Carbon monoxide activated adsorption

Pressure swing adsorption (PSA) is a gas purification process, which consists of the removal of impurities on adsorbent beds. The usual adsorbents and gases adsorbed thereon are molecular sieves for carbon monoxide, activated carbon for carbon dioxide, activated alumina or silica gel. lyuke et td. reported that the addition of tin onto activated carbon improved the efficiency of the adsorptive removal of carbon monoxide from hydrogen [420]. 

The following test for palladium is based on a combination of the activation of carbon monoxide by adsorption on finely divided palladium and the activation of Mo i in phosphomolybdic acid. Through these dual effects, palladium salts bring about a catalytic acceleration of the redox reaction (1). 

We consider first some experimental observations. In general, the initial heats of adsorption on metals tend to follow a common pattern, similar for such common adsorbates as hydrogen, nitrogen, ammonia, carbon monoxide, and ethylene. The usual order of decreasing Q values is Ta > W > Cr > Fe > Ni > Rh > Cu > Au a traditional illustration may be found in Refs. 81, 84, and 165. It appears, first, that transition metals are the most active ones in chemisorption and, second, that the activity correlates with the percent of d character in the metallic bond. What appears to be involved is the ability of a metal to use d orbitals in forming an adsorption bond. An old but still illustrative example is shown in Fig. XVIII-17, for the case of ethylene hydrogenation. 

The oxidation of CO at low temperatures was the first reaction discovered as an example of the highly active catalysis by gold [1]. Carbon monoxide is a very toxic gas and its concentration in indoor air is regulated to 10-50 ppm depending on the conditions [61]. An important point is that CO is the only gas that cannot be removed from indoor air by gas adsorption with activated carbon. On the other hand, metal oxides or noble metal catalysts can oxidize CO at room temperature. 

On the surface of metal electrodes, one also hnds almost always some kind or other of adsorbed oxygen or phase oxide layer produced by interaction with the surrounding air (air-oxidized electrodes). The adsorption of foreign matter on an electrode surface as a rule leads to a lower catalytic activity. In some cases this effect may be very pronounced. For instance, the adsorption of mercury ions, arsenic compounds, or carbon monoxide on platinum electrodes leads to a strong decrease (and sometimes total suppression) of their catalytic activity toward many reactions. These substances then are spoken of as catalyst poisons. The reasons for retardation of a reaction by such poisons most often reside in an adsorptive displacement of the reaction components from the electrode surface by adsorption of the foreign species. 

The 5% Pd/C catalysts, with an increasing amount of tin (from 0 to 1%), were activated in the same way described above and titrated with both carbon monoxide and hydrogen sulfide, up to 800 Torr, at 30°C. Figure 15.4 indicates a constant volume of carbon monoxide adsorbed, as expected from the above relationship for a fixed amoimt of %Pd on the catalyst. However, there does appear to be a relationship between H2S adsorption and the Sn/Pd ratio at constant 5 wt% Pd concentration on the catalyst. When there is little or no tin associated with the Pd-catalyst, the H2S is irreversibly adsorbed, resulting in high voliunetric uptake of... 

Heat-flow calorimetry may be used also to detect the surface modifications which occur very frequently when a freshly prepared catalyst contacts the reaction mixture. Reduction of titanium oxide at 450°C by carbon monoxide for 15 hr, for instance, enhances the catalytic activity of the solid for the oxidation of carbon monoxide at 450°C (84) and creates very active sites with respect to oxygen. The differential heats of adsorption of oxygen at 450°C on the surface of reduced titanium dioxide (anatase) have been measured with a high-temperature Calvet calorimeter (67). The results of two separate experiments on different samples are presented on Fig. 34 in order to show the reproducibility of the determination of differential heats and of the sample preparation. 

All preparations were structurally characterized by means of XRD (Siemens 5005). TEM imaging was performed with a Philips CM200 instrument. 27A1 and 29Si MAS NMR (Broker 500 MFlz and 360 MFlz respectively) was used to study the microporous phase and the kinetic of its formation. The relaxation delays were 0.2s and 200s respectively. Acidity was determined by the adsorption of carbon monoxide after activating the samples in vacuum (10 6 mbar) at 450°C for 1 h. The spectra were recorded on a Equinox 55 Broker spectrometer with a resolution of 2 cm 1 and normalized to 10 mg of sample. 

XL30). Mossbauer spectroscopy (KFKIj was applied to follow the state of Fe species in the zeolites. Carbon monoxide and ammonia adsorption (monitored with FTIR) (EQUINOX 55) was used to determine the nature, concentration and acid strength of the active sites in the Fe-TON zeolites. 

It is generally accepted that localization and coordination of monovalent Cu ions in different zeolites have significant influence on the catalytic activity. The localization and coordination of Cu ions was studied by means of adsorption of small probe molecules, in particular, carbon monoxide was used often due to its ability to form a stable mono-carbonyl complex with the Cu+ ion. The formation of this complex was investigated by the FTIR and by the microcalorimetry [1-3]. 

Conversly, the Fe3(C0)12 NaY adduct is active for syngas conversion. A non-decomposed sample exhibits a significant activity at 230°C whereas the catalytic efficiency for the decar-bonylated one already appears at 200°C. Infrared experiments show an increase in the stability of the Fe3(C0)- 2 units upon thermal treatment under CO atmosphere so that total carbon monoxide evolution only takes place at 230°C thus suggesting that the catalyst is certainly not Fe3(C0)- 2. This cluster has to be transformed into higher nuclearity species which bind less strongly with carbon monoxide upon CO re-adsorption (1 7). 

COPISA [CO pressure induced selective adsorption] A process for separating carbon monoxide from the effluent gases from steel mills by a two-stage PSA unit. Developed jointly by Kawasaki Steel Corporation and Osaka Oxygen Industry. In the first stage, carbon dioxide is removed by activated carbon. In the second stage, carbon monoxide is removed by sodium mordenite. 

COPSA [CO pressure swing adsorption] A process similar to COPISA but using activated charcoal impregnated with cuprous chloride as the adsorbent for carbon monoxide. Developed by Mitsubishi Kakoki Kaisha. 

Novacon An adsorptive process for removing oxides of sulfur and nitrogen, and carbon monoxide, from combustion gases. The adsorbent is an active form of natural marble. 

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. 

Based on the experimental data and some speculations on detailed elementary steps taking place over the catalyst, one can propose the dynamic model. The model discriminates between adsorption of carbon monoxide on catalyst inert sites as well as on oxidized and reduced catalyst active sites. Apart from that, the diffusion of the subsurface species in the catalyst and the reoxidation of reduced catalyst sites by subsurface lattice oxygen species is considered in the model. The model allows us to calculate activation energies of all elementary steps considered, as well as the bulk... 

Carbon monoxide oxidation is a relatively simple reaction, and generally its structurally insensitive nature makes it an ideal model of heterogeneous catalytic reactions. Each of the important mechanistic steps of this reaction, such as reactant adsorption and desorption, surface reaction, and desorption of products, has been studied extensively using modem surface-science techniques.17 The structure insensitivity of this reaction is illustrated in Figure 10.4. Here, carbon dioxide turnover frequencies over Rh(l 11) and Rh(100) surfaces are compared with supported Rh catalysts.3 As with CO hydrogenation on nickel, it is readily apparent that, not only does the choice of surface plane matters, but also the size of the active species.18-21 Studies of this system also indicated that, under the reaction conditions of Figure 10.4, the rhodium surface was covered with CO. This means that the reaction is limited by the desorption of carbon monoxide and the adsorption of oxygen. 

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