International CAFENOx Symposium

Primary DeNOx Measures in Large Pulverized Coal and Lignite Units Practical Solutions for Existing Units

Jacques BLONDIN
Tel : +33 3 21 72 8432 Fax : +33 3 21 72 8351 jacques.blondin@snet-electricite.fr

FP5 CAFENOx project - NNE5-2001-830 2003 mid 2005

June 23 & 24th, 2005

International Symposium June 23rd 24th, 2005

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INTRODUCTION

Main objectives of the CERCHAR study Large SNET coal fired units
NOx emission reduction strategy Financial impact of 900650500 mg/Nm3 primary NOx emission reduction

Primary DeNOx measure experiments

3MW CERCHAR furnace 2 x 600 MWe pulverized coal fired SNET units

Practical approach for existing units

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Main objectives of the CERCHAR study

From semi-industrial tests (3 MWth furnace pilot facility) and industrial tests (1500 MWth commercial units) : A wide range of simple and cheap primary DeNOx measures were carried out with a collection of continuous data (up to 200 measurements/analysis 5 min refreshment Implog software Excel files) during long periods of time in different configurations Combustion and NOx models were developed thanks to accurate and various data collection

Economical measures were selected for reducing NOx emission in 2 x 600 MWe units having their own specificities clearly identified, confirmed and explained to the operators
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Large SNET coal fired units NOx emission reduction strategy

2 x 600 MWe coal fired F units once through Alstom boiler Provence unit 5 at Meyreuil E. Huchet unit 6 at Carling (Lorraine) Concerned by Directive 2001/80 as far as these 2 units will be operated after 2015 and dont yet fulfill NOx emission limit values DeNOx technique implementation became compulsory 2 x Alstom-Lurgi CFBC units : Concerned by Directive 2001/80 but 125 MWe SODELIF unit 4 at Carling already fulfill NOx emission limit values 250 MWe SOPROLIF unit 4 at Meyreuil Nothing to be done regarding NOx emission in flue gas (EDF main shareholder) 1 x 343 MWe coal + gas combined cycle at Decision taken on June 30th 2004 to stop Carling these units 20000 h after January 1st 2008 E. Huchet unit 5 Nothing to be done regarding NOx emission in flue gas 2 x 250 MWe coal fired units Hornaing unit 3 at Hornaing (North) Lucy unit 3 at Montceau les Mines
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Financial impact of primary NOx emission reduction for SNET 600MWe units
Taxes and penalties linear to NOx emitted Primary DeNOx technique implementation implies : pay off in 7 years a long period of shunt down for modifications no clear interest as far as SCR is compulsory after 2015 technical risks for the boiler Temporary measures (< 200 h/yr) linear to effective application (the shorter, the cheaper) clearly correlated to coal selection 900 650 mg/Nm NOx at 900 500 mg/Nm NOx at 6% O2 6% O2 0.20 0.27 M/yr 0.15 0.21 M/yr about 0.7 0.9 M/yr about 1.1 1.3 M/yr
3 3

0.1 M/yr to 1 M/yr maximum for max 200 h/yr but the costs may be dissuasive for a continuous application (3000 h/yr)

impossible without primary DeNOx technique implementation

Based on that analysis, SNET decided at the end of 2001 to invest (2 x 25-30 M) in SCR equipments for its 2 x 600 MWe units
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Primary DeNOx measure experiments 3MW CERCHAR furnace

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3MW CERCHAR flame furnace ATC coal Low NOx combustion test

low NOx = 500 ppm C N VM ash distance from the burner

ATC coal 72.62 1.63 25.7 13.4 0

char 1 72.95 1.45 12.3 21.35 100

char 2 72.21 1.34 3.02 24.88 300

char 3 56.1 0.39 5.61 42.09 500

char 4 34.08 0.4 4.89 64.9 1000

fly ash 7.42 0.41 5.3 91.98 > 7000

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3MW CERCHAR flame furnace ATC coal High NOx combustion test

High NOx = 1000 ppm C N VM ash distance from the burner

ATC coal 72.62 1.63 25.7 13.4 0

char 1 55.9 0.63 5.89 42.51 100

char 2 54.62 0.48 3.75 44.02 300

char 3 62.36 0.54 2.72 45.03 500

char 4 18.12 0.22 78.66 1000

fly ash 5.96 0.15 3.55 92.19 > 7000

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3MW CERCHAR flame furnace N combustion in ATC coal

C & N - coal combustion
100 90
ignition in reducing Char 1 at conditions 1380C at 1380C Low NOx ignition in Char 1 at oxidizing 1570C conditions atHigh 1570C NOx

residual N in char (%)

80 70 60 50 40 30 20 10 0 20 40

% residual N low NOx % residual N high NOx

end of volatile matters combustion

60

80

100

C coal burn out (%)

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3MW CERCHAR flame furnace N combustion in ATC coal

N behaviour along ATC coal combustion process
1600 1550
oxidizing ignition zone CO = 900 ppm O2 = 7.5 % reducing ignition zone CO = 55000 ppm O2 = 0.5 %

TC of the flame

1500 1450 1400 1350 1300 30 40 50

TC - low NOx TC - high NOx

final 1000 ppm NO in flue gas final 500 ppm NO in flue gas

60

70

80

90

100

percent of burnt N from coal

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Synthesis of 3 MW CERCHAR combustion tests Char, temperatures and gas composition measurements possible along a 5 m in length flame having different NOx emission configurations available for other experiments (e.g. O2 enriched flame) Selection/classification of low NOx coals and fuel blends, when no information available at industrial scale Data collection available for modeling Training of thermal plant operators and probe/analyser testing
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2 SNET 600 MWe pulverized units

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Comparison of the 2 SNET 600 MWe units

Provence 5 designed for Gardanne lignite 7 mills A to G furnace section 19.9 x 19.9 m2 now fed with imported coal 4/3 mills in use for PC max/mid OFA possibilities by switching off the upper burners SCR to be implemented between ECO and Air Reheater (too cold zone) SCR designed for 1000 mg/Nm3 at 6% O2 NOx inlet CEH 6 designed for Freyming hard coal 6 mills 61 to 66 furnace section16.6 x 16.6 m2 now fed with a mixture of imported coal + ashy colliery residues 5/4 mills in use for PC max/mid lack of flexibility for OFA SCR to be implemented between ECO2 and ECO1 (too hot zone) SCR designed for 800 mg/Nm3 at 6% O2 NOx inlet

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Design of tangential burners

Provence unit 5
ABCE configuration
Air II-1

Huchet unit 6
62-63-64-65 configuration

Air II-2

coal burner + air I

oil fuel burner

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Critical limits Provence unit 5

1000

Provence 5 - NOx versus reheated steam temperatures as a function of fuel ratio of differents coals 1.47
TC must be > 525C at MP turbine inlet possible compromise

NOx mg/Nm3 - 6% O2

900 800 700 600 500

2.27 1.5 2.1 1.8 1.46 1.42

"Low NOx" coal selected 400 480 490 500 510 520 530 540 550

threshold

TC reheated steam

OFA through BOOS induced a dramatic decrease of reheated steam temperatures and a subsequent reduction of global efficiency
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Critical limits Huchet unit 6

CEH 6 - Low NOx possibilities
NOx mg/Nm3 - 6% O2
900 850 800 750 700 650 600 550 500 1.6

goal for optimizing SCR 1.82 2.16 goal

but 4 mills + OFA

1.8 2 2.2 2.4

Fuel ratio
OFA through BOOS was only possible with 4 mills in service when pure imported coal was burnt instead of cheaper blends of coals with old ashy colliery residues
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Synthesis of combustion tests carried out on the 2 SNET 600 MWe PF units
Primary DeNOx measures based on OFA through BOOS allowed an emission reduction from about 800-1100 to an absolute minimum 600 mg/Nm3 NOx at 6% O2 without any investments, but with determinal impact on operating costs NOx emission reduction possible at full load, but very poor at middle load Selection of low NOx coals would rather be made through industrial scale tests carried out on the concerned units than based on index such fuel ratio or N content Temporary reduction methods of NOx emission were defined for both units : they are available for local Authority requirements before SCR commissioning date in 2007-2008 At Huchet unit 6, SCR will have to be completed with moderate but continuous primary DeNOx measures (target : 700 800 mg/Nm3 at 6% O2)

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Practical approach for existing units

Return of experience
normal NOx emission hard coals lignites 800 - 1200 400 - 600 with primary low NOx measures 500 - 700 250 - 350 with SCR < 200 < 200

Fractional conversion of char-N into NO and N2O at total char burnout (de Soete)
Char from Low and high volatiles bituminous coals Lignite FNO (range) 0.35 0.67 0.084 FN2O (range) 0.013 - 0.057 0.006 0.012

SCR more or less compulsory after 2015

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Mechanisms of SCR catalyst deterioration Thermal reaction : rapid and irreversible deterioration when temperatures > 450C, even locally and on a quite short period of operating time Mechanical plugging up : by ultra-fine and coarse particles > 1/3 honeycomb pitch (6.4 9.2 mm for coal from Cormetech) Chemical plugging up including :
Ammonia-sulfur compounds, especially when temperatures < 320C Alkaline metals from fuel (e.g. As) Non metals, such Ca, P
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Data collection of measurements in a view of SCR equipment implementation

Measurements and analysis in various configurations having an impact on Coal, fuel oil and secondary fuels characteristics, including Duration life of SCR catalyst (poisons) trace-elements Limestone or lime injection when primary DeSO2 is Duration life of SCR catalyst (poisons) implemented Flue gas characteristics (average and extreme values) at the SCR catalyst design, dimension and location point of SCR implementation Detailed mapping: implementation flow rate (dry and wet), local velocity Probes, instrumentation, control temperatures regulation NOx, SO2, O2, CO2, CO Geometric design of the unit SCR casing implementation including a possible hopper to trap coarse particles By-pass of SCR Maintenance of NH3 injection Fly ash at the point of SCR implementation : Dimension of catalyst channel flow rate, including peaks during soot blowing section size dimension distribution popcorn Risk of catalyst channels or cells chemistry and mineralogy slagging detection plugging up Additional hopper to trap coarse particles
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Consequences of SCR equipment implementation

Modification induced by having an incidence on SCR implementation Pressure drop : Pressure profile of downstream flue gas pass-by normal Mechanical strength resistance of flue gas duct, ESP accidental (plugging up) Fan design and dimension Safety equipments Reinforcement of structures Decrease of global efficiency due to the rise of auxiliary consumption Leakage of NH3 in fly ash Fly ash quality, market, smelliness Additional cost of disposal SO3 in flue gas Risk of acidic corrosion of metallic components Atmospheric SO3 release in flue gas Acidic attack of concrete chimney (in case of DeSO2 wet scrubber without final flue gas reheater) Weight and dimension Whole installation stability Maintenance design especially when SCR catalyst modules should be changed
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Practical approach for existing units

higher NOx at SCR inlet NOx at SCR inlet (mg/Nm3 at 6% O2) initial percent of SCR abatement SCR Catalyst operating NH3 slip potential hours ppm K/Ko initial NOx at SCR outlet (mg/Nm3 at 6% O2) normal design lower NOx at SCR inlet

1 000

800

600

90

90

90

Primary DeNOx measures may reduce SCR costs by postponing SCR catalyst module replacements
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5 000 10 000 15 000 20 000 25 000 30 000 35 000

0.29 0.57 0.86 1.14 1.43 1.71 2.00

1.00 0.95 0.90 0.85 0.80 0.75 0.70 0.65

100 105 111 118 125 133 143 154

80 84 89 94 100 107 114 123

60 63 67 71 75 80 86 92

reinvestment of a catalyst module

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Primary DENOx measure application possibilities

Small PF units (50 < P < 500 MWth) may fulfill 600 mg/Nm3 at 6% O2 without any problems and at moderate costs thanks to existing primary DeNOx techniques Large pulverized lignite fired units (P > 500 MWth) should fulfill 200 mg/Nm3 at 6% O2 in due time (before 2015) thanks to further technical enhancements of primary DeNOx measures Think about NOx emission expression (mg/Nm3 at 6% O2 mg/MWh at 6% O2) Large pulverized coal fired units (P > 500 MWth) should need SCR, but SCR operating costs may be reduced Think about end of life of unit without any SCR catalyst module replacement thanks to primary DeNOx measures
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Thanks for your attention

The final report of the CAFENOx project will be available before the end of 2005 after its approval by the Commission
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