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Project 1481

Ash Behavior in E-Gas Gasification Systems Training Workshops

Presented to:

Reliance Industries Ltd.

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Presentation Overview Agenda for Workshop

Microbeam – description of company

Capabilities

Databases

Tools – Analysis, testing, mechanisms, and modeling

Workshop goal and objectives

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Subject Areas

1. Fuel impurities and measurement

2. Impurity transformations in gasification systems

3. Impurity transport and deposit growth in gasification systems

4. Managing/predicting ash behavior in gasifiers and syngas coolers

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Day 1. Workshop Overview and Subject Area 1. Fuel impurities and measurement

900 Introductions

930 Workshop Overview

1030 WS - 1 - Fuel Impurities: Fuel impurities - abundance and forms in Fuels

11:30 WS - 2 - Fuel Impurities Measurement: Fuel impurities - Methods of measurement – Overview

1230 Lunch

1330 WS - 3 - Standard methods of Measurement - Standards for analyzing fuel impurities

1430 WS - 4 - Advanced methods (minerals) - Scanning electron microscopy and x-ray diffraction

1530 Break

1600 WS - 5 - Advanced analysis (organic bound) - Chemical Fractionation

1730 WS - 6 - Review literature on subject area -- Discussion/Questions

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Day 2. Subject Area 2: Impurity transformations in gasification systems

900 Introductions

930 WS - 7 - Mineral forms - Thermal properties of mineral phases

1030 WS - 8 - Organic impurity forms - Thermal properties of organically associated elements

1130 WS - 9 - Gasification process - Partitioning impacts - slag formation/deposit growth

1230 Lunch

1330 WS - 10 - Impurity transformations-coarse ash particle formation and coalescence - coarse particle formation

1430 WS - 11 - Impurity transformations-fine particle formation through release of organically associated elements and vaporization/condensation

1530 Break

1600 WS - 12 - Impurity transformations-ultrafine particle formation - Homogeneous and heterogeneous condensation

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Day 3. Subject Area 2: Impurity transformations in gasification systems (continued)

900 Introductions

930 WS - 13 - Ash particle size composition - Particle size composition distribution (PSCD) of ash

1200 Lunch

1300 WS - 14 - Fuel type Impacts on PSCD - Impacts of coal rank and fuel properties

1500 Break

1530 WS - 15 - Review literature on subject area 2

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Day 4. Subject Area 3: Impurity transport and deposit growth in gasification systems

900 Introductions

930 WS - 16 - Intermediate Transport - Ash particle and vapor phase transport mechanisms

10:30 WS - 17 - Bonding phases/flow behavior - Chemistry and physical properties of phases responsible for ash bonding/sticking/flow

1200 Lunch

1300 WS - 18 - Corrosion layer - Steel/Alloy corrosion processes

1500 Break

1530 WS -18 - Continued

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Day 5. Subject Area 3: Impurity transport and deposit growth in gasification systems (Continued)

900 Introductions

930 WS - 19 - Ash particle sticking mechanisms - Sticking mechanisms - surface and particle properties - deposit growth

1030 WS - 20 - Initial layer composition - Impacts of vapor phase species on initial layers

1200 Lunch

1300 WS - 21 - Ash particle sticking -- Particle properties

1500 Break

1530 Discussion/ Questions

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Day 6. Subject Area 3: Impurity transport and deposit growth in gasification systems (Continued)

900 Introductions

930 WS - 22 - Sintering processes - General sintering processes in gasifiers

1030 WS - 23 - Sintering processes - high temp Sintering with reactive liquids - silicate based sintering/crystallization

1200 Lunch

1300 WS - 24 - Sintering processes - Low temp Sintering with less reactive liquids - sulfide and halogen based sintering

1500 Break

1530 WS - 25 - Sintering processes - Gas/Solid Sintering with less reactive liquids - pore filling - molecular cramming

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Day 7. Subject Area 3: Impurity transport and deposit growth in gasification systems (Continued)

900 Introductions

930 WS - 26 - Deposit thermal properties - Heat transfer through deposits - Dependency on deposit properties

1030 WS - 27 - Development of a captive surface -- Deposit surface properties - sintering liquid phase formation - slag flow behavior

1200 Lunch

1300 WS - 28 - Review literature on subject area -- Literature in this area will be provided and reviewed

1500 Break

1530 General discussion – review of key chemical and physical process important to managing/predicting

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Day 8. Subject Area 4: Managing/predicting ash behavior in gasifiers and syngas coolers

900 Introductions

930 WS - 29 - Past evolution of PC and CFB - Fuel type impacts on system design - Gasifier/syngas coolers

1030 WS - 30 - Ash formation -- Models to predict the particle size composition distribution in gasification systems

1130 WS - 31 - Slag flow -- Models to predict the flow behavior of ash/slag (T250, T80, TCV)

1230 Lunch

1330 WS - 32 - Transport models -- Models to predict the transport of ash particles to surfaces

1500 Break

1530 WS - 33 - Growth/sintering - Models to predict ash particle sticking behavior/growth/strength development

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Day 9. Subject Area 4: Managing/predicting ash behavior in gasifiers and syngas coolers (continued)

900 Introductions

930 WS - 34 - Deposit thermal property -- Models to predict deposit thermal properties

1030 WS - 35 - Integrated models -- Application of combustion system models to gasification - CFD based

1130 WS - 36 - Simplified integrated models - Advanced indices for gasifiers/syngas coolers

1230 Lunch

1330 WS - 37 - Deposit shedding - Impacts of fuel properties and operating parameters

1500 Break

1530 WS - 38 - On-line cleaning -- Force required to remove deposit - peak impact pressure

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Day 10. Subject Area 4: Managing/predicting ash behavior in gasifiers and syngas coolers (continued)

900 Introductions

930 WS - 39 - On-line cleaning - Effectiveness of soot blower, horn, pulse detonation, thermal shock etc

1030 WS - 40 - Additives to manage fouling - Overview of additives such as clays, bauxite, kaolinite, magnesium oxide etc

1130 WS - 41 - Synthetic slag formulations - Synthetic slags to optimize slag flow and minimize ash deposition

1230 Lunch

1330 WS - 42 - Laboratory methods -- Laboratory support for Reliance Gasification Technologies

1500 Break

1530 WS - 43 - Review literature on subject area

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Microbeam Technologies Inc. Commercial spin-off from the University

of North Dakota

Mission Provide advanced combustion and

gasification system analysis and consulting services to minimize the impact of fuel impurities on combustion and gasification system performance

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Experience Base Conducted over 1480 projects for utilities, coal

companies, power system developers, and research organizations worldwide since 1992

Advanced tools to predict the impacts of fuel impurities on gasification and combustion system performance

Analysis of fuels, fly ash, corrosion products, deposit characteristics ~10,000 samples

Behavior of inorganic components in combustion and gasification systems

Characterization and optimization of system operating conditions

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Experience – Plant Performance Fuel properties – Coal (brown to anthracite), petroleum (coke and

fuel oils), biomass (wood, grasses…), waste wood (hog fuels), waste paper

Sorbent properties – limestone attrition and reactivity testing

Plants

Combustion – PC, cyclone, fluid bed

Air pollution control systems – NOx (staging, SNCR, SCR), SO2/SO3 (SDA, WFGD, DSI), particulate (ESP, FF), Mercury (oxidation, sorbents)

Gasification – entrained flow, fixed bed, fluid bed, transport reactors

Advanced systems – chemical looping

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Examples of Recent Projects Cyclone fired combustion systems

Impacts of NOx reduction strategies on slag flow, ash partitioning (particulate loading), fouling/slagging

Fuel properties – fuel selection and blending

Entrained flow gasification

Synthetic slag formulations for Pet coke fired slagging gasifiers

Syngas cooler fouling

Pulverized coal fired systems

Blending to manage fuel properties

Slag deposit strength for ash handling systems

Particulate control – ash resistivity and cohesivity

Fluidized bed combustion

Small scale combustion testing - Ash properties – pH and leachability

Bed agglomeration management for pet coke, biomass, waste combustion

Mercury control

Impacts of oxidizing agents – Hg capture and corrosion issues

Additives for reduction of fine particulate and deposit formation

Roadmap – Technology applications for the ND lignite industry

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Microbeam Capabilities Fuel characterization techniques

Computer-controlled scanning electron microscopy

Chemical fractionation

Deposit/slag characterization techniques

Morphology

Scanning electron microscopy point count – viscosity/porosity

High temperature equipment

Slag flow

Refractory corrosion testing – static and dynamic testing

Pilot and full-scale testing equipment

Syngas cooler fouling simulator

Deposit recovery

Limestone attrition and reactivity testing

Plant performance assessment

Sampling fly ash (impactors/filters), slag, deposits

Modeling and predictive methods

Viscosity versus temperature for slag

Predictive indices for slag flow, ash deposition, ash handling, particulate control

Training

Impacts of fuel properties on plant performance

Advanced analysis methods to analyze fuels and associated materials

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Workshop Goal and Objectives Goal is to provide Reliance Industries personnel with a

fundamental understanding of the behavior of ash-related materials that will facilitate reliable and efficient operation of the E-Gas gasification system.

Objectives include providing the following information

Detailed workshop summary document

Copies of slides used in the lectures

Presentation of lectures on specific topics

Research papers and other reports.

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Fuel Properties

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1. Initial Fuel

Coal

Wood (waste, bark, chips,

saw dust), sunflower hulls,

Rice hulls, corn stover,

Bagasse, switch grass,

Yard waste,

Cl, P

Na+,K

+

Amorphous

silica

Biomass Petroleum Coke

Transformations – Fuel Impurities

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Ash formation during Oil/Petcoke Conversion

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Oil Ash Particle Size Distribution Miller and Linak, 2002

Transport Mechanisms

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Ash Transport to Heat Transfer Surfaces

The transport of intermediate ash species (inorganic vapors, liquids, and solids) is function of:

State and size of the ash species

System design – burner type, heat transfer surface configuration

System conditions such as gas flow patterns, gas velocity, and temperature

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Ash Transport Mechanisms

eddy

Sticking

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Heat transfer

surface

Ash

Fe0

Fe0

Fe0

Fe0

Fe0

Fe0

Fe0

Fe0

Fe2+

Fe0

Fe0

Fe2+

Fe2+

Fe2+

S2-

S2-

S2-

S2-

S2-

Growth – Bonding Phases

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Ash intermediate transport and deposition

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Vapor phase

Homogeneous

condensation

Heterogeneous

condensation

Na

S

Cl

K

P

Fe

Ni

Zn

SO2

SO3

Aerosols

(0.02 – 0.2 µm)

Fuel Impurity Derived

Materials from Combustion

Process – Vapors, liquids,

and solidsQuartz

Clay

Pyrite

Calcite

Organic Ca

Coalescence

Fragmentation

shedding

Steel Tube

Corrosion and bonding

layer - Gas-solid reaction

Sulfide rich layer

Layered Deposit Transport Process Ash Intermediates – gas liquid and solid

Diffusion

Thermophoresis

Inertial Impaction

Sintered layer - Gas-solid reaction, molecular

cramming-expansion due to reaction of S with

Deposited particles,

Ostwald ripening

Sulfate coated particles and sulfate pore filling

SO2/

SO3

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Bonding/Sticking Phases P

ha

se

Ab

un

da

nce

1200 ºF

FeS (1810 ºF)

ZnS (>1450 ºF)

Na-FeS (~1380 ºF)

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Sintering – strength development

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Viscosity versus temperature for day 2 ash

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Significant strength would develop at temperatures above 1900 ºF. The materials would flow at about 2200 ºF

Measured T250 – 2045 ºF

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Sintering

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Transport of Particles <5 µm – Forming the Initial Deposit Layers

Benson and others, 1993

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Formation of Deposit Outer Layers Via Inertial Impaction and Capture Due to a Captive Liquid Phase

Benson and others, 1993

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Transport of particles <5 µm, forming the initial deposit layers

Steel Tube

(T = 540°C/1000°F)

Fly Ash and

Products of Combustio

n

T gas= 2000°F

V gas= 25 ft/

sec

Vapor-Phase and

Small-Particle Diffusion

Flue Gas Boundary Layer,

Particle Size <5 mBenson and others, 1993

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Sticking Probability – ash

particle size

Huang and others, 1996

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Transport and sticking of inner sinter layer or

intermediate layer of the deposits

Fly Ash and

Products of Combustio

n

Rebounding Particles

Liquid in Deposits Due to

Temperature IncreaseBenson and others, 1993

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Formation of deposit outer layers via inertial impaction and capture due to a captive liquid phase

Molten Captive Surface

Benson and others, 1993

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Captive surface

Amorphous material filling spaces between fly ash particles

Melting, assimilation, and chemical interactions

Captive surface

Benson and others, 1993

Thermal Properties

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Effect of temperature and ash properties on thermal conductivity

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The ash materials A, B, C, and D represent ash materials of varying composition. Ash A has sodium content of 5% The slag – was molten The particles – not sintered – represents the boundaries for thermal conductivity

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Deposit Strength and Porosity Kaliazine and others, 1997

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Mechanism of Heat transfer and deposit growth

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Ni and Others*

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Slag formation and Flow

Partitioning

Impurities

Gas, liquid, solid

Impurity Transport

Diffusion, Thermophoresis

Inertial Impaction

Impurity materials

Interaction

Refractories

Metals

Impurity

accumulation

Growth

Sintering

Flow

Impurity

Accumulation

Thermal behavior

Strength

Heat transfer

surface

Ash

Fe0

Fe0

Fe0

Fe0

Fe0

Fe0

Fe0

Fe0

Fe2+

Fe0

Fe0

Fe2+

Fe2+

Fe2+

S2-

S2-

S2-

S2-

S2-

Syngas

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Slag Layer Thickness Calculation

Solid Slag

Liquid Slag

Twall

T250

Tsurface, gas

Vapors, fine, and non-impinging particles

Heat Flux- Volatiles and Char Gasification

XT = k • (Tgas – Twall) / H

Assim Slag

Xs = k • (T250 – Twall) / H

TAssim Xa = k • (Tgas – Tassim) / H

Xl = XT - Xa - Xs

Syngas Cooler Wall

Slag Layer Formation Model Solid Slag Liquid Slag

Twall T250 Tsurface, gas

Impingement Rate (char + ash particles)

Gas

Slag Flow

xi

viscosityi

Shear forcei = density • g • xi

Slag flow ratei = Sheari • xi / Viscosityi

Deposition rate = Ash impingement rate • sticking fraction

Sticking fraction = 0 for viscosity > log10 5.5 poise 0 to 1 for viscosity log10 5.5 -250 poise

Accumulation rate = Deposition rate – Slag flow rate

Slag flow rate = density • average(Slag flow ratei )

Heat Flux- Volatiles and Char Combustion

Gasifie

r Wall

Modeling Ash Behavior

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Partitioning

Impurities

Gas, liquid, solid

Impurity Transport

Diffusion, Thermophoresis

Inertial Impaction

Particle Sticking

Coefficients

Deposit

Accumulation

Surface sticking

Coefficient

Growth/Erosion

Heat Transfer

Thermal/mechancial

properties

Growth/shedding

Impinging Flow

Non-Impinging Flow

Processes – chemical,

physical properties and

thermal mechanical

behavior

Algorithms to predict the

size and composition

distribution of the ash

Fuel composition

Size, composition, type,

and abundance of mineral

grains

Abundance of organically

associated elements

Viscosity Calculations –

Particle size fractions

High temperature sintering

processes

Viscosity, surface tension,

particle size, time

Porosity/density

Tensile Strength

Thermal conductivity

Low temperature (<800 ºC)

Sulfide/halogen bonding

Warn Gas

Filter