RPT L10 Lhoist

1 CONTENTS 2
What we will talk about
› Introduce Lhoist and myself

CHEMICAL REACTOR
ENGINEERING › Use of our materials
FROM INDUSTRIAL FLUE GAS
TREATMENT PERSPECTIVE › Introduction flue gas cleaning
6 December 2023
› Reaction of SO2 with a solid at low temperatures
Dr. Johan J. Heiszwolf
› Reaction of SO2 at high temperatures
› Anti-Fouling Anit-Slagging in Furnace sorbent injection
Gast College KULeuven, Reactor and Procestechnologie: Chemie, B-KUL-T4BRP1, 6 December 2023 Gast College KULeuven, Reactor and Procestechnologie: Chemie, B-KUL-T4BRP1, 6 December 2023
WHO IS THIS GUY JOHAN HEISZWOLF? 3 4
Different companies
› Always in Research and Development
› More than thirty years of experience
› Various reaction systems
› Hydrogen production, Hydrocracking, Desulfurization
› Catalysts and Adsorbents
› Multiphase (GLS) or two phase (GS) reaction systems
› Solid material is key !!!
The Lhoist
› Morphology plays role in reaction
› Mass transport limitations may control Company
› Solids reactants can be engineered!
› Manufacturing of the solid is key
and
› Large scale manufacturing is required
Products
LHOIST COMPANY 5 THE LHOIST PRODUCTS IN ACTION 6
The Lhoist Identity Portfolio of Applications of our Lime and Dolime Products in Industry
› Family-owned company with 135 years of expertise

› We cherish long term relationships with our customers
Quarry in Belgium Rodney Graham Gabriel Orozco Richard Prince Michel François
Lhoist Group Collection The Soldier’s Tree, 1993 Green Ball, 1995 Untitled (Cowboys), 1990 Les joueurs, 1991
Lhoist Group Collection Lhoist Group Collection Lhoist Group Collection Lhoist Group Collection
WE ARE PROUD WE ARE A WE ARE WE ARE OUR PEOPLE

INDUSTRIALISTS FAMILY-OWNED COMPANY DRIVEN BY OUR PIONEERS MAKE IT ALL
CUSTOMERS AND HAPPEN
MARKETS
LHOIST COMPANY WORLDWIDE 7 WHAT IS ARE THE LHOIST PRODUCTS IN TERMS OF CHEMISTRY 8
Global Presence Product Manufacturing
› Our products are near to you
CaCO3 → CaO + CO2 CaO + H2O → Ca(OH)2
› Environmental Applications 20% of sales

9 WHY AND WHERE FLUE GAS CLEANING? 10
Flue gas treatment is a legal requirement to comply with ELV’s
› Removal of pollutants
› Dust, NOx, SOx, HCl, HF, Dioxins, Mercury
› Emissios are regulated by so called BREF (Best Available Techonogly Reference Documents)
› Emission Limit Values (ELV)
› Each pollutant will have an associated ELV
› The ELV is dependent on industry and type of FGT technology installed
› Industries that emit flue gas that requires cleaning
› Power Plants
Flue Gas › Waste to Energy
› Glass
› Steel Industry
Treatment › Secondary Smelters
› Biomass combustion
› Ceramic Industry
CDS : Circulating Dry scrubber CDS : Circulating Dry scrubber

FLUE GAS TREATMENT TECHNOLOGY DSI : Dry Sorbent Injection
11 FLUE GAS TREATMENT TECHNOLOGY DSI : Dry Sorbent Injection
12
FGT : Flue Gas Treatment FGT : Flue Gas Treatment

High level classification of technologies FSI : Furnace Sorbent Injection High level classification of technologies FSI : Furnace Sorbent Injection
WET : Wet scrubber WET : Wet scrubber
› De NOx SDA DSI › Operating Temperatures SDA DSI

› Catalytic over honeycomb catalyst › Different technologies operate with different conditions
› Non catalytic by injection of ammonia in furnace
DRY DRY
› Dedusting
› Electrostatic Precipitator Semi FGT Process Role of Temperature
Semi
› Bag House Filter SCR Water (oC)
Dry CDS Wet Scrubing 60 - 80 Dry CDS
Spray Dry Absorber 140 - 160
› Acid gas control with base Circulating Dry Scrubbers WtE 140 - 160
› Reaction with dry powder Circulating Dry Scrubbers SO2 80 - 100
Bag house filter Frabric 120 - 250
› Liquid phase with slurry Stack
Ceramic filters 300 - 400
Stack
ESP Furnace Sorbent Injection 800 - 1200 ESP

› Micro pollutant control WET WET
› Adsorption with dry powder WET WET
› Often combination of technologies in real plants

13 14
SORBACAL® SPECIALTY PRODUCTS
Problem Solution Mechanism
Acid Gases Sorbacal® SP / SPS / CDS Acid-Base Reaction

Micro Pollutants Sorbacal® Micro Physical Adsorption
Boiler Fouling Sorbacal® Heat Melting Point Increase Reactions
with Acids
ACID BASE REACTION 15 CHEMICAL REACTION DURING SO2 REMOVAL FROM THE FLUE GAS 16
Neutralization forms a salt from the acid and base Gas-Solid Reaction Gives Product Layer Inhibition
› The acid and base › The chemical reaction

› Different strength depending on chemistry › Is a reaction between a gases and a solids
Acid + Base → Salt Ca(OH)2 (S)+ SO2 (G)+ ½ O2 (G) → CaSO4 (S) + H2O (G)
H2SO4 + 2 NaOH → Na2SO4 + 2 H2O › Phenomena during the Gas-Solid reaction

› The solid expands because the difference in molar volume
› The gas reactant has to diffuse through the product layer
› In the liquid phase
› Complex interaction between ions SO2 SO2 SO2
› Chemistry rules the observed reactivity
› Hardly any product differentiation possible Ca(OH)2 CaSO4
› One sulfuric acid molecule (Supplier A) does not react differently than another (Supplier B)
Molar mass = 71.1 (g/mol) Molar mass = 136.1 (g/mol)
Solid Density = 2.24 (g/ml) Solid Density = 2.97(g/ml)
Molar volume = 33 (ml/mol) Molar volume = 46 (ml/mol)
CHEMICAL REACTION DURING SO2 REMOVAL FROM THE FLUE GAS 17 INNOVATIVE ENHANCED HYDRATES 18
Mitigation of Product Layer Effects Sorbacal® SP and SPS proven solutions for the industry
› Surface Area ▪Engineered pore structure

› High surface area → large surface for reaction → high reaction rate ▪ Increased pore volume gives better accessibility to calcium hydroxide surface
› Large surface → thinner initial diffusion layer → higher rate ▪ Reduces blocking of the pores by reaction product
Thick Layer
Thin Layer
Low Surface Area High Surface area

› Pore Volume
› High pore volume ensures accessibility of the surface Local Hydrate Sorbacal® H Sorbacal® SP Sorbacal® SPS
Parameter Local Hydrate Sorbacal® H Sorbacal® SP Sorbacal® SPS
Available Lime (EN-459) 70 - 90 >90 >90 >90 (wt%)
Surface Area (BET) 5 - 15 >20 >40 >38 (m2/g)
Low Pore Volume High Pore Volume Pore Volume (BJH) 0.02 - 0.08 0.1 > 0.2 > 0.2 (ml/g)
Pores blocked Pores open and connected
Fresh reagent not accessible Fresh reagent accessible Particle Size (d 50) 4 - 25 5 - 15 5 - 15 5 - 15 (mm)
Strong diffusion resistance Small diffusion resistance
SO2 removal performance 20 - 50 100 200 220 - 300 (%)
CHEMICAL REACTION DURING SO2 REMOVAL FROM THE FLUE GAS 19 ENHANCED HYDRATE PERFORMANCE IN DSI APPLICATION 20
Mitigation of Product Layer Effects Sorbacal® SP and SPS give better performance in Dry Sorbent Injection (DSI)
› Modification of surface of the hydrated lime Ca(OH)2

› Increase in pore volume and surface area increases SO2 capture. ▪ Lower dosing rates at equal performance ▪ Better acid gas removal at equal dosing
▪ Savings on sorbent consumption ▪ Compliance with regulations
Conclusions
Textural properties affect performance
Higher surface and pore volume boost reaction
Chemical modification adds additional reactivity
21 22
HOW BIG IS A SORBACAL® SP CRYSTAL?
COMPARED TO A HUMAN HAIR?
Engineered A ABOUT THE SAME SIZE

Sorbent & B TEN TIMES SMALLER
C THOUSAND TIMES SMALLER
Laboratory
Testing
23 24
A THOUSAND TIMES SMALLER THAN THE HUMAN HAIR Automated Reactor System
High Throughput testing set-up
Fixed bed reactor w. FTIR analysis
Acid gas reactivity (SO2, HCl, CO2)
Flow rate = 4 L/min
Lhoist Irving Dynamic Adsorption Test

Laboratory (TX) Adsorption capacity for organics
Mercury with speciation
CHEMISTRY DURING COMBUSTION IN THE FURNACE 25 26
Fuel changes in combustion
› Energy generation by combustion of solid fuels
Reaction
Kinetics
Entrained Flow Reactor
Simulation of process conditions Low
Comparison of sorbents
Flow rate = 4 Nm3/hr Temperature
TEMPERATURE DEPENDENCE OF THE REAL REACTION 27 REACTION RATE OF SO2 REACTION WITH HYDRATED LIME 28
How does the reaction rate depend on temperature Measured in an Entrained Flow Reactor with Fixed Stoichiometry
› Arrhenius (1859 – 1927) ▪Strong non-linear dependence of SO2 reaction on temperature

› Nobel prize winner ▪ What is happening here?
› Fundamental law for reaction kinetics
› Arrhenius Law
› Exponential dependence on temperature
𝐸𝐴
𝑟 = 𝑘0 𝑒𝑥𝑝 − 𝑘
𝑅𝑇
𝑘𝑟𝑒𝑓
› Reaction rate
› For first order in A
𝑟 = 𝑘𝐶𝐴 2x
› If Arrhenius law does not hold → apparent reaction rate
› Mass transport limitations (lower EA)
› Change in reaction mechanism
https://en.wikipedia.org/wiki/Svante_ArrheniusGast College KULeuven, Reactor and Procestechnologie: Chemie, B-KUL-T4BRP1, 6 December 2023 Gast College KULeuven, Reactor and Procestechnologie: Chemie, B-KUL-T4BRP1, 6 December 2023
REACTION RATE OF SO2 REACTION WITH HYDRATED LIME 29 THE ROLE OF CARBONATOIN 30
Measured in an Entrained Flow Reactor with Fixed Stoichiometry Completing reactions
▪Strong non-linear dependence of SO2 reaction on temperature › Two competing reactions

Ca(OH)2 (S)+ CO2 (G) → CaCO3 (S) + H2O (G)
I III
▪ Decrease with Temperature ▪ Increase with Temperature Ca(OH)2 (S)+ SO2 (G) + ½ O2→ CaCO3 (S) + H2O (G)
▪ Moisture desorbs ▪ Kinetics increase
▪ Moisture not relevant
𝑘
𝑘𝑟𝑒𝑓 › Have different activation energy
› CO2 reaction proceeds faster at higher temperatures
› CO2 starts to dominate the overall reaction
II 2x IV › Selectivity towards SO2 drops
▪ Constant with Temperature ▪ Decrease with Temperature › Apparent reaction rate shows optimum
▪ Moisture desorbs I II III IV ▪ Kinetics increase › Sweet spot for operation
▪ Kinetics increase ▪ Carbonation dominates
THE ROLE OF WATER ON REACTIVITY 31 THE ROLE OF WATER ON REACTIVITY 32
Evidence by Infrared microscopy on calcium hydroxide particles Evidence by Infrared microscopy on calcium hydroxide particles
› At low temperature adsorbed water is mandatory for reaction › Strong acceleration of moisture at low temperatures
› After reaction proceeds, the surface gets moisturized › Without gas phase moisture nearly no acceleration
› Presence of moisture greatly accelerates reaction
𝑘
𝑘𝑟𝑒𝑓
Ca(OH)2 (S)+ CO2 (G) → CaCO3 (S) + H2O (G)

CIRCULATING DRY SCRUBBERS (CDS) 33 THE ROLE OF WATER 34
High Gas Cleaning Efficiency & High Lime Utilization A versatile (and cheap) catalyst for the CDS process. The more the better!
› Two principal types of CDS processes

› Circulating Fluidized Bed units Effect How
› Conditioning Drum Units
Gas conditioning Water vaporizes, decreasing gas
temperature and increasing relative
› High Acid-Gas Cleaning Efficiency humidity
› Intensive Gas-Solid contacting reactor Circulating Fluidized Bed Process Residue rejuvenation Removes diffusion barrier at the
› Reaction acceleration with water Example from Hamon surface of the sorbent
Reaction Accelerates Gas-Solid reaction via
Enhancement dissolution of acid gas and calcium in
› High Lime Utilization the water layer
› Lime circulates multiple times between reactor and bag filter
› Lime rejuvenation with water
Traditional sorbents have only limited water capacity (3 – 8%)

Conditioning Drum Process more water will cause clogging and flow issues
Example from Luehr
INDUSTRIAL SUCCESS VOESTALPINE DONAWITZ STAHL 35 COMPETING SELECTIVITY OF SO2 AND CO2 AT HIGH TEMPERATURES 36
Linear relationship between FGT performance and residue moisture content

Reaction
› With increased moisture Sorbacal® CDS demonstrated large savings
› Sorbent consumption reduction › Competing reactions for acid species
› Lower pressure drop over bag filter › Both SO2 and CO2 are acids
› They compete for the calcium hydroxide basic sites
Ca(OH)2 + SO2 + ½ O2 → CaSO4 Conclusions

Temperature dependency is very non-linear
Ca(OH) 2 + CO
Moisture 2 → CaCOaccelerates
adsorption 3 the reaction at low temperatures
At high temperatures carbonation becomes dominant reaction
› Activation EnergyEngineered
is not the same
Sorbent allows for higher water uptake
FGT of Sinter Belt Flue Gas › CO2 has different activation energy
Demonstration of Moisture increase › Starts to react faster than SO2
Flow rate = 4 x 100 kNm3/hr › Dominates the lime conversion
Normal Operation
37 FURNACE SORBENT INJECTION (FSI) 38
Additional injection of sorbents into the boiler
› Additional acid gas removal SDA DSI

› Debottleneck the FGT system FSI
› Save on incumbent FGT reagent
› Reduce residue disposal cost DRY
› Improve HF capture
Semi
Reaction › Anti Slagging & Anti Fouling
Dry CDS
› Reduce maintenance cost
Kinetics › Increase efficiency Stack
High CDS : Circulating Dry scrubber

DSI : Dry Sorbent Injection
WET WET
Temperature FGT : Flue Gas Treatment

FSI : Furnace Sorbent Injection
WET : Wet scrubber
REACTION KINETICS FOR FURNACE SORBENT INJECTION 39 REACTION KINETICS FOR FURNACE SORBENT INJECTION 40
High temperature reactions of dual function sorbents High temperature reactions of dual function sorbents
› Capture of SO2 in the furnace is very effective

› High reaction rate (high temperatures Arrhenius)
› Very selective (carbonation cannot take place)
› Creation of highly reactive calcium carbonate
› Proof of high surface area material created shortly after formation
Ca(OH)2 → CaO + H2O
› Rapid SO2 capture
› Reaction rates fasts CaO + SO2 + ½ O2 → CaSO4
High Temperature Reactor
› Calcium carbonate decomposes
› Is not thermodynamically stable CaO + CO2 → CaCO3 → CaO + CO2 Simulation of combustion conditions
Comparison of sorbents
Flow rate = 1 L/min
REACTION KINETICS FOR FURNACE SORBENT INJECTION 41 INDUSTRIAL APPLICATION OF FURNACE SORBENT INJECTION 42
Optimal temperature for high temperature reaction Long term industrial tests
› There exists an optimum temperature for the reaction › ARN BV in Weurt, The Netherlands
› Non-linear behavior of observed reaction rate › Incineration Capacity 290 000 ton
› Anearobic Digestion Capacity 70 000 ton
› Diaper recycling 15 000 ton
› Temperatures < 1000 oC
› Increasing reaction rate › FSI with Sorbacal® Heat
› Reaction increases with Arrhenius › Trial period of six months
𝑘 › Lhoist rental system for injection
𝑘𝑟𝑒𝑓 › Mobile silo
› Temperatures > 1000 oC › Venturi injectors
› Decreasing reaction rate
› Reaction surface sinters
› Calcium sulfate can decompose at high temperature › Injection strategy
› Dosing coupled to SO2 raw gas composition
› Base load low dosing to mitigate fouling
FURNACE SORBENT INJECTION (FSI): CONTROL DYNAMICS 43 FURNACE SORBENT INJECTION (FSI): CONTROL DYNAMICS 44
Industrially Achieved Results Industrially Achieved Results
› Measurement of Acid Gas Reactivity at commercial waste to energy plant › Dynamics of Furnace Sorbent Injection
› Raw gas composition measured with FTIR at high temperature (600 oC) › Start-stop tests carried out in commercial Waste to Energy plant
› Very difficult conditions, high dust, high acid, high temperature › Raw gas composition measured at ESP outlet
› Adaptation of the probe design to allow measurements
› Start-Stop Tests
› Rapid SO2 response time
› 0.5 – 1.5 hour
Automatic Dosing Start-Stop Tests

Full Scale Tests WtE
Reaction Kinetics at high temperature
Flow rate = 140 kNm3/hr
REACTION KINETICS FOR FURNACE SORBENT INJECTION 45 FURNACE SORBENT INJECTION (FSI): SO2 ACID GAS CAPTURE 46
Reactivity at high temperatures 800 – 1200 oC SO2 Industrially Achieved Results
› Industrial reactivity in the furnace › Industrial conditions

› SO2 very high reactivity › Maximum dosing at overstep of SO2 concentration in raw gas CEMS
› Low Stoichiometric Ratio SR › Maintain minimum dosing rate even at low SO2 concentrations
› HCl also reacts
› Less effective than SO2 but significant › Reduction in SO2 and HCl
› 42 and 12 % respectively
› Laboratory reactivity of Sorbents HCl
› Measured at 1000 oC
› For sorbent formulation design
› Custom FSI Sorbacal® Products

› Benchmarked reactivity
› For different anti-fouling action
Laboratory Tests Industrial Tests Start of Dosing

- 4 months +4 months
ENHANCED HYDRATE PERFORMANCE IN DSI APPLICATION 47 48
Sorbacal® SP and SPSConclusions

give better performance in Dry Sorbent Injection (DSI)
Very efficient SO2 removal at high temperaures
Fast reaction rate due to high temperatrures
No competitive reaction with CO2
Industrially demonstrated
Wrap-Up
CDS : Circulating Dry scrubber
FLUE GAS TREATMENT TECHNOLOGY DSI : Dry Sorbent Injection
49 50
FGT : Flue Gas Treatment

High level classification of technologies FSI : Furnace Sorbent Injection
WET : Wet scrubber
› Operating Temperatures SDA DSI

› Different technologies operate with different conditions
› Role of water DRY Conclusions
› Important co-reagent for some FGT
› Not relevant for other FGT systems Reaction acids with lime is very rich in terms of chemistry
Semi Different FGT Technologies have different optimal conditions
FGT Process Role of Temperature
Dry CDS Industrial R&D is done with many partners
Water (oC)
Wet Scrubing Essential 60 - 80
Lime sorbent can be engineered to optimize performance
Spray Dry Absorber Wet --> Dry 140 - 160
Stack
Circulating Dry Scrubbers WtE Very improtant 140 - 160
Circulating Dry Scrubbers SO2 Very improtant 80 - 100
ESP
Bag house filter Frabric Important 120 - 250
Ceramic filters Not important 300 - 400 WET WET
Furnace Sorbent Injection Not relevant 800 - 1200
51 52
Young Engineers in Action

Trials at customers and pilot plants
All over the world
Netherlands Italy
Questions? India
Your Partner for
Environmental Solutions
Czech Republic South Korea


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1 CONTENTS 2

What we will talk about

› Introduce Lhoist and myself

› Anti-Fouling Anit-Slagging in Furnace sorbent injection

WHO IS THIS GUY JOHAN HEISZWOLF? 3 4

› Family-owned company with 135 years of expertise

WE ARE PROUD WE ARE A WE ARE WE ARE OUR PEOPLE

Global Presence Product Manufacturing

› Our products are near to you

CaCO3 → CaO + CO2 CaO + H2O → Ca(OH)2

› Environmental Applications 20% of sales

Flue gas treatment is a legal requirement to comply with ELV’s

CDS : Circulating Dry scrubber CDS : Circulating Dry scrubber

FGT : Flue Gas Treatment FGT : Flue Gas Treatment

› De NOx SDA DSI › Operating Temperatures SDA DSI

ESP Furnace Sorbent Injection 800 - 1200 ESP

› Often combination of technologies in real plants

SORBACAL® SPECIALTY PRODUCTS

Problem Solution Mechanism

Acid Gases Sorbacal® SP / SPS / CDS Acid-Base Reaction

› The acid and base › The chemical reaction

H2SO4 + 2 NaOH → Na2SO4 + 2 H2O › Phenomena during the Gas-Solid reaction

› Surface Area ▪Engineered pore structure

Low Surface Area High Surface area

Parameter Local Hydrate Sorbacal® H Sorbacal® SP Sorbacal® SPS

Available Lime (EN-459) 70 - 90 >90 >90 >90 (wt%)

Surface Area (BET) 5 - 15 >20 >40 >38 (m2/g)

› Modification of surface of the hydrated lime Ca(OH)2

HOW BIG IS A SORBACAL® SP CRYSTAL?

COMPARED TO A HUMAN HAIR?

Engineered A ABOUT THE SAME SIZE

Lhoist Irving Dynamic Adsorption Test

Fuel changes in combustion

› Energy generation by combustion of solid fuels

› Arrhenius (1859 – 1927) ▪Strong non-linear dependence of SO2 reaction on temperature

Measured in an Entrained Flow Reactor with Fixed Stoichiometry Completing reactions

▪Strong non-linear dependence of SO2 reaction on temperature › Two competing reactions

THE ROLE OF WATER ON REACTIVITY 31 THE ROLE OF WATER ON REACTIVITY 32

Ca(OH)2 (S)+ CO2 (G) → CaCO3 (S) + H2O (G)

› Two principal types of CDS processes

Traditional sorbents have only limited water capacity (3 – 8%)

Linear relationship between FGT performance and residue moisture content

Ca(OH)2 + SO2 + ½ O2 → CaSO4 Conclusions

Additional injection of sorbents into the boiler

› Additional acid gas removal SDA DSI

High CDS : Circulating Dry scrubber

Temperature FGT : Flue Gas Treatment

› Capture of SO2 in the furnace is very effective

Industrially Achieved Results Industrially Achieved Results

Automatic Dosing Start-Stop Tests

Reactivity at high temperatures 800 – 1200 oC SO2 Industrially Achieved Results

› Industrial reactivity in the furnace › Industrial conditions

› Custom FSI Sorbacal® Products

Laboratory Tests Industrial Tests Start of Dosing

ENHANCED HYDRATE PERFORMANCE IN DSI APPLICATION 47 48

Sorbacal® SP and SPSConclusions

FGT : Flue Gas Treatment

› Operating Temperatures SDA DSI

Young Engineers in Action