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NOx in Cement Clinker Production -

Formation and Measures to minimize NOx-Emission


June 22st, 2016 | Reinhard Beilmann | tkIS
Lima, Peru, Technical Symposium for Reduction of Emissions
NOx – Emissions by Source in EEA member countries (2009)

Emissions Cement
Plants are
contributing to

2 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
Development of NOX Limits for Cement Plants in Germany

1500 mg/Nm³

800 mg/Nm³
existing plants

500 mg/Nm³
350 mg/Nm³
500 mg/m³ NH3=30mg/Nm³ 200 mg/Nm³
new plants NH3=30mg/Nm³

1986 1991 2002 2016 2019


17. BlmSchV
Nm³ = dry at 10% O2. Conversion to 10% O2 permitted in Germany only until 2012.

3
3 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
Capability of NOx-Abatement Technologies in Cement Plants

1500
Emission without Abatement

MSC+SNCR

SCR
MSC
mg NOx/m3

800

500

200

4 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
NOx Sources in the Clinker Burning Process
Sintering zone
Calciner firing

• High temperatures
• High oxygen levels at the flame
• Low oxygen levels
N2 + O2 → 2 NO
• Substoichiometric at the
ignition zone (N2 + 2 O2 → 2 NO2)
• Flameless oxidation  Formation of thermal NOx
• Uniform temperature unavoidable
 No thermal NOX
 Fuel NOX only
 Partly reduction of (kiln) NOX

5 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
Measures to influence the NOX emission – Theory of Low NOx Burner
CO
NOx
Sintering zone

Theory of Low NOX Burner:


Reduce flame temperature

• Switch to low reactivity fuel, increase


particle size
• Increase flame length (reduce swirl)
• High temperatures
• High oxygen levels at the flame
Reduce oxygen content
N2 + O2 → 2 NO
(N2 + 2 O2 → 2 NO2) • Reduce primary air
• Reduce momentum of primary air
 Formation of thermal NOx unavoidable

6 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
Measures to influence the NOX emission – Theory of Low NOx Burner

clinker
quality

Options for lowering the thermal NOx Oxygen


formation in the sintering
Temperature Level
zone are limited, as clinker quality is always affected.
 NOx emission should be adjusted in the calciner by MSC

Thermal
NOx

Theory of Low NOX Burner:

7 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
NOx Development in the Calciner

Calciner Fuel N HCN NHi - radicals NOx

Air Excess

Lack of Air

N2

8 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
MSC Multi-Stage-Combustion - A Primary Measure for NOx-Abatement

1. Air excess number below 1


2. High temperature in substoichiometric zone
3. Long retention time in substoichiometric zone

1 top air: ~ 0,85-0,95,lower values possible


2
2 meal staging for flexible temperature control

3 retention time of ~ 1 second


1 
Air excess
3 Area of reduced
combustion condition
with flexible temperature
control and sufficient MSC
retention time
t
T
Retention
Temperature
time

9 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
Latest References for MSC-Calciner Systems of TKIS

< 500 mg/Nm³


~ 500 mg/Nm³ ~ 650
500 mg/Nm³
mg/Nm³ ~ 800
mg/Nm³

Natural Gas
RDF
Coal (40%)
Coal (28 %)
Coal (21%)/
Petcoke

> 30 units sold

10 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
SNCR - Selective Non Catalytic Reduction –
Secondary Measure for NOx-Abatement
2 NO + 2 NH3 + 0,5 O2  2 N2 + 3 H2O
2 NO + CH4N2O  2 N2 + 2 H2O + CO
Typical Calciner Temperature
Combustion,
NH3-Slip
NO formation
Ammonia

Urea

11 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
SNCR - Selective Non Catalytic Reduction –
Secondary Measure for NOx-Abatement

12 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
SNCR - Selective Non Catalytic Reduction –
Secondary Measure for NOx-Abatement

Risk of secondary
Emissions at higher
Reduction levels

Increase of CO likely

13 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
SCR - Selective Catalytic Reduction –
Secondary Measure for NOx-Abatement
NOX

Raw NOX
~300°C
Gas

NH4OH
SCR TiO2
Storage V2O5
reactor
WO3

NOx Set point


Controller

4NO + 4NH3 + O2 4N2 + 6H2O


H2O

14 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
SCR - Selective Catalytic Reduction – SCR Configurations
Secondary Measure for NOx-Abatement
 Lowest investment costs High Dust (HD)
 Suitable flue gas temperature
 No interference with main process
 Easiest option for retrofits
- Frequent cleaning of catalyst

 Suitable flue gas temperature


Semi Dust (SD)  Easier cleaning of catalyst
- Higher cost of installation
- Complex duct routings in retrofits
- Additional power for ESP

Tail End (TE)


 No dust cleaning required
 Longer lifetime of catalyst
- Highest cost of installation
- Requires reheating of flue gas
- Complex system
- Higher operating costs

15 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
SCR References / Projects of Elex CemCat

Rezatto (2014)
Mergelstetten
(2010)

Joppa (2013)
Monselice (2006)

Start up of SCR-Systems in 2017:


Solnhofen, Phönix, Göllheim

16 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
SCR versus SNCR - Performance of NOx Abatement

100
90
SCR
NO-Abatement [%] 80
Monselice
70
60
50
40
SNCR
30
20
10
0
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5
NH3/NO

17 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
CemCat a Joint Venture of Elex and TKIS (Polysius)

Catalysts Preheater / Calciner

Combustion/Fuels
Industrial References
SNCR

ESP
New products

Patents Patents

18 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
Conclusion - NOx in Cement Clinker Production
Formation and Measures to minimize Emissions

• Primary NOx Emission can be reduced significantly with modern MSC Calciners down to
500 – 800 mg/Nm³

• SCNR is effective for NOx abatements of 50-60%, further reduction only with secondary
emissions, mainly NH3

• SCR abatement is nearly unlimited, secondary Ammonia emissions are not only avoided,
but Ammonia is effectively used for the NO reduction

• High Dust is the favorite solution:


• lowest investment
• no extra energy
• TOC oxidation
• positive effect on downstream Hg capture

19 | June 22st, 2016 | Formation and Abatement of NOx-Emissions | Reinhard Beilmann tkIS
NOx in Cement Clinker Production
Formation and Measures to minimize Emissions

Thank you for your attention!

Any questions?

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