NITROGEN OXIDES FORMATION in combustion processes

COMBUSTION AND FUELS

NITROGEN OXIDES FORMED DURING COMBUSTION

N2O - nitrous oxide NO - nitric oxide NO2 - nitrogen dioxide N = 14, O2 =16, NO = 30, NO2= 46

COMBUSTION AND FUELS

CONTRIBUTION OF PARTICULAR NITROGEN OXIDES IN TOTAL NOX PRODUCTION

the biggest contribution has nitric oxide (NO) its content in flue gas is in the range of: 100 1000 mg/m3 next is nitrogen dioxide NO2 in proportion 5-10% of NO its content in flue gas is in the range of: 10 100 mg/m3 N2O has the least contribution: its content in flue gas is in the range of: 110 mg/m3

COMBUSTION AND FUELS

WHAT DOES NOX MEAN ?

COMBUSTION AND FUELS

DEFINITION OF NOX
NOX means the sum of NO and NO2 contents in flue gas recalculated on NO2

NOx = NO + NO2
(expressed in NO2)

COMBUSTION AND FUELS

UNITS OF NOX

COMBUSTION AND FUELS

Units of NOx content in flue gas

mg/m3 ppm (emission) g/m3 (imission) g/GJ
Remarks: 1. The NOx content in flue gas is given for a certain content of oxygen (O2) in flue gas. 2. The NOx content in flue gas is given for normal conditions. 3. ppm - unite part per million (x10-6)

COMBUSTION AND FUELS

NOX emissions conversion chart

ppm: NOx [ppm] = NO [ppm] + NO2 [ppm] ppm mg/m3 NO [mg/m3] = 1.3387 NO [ppm] NOx [mg/m3] = 2.0525 NOx [ppm] mg/m3 GJ (dla NOx) 1 g/GJ = 2.7 [mg/m3] for bituminous coal 1 g/GJ = 2.35 [mg/m3] for lignite

COMBUSTION AND FUELS

NOX emission units which are in use in the power generation industry In Poland (and in EU) NOx is expressed as follows: [mg NO2/m3] for 6% O2 in dry flue gas at normal conditions
COMBUSTION AND FUELS

NOX FORMATION IN COMBUSTION PROCESSES

COMBUSTION AND FUELS

COMBUSTION CHEMISTRY OF NITROGEN OXIDES

The chemical mechanism of NOx (NO and NO2) formation during combustion obeys hundreds of elementary chemical reactions. Depending on the temperature range, stoichiometric ratio and type of nitrous species present in the combustion zone, it is possible to distinguish predominant groups of chemical reactions, which are called the mechanisms of nitrogen oxides formation. Usually the type of flame determines the conditions of the predominant mechanism of NOx formation. COMBUSTION AND FUELS

MAJOR SOURCES OF NOX FORMATION DURING COMBUSTION

1. Air nitrogen (N2) thermal NOx prompt NOx 2. Fuel nitrogen (NF) fuel NOx

COMBUSTION AND FUELS

MAJOR MECHANISMS OF NITRIC OXIDE (NO) FORMATION DURING COMBUSTION

Thermal Prompt Fuel

COMBUSTION AND FUELS

THERMAL NITRIC OXIDE MECHANISM

COMBUSTION AND FUELS

ZELDOVICHs MECHANISM OF NO FORMATION

O2 + M = O + O + M (3) (dissociation)
Where M is stable molecule of high energy necessary to break the bounds of O2 [10]. The liberated O atoms can react with N2 through a relatively slow reaction:

O + N2 NO + N, (4)
the N atoms liberated in this reaction quickly react with O2

N + O2 NO + O
also giving NO.

(5)

COMBUSTION AND FUELS

RATE OF NOX FORMATION via ZELDOVICH MECHANISM

Rate of NOx formation by thermal mechanism d[NO]/dt = kp[O2]1/2[N2]
where kp 2K31/2k2, which is in accord with the experimental.
50000 40000 [NO]r, ppm 30000 20000 10000 0 1000 1500 2000 T, K 2500 1,0E+05 1,0E+03 1,0E+01 1,0E-01 1,0E-03 1,0E-05 3000 czas do 0,5 [NO]r, s

Equilibrium concentration of NO, [NO]r, and time to reach 0,5[NO]r versus the temperature

It shows that the Zeldovich mechanism becomes important when the temperature reaches the COMBUSTION AND FUELS range of 1600-1800 K.

PROMPT NITRIC OXIDE MECHANISM

COMBUSTION AND FUELS

REACTIONS OF HYDROCARBON RADICALS WITH N2

There are many hydrocarbon radicals in flame (CH, CH2, CH3, C2H4, C2H5, C3H7, C, C2...), which can react with molecular nitrogen (N2).

CH2 + N2 HCN + NH CH + N2 HCN + N C + N2 CN + N

general CHx + N2 HCN and other radicals (CN, NH, N...) As a result: HCN, NH i CN are easily oxidized to NO in flame.

COMBUSTION AND FUELS

FUEL NITRIC OXIDE MECHANISM

COMBUSTION AND FUELS

WHAT IS A SOURCE OF FUEL NITRIC OXIDE

1. The source of fuel NO are nitric compounds in fuel, often called fuel nitrogen (denoted NF). 2. The content of fuel nitrogen in fuels is very different!!!!

3. Fuel nitrogen can be a very important source of nitric oxides.

COMBUSTION AND FUELS

FUEL NITROGEN (NF) IN FUELS

COMBUSTION AND FUELS

FUEL NITROGEN IN GAS

Natural gas practically doesnt have fuel nitrogen.

COMBUSTION AND FUELS

FUEL NITROGEN IN LIQUID FUELS

Crude oil has fuel nitrogen in the range of

0.01 do 0.3% wt.

Only exceptionally NF content excess 0.9%. Major groups of nitric compounds are: pyridyne, indoles, chinolines, tetrahydrochinolines, carbazoles i pyroles. Nitric compounds in oil are relatively stable in the elevated temperature, therefore during crude oil destillation they are cumulated in heavy fractions of oil. For example, the content of NF in asphaltes reaches 1.5%.

COMBUSTION AND FUELS

FUEL NITROGEN IN HEATING OILS

Content, % Fuel
C H 15 12,5 13 11,4

Wd MJ/kg

Va, min m3/kg

Tcomb C

Gas
Heating oil 1 Heating oil 2 Heating oil 3

85 86,4 85,5 87

47 45,2 43,6 43,1

11,57 11,18 11,96 10,74

2263 2258 2210 2262

0,05 0,4 0,5

0.05 0.3 0.6

1 0,8 0,3

COMBUSTION AND FUELS

THE INFLUENCE OF NF CONTENT ON NOX EMISSION

COMBUSTION AND FUELS

FUEL NITROGEN IN COAL

The origin of fuel nitrogen in coal is organic material of coal, these are vegetables, bacteria and fungi containing amines, alkaloid and chlorophyll being source of nitrogen.

NF in different coals: Bituminous coal: Anthracite Lignite: 0.6 - 2.8% N (85% C) <1% N 0.6 - 2% N.

COMBUSTION AND FUELS

SELECTED NITRIC COMPOUNDS IN COAL

COMBUSTION AND FUELS

Major nitric compounds in coal

COMBUSTION AND FUELS

CONVERSION OF FUEL NITROGEN DURING COAL COMBUSTION

COMBUSTION AND FUELS

CONVERSION OF FUEL NITROGEN DURING COAL PARTICLE BURNING

Pirolysis Rapid combustion of v.m. Slow burning of char

Coal particle

Products: HCN, NH3, tar, aromatic compounds

Conversion of v.m. into CO, CO2, H2O, N2, N2O, NO etc.

Gasification of char, releasing of: CO, CO2, N2, N2O, NO etc.; reduction of NO on the surface and in the pores of char

COMBUSTION AND FUELS

EVALUATION OF FUEL NITROGEN DURING COAL PYROLYSIS

COMBUSTION AND FUELS

NITRIC OXIDE FORMATION DURING COAL COMBUSTION

COMBUSTION AND FUELS

FUEL NITRIC OXIDE FORMATION DURING COAL COMBUSTION

OH, O, O2
nitrogen in volatile matter

C(s) NO C(s) N2

NH3
nitrogen in char residue

N, czci lotne

N koks.

OH, O, O2
nitrogen in fuel

HCN
nitrogen in char residue

NO 2

N paliwowy N koks.
NO

N poz. koks.
nitrogen in char residue

O2

COMBUSTION AND FUELS

CONVERSION OF GAS-PHASE FUELN TO NO

COMBUSTION AND FUELS

CONVERSION OF CHAR FUELN TO NO

COMBUSTION AND FUELS

NITRIC OXIDE REDUCTION ON CHAR

COMBUSTION AND FUELS

NITROGEN DIOXIDE (NO2) FORMATION IN FLAMES

COMBUSTION AND FUELS

CONDITIONS OF NITROGEN DIOXIDE (NO2) FORMATION IN FLAMES

NO2 is a secondary product, and is formed by oxidation of NO in combustion processes. NO2 is formed in cooler regions of flame, in the temperature range of:

T < 800 C
NO2 undergoes destruction on tat higher temperatures:

T > 1200 C
COMBUSTION AND FUELS

BASIC MECHANISM OF NITROGEN DIOXIDE (NO2) FORMATION IN FLAMES

The major reaction of NO2 formation is with hydroperoxide radical HO2 :

NO + HO2 NO2 + OH
(where from HO2: H + O2 + M HO2 + M)

The temperature range of this reaction:

T < 1000 K
COMBUSTION AND FUELS

ADDITIONAL MECHANISM OF NO2 FORMATION

Hydrocarbonperoxides RO2 plays a considerable part in NO2 formation:

NO + RO2 NO2 + RO
(where from RO2: R + O2 + M ROO + M)

where R are alkil radicals:

CH3, C2H5 and higher

COMBUSTION AND FUELS

NITROGEN DIOXIDE FORMATION IN REACTION WITH ATOMIC OXYGEN

The three body reaction:

NO + O + M NO2 +M
NO2 also is generated, but the contribution of this reaction is not important. The temperature range: T < 800 K.

COMBUSTION AND FUELS

CONTRIBUTION OF NITROGEN DIOXIDE NO2 TO THE TOTAL NOX

The NO2 contribution to the total NOx formation during pulverized coal combustion is minor:

[NO2]/[NOx]100% 5%
More important contribution to the total production of NOx NO2 introduces during combustion in gas turbines:

[NO2]/[NOx]100% 10-15%
COMBUSTION AND FUELS

NITROUS OXIDE (N2O) FORMATION IN FLAMES

COMBUSTION AND FUELS

CONDITIONS OF NITROUS OXIDE (N2O) FORMATION

NO2 is produced in flames due to: 1. Oxidation of amine radicals (mainly Nhand less significant CN2). 2. In lean regions of gas flames. 3. In fluidized bed furnaces (T approx. 850 C)
COMBUSTION AND FUELS

MAJOR SOURCES OF NIROUS OXIDE N2O IN FLAMES Major reaction NH + NO N2O + H

NH amine radical Where is from NH? Mainly, from decomposition of ammonia (NH3, perhaps also hydrogen cyjanide (HCN).

COMBUSTION AND FUELS

NIROUS OXIDE N2O FORMATION IN LEAN FLAMES (<1)

O + N 2 + M N 2O + M
The temperature range of the chemical reaction: T < 1500 C

COMBUSTION AND FUELS

NIROUS OXIDE N2O FORMATION IN FLUIDIZED BEDS

In catalytic reaction:

2NO N2O + 0.5O2

Catalysts in fluidized bed: 1. char 2. Limestone COMBUSTION AND FUELS

HOW IMPORTANT IS NITROUS OXIDE N2O?

N2O is known is the as laughing gas. N2O has contribution to the stratospheric ozone destruction In combustion processes N2O is formed mainly in fluidized beds (N2O content in flue gas up to 50 ppm). N2O has also some contribution to NO emission, by chemical reactions with radicals O i OH:

N2O + O NO + NO
COMBUSTION AND FUELS

DOMINATING MECHANISMS OF NOx IN FLAMES

COMBUSTION AND FUELS

MAJOR FACTORS INFLUENCING NOx FORMATION

fuel nitrogen NF flame temperature air excess () residence time in flame

COMBUSTION AND FUELS

NOX FORMATION IN PULVERIZED COAL FLAME

COMBUSTION AND FUELS

SOURCES OF NOX EMISSION IN PULVERIZED COAL FLAME

COMBUSTION AND FUELS

CONTRIBUTION OF PARTICULAR NITRIC OXIDES IN TOTAL NOX EMISSION FROM PF

Fuel NOx is dominating NOx
lN tota O

O al N m r the

Bituminous coal (Tp = 1650 C)

volatile matter NO

Lignite (Tflame = 1250 C): approx.95% of NOx is fuel NOx

NO from char

COMBUSTION AND FUELS

NOx EMISSION vs. FURNACE TYPE (PF BOILERS)

Furnace type Power MWe 650750 465490 200360 425460 110 160 230 Coal type NOx mg/m3 71060 7501000 500900 1360110 40080 52080 280 50

Tangencial Tangencial Tangencial Wall fired FBB FBB FBB

bituminous bituminous bituminous bituminous bituminous bituminous lignite

COMBUSTION AND FUELS

OIL FLAMES
Heavy heating oil has much of fuel nitrogen NF > 0,5%. NOx emission from oil burners operating on heating oils nr 2 and 3 is in the range:

300-700 mg/m3
(mainly fuel NOx).
Fuel nitrogen NF is a dominating factor.

Light heating oil has less fuel nitrogen NF < 0,05% NOx emission form oil burners operating on light heating oil (nr 1) is in the range:

180-220 mg/m3
(mainly thermal NOx).

COMBUSTION AND FUELS

GAS FLAMES
No fuel nitrogen NF in gas. Industrial gas burners (flames). Range of NOx emission:

100-300 mg/m3

Dominating mechanism: thermal Small gas burners (flames): Range of NOx emission:

10-100 mg/m3

Dominating mechanism: thermal + prompt (20%) COMBUSTION AND FUELS