additions to Cr2O3 DOE ARC NETL development of phosphate additions to Cr2O3

DOE ORNL studies on MgO aluminate spinels

Frauenhofer Institute studies on SiC/AlN refractories

GE Gen II Advanced Refractoryy

THE FUTURE OF REFRACTORIES FOR GASIFICATION

25

HEXAVALENT CHROMIUM CONCERNS

Indication in MSDS

Measurement according NF EN 689 France8h VME (mg/m3)

USA (ACGIH)8h TWA (mg/m3)

N ifi d tNon specific dust-Total dust-Respirable dust

105

103Respirable dust 5 3

Chromium (hexavalent compound) 0.05

Chromium (hexa) soluble in water 0.05( )

Chromium (hexa) insoluble 0.01

Raw Material Prices

1200

1400

Chromite1

Soda Ash2

800

1000

or T

onne

Soda Ash2

Fused Alumina3

Calcined Alumina4

400

600

SD P

er T

on o

2 per. Mov. Avg. (Chromite1)

2 per. Mov. Avg. (Soda Ash2)

200

400US

2 per. Mov. Avg. (Fused Alumina3)2 per. Mov. Avg. (Calcined Alumina4)

0May-05Mar-06Jan-07Nov-07Sep-08Jul-09May-10Feb-11Dec-11Oct-12

DateSource – Industrial Minerals magazine

RAW MATERIAL VOLATILITY

ALTERNATIVE SOLUTIONS

What else can be done in the field of thermal management?

More matching of refractory qualities to life by zone More matching of refractory qualities to life by zone

Non-chromia containing refractories

Fused cast refractories? Composites? Coatings?

Thin membrane refractory barriersy

Systems with no refractories

B tt l t t t f lid f d it Better slag treatment for solid feed units

Coal beneficiation

MAIN CONSIDERATIONS

Always weigh cost vs. performancey g p

Manufacturability

Raw material availability

Slag compatibility

CHANGES IN GASIFICATION TECHNOLOGY

Traditional Process Evolution

Hydrogen economy – smaller, distributed units

Biomass gasification/pyrolysis

Plasma gasification

Domestic waste processesDomestic waste processes

Hazardous waste processesHazardous waste processes

Thank You!