Andrussow process: Difference between revisions
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{{Short description|Process for industrial production of hydrogen cyanide}} |
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The '''Andrussov Oxidation''' is an [[organic reaction]] describing the [[oxidation]] of [[methane]] in the presence of [[oxygen]], [[ammonia]], and a [[platinum]] [[catalyst]] to produce [[hydrogen cyanide]].<ref>{{cite journal |
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[[File:1931.01.31 23 Andrussow Pilot Plant diagramm Herne Germany.jpg|thumb|right|Diagram from 1931 showing the Andrussow process]] |
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The '''Andrussow process''' is the dominant industrial process for the production of [[hydrogen cyanide]].<ref name=Ullmann>{{ Ullmann |last1=Gail|first1=E.|last2=Gos|first2=S.|last3=Kulzer|first3=R.|last4=Lorösch |first4=J.|last5=Rubo|first5=A.|last6=Sauer|first6=M. | title = Cyano Compounds, Inorganic | doi = 10.1002/14356007.a08_159.pub2 }}</ref> It involves the reaction of [[methane]], [[ammonia]], and [[oxygen]]. The process is [[catalyst|catalyzed]] by a [[platinum]]-[[rhodium]] alloy.<ref>{{cite journal |doi=10.1016/j.apcata.2010.03.046 |title=Mechanistic aspects of the Andrussow process over Pt-Rh gauzes. Effect of gauze morphology and oxygen coverage on primary O2–NH3–CH4 interactions |date=2010 |last1=Kondratenko |first1=V.A. |last2=Weinberg |first2=G. |last3=Pohl |first3=M.-M. |last4=Su |first4=D.S. |journal=Applied Catalysis A: General |volume=381 |issue=1–2 |pages=66–73 }}</ref> |
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Hydrogen cyanide is highly valued for the production or [[acrylonitrile]] and [[adiponitrile]], as well as alkali metal salts such as [[potassium cyanide]].<ref name=Ullmann/> |
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==Process details== |
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This reaction is very [[exothermic reaction|exothermic]]. The change of [[Standard enthalpy of formation|enthalpy]] of this reaction is equal to ''-481.06 kJ''.<ref>{{Citation | first=Gyula | last=Deák | title=Menné reakcie v organickej chémii|year = 1980|publisher=Vydavateľstvo technickej a ekonomickej literatúry| location = Bratislava| page = 14}}</ref> The [[heat]] provided by the main reaction serves as a catalyst for other side reactions. |
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:CH<sub>4</sub> + H<sub>2</sub>O → CO + 3 H<sub>2</sub> |
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:2 CH<sub>4</sub> + 3 O<sub>2</sub> → 2 CO + 4 H<sub>2</sub>O |
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:4 NH<sub>3</sub> + 3 O<sub>2</sub> → 2 N<sub>2</sub> + 6 H<sub>2</sub>O |
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These side reactions can be minimized by only short exposures to the catalyst of the order of 0.0003 s.<ref>{{cite journal|last=Pirie|first=J M|title=The Manufacture of Hydrocyanic Acid by the Andrussow Process|journal=Platinum Metals Rev.|year=1958|volume=2|issue=1|pages=7–11|doi=10.1595/003214058X21711 |url=http://www.platinummetalsreview.com/pdf/pmr-v2-i1-007-011.pdf|access-date=28 March 2014|archive-date=31 January 2013|archive-url=https://web.archive.org/web/20130131122838/http://www.platinummetalsreview.com/pdf/pmr-v2-i1-007-011.pdf|url-status=dead}}</ref> |
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==Historical articles== |
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The process is based on a reaction that was discovered by [[Leonid Andrussow]] in 1927. In the following years he developed the process that is named after him. HCN is also produced in the [[BMA process]].<ref>{{cite journal |
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| title = Über die schnell verlaufenden katalytischen Prozesse in strömenden Gasen und die Ammoniak-Oxydation (V) |
| title = Über die schnell verlaufenden katalytischen Prozesse in strömenden Gasen und die Ammoniak-Oxydation (V) |
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| author = [[Leonid Andrussow]] |
| author = [[Leonid Andrussow]] |
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| journal = Berichte der |
| journal = Berichte der Deutschen Chemischen Gesellschaft |
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| volume = 60 |
| volume = 60 |
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| issue = 8 |
| issue = 8 |
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| pages = 2005–2018 |
| pages = 2005–2018 |
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| year = 1927 |
| year = 1927 |
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| url = |
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| doi = 10.1002/cber.19270600857 }}</ref><ref>{{cite journal |
| doi = 10.1002/cber.19270600857 }}</ref><ref>{{cite journal |
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| title = Über die katalytische Oxydation von Ammoniak-Methan-Gemischen zu Blausäure |
| title = Über die katalytische Oxydation von Ammoniak-Methan-Gemischen zu Blausäure (The catalytic oxidation of ammonia-methane-mixtures to hydrogen cyanide) |
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| author = L. Andrussow |
| author = L. Andrussow |
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| journal = [[Angewandte Chemie]] |
| journal = [[Angewandte Chemie]] |
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| pages = 593–595 |
| pages = 593–595 |
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| year = 1935 |
| year = 1935 |
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| url = |
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| doi = 10.1002/ange.19350483702 }}</ref> |
| doi = 10.1002/ange.19350483702 }}</ref> |
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The reaction was discovered by [[Leonid Andrussow]] in 1927. |
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==References== |
==References== |
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{{Reflist}} |
{{Reflist}} |
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{{Organic reactions}} |
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{{DEFAULTSORT:Andrussow Oxidation}} |
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[[Category:Organic redox reactions]] |
[[Category:Organic redox reactions]] |
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[[Category:Industrial processes]] |
[[Category:Industrial processes]] |
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[[Category:Catalysis]] |
[[Category:Catalysis]] |
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[[de:Andrussow-Verfahren]] |
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[[fr:Procédé Andrussow]] |
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[[Category:Name reactions]] |
[[Category:Name reactions]] |
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Latest revision as of 14:34, 10 November 2024
The Andrussow process is the dominant industrial process for the production of hydrogen cyanide.[1] It involves the reaction of methane, ammonia, and oxygen. The process is catalyzed by a platinum-rhodium alloy.[2]
- 2 CH4 + 2 NH3 + 3 O2 → 2 HCN + 6 H2O
Hydrogen cyanide is highly valued for the production or acrylonitrile and adiponitrile, as well as alkali metal salts such as potassium cyanide.[1]
Process details
[edit]This reaction is very exothermic. The change of enthalpy of this reaction is equal to -481.06 kJ.[3] The heat provided by the main reaction serves as a catalyst for other side reactions.
- CH4 + H2O → CO + 3 H2
- 2 CH4 + 3 O2 → 2 CO + 4 H2O
- 4 NH3 + 3 O2 → 2 N2 + 6 H2O
These side reactions can be minimized by only short exposures to the catalyst of the order of 0.0003 s.[4]
Historical articles
[edit]The process is based on a reaction that was discovered by Leonid Andrussow in 1927. In the following years he developed the process that is named after him. HCN is also produced in the BMA process.[5][6]
References
[edit]- ^ a b Gail, E.; Gos, S.; Kulzer, R.; Lorösch, J.; Rubo, A.; Sauer, M. "Cyano Compounds, Inorganic". Ullmann's Encyclopedia of Industrial Chemistry. Weinheim: Wiley-VCH. doi:10.1002/14356007.a08_159.pub2. ISBN 978-3527306732.
- ^ Kondratenko, V.A.; Weinberg, G.; Pohl, M.-M.; Su, D.S. (2010). "Mechanistic aspects of the Andrussow process over Pt-Rh gauzes. Effect of gauze morphology and oxygen coverage on primary O2–NH3–CH4 interactions". Applied Catalysis A: General. 381 (1–2): 66–73. doi:10.1016/j.apcata.2010.03.046.
- ^ Deák, Gyula (1980), Menné reakcie v organickej chémii, Bratislava: Vydavateľstvo technickej a ekonomickej literatúry, p. 14
- ^ Pirie, J M (1958). "The Manufacture of Hydrocyanic Acid by the Andrussow Process" (PDF). Platinum Metals Rev. 2 (1): 7–11. doi:10.1595/003214058X21711. Archived from the original (PDF) on 31 January 2013. Retrieved 28 March 2014.
- ^ Leonid Andrussow (1927). "Über die schnell verlaufenden katalytischen Prozesse in strömenden Gasen und die Ammoniak-Oxydation (V)". Berichte der Deutschen Chemischen Gesellschaft. 60 (8): 2005–2018. doi:10.1002/cber.19270600857.
- ^ L. Andrussow (1935). "Über die katalytische Oxydation von Ammoniak-Methan-Gemischen zu Blausäure (The catalytic oxidation of ammonia-methane-mixtures to hydrogen cyanide)". Angewandte Chemie. 48 (37): 593–595. doi:10.1002/ange.19350483702.