Industrial processes hydrogen peroxide

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). 

P. T. Witte, P. L. Alsters, W. Jary, R. Milliner, P. Pochlauer, D. Sloboda-Rozner, R. Neumann, Self-assembled Nai2[WZn3(Zn Wg034)2] as an industrially attractive multi-purpose catalyst for oxidations with aqueous hydrogen peroxide, Org. Process Res. Dev. 8 (2004) 524. 

Semi-dead end UF/MF membranes (effective pore size of the membrane is <0.1 pm) with intermittent backwash are being increasingly used for surface water and wastewater treatment for re-use, e.g. secondary or tertiary effluent is treated for industrial, non-potable and, in some cases, potable water reuse using UF/RO (or MF/RO) plus advanced oxidation techniques such as UV disinfection and hydrogen peroxide. The process is described in detail in Chapters 2 and 4 and several examples discussed in Chapter 3. Prominent examples of advanced reclamation plants include Water Factory 21 in Cahfornia, NEWater Factory in Singapore and the Goreangab Reclamation plant in Namibia [2]. 

This process has been widely studied and led to the constmction of new and original industrial units. Interest in the reaction stems from the simplicity of the process as well as the absence of undesirable by-products. However, in order to be economically rehable, such a process has to give high yield of dihydroxybenzenes (based on hydrogen peroxide as well as phenol) and a great flexibiUty for the isomeric ratio of hydroquinone to catechol. This last point generated more research and led to original and commercial processes. 

PoUowing further development (38), a two-cycle process has been adopted by industry. In the first concentration cycle, the clarified feed acid containing 100—200 mg/L U Og [1334-59-8] is oxidized, for example, with hydrogen peroxide or sodium chlorate [7775-09-9] to ensure that uranium is in its 6+ valence state is not extracted. Uranium is extracted with a solvent composed of 0.5 Af D2EHPA and 0.125 Af TOPO dissolved in an aUphatic hydrocarbon diluent. 

The noncatalytic oxidation of propane in the vapor phase is nonselec-tive and produces a mixture of oxygenated products. Oxidation at temperatures below 400°C produces a mixture of aldehydes (acetaldehyde and formaldehyde) and alcohols (methyl and ethyl alcohols). At higher temperatures, propylene and ethylene are obtained in addition to hydrogen peroxide. Due to the nonselectivity of this reaction, separation of the products is complex, and the process is not industrially attractive. 

The Payne epoxidation with benzonitrile/ hydrogen peroxide is also an efficient epoxidation process. It is often the method of choice for industrial batch-type applications, but on a small scale the need for continuous pH control is inconvenient. 

Figure 4-13 shows an example from a three-dimensional model simulation of the global atmospheric sulfur balance (Feichter et al, 1996). The model had a grid resolution of about 500 km in the horizontal and on average 1 km in the vertical. The chemical scheme of the model included emissions of dimethyl sulfide (DMS) from the oceans and SO2 from industrial processes and volcanoes. Atmospheric DMS is oxidized by the hydroxyl radical to form SO2, which, in turn, is further oxidized to sulfuric acid and sulfates by reaction with either hydroxyl radical in the gas phase or with hydrogen peroxide or ozone in cloud droplets. Both SO2 and aerosol sulfate are removed from the atmosphere by dry and wet deposition processes. The reasonable agreement between the simulated and observed wet deposition of sulfate indicates that the most important processes affecting the atmospheric sulfur balance have been adequately treated in the model. 

New materials are also finding application in the area of catalysis reiated to the Chemicals industry. For example, microporous [10] materials which have titanium incorporated into the framework structure (e.g. so-calied TS-1) show selective oxidation behaviour with aqueous hydrogen peroxide as oxidizing agent (Figure 5). Two processes based on these new catalytic materials have now been developed and commercialized by ENl. These include the selective oxidation of phenol to catechol and hydroquinone and the ammoxidation of cyclohexanone to e-caproiactam. 

Somewhat unanticipated applications can arise. For example, a process for the production of ultrapure hydrogen peroxide for the electronics industry has been patented recently,1425 which uses the macrobicyclic hexamine complex (29) supported on an inert material for dioxygen... 

The first is an alkaline solution of hydrogen peroxide, which oxidizes organic matter. The second is an acid fluoride solution which removes silica. The third is an acid solution of hydrogen peroxide which removes transition metals. The process was developed by RCA Corporation in 1970 and widely used thereafter by the electronics industry. 

The second option involves the use of a CIO2 scrubber. This is a technique presently used in the paper and pulp industry. In the scrubber, the chlorine dioxide reacts with another chemical, such as a sulphite, DMSO, white spirit or an alkaline hydrogen peroxide solution. The hydrogen peroxide solution is most suited to the process described in this chapter as there are no waste streams. The reaction of chlorine dioxide with the alkaline hydrogen peroxide solution is rapid [10]. The reaction equation is as follows ... 

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