The Peroxide process is a method for the industrial production of hydrazine. In this process hydrogen peroxide is used as an oxidant instead of sodium hypochlorite, which is traditionally used to generate hydrazine. The main advantage of the Peroxide process to hydrazine relative to the traditional Raschig process is that it does not coproduce salt. In this respect, the Peroxide process is an example of Green Chemistry. Since many millions of kilograms of hydrazine are produced annually, this method is of both commercial and environmental significance.
In the usual implementation, hydrogen peroxide is used together with acetamide. This mixture does not react with ammonia directly but does so in the presence of methyl ethyl ketone to give the oxaziridine.
Balanced equations for the individual steps are as follows. Imine formation via condensation:
- Me(Et)C=O + NH3 → Me(Et)C=NH + H2O
Oxidation of the imine to the oxaziridine:
- Me(Et)C=NH + H2O2 → Me(Et)CONH + H2O
Condensation of the oxaziridine with a second molecule of ammonia to give the hydrazone:
- Me(Et)CONH + NH3 → Me(Et)C=NNH2 + H2O
The hydrazone then condenses with a second equivalent of ketone to give the ketazine:
- Me(Et)C=O + Me(Et)C=NNH2 → Me(Et)C=NN=C(Et)Me + H2O
Typical process conditions are 50 °C and atmospheric pressure, with a feed mix of H2O2:ketone:NH3 in a molar ratio of about 1:2:4. A similar process based on benzophenone has also been described.
Ketazine to hydrazine
The final stage involves hydrolysis of the purified ketazine:
- Me(Et)C=NN=C(Et)Me + 2 H2O → 2 Me(Et)C=O + N2H4
The hydrolysis of the azine is acid-catalyzed, hence the need to isolate the azine from the initial ammonia-containing reaction mixture. It is also endothermic, and so requires an increase in temperature (and pressure) to shift the equilibrium in favour of the desired products: ketone (which is recycled) and hydrazine hydrate. The reaction is carried out by simple distillation of the azeotrope: typical conditions are a pressure of 8 bar and temperatures of 130 °C at the base of the column and 179 °C at the top of the column. The hydrazine hydrate (30–45% aqueous solution) is run off from the base of the column, while the acetone is distilled off from the top of the column and recycled.
The Peroxide process, also called the Pechiney–Ugine–Kuhlmann process, was developed in the early 1970s by Produits Chimiques Ugine Kuhlmann. Originally the process used acetone instead of methyl ethyl ketone. Methyl ethyl ketone is advantageous because the resulting ketazine is immiscible in the reaction mixture and can be separated by decantation. The world's largest hydrazine hydrate plant is in Lannemezan, France, producing 17,000 tonnes of hydrazine products per year.
Bayer Ketazine Process
Before invention of the Peroxide process, the Bayer Ketazine process had been commercialized. In the Bayer process, the oxidation of ammonia by sodium hypochlorite is conducted in the presence of acetone. The process generates the ketazine but also sodium chloride:
- 2 Me2CO + 2 NH3 + NaOCl → Me2C=NN=CMe2 + 3 H2O + NaCl
- Me2C=NN=CMe2 + 2 H2O → N2H4 + 2 Me2CO
- Jean-Pierre Schirmann, Paul Bourdauducq "Hydrazine" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2002. doi:10.1002/14356007.a13_177.
- Maxwell, Gary R. (2004), Synthetic nitrogen products: a practical guide to the products and processes, Springer, pp. 342–44, ISBN 0-306-48225-8.
- Hayashi, Hiromu; Kainoh, Akihiko; Katayama, Masayoshi; Kawasaki, Kengo; Okazaki, Tatsuya (1976), "Hydrazine Production from Ammonia via Azine", Ind. Eng. Chem. Prod. Res. Dev. 15 (4): 299–303, doi:10.1021/i360060a016.
- Gilbert, E. C. (1929), "Studies on Hydrazine. The Hydrolysis of Dimethylketazine and the Equilibrium between Hydrazine and Acetone", J. Am. Chem. Soc. 51 (11): 3394–3409, doi:10.1021/ja01386a032.
- US 4724133, Schirmann, Jean-Pierre; Jean Combroux & Serge Y. Delavarenne, "Preparation of a concentrated aqueous solution of hydrazine hydrate", issued 1988-02-09 .
- US 3972878, Schirmann, Jean-Pierre; Jean Combroux & Serge Yvon Delavarenne, "Method for preparing azines and hydrazones", issued 1976-08-03 . US 3978049, Schirmann, Jean-Pierre; Pierre Tellier & Henri Mathais et al., "Process for the preparation of hydrazine compounds", issued 1976-08-31 .
- Cotton, F. Albert; Wilkinson, Geoffrey (1988), Advanced Inorganic Chemistry (5th ed.), New York: Wiley-Interscience, pp. 317–18, ISBN 0-471-84997-9.
- Site industriel de Lannemezan, Arkema, retrieved 2010-07-02.
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