Reingas SCR – Zementwerk RohrdorfAK-NOx Minderung 11.10.2011

Dr. Helmut LEIBINGERSPZ Rohrdorf

Tail-End SCR Technology for Mitigation of NOx and NH3 - Operational Experience at Rohrdorfer Zement

Dr. Helmut Leibinger, SPZ Rohrdorf7th International VDZ Congress, 25-27 September 2013, Duesseldorf

Contents

1. Introduction SPZ Rohrdorf

2. Initial Conditions & Considerations

3. Design & Realization

4. Operating Experience

5. Resume

2

Tail-End SCR Rohrdorf

private shareholder by the majority (HC 25 %) Company Foundation – 1930 Site Location – Rohrdorf/Bavaria/Germany

Nominal Clinker Production: 3.500 to/d 4 Stage PH Tower, No Precalciner (!) Pendulum Grate Cooler VR-Mill for Raw Meal Preparation WHR-Plant 4 Cement Mills

3

Tail-End SCR Rohrdorf Introduction SPZ Rohrdorf

Tail-End SCR Rohrdorf Initial Conditions & Considerations

*) Emission limit for Incineration- and Co-Incineration-Plants (200 mg/m³ STP dry @ 100 % AF-Rate) 4

NOx – ELV

475

295200

90 85 100

350

Kiln exhaust gas temperature > 425 °C(phase transition TiO2: Anatase Rutile; loss of active surface)

Mechanical wear(experience from AE&E at Gmunden site, 1999)

Chemical deactivation by heavy metals(thallium poisoning at Gmunden 1999 and Wopfing 2010)

Availability of heat (> 3 MWth)

5

Tail-End SCR

Tail-End SCR Rohrdorf Initial Conditions & Considerations

Main reactions at catalyst:

Undesired side reactions (Coating):

Poisoning

Thallium, Arsenic, …

6

OHNNHNOOHNONHNOOHNNHNOOHNONHNO

2232

22232

223

2223

12786634265466444

424233

44233

322

)(2

22

SONHOHSONHHSONHOHSONH

SOOSO

(ammonium hydrogen sulfate)(ammonium sulfate)

Tail-End SCR Rohrdorf Initial Conditions & Considerations

reversible

irreversible

Tail-End SCR Rohrdorf Initial Conditions & Considerations

7 Source: GEA Bischoff GmbHOperating Data: HHMV Stack (2012)

0

25

50

75

100

125

150

175

200

225

250

245 247,5 250 252,5 255 257,5 260 262,5 265 267,5

SO2-

conc

entr

atio

n[m

g/m

³ STP

dry

, ref

. 10

Vol-%

O2]

Temperature[°C]

BYPASS

OPERATION

BYPASS OPERATION247,5

8

Tail-End SCR Rohrdorf Design & Realization GEA Bischoff

Δp=24 mbar

Optimum Operation Temp.

1

Compensate Heat Transfer Losses4

Heat Recovery3

Minimum Temp. at Stack2

9

Tail-End SCR Rohrdorf Design & Realization

Clinker Cooler Raw Meal Silo

TG BuildingSCR-PlantRaw Mill

WHR-BoilerKiln

4 Stage PH-Tower

Clinker Silo

Stack

10

Producer of catalyst Haldor TopsøeLayers Installed 2Volume of catalyst 65,84 m³Active surface 58.300 m²Chem. composition V2O5 = 3 %

WO3 = 3 %

Tail-End SCR Rohrdorf Design & Realization

Tail-End SCR Rohrdorf Operation Experience // 2011 → 2013

11

12

-76,3 %

-76,0 %

-89,4 % -92,5 %

NOx-reduction NH3-reduction

*) Mass flows in relation to 6.500 hours of operation per year2012: exkl. Plant stop because of fire

Mass flow NOx Mass flow NH3

[t/year]

Tail-End SCR Rohrdorf Operation Experience

NOx before cat

NOx stack

NH3 before cat

NH3 stack

Clin

kerC

oole

r Con

vers

ion

Clin

kerC

oole

r Con

vers

ion

13

Tail-End SCR Rohrdorf Operation Experience

0,0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

1,0

0 2.000 4.000 6.000 8.000 10.000 12.000

K /K

0 [-]

Operating Hours [h]

Activity History of 1st Layer

Wood Chips*

Sub-bituminous Coal*

Bituminous Coal*

Light Fuel Oil*

Heavy Fuel Oil*

*Additional data based on Jensen‐Holm, Castellino, SCR DeNOx catalyst considerations when using biomass in power generation,Haldor‐Topsoe (2012)

Rohrdorfer Zement

14

Tail-End SCR Rohrdorf Operation Experience

Kiln Exhaust Gas

sp. el. Energy Consumption of SCR

Production of Clinker

15

Ecology

76 % abatement of NOx (setpoint 200 mg/m³ STP dry)

92 % abatement of NH3

40 % abatement of VOC

Operation Experience

90 % activity of catalyst after 2 years of operation

92 - 97 % availability of SCR-plant (start-up time excluded)

sp. electrical energy consumption: 5 - 6 kWh/tclinker

NH4OH injection at molar ratio < 1 (0,7 – 0,8)

Tail-End SCR Rohrdorf Resume

16

Many thanks to:

Shareholders of Südbayerisches Portland-Zementwerk Gebr. Wiesböck & Co. GmbH who have made this projectpossible and have financally supported it to a great extent

Federal Ministry for the Environment, Nature Conservationand Nuclear Safety which has supported this project givinggrants from the Environmental Innovation Programme (Umweltinnovationsprogramm)

Tail-End SCR Rohrdorf Acknowledgment

Thanksforyourkindattention