Manufacture of Hydrogen Peroxide

The first hydrogen peroxide plant to go on-stream based on the electrochemical process was in 1908 at the Osterreichische Chemische Werke in Weissenstein. The Weissenstein process was adapted in 1910 to afford the Miincher process developed by Pietzsch and Adolph at the Elecktrochemische Werke, Munich. In 1924, Reidel and Lowenstein used ammonium sulfate under the conditions of electrolysis instead of sulfuric acid, and the resulting ammonium peroxodisulfate (Reidel-Lowenstein process) or potassium peroxo-disulfate (Pietzsch-Adolph process) was hydrolysed to hydrogen peroxide. As a result of this process, production of hydrogen peroxide as 100% m/m rose to approximately 35 000 metric tonnes per annum.5 

The 2-alkylhydroanthraquinone (A) when in contact with the catalyst will undergo a small amount of catalytic reduction (B) on the ring, initially on the unsubstituted ring, yielding a tetrahydroalkylanthrahydroquinone. Unfortu- 

A number of additional processes are also required to maintain the AO process. For example, in order for the hydrogenation phase to run efficiently, 

The Laporte hydrogenator contains a series of tubes which dip just below the surface of the liquid. Hydrogen is then fed into the bottom of each tube, and small gas bubbles are formed. A counter current flow is set up due to the density difference between the solutions in the tube and the reactor. The palladium catalyst suspension is drawn into the tubes by a continuous movement of the working solution. 

The problem with all three methods thus far discussed is the fact that the hydrogenator catalyst has to be removed prior to the formation of hydrogen peroxide. If the catalyst is not removed, then catastrophic dismutation of the hydrogen peroxide can occur. In response to the problem, FMC developed a mixed-bed hydrogenation process. The bed is impregnated with palladium, and hence the problem associated with catalyst removal is alleviated.15 

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Interest has continued in on-site manufacture of hydrogen peroxide from the elements, particularly for remote sites located considerable distances from wodd-scale anthraquinone processes. However, no commercial-scale direct combination plants have been constmcted as of this writing. 

Table 7. U.S. and North American Manufacturers of Hydrogen Peroxide, ...

Beccs Chemical Div, Food Machinery Chemi cal Carp, Buffalo 7,NY, manufacturers of hydrogen peroxide, peracetic acid, urea peroxide ahd several other peroxides as well as sodium perborate and other chemicals used in propints expis... 

The manufacturers of hydrogen peroxide 400 million by the European Commis-... 

C. THE MANUFACTURE OF HYDROGEN PEROXIDE BY SILENT ELECTRIC DISCHARGE ... 

From this equation it is obvious that water is the only raw material in the manufacture of hydrogen peroxide. The other chemicals H2S04, (NH4)2 S04 etc. are auxiliary substances which return to the production cycle and are added only in an amount necessary to replace mechanical losses. 

Fig. 140. Plow sheet of manufacture of hydrogen peroxide from persulphuric acid.

Ftg. 146. Distillation equipment for the manufacture of hydrogen peroxide According... 

The industrial manufacture of hydrogen peroxide can be traced back to its isolation in 1818 by L. J. Thenard.1 Thenard reacted barium peroxide with nitric acid to produce a low concentration of aqueous hydrogen peroxide the process can, however, be significantly improved by the use of hydrochloric acid. The hydrogen peroxide is formed in conjunction with barium chloride, both of which are soluble in water. The barium chloride is subsequently removed by precipitation with sulfuric acid (Figure 1.1). 

Derivation (1) By treating a solution of a barium salt with sodium sulfate (salt cake), (2) by-product in manufacture of hydrogen peroxide, (3) occurs in nature as the mineral barite (Arkansas, Missouri, Georgia, Nevada, Canada, Mexico). 

Mention must also be made of certain peroxy compounds, some of which have attained considerable technical importance in comparatively recent times. Sodium peroxide is obtained by the action of hot air on sodium contained in aluminium trays. The per-carbonates and persulphates of sodium, potassium, and ammonium are prepared by methods of electrolysis. Barium peroxide is made by heating the oxide to a dull redness in dry air, free from carbon-dioxide, and is used in the manufacture of hydrogen peroxide, which, as are other peroxy compounds, is largely applied as a bleaching agent for cellulose materials. 

Fig. 15.8 The catalytic cycle used in the industrial manufacture of hydrogen peroxide O2 is converted to H2O2 during the oxidation of the organic alkylanthraquinol. The organic product is reduced by H2 in a Pd- or Ni-catalysed reaction. Such cycles are discussed in detail in Chapter 26.

Alternative, albeit minor processes for the production of hydrogen peroxide include other autoxidation processes, notably the 2-Propanol Process (Shell Process) and electrochemical processes, including the Degussa-Weissenstein, Munchner, and Riedel-Loewenstein Processes. See, (a) Harris, C.R. (1945) Production of hydrogen peroxide by partial oxidation of alcohols. US Patent 2,479,1 llA, filed Jun. 29, 1945 and issued Aug. 16, 1949 (E. I. du Pont de Nemours) (b) Rust, F.F. (1955) Manufacture of hydrogen peroxide. US Patent 2,871,104A, filed Jan. 31, 1955 and issued Jan. 27, 1959 (Shell Dev) (c)N. 

Process industries. In the chemical industries aluminum is used for the manufacture of hydrogen peroxide and the production and distribution of nitric acid. It is also used in the manufacture and distribution of liquefied gases, because it retains its strength and ductility at low temperatures, and its lower density is also an advantage over nickel steels. 

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