•

November 18,2009.

By: Craig Sharp and Bryan Pourchot

HALDOR TOPSDE (]j
Table of contents

• Trends in SCR DeNOx

applications

- Coal fired power plants

- Biomass

- Gas turbines

• New catalyst developments

- Cerafil TopKat

- Monolith catalysts

HALDOR TOPSCE III
Coal-fired power plants

• Biomass firing and co-firing

- SCR catalyst deactivation.

II Lower temperature operation

- Minimum temperature issues

II SCR in low'-rank coal fired units

- Catalyst deactivation

II Catalyst regeneration

HALDOR TOPSDE rJj
DONG Energy, Studstrup Power Station

• 2 x 350 MWe

• 10% straw on energy basis has been co-fired since 2002

and 2005 in the two units

HALDOR TOPSOE [I]
Coal/straw co-firing at Studstup Power Station

___

- Plugging l!Ii!IiBiillllBifB!Jj du~e to incomplete burn-out of the straw

Ref: Dong Energy, Expperts 2008 Brussels HALDOR TOPSDE [Ij
Biomass and SCR deactivation

III Evaporation of potassium in the furnace

- Deactivation rate: Different furnace types have different catalyst

deactivation rates

III Nucleation of fine sub-micron potassium aerosols

III Deposition of aerosols on catalysts surface

III Diffusion into catalyst by surface diffusion

III Reaction with active site

4,600 service hours at Nassjo

Power Plant (accelerated test)

Quantitative chemical analysis

shows 7,000 ppmw potassium

HALDOR TOPSDE L!:l
Bench scale experiments with furnace

Injection of potassium salt solutions _____.wr£illg!E\~!;'/"·i,;

III Continuous flow of aerosol through the catalyst is required for deactivation

III Impregnation experiments show the same effect of sulphate and chloride

III Difference between sulphate and chloride deactivation rates indicates an

effect of surface diffusion mobility or aerosol deposition rate

KCI aerosols

!3D

20

& 2nd! iKeI exp,osetl, acWr'j

--e- 2nd! Kel ex(XJsetl, &he Borbed NHlli

D --of---r---.----...----r---r---,----,.---,---,,.---i. I)

2'(10 4'11(1 ·IltOO 800 1000

I:hcposlJ!re time llhj

Deactivation 50%/1 GOGh

Zheng et. al Applied catalysis B: Environmental

K2SO4 aerosols

1{!1J) .

!l0

10 i

I

(I' 500' 10(1) 1M!!ll' ~MO :2500 ;'!I)I){J!

E:lCpMum, time ·th]'

Deactivation 300/0/1000h

HALDOR TOPSDE l[]
KCI powder deactivation experiments ____.il1Si~)]jf

• Commercial grade KCI placed on catalyst

- Almost no deactivation of center catalyst

- No deactivation of downstream catalyst

• Fly ash recovered from full scale reactor placed on

catalyst

- No deactivation observed

350°C, 2500 hours

HALDOR TOPSDE L!j

Zheng et. 81 Applied catalysis B: Environmental
Lower Temperature SCR Operation

Improved activity at lower temperature

Ko Type factor as a function of

NOx level at various temperature, ANF = 1.0

2.5

2

350 400 450 500 550 600

D ~-...I---J..-.L.--4---l..---L--...JI...--..J---i-...L--..l.---L-......J--+--L--.l...-..J..-....,L...-.....j---.L-....I.---L-..L.--l--.J--L.--L--L-....j

300

Gas Temperature,OF

HALDOR TOPSCE (1j
Undisclosed Site 16 MW CHP

II Grate fired boiler

II Fuel: Wood chips

II SCR installed in 2008

III Low dust, vertical up &down

flow

II NOx Inlet, O.118lbs/mmBtu

II NOx reduction, 64%

II SCR temperature 340 - 360°F

III On line catalyst cleaning

- reverse flow

II Catalyst deactivation is less

than expected

II SCR inlet SOl3 < 0.5 Rpm (calc.

ASS dew point> 450°F

HALOOR TOPSCE []j
Lower Temperature Operation

• ASS inhibition at typical coal-fired conditions

HALDOR TOPSDE []j
Tail End SCR

• 2 x 260 MWe, 2 x 300 MWe

PC boilers, PRS fired

• Low Dust, Tail End SCR

• Vertical down flow

• NOx Inlet, 100 ppm

II NOx reduction, 570/0

II SCR temperature 490°F

II Service Life - 32,000 Hours

• SCR inlet 803 < 1 ppm (calc. ASS dew point greater

than operating temperature)

• Install Date! - 2011

HALDOR TOPSDE []]
Simple Cycle Gas Turbines __~l!1~!!ir01!0;;"

• High temperature SCR (900 - 1,1 OO°F)

• Frequent start ups

• Fast temperature ramps

HALDOR TOPSDE (]j
High Temperature SCR Operation __...._.M~t;}~l'···''''''

o StrongE~r NH3 absorption

o Lower NH3 oxidation rate

o Higher DeNOx activity

100.0

80.0 ,..----- ?.,.----.... )(

0

z 60.0

."

J:

a. 40.0 ...... - -

c

20.0

0.0 . £

I I

0.5 'I 1.5 2

ANF

-.-20ppn NOr- IHI @01OD6-2-i2) ___ OOppm NO); IHI @0'1006-2-2)

;-lJppm NO xIHl (D NXJJD) -.-C5ppm rKix IHI I]HH<JOCl)

Improved activity at higher temperature

DNX-()29HiTe

HALDOR TOPSDE IIi
New DNX-029HiTe Catalyst

Vra Power Plant

III Power Output - 5 Mwe

III Flue gas flow - 150,000 Ibs/hr

Flue gas temp. - 1,050 deg. F

III NOx inlet - 110 ppm

III DNX-029 Installed - June 2008

Performance:

III Daily Start ups

III Over 4,000 operating. hours

III NOx Reduction - 80%

III Zero Catalyst Deactivation

HALDO~ TOPSOE []j
DNX-029HiTe Catalyst Field Experience

• ~a surelTJ:!nts Sep 200e

¢ ~a surelTJ:!nts June 200e

• • • • Performance Guarantee

II ~asurelTJ:!nts Jan 2009 ~~ ~a surelTJ:!nts Jun 2009

a Ni3 slip Ju n2009 -

£:

z

C

Q.

Q.

...... 10 Q.

15

5

20

o

0.5 1 1.5 2 2.5

NH3 injeetediNOX inlet

- .. V" v - - - - - - - - - - - - - - - ... ,. r ..

•

• -I-

.. .- J.

.,...- . -.:.J;

.. •

.:.

• h h

h

• tJ.

I I I I

o

o

20

80

100

6 60

z

I]J

o

'#. 40

HALDO~ TOPSDE I]j
TopKat technology __"_ii_I~&7JIft'

CLEAR EDGE"

Filtration

0.3mm

Ceramic film

!

10-20 mm wall ceramic fiber matrix

Dust layer with catalyst particles

\ I I . '.:n . : .. ).-

.~ \

• Ceramic filter

Tolerates high temperature

and temperature excursions

Acid gas resistant

Impregnated for catalytic

activity

HALOO~ TOPSOE !]j
Equipment train options

for dust, SOx and NOx

ESP based

TopKat based

Fabric filter

based

HALDOR TOPSCE []j
TopKat operation below ASS dew point __....i_twA?Y'·········

30 ppm 503

1500 ppm NH3

1

I

I

,

1

,

'. 12 ppm NH3

\, J \ 1.4 ppm 503,

'... ---- -------------------.0.1 ppm NH3

i

225°C 193°C

Catalyst

1

Filter cake

+

oppm

TASS bulk dew point

HALDOR TOPSDE LIj
TopKat reference list ___IIiIIII.i!Ji£Q•.,,~'!fJlfii;'Yi·

II References and projects

5 waste incineration plants

III Cooperl

III Andouillettes Troyes

III Addenbrook

III Uchiko

III Perfect Metal (start up 2009)

France

France

France

Japan

Romania

No. of CTK-3000 filters

672

80

270 (CTK-1000)

540

900

CLEi\R'EDGEN

Filtratlon

HALDOR TOPSDE [Jj
Colombo Barge, Sri Lanka

TopKat pilot trial

• 2T 12K50MC-S 18 MW

II 250-300°C in stack

II 2-2.5% S HFO

• 500 ppm S()2

• 5% H20

• 150/0 O2

II 1500 ppm NOx

HALDOR TOPSOE []j
SCR catalyst developments ____i~~&g;''';

• Biomass optimised catalyst

- Competitive sites for poison binding

- Catalyst system with inhibition of poison diffusion

• Lower temperature operation catalyst

- Improved activity with lower deactivation

• High temperature gas turbine catalyst

- Improved activity and durability at high temperatures

• New SCR DeNOx technologies

- Cerafil TopKat

HALDOR TOPSCE L!j
Questions?

Thank you

HALDOR TOPSCE []j