Carbon monoxide hydrogenation reduction temperature

In this chapter, recent results are discussed In which the adsorption of nitric oxide and its Interaction with co-adsorbed carbon monoxide, hydrogen, and Its own dissociation products on the hexagonally close-packed (001) surface of Ru have been characterized using EELS (13,14, 15). The data are interpreted In terms of a site-dependent model for adsorption of molecular NO at 150 K. Competition between co-adsorbed species can be observed directly, and this supports and clarifies the models of adsorption site geometries proposed for the individual adsorbates. Dissociation of one of the molecular states of NO occurs preferentially at temperatures above 150 K, with a coverage-dependent activation barrier. The data are discussed in terms of their relevance to heterogeneous catalytic reduction of NO, and in terms of their relationship to the metal-nitrosyl chemistry of metallic complexes. 

Synthesis of Liquid Hydrocarbons by the Reduction of Carbon Mon-dxide. When carbon monoxide-hydrogen mixtures are passed over cobalt, iron, nickel, and some copper catalysts that are promoted with certain metallic oxides, particularly oxides of the alkali mietals, at temperatures in the range frmn about 200-300°C and pressures from about 1-25 atm, various hydrocarbons are formed according to the following type of reactions ... 

Nickel is the only metal to react directly with carbon monoxide at room temperature at an appreciable rate, although iron does so on heating under pressure. Cobalt affords HCo(CO)4 with a mixture of hydrogen and carbon monoxide (p. 387). In general, therefore, direct reaction does not provide a route to metal carbonyls. The metal atom technique (p. 313) has been used to prepare carbonyls of other metals in the laboratory e.g. Cr(CO)g, but it offers no advantages over the reduction method discussed below. When metal vapours are cocondensed with carbon monoxide in frozen noble gas matrices at very low temperatures (4-20K) the formation of carbonyl complexes is observed. These include compounds of metals which do not form any stable isolable derivatives e.g. Ti(CO), Nb(CO) and Ta(CO)g as well as Pd(C0)4 and Pt(C0)4. Vibrational spectra of the matrix show that coordinatively unsaturated species such as Ni(CO) n = 1-3) or Cr(CO) (n = 3-5) are also formed under these conditions. 

The iron carbide process is alow temperature, gas-based, fluidized-bed process. Sized iron oxide fines (0.1—1.0 mm) are preheated in cyclones or a rotary kiln to 500°C and reduced to iron carbide in a single-stage, fluidized-bed reactor system at about 590°C in a process gas consisting primarily of methane, hydrogen, and some carbon monoxide. Reduction time is up to 18 hours owing to the low reduction temperature and slow rate of carburization. The product has the consistency of sand, is very britde, and contains approximately 6% carbon, mostly in the form of Ee C. 

The substitution of trialkylphosphine for carbon monoxide also makes the metal-hydrogen bond more hydridic in character and results in increased reduction of the initially formed aldehyde to alcohol. Slaugh and Mullineaux (52) compared Co2(CO)g and [Co2(CO)8 + 2PBu3], each at reaction conditions of 150°C, 500 psi, H2/CO I.0, for the hydroformylation of 1-pentene. The products consisted of hexyl aldehydes and hexyl alcohols in the ratios of 95 5 and 30 70, respectively. In a negative aspect of the reaction, they observed 23% hydrogenation of alkene to alkane at a reaction temperature of 195°C with the phosphine-modified catalyst. Tucci (54) reported less alkane formation (4-5%) under more favorable reaction conditions (I60°C, H2/CO 1.2, 1 hour reaction time). 

In related studies, Cp2ZrCl2 has been found to catalyze at room temperature an aluminum hydride (i-Bu2AlH) reduction of CO to linear Ci-C5 alcohols (430). The system involves reaction of complex 55 with CO, which precipitates the starting zirconium(IV) complex and leaves a yellow solution, that on hydrolysis yields the alcohols. Toluene solutions of Cp2Ti(CO)2 complex under H2/CO effect Eq.(69), i.e., a homogeneous stoichiometric hydrogenation of carbon monoxide to methane (426). 

The structure of supported rhodium catalysts has been the subject of intensive research during the last decade. Rhodium is the component of the automotive exhaust catalyst (the three-way catalyst) responsible for the reduction of NO by CO [1], In addition, it exhibits a number of fundamentally interesting phenomena, such as strong metal-support interaction after high temperature treatment in hydrogen [21, and particle disintegration under carbon monoxide [3]. In this section we illustrate how techniques such as XPS, STMS, EXAFS, TEM and infrared spectroscopy have led to a fairly detailed understanding of supported rhodium catalysts. 

The reduction of carbon monoxide also suffers deactivation by a surface species similar to that for carbon dioxide reduction but which forms at lower temperatures. The reduction of carbon monoxide does appear to proceed via a path similar to that which the reduction of carbon dioxide follows. Rates for methanol reduction are extremely variable. Methanol reduction, like carbon dioxide reduction, both increases in rate with decreasing pH until the surface becomes blocked with surface hydrogen and is also deactivated by increased temperature. For methanol, deactivation does not occur by the formation of the same surface species. 

The present paper focuses on the interactions between iron and titania for samples prepared via the thermal decomposition of iron pentacarbonyl. (The results of ammonia synthesis studies over these samples have been reported elsewhere (4).) Since it has been reported that standard impregnation techniques cannot be used to prepare highly dispersed iron on titania (4), the use of iron carbonyl decomposition provides a potentially important catalyst preparation route. Studies of the decomposition process as a function of temperature are pertinent to the genesis of such Fe/Ti02 catalysts. For example, these studies are necessary to determine the state and dispersion of iron after the various activation or pretreatment steps. Moreover, such studies are required to understand the catalytic and adsorptive properties of these materials after partial decomposition, complete decarbonylation or hydrogen reduction. In short, Mossbauer spectroscopy was used in this study to monitor the state of iron in catalysts prepared by the decomposition of iron carbonyl. Complementary information about the amount of carbon monoxide associated with iron was provided by volumetric measurements. 

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