Hydrogen peroxide commercial manufacture

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. 

Acid-cataly2ed hydroxylation of naphthalene with 90% hydrogen peroxide gives either 1-naphthol or 2-naphthiol at a 98% yield, depending on the acidity of the system and the solvent used. In anhydrous hydrogen fluoride or 70% HF—30% pyridine solution at — 10 to + 20°C, 1-naphthol is the product formed in > 98% selectivity. In contrast, 2-naphthol is obtained in hydroxylation in super acid (HF—BF, HF—SbF, HF—TaF, FSO H—SbF ) solution at — 60 to — 78°C in > 98% selectivity (57). Of the three commercial methods of manufacture, the pressure hydrolysis of 1-naphthaleneamine with aqueous sulfuric acid at 180°C has been abandoned, at least in the United States. The caustic fusion of sodium 1-naphthalenesulfonate with 50 wt % aqueous sodium hydroxide at ca 290°C followed by the neutralization gives 1-naphthalenol in a ca 90% yield. 

Because the peroxodisulfate salts are all made electrochemicaHy, the electrical energy cost is a significant part of thek manufacturing cost. The 1994 world capacity for peroxodisulfate salts was about 75,000 metric tons, valued at about 30 x 10 . The principal appHcations are in polymerization catalysis and the market broadly tracks the plastics business. The Caro s acid business is difficult to quantify because the product itself is not commercial but made on-site from purchased hydrogen peroxide. 

The commercial manufacture of sodium chlorite is based almost entirely on the reduction of chlorine dioxide gas in a sodium hydroxide solution containing hydrogen peroxide [7722-84-1] as the reducing agent. The chlorine dioxide is generated from the chemical or electrochemical reduction of sodium chlorate under acidic conditions. 

In bulk chemicals manufacture economic considerations usually dictate the use of molecular oxygen as the oxidant. In fine chemicals, on the other hand, other oxidants may be commercially feasible (see table 1). Indeed, other oxidants (e.g. 30% hydrogen peroxide) may even be preferred for reasons of selectivity and ease of handling, i.e. it is not a question of price per se but price/performance ratio. Although molecular oxygen is the least expensive oxidant it requires elaborate safety precautions, and the associated costs, in order to avoid working within explosion limits. 

Hydrogen peroxide applications include commercial bleaching dye oxidation, the manufacture of organic and peroxide chemicals. Hydrogen peroxide is also used in pulp and paper chemical synthesis, textiles, and environmental control, including municipal and industrial water treatment. 

The key to the success of the oxidation examples cited above is the ability of the catalysts used to exert proper kinetic control on the possible side reactions. Without it, thermodynamically favorable but undesired products such as CO2 and H2O are made instead. Controlling oxidation kinetics to stop at the desired oxygenated products is quite difficult, and has yet to be solved for many other systems. For instance, although many attempts have been made to develop a commercial process for the oxidation of propylene to propylene oxide, both the activity and the selectivity of the systems proposed to date, mostly based on silver catalysts, are still too low to be of industrial interest " propylene oxide is presently manufactured by processes based on chlorohydrin or hydrogen peroxide instead. In spite of these difficulties, though, recent advances in selective liquid phase oxidation of fine chemicals on supported metal catalysts have shown some promise, offering high yields (close to 100%) under mild reaction conditions." ... 

The industrial process for propene oxide manufacture is commonly referred to as the HPPO (hydrogen peroxide propene oxide) process. EniChem set up a prototype plant in 2002 [150]. BASF/Dow Chemicals and Degussa, in turn, have the construction of commercial plants already in progress or at the planning stage [151]. 

In the manufacture of CAPIC, the reaction conditions were found to be quite acceptable for commercial operations, with minimal process modifications required to maximize the reactor utilization. However, reaction selectivity problems were encountered with Step 4 during pilot runs that had not been observed in previous work. An alternative set of reaction conditions was established that employed hydrochloric acid and hydrogen peroxide to selectively chlorinate the 2-positionof (13). Process research established that a very narrow temperature range is required for this step, and the reaction temperature is controlled by the rate of addition of the hydrogen peroxide. 

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