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NO x is the sum of NO and NO 2 contents in flue gas recalculated on NO 2 NO x = NO + NO 2 (expressed in NO 2 ) ppm - unite - part per million (x10 -6) NO x [ppm] = NO [mg / m 3] = 1.3387 NO x ppm = NO x (ppm)
NO x is the sum of NO and NO 2 contents in flue gas recalculated on NO 2 NO x = NO + NO 2 (expressed in NO 2 ) ppm - unite - part per million (x10 -6) NO x [ppm] = NO [mg / m 3] = 1.3387 NO x ppm = NO x (ppm)
NO x is the sum of NO and NO 2 contents in flue gas recalculated on NO 2 NO x = NO + NO 2 (expressed in NO 2 ) ppm - unite - part per million (x10 -6) NO x [ppm] = NO [mg / m 3] = 1.3387 NO x ppm = NO x (ppm)
in combustion processes COMBUSTION AND FUELS NITROGEN OXIDES FORMED DURING COMBUSTION N 2 O - nitrous oxide NO - nitric oxide NO 2 - nitrogen dioxide N = 14, O 2 =16, NO = 30, NO 2 = 46 COMBUSTION AND FUELS CONTRIBUTION OF PARTICULAR NITROGEN OXIDES IN TOTAL NO X PRODUCTION the biggest contribution has nitric oxide (NO) its content in flue gas is in the range of: 100 1000 mg/m 3 next is nitrogen dioxide NO 2 in proportion 5-10% of NO its content in flue gas is in the range of: 10 100 mg/m3 N 2 O has the least contribution: its content in flue gas is in the range of: 110 mg/m 3 COMBUSTION AND FUELS WHAT DOES NO X MEAN ? COMBUSTION AND FUELS DEFINITION OF NO X NO X means the sum of NO and NO 2 contents in flue gas recalculated on NO 2 NO x = NO + NO 2 (expressed in NO 2 ) COMBUSTION AND FUELS UNITS OF NO X COMBUSTION AND FUELS Units of NOx content in flue gas mg/m 3 ppm (emission) g/m 3 (imission) g/GJ Remarks: 1. The NO x content in flue gas is given for a certain content of oxygen (O 2 ) in flue gas. 2. The NO x content in flue gas is given for normal conditions. 3. ppm - unite part per million (x10 -6 ) COMBUSTION AND FUELS NO X emissions conversion chart ppm: NO x [ppm] = NO [ppm] + NO 2 [ppm] ppm mg/m 3 NO [mg/m 3 ] = 1.3387 NO [ppm] NO x [mg/m 3 ] = 2.0525 NO x [ppm] mg/m 3 GJ (dla NOx) 1 g/GJ = 2.7 [mg/m 3 ] for bituminous coal 1 g/GJ = 2.35 [mg/m 3 ] for lignite COMBUSTION AND FUELS NO X emission units which are in use in the power generation industry In Poland (and in EU) NO x is expressed as follows: [mg NO 2 /m 3 ] for 6% O 2 in dry flue gas at normal conditions COMBUSTION AND FUELS NO X FORMATION IN COMBUSTION PROCESSES COMBUSTION AND FUELS COMBUSTION CHEMISTRY OF NITROGEN OXIDES The chemical mechanism of NO x (NO and NO 2 ) 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 NO x formation. COMBUSTION AND FUELS MAJOR SOURCES OF NO X FORMATION DURING COMBUSTION 1. Air nitrogen (N 2 ) thermal NO x prompt NO x 2. Fuel nitrogen (N F ) fuel NO x 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 O 2 + ++ + M = == = O + ++ + O + ++ + M (3) (dissociation) Where M is stable molecule of high energy necessary to break the bounds of O 2 [10]. The liberated O atoms can react with N 2 through a relatively slow reaction: O + ++ + N 2 NO + ++ + N, (4) the N atoms liberated in this reaction quickly react with O 2 N + ++ + O 2 NO + ++ + O (5) also giving NO. COMBUSTION AND FUELS RATE OF NO X FORMATION via ZELDOVICH MECHANISM It shows that the Zeldovich mechanism becomes important when the temperature reaches the range of 1600-1800 K. Rate of NO x formation by thermal mechanism d[NO]/dt = == = k p [O 2 ] 1/2 [N 2 ] where k p 2K 3 1/2 k 2 , which is in accord with the experimental. 0 10000 20000 30000 40000 50000 1000 1500 2000 2500 3000 T, K [ N O ] r ,
p p m 1,0E-05 1,0E-03 1,0E-01 1,0E+01 1,0E+03 1,0E+05 c z a s
d o
0 , 5
[ N O ] r ,
s Equilibrium concentration of NO, [NO] r , and time to reach 0,5[NO] r versus the temperature COMBUSTION AND FUELS PROMPT NITRIC OXIDE MECHANISM COMBUSTION AND FUELS REACTIONS OF HYDROCARBON RADICALS WITH N 2 There are many hydrocarbon radicals in flame (CH, CH 2 , CH 3 , C 2 H 4 , C 2 H 5 , C 3 H 7 , C, C 2 ...), which can react with molecular nitrogen (N 2 ). CH 2 + ++ + N 2 HCN + ++ + NH CH + ++ + N 2 HCN + ++ + N C + ++ + N 2 CN + ++ + N general CH x + ++ + N 2 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 N F ). 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 N F 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 N F in asphaltes reaches 1.5%. COMBUSTION AND FUELS FUEL NITROGEN IN HEATING OILS Fuel Content, % W d MJ/kg V a, min m 3 /kg T comb C C H S N O Gas 85 15
47 11,57 2263 Heating oil 1 86,4 12,5 0,05 0.05 1 45,2 11,18 2258 Heating oil 2 85,5 13 0,4 0.3 0,8 43,6 11,96 2210 Heating oil 3 87 11,4 0,5 0.6 0,3 43,1 10,74 2262 COMBUSTION AND FUELS THE INFLUENCE OF NF CONTENT ON NO X 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. N F in different coals: Bituminous coal: 0.6 - 2.8% N (85% C) Anthracite <1% N Lignite: 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 Coal particle Rapid combustion of v.m. Slow burning of char Conversion of v.m. into CO, CO 2 , H 2 O, N 2 , N 2 O, NO etc. Products: HCN, NH 3 , tar, aromatic compounds Gasification of char, releasing of: CO, CO 2 , N 2 , N 2 O, 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 N paliwowy N, czci lotne NH 3 HCN OH, O, O 2 NO NO 2 N koks. N 2 C(s) C(s) N poz. koks. NO N koks. O 2 OH, O, O 2 nitrogen in volatile matter nitrogen in fuel nitrogen in char residue nitrogen in char residue nitrogen in char residue 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 (NO 2 ) FORMATION IN FLAMES COMBUSTION AND FUELS CONDITIONS OF NITROGEN DIOXIDE (NO 2 ) FORMATION IN FLAMES NO 2 is a secondary product, and is formed by oxidation of NO in combustion processes. NO 2 is formed in cooler regions of flame, in the temperature range of: T < 800 C NO 2 undergoes destruction on tat higher temperatures: T > 1200 C COMBUSTION AND FUELS BASIC MECHANISM OF NITROGEN DIOXIDE (NO 2 ) FORMATION IN FLAMES The major reaction of NO 2 formation is with hydroperoxide radical HO 2 : NO + HO 2 NO 2 + OH (where from HO 2 : H + O 2 + M HO 2 + M) The temperature range of this reaction: T < 1000 K COMBUSTION AND FUELS ADDITIONAL MECHANISM OF NO 2 FORMATION Hydrocarbonperoxides RO 2 plays a considerable part in NO 2 formation: NO + RO 2 NO 2 + RO (where from RO 2 : R + O 2 + M ROO + M) where R are alkil radicals: CH 3 , C 2 H 5 and higher COMBUSTION AND FUELS NITROGEN DIOXIDE FORMATION IN REACTION WITH ATOMIC OXYGEN The three body reaction: NO + O + M NO 2 +M NO 2 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 NO 2 TO THE TOTAL NO X The NO 2 contribution to the total NO x formation during pulverized coal combustion is minor: [NO 2 ]/[NO x ]100% 5% More important contribution to the total production of NO x NO 2 introduces during combustion in gas turbines: [NO 2 ]/[NO x ]100% 10-15% COMBUSTION AND FUELS NITROUS OXIDE (N 2 O) FORMATION IN FLAMES COMBUSTION AND FUELS CONDITIONS OF NITROUS OXIDE (N 2 O) FORMATION NO 2 is produced in flames due to: 1. Oxidation of amine radicals (mainly Nhand less significant CN 2 ). 2. In lean regions of gas flames. 3. In fluidized bed furnaces (T approx. 850 C) COMBUSTION AND FUELS MAJOR SOURCES OF NIROUS OXIDE N 2 O IN FLAMES Major reaction NH + NO N 2 O + H NH amine radical Where is from NH? Mainly, from decomposition of ammonia (NH 3 , perhaps also hydrogen cyjanide (HCN). COMBUSTION AND FUELS NIROUS OXIDE N 2 O FORMATION IN LEAN FLAMES (<1) O + N 2 + M N 2 O + M The temperature range of the chemical reaction: T < 1500 C COMBUSTION AND FUELS NIROUS OXIDE N 2 O FORMATION IN FLUIDIZED BEDS In catalytic reaction: 2NO N 2 O + 0.5O 2 Catalysts in fluidized bed: 1. char 2. Limestone COMBUSTION AND FUELS HOW IMPORTANT IS NITROUS OXIDE N 2 O? N 2 O is known is the as laughing gas. N 2 O has contribution to the stratospheric ozone destruction In combustion processes N 2 O is formed mainly in fluidized beds (N 2 O content in flue gas up to 50 ppm). N 2 O has also some contribution to NO emission, by chemical reactions with radicals O i OH: N 2 O + O NO + NO COMBUSTION AND FUELS DOMINATING MECHANISMS OF NOx IN FLAMES COMBUSTION AND FUELS MAJOR FACTORS INFLUENCING NO x FORMATION fuel nitrogen N F flame temperature air excess () residence time in flame COMBUSTION AND FUELS NO X FORMATION IN PULVERIZED COAL FLAME COMBUSTION AND FUELS SOURCES OF NO X EMISSION IN PULVERIZED COAL FLAME COMBUSTION AND FUELS CONTRIBUTION OF PARTICULAR NITRIC OXIDES IN TOTAL NOX EMISSION FROM PF Fuel NO x is dominating NO x Lignite (T flame = 1250 C): approx.95% of NO x is fuel NO x Bituminous coal (T p = 1650 C) t o t a l
N O t h e r m a l
N O volatile matter NO NO from char COMBUSTION AND FUELS NOx EMISSION vs. FURNACE TYPE (PF BOILERS) Furnace type Power MW e Coal type NO x mg/m 3 Tangencial Tangencial Tangencial Wall fired FBB FBB FBB 650750 465490 200360 425460 110 160 230 bituminous bituminous bituminous bituminous bituminous bituminous lignite 71060 7501000 500900 1360110 40080 52080 280 50 COMBUSTION AND FUELS OIL FLAMES Heavy heating oil has much of fuel nitrogen N F > 0,5%. NO x emission from oil burners operating on heating oils nr 2 and 3 is in the range: 300-700 mg/m 3 (mainly fuel NOx). Light heating oil has less fuel nitrogen N F < 0,05% NO x emission form oil burners operating on light heating oil (nr 1) is in the range: 180-220 mg/m 3 (mainly thermal NO x ). Fuel nitrogen N F is a dominating factor. COMBUSTION AND FUELS GAS FLAMES No fuel nitrogen N F in gas. Industrial gas burners (flames). Range of NOx emission: 100-300 mg/m 3 Dominating mechanism: thermal Small gas burners (flames): Range of NOx emission: 10-100 mg/m 3 Dominating mechanism: thermal + prompt (20%)