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NITROGEN #2
• Costs related to NOx reduction for burner combustion processes
• NOx and N2O chemistry in atmospheric fluidised bed combustion
• NOx and N2O chemistry in pressurised fluidised bed combustion
• Nitrogen control (NH3, HCN, ....) for gasifier product gas
• NOx control in relation to gas turbine combustion
• NOx control in relation to (transport vehicle) engines

NOTE : NOx = NO + NO2

see: www.hut.fi/~rzevenho
www.hut.fi/~rzevenho/
/gasbook

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Costs related to NOx control

Method NO reduction capital cost levelised costs
efficiency (%) (US$/kW) NOx removal
(US$/ton)
Primary measures
Low Nox burners ~50 10 – 20 110 - 200
Coal reburning ~50 38 – 50 360 - 470
Low NOx burners + ~60 12 – 28
OFA (over-fire air)
Gas reburning, no FGR ~60 15 370 - 620
(flue gas recycling)
Gas reburning + FGR 60 - 70 15 – 40 260 - 400
Low NOx burners + gas ~70 25 – 60 730 - 960
reburning
Flue gas treatment
SNCR 30 - 50 5 – 15 500 - 1100
SCR ~80 50 – 80 820 - 990

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Nitrogen oxides formation and reduction in FBC

PYROLYSIS / COMBUSTION EXIT
DEVOLATILISATION formation reduction
1,2,3 NO
4,5,6
HCN N2 O
volatile- N N 2O
10 7,8,9 N2 21,22
11,12,13
NO NO NO
NH3
fuel- N N2 23,24, N2
14,15,16 N2 25,26

NO 27,28,29,
17 30,31 N2
N2 O
18,21
char - N N2 O N 2 O

19,20 N2

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N2O formation via

HCN combustion.

Detailed kinetic modelling at

1000-1300 K

Inlet 500 ppm HCN, staging

with λprimary = 0.7, λtotal = 1.2

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Effect of temperature and air factor on

NO and N2O in circulating FBC

Effect of temperature Effect of air factor Typical NO and N2O

(air factor 1.2) profiles
(850°C, air factor 1.2)

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NH3 and HCN concentration in CBFC

12 MW CFBC, bituminous coal, air factor 1.2-1.25, bed temperature 850°C

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NOx emissions
from coal/wood
co-firing in CFBC

850°C, air factor 1.25

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Effect of limestone
on NO and N2O
emissions from
CFBC

Coal, Ca/S = 1.5,

Gotland limestone

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NOx and N2O from atmospheric FBC

Increasing parameter N2O emissions NO emissions
Temperature ↓ ↑
Fuel volatile nitrogen content ↓ (BFB), ↓ (CFB) ↓ (BFB), ↑ (CFB)
Fuel nitrogen content ↑ ↑
Excess air ↑ ↑
Air staging ↓ ↓
Limestone addition ↓, - ↓ (BFB), ↑ (CFB)
SO2 level ↑ ↓
SNCR – NH3 ↑, - ↓
SNCR – urea ↑ ↓
SCR - ↓
Pressure ↑, ↓ ↓ (but NO2 ↑ )

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Fuel-N conversion to NO, N2O, N2 in FBC (coal)

lab. scale FBC,

850°C, 6% O2

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NOx and N2O emissions from coal-fired CFBC

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NO & N2O from char-N in FBC:

effect of fuel type

char-N to NO char-N to N2O

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NO emissions: FBC versus pulverised fuel firing

(atmospheric)

ppm-vol

Typical values for N2O 0.5 - 2 50 - 150

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Two approaches to simultaneous

N2O/NO/SO2 control from FBC

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fuel-Nconversion
fuel-N toNO
conversionto (%)
NO(%) NO from pressurised FBC

Pressure
Pressure(bar)
(bar)

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NO and N2O from pressurised FBC

SINGLE
SINGLEPARTICLE
PARTICLE NN2OO
2

NO
NO
BFBC
BFBC NN2OO
2
NO
NO

Modelling: fuel-N to NO or N2O NO versus N2O in PFBC

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Gasification of solid fuels

Reactors

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Tampa Electric IGCC process (250 MWe)

Other units,
similar size:
Buggenum
(Holland)
Puertollano
(Spain)
Wabash River
(Indiana, USA)
Near future :
650 MWe
“Buggenum”
Buggenum”
@ Sardinia

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NH3 and HCN in gasifier product gas

Gasifier facility Fuel NH3 (ppmv) HCN (ppmv)

Texaco-type entrained bed Coal ~ 800 ~40
Shell-type entrained bed Coal ~ 300 ~150
VTT air blown FB Coal ~2000 ~ 50
“ Peat ~3000 ~100
“ Wood ~ 600 ~ 20

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NH3 from fluidised bed gasification

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NH3 , HCN, .... in gasifier product gas

• Removal at low temperatures :
– absorb in water (pH < 7)
– selective sorbent (ketones/aldehydes or polysulphides)
• High temperature, high pressure (HTHP) removal before gas
combustion in gas turbine
– Catalytic decomposition to N2 and H2 at 550 - 900°C
– Selective catalytic oxidation (SCO) at 300-550°C or higher
– adsorption/desorption on zeolites
• Adjustment of gas turbine combustion chamber design
• Let it be oxidised to NO and apply S(N)CR to exit gas

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Catalysts for in situ NH3 and HCN

conversion for FB gasification

NH3 HCN

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Gas turbine, gas turbine combustion chamber

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NOx and CO from gas turbine combustion

Effect of turbine inlet temperature Effect of diluent or catalyst

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Gas turbine NOx

versus air factor

equivalence ratio = 1 / air factor

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Low NOx gas

turbine designs
(CRIEPI, Japan)

Catalytic combustion ↑

Two-stage combustion →

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NOx from gas turbines:

natural gas versus coal gasifier gas

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The role of NO in ground-level ozone formation

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Emission standards for passenger cars in the EU

1996/1997 2000 2005

Petrol Driven
CO 2.7 2.3 1.0 g / km
Hydrocarbons 0.341 0.20 0.10
NOx 0.252 0.15 0.08

Diesel
CO 1.06 0.64 0.50
Hydrocarbons 0.71 0.56 0.30
NOx 0.63 0.50 0.25
Particulates 0.08 0.05 0.025

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NO, CO and CxHy pollutant formation in

a spark-injection engine

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NO, CO and CxHy

pollutant formation in
a spark-injection
engine :

effect of air factor

equivalence ratio = 1 / air factor

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Operating window for a three-way car

exhaust gas catalyst

A/F =
air-to-fuel ratio
(kg/kg)

S = air factor

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