NOx

This article is about nitrogen oxides produced during combustion. For a more extensive list of nitrogen oxides, see nitrogen oxide. For other meanings of "Nox", see Nox (disambiguation).

NOx is a generic term for the mono-nitrogen oxides NO and NO2 (nitric oxide and nitrogen dioxide).[1][2] They are produced from the reaction among nitrogen, oxygen and even hydrocarbons (during combustion), especially at high temperatures.[1][2][3] In areas of high motor vehicle traffic, such as in large cities, the amount of nitrogen oxides emitted into the atmosphere as air pollution can be significant. NOx gases are formed whenever combustion occurs in the presence of nitrogen – as in an air-breathing engine; they also are produced naturally by lightning. In atmospheric chemistry, the term means the total concentration of NO and NO2. NOx gases react to form smog and acid rain as well as being central to the formation of tropospheric ozone.

NOx should not be confused with nitrous oxide (N2O),[1] which is a greenhouse gas and has many uses as an oxidizer, an anesthetic, and a food additive.

NOy (reactive, odd nitrogen) is defined as the sum of NOx plus the compounds produced from the oxidation of NOx which include nitric acid.

Formation and reactions

Oxygen and nitrogen do not react at ambient temperatures. But at high temperatures, they undergo an endothermic reaction producing various oxides of nitrogen. Such temperatures arise inside an internal combustion engine or a power station boiler, during the combustion of a mixture of air and fuel, and naturally in a lightning flash.

In atmospheric chemistry, the term NOx means the total concentration of NO and NO2. During daylight, these concentrations are in equilibrium; the ratio NO / NO2 is determined by the intensity of sunshine (which converts NO2 to NO) and the concentration of ozone (which reacts with NO to again form NO2).

In the presence of excess oxygen (O2), nitric oxide (NO) reacts with the oxygen to form nitrogen dioxide (NO2). The time required depends on the concentration in air as shown below:[4]

NO concentration in air (ppm) Time required for half NO to be oxidized to NO2 (min)
20,000 0.175
10,000 0.35
1,000 3.5
100 35
10 350
1 3500

When NOx and volatile organic compounds (VOCs) react in the presence of sunlight, they form photochemical smog, a significant form of air pollution, especially in the summer. Children, people with lung diseases such as asthma, and people who work or exercise outside are particularly susceptible to adverse effects of smog such as damage to lung tissue and reduction in lung function.[5]

Formation of nitric acid and acid rain

Mono-nitrogen oxides eventually form nitric acid when dissolved in atmospheric moisture, forming a component of acid rain. This chemical reaction occurs when nitrogen dioxide reacts with water:

2 NO2 + H2O → HNO2 + HNO3

where nitric oxide will oxidize to form nitrogen dioxide that again reacts with water, ultimately forming nitric acid:

4 NO + 3 O2 + 2 H2O → 4 HNO3

Combining these three equations gives a single equation that describes the aerobic conversion of nitrogen dioxide to nitric acid:

4 NO2 + 2 H2O + O2 → 4 HNO3

Mono-nitrogen oxides are also involved in tropospheric production of ozone.[6]

This nitric acid may end up in the soil, where it makes nitrate, where it is of use to growing plants.

Sources

Natural sources

Nitric oxide is produced during thunderstorms due to the extreme heat of lightning,[7] and is caused by the splitting of nitrogen molecules. This can result in the production of acid rain, if nitric oxide forms compounds with the water molecules in precipitation.

Scientists Ott et al.[8] estimated that each flash of lightning on average in the several mid-latitude and subtropical thunderstorms studied turned 7 kg (15 lb) of nitrogen into chemically reactive NOx. With 1.4 billion lightning flashes per year, multiplied by 7 kilograms per lightning strike, they estimated the total amount of NOx produced by lightning per year is 8.6 million tonnes. However, NOx emissions resulting from fossil fuel combustion are estimated at 28.5 million tonnes.[9]

A recent discovery indicated that cosmic ray and solar flares can significantly influence the number of lightning strikes occurring on Earth. Therefore, space weather can be a major driving force of lightning-produced atmospheric NOx.[3] It should also be noted that atmospheric constituents such as nitrogen oxides can be stratified vertically in the atmosphere. Ott noted that the lightning-produced NOx is typically found at altitudes greater than 5 km, while combustion and biogenic (soil) NOx are typically found near the sources at near surface elevation (where it can cause the most significant health effects).[10]

Biogenic sources

Agricultural fertilization and the use of nitrogen fixing plants also contribute to atmospheric NOx, by promoting nitrogen fixation by microorganisms.[11][12]

Industrial sources (anthropogenic sources)

The three primary sources of NOx in combustion processes:

Thermal NOx formation, which is highly temperature dependent, is recognized as the most relevant source when combusting natural gas. Fuel NOx tends to dominate during the combustion of fuels, such as coal, which have a significant nitrogen content, particularly when burned in combustors designed to minimise thermal NOx. The contribution of prompt NOx is normally considered negligible. A fourth source, called feed NOx is associated with the combustion of nitrogen present in the feed material of cement rotary kilns, at between 300 and 800 °C, where it is also a minor contributor.

Thermal

Thermal NOx refers to NOx formed through high temperature oxidation of the diatomic nitrogen found in combustion air.[13] The formation rate is primarily a function of temperature and the residence time of nitrogen at that temperature. At high temperatures, usually above 1600 °C (2900 °F), molecular nitrogen (N2) and oxygen (O2) in the combustion air disassociate into their atomic states and participate in a series of reactions.

The three principal reactions (the extended Zeldovich mechanism) producing thermal NOx are:

N2 + O → NO + N
N + O2 → NO + O
N + OH → NO + H

All three reactions are reversible. Zeldovich was the first to suggest the importance of the first two reactions.[14] The last reaction of atomic nitrogen with the hydroxyl radical, •HO, was added by Lavoie, Heywood and Keck[15] to the mechanism and makes a significant contribution to the formation of thermal NOx.

Fuel

It is estimated that transportation fuels cause 54% of the anthropogenic (i.e. human-caused) NOx. The major source of NOx production from nitrogen-bearing fuels such as certain coals and oil, is the conversion of fuel bound nitrogen to NOx during combustion.[13] During combustion, the nitrogen bound in the fuel is released as a free radical and ultimately forms free N2, or NO. Fuel NOx can contribute as much as 50% of total emissions when combusting oil and as much as 80% when combusting coal.

Although the complete mechanism is not fully understood, there are two primary paths of formation. The first involves the oxidation of volatile nitrogen species during the initial stages of combustion. During the release and before the oxidation of the volatiles, nitrogen reacts to form several intermediaries which are then oxidized into NO. If the volatiles evolve into a reducing atmosphere, the nitrogen evolved can readily be made to form nitrogen gas, rather than NOx. The second path involves the combustion of nitrogen contained in the char matrix during the combustion of the char portion of the fuels. This reaction occurs much more slowly than the volatile phase. Only around 20% of the char nitrogen is ultimately emitted as NOx, since much of the NOx that forms during this process is reduced to nitrogen by the char, which is nearly pure carbon.

Prompt

This third source is attributed to the reaction of atmospheric nitrogen, N2, with radicals such as C, CH, and CH2 fragments derived from fuel, where this cannot be explained by either the aforementioned thermal or fuel processes. Occurring in the earliest stage of combustion, this results in the formation of fixed species of nitrogen such as NH (nitrogen monohydride), HCN (hydrogen cyanide), H2CN (dihydrogen cyanide) and •CN (cyano radical) which can oxidize to NO. In fuels that contain nitrogen, the incidence of prompt NOx is especially minimal and it is generally only of interest for the most exacting emission targets. Prompt NOx can be a major source on formation of NOx at low-temperature combustion of oxygenated fuels such as biodiesel.[2]

NO from N2O

At high pressures NO formation via N2O becomes important:

N2 + O + M → N2O + M
N2O + O → 2 NO (activation energy 97 kJ/mol)
N2O + O → N2 + O2

Competing Reactions :

N2O + O → NO + N     (thermal NO)
N2O + O + M → N2O2 + M

Environmental effects

NOx reacts with ammonia, moisture, and other compounds to form nitric acid vapor and related particles. Small particles can penetrate deeply into sensitive lung tissue and damage it, causing premature death in extreme cases. Inhalation of such particles may cause or worsen respiratory diseases, such as emphysema or bronchitis, or may also aggravate existing heart disease.[16]

NOx reacts with volatile organic compounds in the presence of sunlight to form ozone. Ozone can cause adverse effects such as damage to lung tissue and reduction in lung function mostly in susceptible populations (children, elderly, asthmatics). Ozone can be transported by wind currents and cause health impacts far from the original sources. The American Lung Association estimates that nearly 50 percent of United States inhabitants live in counties that are not in ozone compliance.[17]

NOx also readily reacts with common organic chemicals, and even ozone, to form a wide variety of toxic products: nitroarenes, nitrosamines and also the nitrate radical some of which may cause biological mutations. Recently another pathway, via NOx, to ozone has been found that predominantly occurs in coastal areas via formation of nitryl chloride when NOx comes into contact with salt mist.[18]

NOx emissions also cause global cooling through the formation of •OH radicals that destroy methane molecules, countering the effect of greenhouse gases. The effect can be significant. For instance, according to the OECD "the large NOx emissions from ship traffic lead to significant increases in hydroxyl (OH), which is the major oxidant in the lower atmosphere. Since reaction with OH is a major way of removing methane from the atmosphere, ship emissions decrease methane concentrations. (Reductions in methane lifetimes due to shipping-based NOx emissions vary between 1.5% and 5% in different calculations)." "In summary, most studies so far indicate that ship emissions actually lead to a net global cooling. This net global cooling effect is not being experienced in other transport sectors. However, it should be stressed that the uncertainties with this conclusion are large, in particular for indirect effects, and global temperature is only a first measure of the extent of climate change in any event."[19]

Biodiesel and NOx

Biodiesel and its blends in general are known to produce lower carbon monoxide, soot, hydrocarbon emissions, and higher NOx emissions compared with regular diesel. Because of the lower heating value of biodiesel, more biodiesel should be burned to produce the equivalent energy of ULSD.[2] Also, due to the presence of high oxygen content in biodiesel fuels, generally biodiesel fuels emit more NOx than regular diesel for the same heat generation. The reduction of NOx emissions is one of the most important technical challenges facing biodiesel, especially in light of the increasingly stringent exhaust emission regulations on diesel engines. NOx formation during biodiesel combustion is associated with a number of factors such as the property of biodiesel and combustion conditions. Combustion temperature influences thermal NOx emissions. Therefore, low-temperature may help thermal NOx reduce during combustion, leading to low-temperature combustion or LTC technology.[2]

Regulation and emission control technologies

Technologies such as flameless oxidation (FLOX) and staged combustion significantly reduce thermal NOx in industrial processes. Bowin low NOx technology is a hybrid of staged-premixed-radiant combustion technology with a major surface combustion preceded by a minor radiant combustion. In the Bowin burner, air and fuel gas are premixed at a ratio greater than or equal to the stoichiometric combustion requirement.[20] Water Injection technology, whereby water is introduced into the combustion chamber, is also becoming an important means of NOx reduction through increased efficiency in the overall combustion process. Alternatively, the water (e.g. 10 to 50%) is emulsified into the fuel oil before the injection and combustion. This emulsification can either be made in-line (unstabilized) just before the injection or as a drop-in fuel with chemical additives for long term emulsion stability (stabilized). Inline emulsified fuel/water mixtures show NOx reductions between 4 and 83%.[21]

Other technologies, such as selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR) reduce post combustion NOx by reacting the exhaust with urea or ammonia to produce nitrogen and water. SCR is now being used in ships,[22] diesel trucks and in some diesel cars. The use of exhaust gas recirculation and catalytic converters in motor vehicle engines have significantly reduced vehicular emissions. NOx was the main focus of the Volkswagen emissions violations.

References

  1. 1 2 3 Mollenhauer, Klaus; Tschöke, Helmut (2010). Handbook of Diesel Engines. Springer. pp. 445–446. ISBN 978-3540890829.
  2. 1 2 3 4 5 Omidvarborna; et al. "NOx emissions from low-temperature combustion of biodiesel made of various feedstocks and blends". Fuel Processing Technology. 140: 113–118. doi:10.1016/j.fuproc.2015.08.031.
  3. 1 2 Annamalai, Kalyan; Puri, Ishwar K. (2007). Combustion Science and Engineering. CRC Press. p. 775. ISBN 978-0-8493-2071-2.
  4. ↑ "NOx Removal". Branch Environmental Corp. Archived from the original on 2007-10-08. Retrieved 2007-12-26.
  5. ↑ "Health and Environmental Impacts of NOx". United States Environmental Protection Agency. Retrieved 2007-12-26.
  6. ↑ D. Fowler; et al. (1998). "The atmospheric budget of oxidized nitrogen and its role in ozone formation and deposition". New Phytologist. 139: 11–23. doi:10.1046/j.1469-8137.1998.00167.x.
  7. ↑ Joel S. Levine; Tommy R. Augustsson; Iris C. Andersont; James M. Hoell Jr. & Dana A. Brewer (1984). "Tropospheric sources of NOx: Lightning and biology". Atmospheric Environment. 18 (9): 1797–1804. doi:10.1016/0004-6981(84)90355-X. PMID 11540827. Retrieved 2009-09-04.
  8. ↑ Lesley E. Ott; Kenneth E. Pickering; Georgiy L. Stenchikov; Dale J. Allen; Alex J. DeCaria; Brian Ridley; Ruei-Fong Lin; Stephen Lang & Wei-Kuo Tao (2010). Journal of Geophysical Research. 115: D04301. doi:10.1029/2009JD011880 http://onlinelibrary.wiley.com/doi/10.1029/2009JD011880/pdf. Retrieved 2015-11-14. Missing or empty |title= (help)
  9. ↑ U. Schumann & H. Huntrieser (2007). "The global lightning-induced nitrogen oxides source" (PDF). Atmos. Chem. Phys. 7: 3823. Retrieved 2016-05-31.
  10. ↑ Lesley E. Ott; Kenneth E. Pickering; Georgiy L. Stenchikov; Dale J. Allen; Alex J. DeCaria; Brian Ridley; Ruei-Fong Lin; Stephen Lang & Wei-Kuo Tao (2010). Journal of Geophysical Research. 115: D04301. doi:10.1029/2009JD011880 http://onlinelibrary.wiley.com/doi/10.1029/2009JD011880/pdf. Retrieved 2016-05-31. Missing or empty |title= (help)
  11. ↑ J.N. Galloway; et al. (September 2004). "Nitrogen cycles: past, present, and future". Biogeochemistry. 70 (2): 153–226. doi:10.1007/s10533-004-0370-0.
  12. ↑ E.A. Davidson & W. Kingerlee (1997). "A global inventory of nitric oxide emissions from soils". Nutrient Cycling in Agroecosystems. 48: 37–50. doi:10.1023/A:1009738715891.
  13. 1 2 Milton R. Beychok (March 1973). "NOX emission from fuel combustion controlled". Oil & Gas Journal: 53–56.
  14. ↑ Y.B. Zel'dovich (1946). "The Oxidation of Nitrogen in Combustion Explosions". Acta Physicochimica U.S.S.R. 21: 577–628.
  15. ↑ G.A. Lavoie; J.B. Heywood; J.C. Keck (1970). "Experimental and Theoretical Study of Nitric Oxide Formation in Internal Combustion Engines". Combust. Sci. Tech. 1 (4): 313–326.
  16. ↑ "How nitrogen oxides affect the way we live and breathe" (PDF). Environmental protection agency. Archived from the original (PDF) on 2008-07-16. Retrieved 2008-12-10.
  17. ↑ Ozone, Environmental Protection Agency.
  18. ↑ Carol Potera (2008). "Air Pollution: Salt Mist Is the Right Seasoning for Ozone". Environ Health Perspect. 116 (7): A288. doi:10.1289/ehp.116-a288. PMC 2453175Freely accessible. PMID 18629329.
  19. ↑ http://www.oecd.org/greengrowth/greening-transport/45095528.pdf
  20. ↑ Bob Joynt & Stephen Wu, Nitrogen oxides emissions standards for domestic gas appliances background study Combustion Engineering Consultant; February 2000
  21. ↑ "NOx-Reduction by Oil/Water-Emulsification". Retrieved 2010-05-18.
  22. ↑ Wärtsilä Low NOx Solutions Wärtsilä, 2008
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