Dry Sorption in Ceramic Industry - Rheinkalk

Rheinkalk
Information
Flue gas treatment with
dry sorption systems in the
ceramic industry
3/04
QUALICER 2004 - World Congress on Ceramic Tile Quality
Castellón/Spain, 7. - 10. March 2004
Olivier Barthe (Balthazard & Cotte, Grenoble)
Dr.-Ing. Burkhard Naffin (Rheinkalk GmbH, Wülfrath)
Xavier Pettiau (Lhoist Coordination Centre, Limelette)
Martin Sindram (Rheinkalk GmbH, Wülfrath)

Flue gas treatment with dry sorption
systems in the ceramic industry
Olivier Barthe, (Balthazard & Cotte, Grenoble)
Dr. Burkhard Naffin, (Rheinkalk GmbH, Wülfrath)
Xavier Pettiau (Lhoist Coordination Centre, Limelette)
Martin Sindram, (Rheinkalk GmbH, Wülfrath)
05/2003

EXPERTS IN LIME AND DOLIME

The Lhoist Group today
Turnover : EUR 1.7 billion
Production : 13.8 million tons burnt products
7 000 employees worldwide
72 plants in 15 countries
5 R&D centers
(2002)
05/2003

An international network of companies
Lime
Europe
Western Europe
Czech/Slovak Rep.
Poland
Rheinkalk
Lime
Divisions
Balthazard
& Cotte
Southern France
Spain
Portugal
Lhoist
Group
(Limelette)
Lime North
America
USA
Canada
Calider JV
Mexico
Refractories
Division
Germany
USA
ROW
05/2003

A broad range of products
Unburnt products - Limestone
- Dolomite
Burnt products - Quicklime
- Hydrated lime
- Soft-burnt dolomite
- Dead-burnt dolomite
Refractories - Dolomite bricks
- Magnesia bricks
Liquid products - Milk of lime
05/2003

A variety of applications
Iron & steel
Environment
Chemical
industry
Agriculture
& forestry
Construction
Civil engineering
Refractories
Pulp & paper
05/2003

A variety of applications
Steel Industry
35%
2002 Group Sales (volume basis)
Environment
20%
Others
25%
Construction
20%
05/2003

A worldwide market
Burnt products
Western
Europe
59,7%
2002 Group Sales (volume basis)
Central Europe
7,8%
North America
& Mexico
32,5%
05/2003

Lhoist in Southern Europe : Balthazard & Cotte
Balthazard & Cotte today :
• Turnover : EUR 150 million
• Sales : 1.6 million tons burnt products
• Head office in Grenoble (France)
• 532 employees
• 25 sites of which 19 plants of production in France,
Spain and Portugal
05/2003

Lhoist in Spain
• Head Office: Govsur in Pamplona
Sales: 315 kT/y
Employees: 69
3
1
2
•Production Plants(CaO/Ca(OH) 2 ):
1
2
3
Calinsa (Pamplona)
Decsa (Gerona)
Calgov (Estepa)
05/2003

Flue gas treatment with dry sorption
systems in the ceramic industry
05/2003

Emission Limits
Pollutant / Limit Vallue
SO2
HCl
HF
Dioxins
Heavy Metals eg. Hg
National Law /Regulation
year to be fullfilled
mg/m³
mg/m³
mg/m³
ngTE/m³
mg/m³
1999/30/EG
350 - 500
< 30
< 3-5
< 0,1 - 0,4
< 0,05
e. g. TA Luft
2002
2005 - 2010
– EU-Air EU Air Quality Regulation 1999/30/EG
Comment
e. g. German
Regulations
Existing Plants
05/2003 Sindram

Tunnel Kiln Process
Maximum Release,
Temperatures:
SOx: 430 und 1.030 °C
HF: 1.050 °C
HCl: 500 °C
Temperature
release of pollutants
130 250 450 950 50°C
Brick / Tiles Tunnel Kiln
HCl, Carbonisation gases
SOx from Pyrites
HF, SOx from sulphate
Air
05/2003 Sindram

High surface Area Hydrate,
Normal hydrated lime / Milled limestone
~ 1200 - 1000 °C
~ 1000 - 850 °C
SO2 Process overview
High surface
Area Hydrate,
NHL
~ 850 - 450 °C ~ 300 - 240 °C ~ 240 - 120 °C
~ 450 - 300 °C
SO 2 + HCl
High surface Area Hydrate,
(e.g. Spongiacal ® ,Captacal ® )
NHL
Limestone,
Calcium Granulates
SO 2 + HCl + HF
05/2003

Gas cleaning
Gas conditions Process Eng. Adsorbents
• Temperature • Process • Type / Specification
• Humidity • Residence time • Mass flow
• Concentration of
acid gases
• Mixing
Ceramic Industry Dry sorption Limestone,
Granulated Materials,
Hydrated limes
05/2003

• Chemical composition
Additive caracterisation
• Particle size distribution (d 50)
• Specific surface
• Pore volume
05/2003

spec. Surface Area
[m²/g] BET
6
5
4
3
2
1
0
Specific surface Limestone, Granules
Ground Limestone 1
Ground Limestone 2
Granulated Material
(e.g. Captagran® /
WÜLFRAgran® )
05/2003

Porosity [%]
30
25
20
15
10
5
0
Porosity Limestone, Granulated Mat.
Ground Limestone 1
Ground Limestone 2
Granulated Material
(e.g. Captagran® /
WÜLFRAgran® )
05/2003

Ground Limestone
(e.g. Ground Limestone Jura)
Calcium granulat
Granulated Material
(e.g. Captagran ® / WÜLFRAgran ® )
05/2003

Calcium granulat
– Microscope 50-/100x
05/2003 Sindram

Conventional Packed Bed Filter
Process:
e.g. Tunnel
Kiln
Raw gas
- HF 70 - 150 mg/m³ N.tr.
-SO250-300 mg/m³ N.tr.
- HCL 30-50 mg/m³ N.tr.
Heat recovery
system
Packed Bed Filter
Sorbent silo
app. 160
bis 270 °C
Others
- Sorbent Consumption:
app. 50 t/mon. Ground
Limestone
HF-Reduction 95-98%
SO 2 -Reduction app.10-20 %
– Example: Ground Limestone in a Packed Bed filter
Stripping
Equipment for
recycling of
Limestone
app. 120
bis 190 °C
Fan
Cleaned gas
to Chimney
Reacted Sorbent
Recycling / Landfilling
Clean gas
-SO240-240 mg/m³ N.tr.
-HF < 5 mg/m³ N.tr.
-O2 16-18 Vol.%
-VGas ca. 15.000 m³/hN.tr- -
tGas app. 170 °C
05/2003 Sindram

Conventional Packed Bed Filter
Process:
e.g. Tunnel
Kiln
Raw gas
- HF 70 - 120 mg/m³N.tr.
- SO2 1.200 - 1.500 mg/m³N.tr.
- HCl 50-100 mg/m³N.tr.
Heat recovery
system
Packed Bed Filter
Sorbent silo
app. 160
bis 270 °C
Others
- Sorbent Consumption:
app. 40 t/mon. WÜLFRAgran ®
HF-Reduction 95-98%
SO2-Reduction app.33 %
Stripping
Equipment for
recycling of
Limestone
app. 120
bis 190 °C
Reacted Sorbent
Recycling / Landfilling
– Example: Granuleted HSA-Sorbent in a Packed Bed filter
Fan
Cleaned gas
to Chimney
Clean gas
- SO2 800 - 1.000
mg/m³N.tr.
- HCl

Modified Packed Bed Filtertechniques
Raw gas
-SO2700 - 1.100 mg/m³ N.tr.
- HCl 30 - 90 mg/m³ N.tr.
- HF 30-80 mg/m³ N.tr.
app. 145
-160 °C
Packed Bed Filter 2-Steps
– Multi stage Packed Bed Filter Processes
ca. 130
-150 °C
Fan
Cleaned gas
to Chimney
Reacted Sorbent
Recycling / Landfilling
Clean gas
-SO2 300 mg/m³ N.tr.
- HCl

Modified Packed Bed Filtertechniques
Option: Boiler for
heat recovery
app. 160
bis 270 °C
Raw gas
-SO21.700 - 2.500 mg/m³ N.tr.
- HCl 50 mg/m³ N.tr.
- HF 100 - 150 mg/m³ N.tr.
Packed Bed Filter 4-Steps
ca. 120
bis 190 °C
Reacted Sorbent
Recycling / Landfilling
Cleaned gas
to Chimney
– Multi stage Packed Bed Filter Processes with Heat Management
Clean gas
-SO 2 < 400 mg/m³ N.tr.
(< 300 mg/m³ N.tr possible
if needed)
- HCl

specific surface (BET)
[m²/g]
50
40
30
20
10
0
Specific surface
Normal hydrated lime
WÜLFRAsorp® A
Spongiacal® /
Captacal® /
WÜLFRAsorp® D SP
05/2003

pore volume
[cm³/g]
0.25
0.2
0.15
0.1
0.05
0
Pore volume
Normal hydrated
lime
WÜLFRAsorp® A
Spongiacal® /
Captacal® /
WÜLFRAsorp® D SP
05/2003

Product development
Normal hydrated lime WÜLFRAsorp ® A Spongiacal ®
/ Captacal ® /
WÜLFRAsorp ® D SP
05/2003

Dry Sorption in Ceramic Industry
Process:
e.g. Tunnel
Kiln
Raw gas
-SO 2 ca. 800 - 1.200
mg/m³ N.tr.
- HCl ca. 50 mg/m³ N.tr.
- HF ca. 40 - 100 mg/m³ N.tr.
Spongiacal
Mixer
Reactor
– Brick factory in France (Typ KHD-R)
Recycling
Others:
- Consumption:
ca. 50 t/mon. Spongiacal ®
HF-Removal 95-98%
SO 2 -Removal 63-75 %
Baghouse
Filter
240°C
(min.150)
Cleaned gas
to Chimney
Reacted Sorbent
Recycling / Landfilling
Clean gas
-SO2 < 300 mg/m³ N.tr.
- HCl

Conclusion
• The Brick and Tile Industry needs simple FGT Processes with
low Investment.
• High performance Sorbents enable Packed Bed- or Baghouse
Filter based Processes to meet high Emission Standards
• Many Customers use High performance Sorbents instead of
Limestone or Normal Hydrated Limes to decrease Costs and
increase Efficiency
05/2003