Hydrogen producing catalysts, development

A route to phenol has been developed starting from cyclohexane, which is first oxidised to a mixture of cyclohexanol and cyclohexanone. In one process the oxidation is carried out in the liquid phase using cobalt naphthenate as catalyst. The cyclohexanone present may be converted to cyclohexanol, in this case the desired intermediate, by catalytic hydrogenation. The cyclohexanol is converted to phenol by a catalytic process using selenium or with palladium on charcoal. The hydrogen produced in this process may be used in the conversion of cyclohexanone to cyclohexanol. It also may be used in the conversion of benzene to cyclohexane in processes where benzene is used as the precursor of the cyclohexane. 

One of the most common heterogeneous organic reactions in the fine chemicals and the specialty chemicals industries is the hydrogenation of carbon-carbon multiple bonds. It is so common that an entire array of specialty catalysts has been developed to accomplish specific hydrogenation reactions. An important goal in this field is selectivity. However, when relatively large quantities of chemicals are produced, concerns also embrace economy, yield, and... 

An industrial process to produce methanol from carbon monoxide and hydrogen was developed by BASF in 1923 using a zinc oxide-chromia catalyst.361 362 Since this catalyst exhibited relatively low specific activity, high temperature was required. The low equilibrium methanol concentration at this high temperature was compensated by using high pressures. This so-called high-pressure process was operated typically at 200 atm and 350°C. The development of the process and early results on methanol synthesis were reviewed by Natta 363... 

A somewhat similar hydrogenation problem arose in a different approach to 1,4-butanediol and tetrahydrofuran.345 In the process developed by Mitsubishi, 1,3-butadiene first undergoes Pd-catalyzed diacetoxylation to yield 1,4-diacetoxy-2-butene. To avoid the further transformation of the diol as in the abovementioned process, l,4-diacetoxy-2-butene is directly hydrogenated in the liquid phase (60°C, 50 atm) on traditional hydrogenation catalysts to produce 1,4-diacetoxybutane in 98% yield, which is then hydrolyzed to 1,4-butanediol. 

One particular application for which supported Au catalysts may find a niche market is in fuel cells [4, 50] and in particular in polymer electrolyte fuel cells (PEFC), which are used in residential electric power and electric vehicles and operate at about 353-473 K. Polymer electrolyte fuel cells are usually operated by hydrogen produced from methane or methanol by steam reforming followed by water-gas shift reaction. Residual CO (about 1 vol.%) in the reformer output after the shift reaction poisons the Pt anode at a relatively low PEFC operating temperature. To solve this problem, the anode of the fuel cell should be improved to become more CO tolerant (Pt-Ru alloying) and secondly catalytic systems should be developed that can remove even trace amounts of CO from H2 in the presence of excess C02 and water. 

PEM fuel cells use a solid proton-conducting polymer as the electrolyte at 50-125 °C. The cathode catalysts are based on Pt alone, but because of the required tolerance to CO a combination of Pt and Ru is preferred for the anode [8]. For low-temperature (80 °C) polymer membrane fuel cells (PEMFC) colloidal Pt/Ru catalysts are currently under broad investigation. These have also been proposed for use in the direct methanol fuel cells (DMFC) or in PEMFC, which are fed with CO-contaminated hydrogen produced in on-board methanol reformers. The ultimate dispersion state of the metals is essential for CO-tolerant PEMFC, and truly alloyed Pt/Ru colloid particles of less than 2-nm size seem to fulfill these requirements [4a,b,d,8a,c,66j. Alternatively, bimetallic Pt/Ru PEM catalysts have been developed for the same purpose, where nonalloyed Pt nanoparticles <2nm and Ru particles <1 nm are dispersed on the carbon support [8c]. From the results it can be concluded that a Pt/Ru interface is essential for the CO tolerance of the catalyst regardless of whether the precious metals are alloyed. For the manufacture of DMFC catalysts, in... 

---