Selectivity temperature programmed desorption

In this contribution, we present computer analyses of several selected temperature-programmed desorption (TPD) and temperature-programmed surface reaction (TPSR) experiments in a microreactor flow system operating under atmospheric pressure. The continuous stirred tank reactor (CSTR) and plug flow reactor (PFR) models have been applied for the design equation as... 

In the case of alkenes, 1-pentene reactions were studied over a catalyst with FAU framework (Si/Al2 = 5, ultrastable Y zeoHte in H-form USHY) in order to establish the relation between acid strength and selectivity [25]. Both fresh and selectively poisoned catalysts were used for the reactivity studies and later characterized by ammonia temperature programmed desorption (TPD). It was determined that for alkene reactions, cracking and hydride transfer required the strongest acidity. Skeletal isomerization required moderate acidity, whereas double-bond isomerization required weak acidity. Also an apparent correlation was established between the molecular weight of the hard coke and the strength of the acid sites that led to coking. 

Fig. 1. The temperature programmed desorption profiles for a-Fe203 (a) Blank desorption without adsorbates (b) ris-2-butene adsorption (c) butadiene adsorption (d) cis-2-butene adsorption from a catalyst depleted of selective oxidation sites. From ref. 5, reprinted with permission, copyright 1979 by the American Chemical Society.

The production of butadiene from butene involves at least three surface intermediates adsorbed butene, 7t-allyl, and butadiene. One or more of these may be particularly vulnerable to attack by gas-phase oxygen on a-Fe203. From the temperature programmed desorption experiments, it was found that the products of isomerization, selective oxidation, and combustion... 

Finally, new methods of analysis have recently been developed that may allow characterization of single atoms on surfaces such as atomic force microscopy.9 In certain cases, in situ experiments can be done such as the study of electrodes, enzymes, minerals and biomolecules. It has even been shown that one atom from a tip can be selectively placed on a desired surface.10 Such processes may one day be used to prepare catalysts that may enhance selectivity. Other methods that show promise as regards detection of surface catalytic intermediates are temperature programmed desorption techniques.11 Selective poisoning of some surface intermediates with monitoring via temperature programming methods may also allow the preparation of more selective catalysts. 

The most likely reason for the high activity of zeolite BEA is the relatively high BET surface area of the catalyst (750 m2/g). Furthermore there are hints by temperature-programmed desorption (TPD) of ammonia that a large amount of acid sites are present. We assume that the alkoxylation of limonene takes place inside the pore structure of the beta zeolite. The high selectivity of zeolite BEA might originate from suitable acid sites in pores of its defined size and shape. 

Uranium oxides have been investigated as catalysts and catalyst components for selective oxidation. They are more commonly used as catalyst components, but there are also reports of uranium oxide alone as a selective oxidation catalyst The oxidation of ethylene over UO3 has been studied by Idriss and Madhavaram [40] using the technique of temperature programmed desorption (TPD). Table 13.3 shows the desorption products formed during TPD after ethylene adsorption at room temperature on UO3. The production of acetaldehyde from ethylene indicates... 

Chemically activated carbon fibers (CACF) manufactured KOH impregnated to ACF and confirmed selective adsorption conduct of NO and NO in fixed bed adsorption column. NOx desorption studied on He at Stl/min up to SOOC using temperature programmed desorption (TPD), and observed surface characteristic at absorption-desorption. CACF was increased adsorptivity with offers selective adsorptivity by KOH in NOx adsorption, and CACF (KOH ACF == I 3) had an adsorptivity that was four times higher than that of ACF. NOx desorption on ACF was mostly occurred within 200 C. The results of surface characterization were found that NOx was produced as a KNOx(x=2,3) after adsorption and potassium ions were distributed without loss after desorption. 

The hydrothermal deactivation of Y zeolite containing 0, 4, 7 and 12 wt.% of REO and its effects on catalytic activity, stability and selectivity were investigated. The Y zeolites were hydrothermally deactivated at 788°C in three consecutive cycles of two hours each. The fresh and deactivated zeolites were characterized by measuring Unit Cell Size (UCS) and surface area. The acidic properties were measured by the Temperature Programmed Desorption (TPD) of ammonia and IR-pyridine desorption. In order to correlate structural, textural and acid properties with catalytic behavior, the zeolites were evaluated in the conversion of cyclohexane. The Hydrogen Transfer Index (HTI) measured as a ratio of paraffins to olefins is a parameter of the selectivity. It was found that the REO was incorporated into zeolite structure up to high concentrations modifying to some extent XRD deflection, the acidic properties and the HTI ratio. After deactivation, the acidity and HTI were diminished and the Lewis/Bronsted acid ratio was modified. HTI decreased as REO concentration increased. 

In this study, suboxides of vanadia catalysts were used in pentane, pentene, dicyclopentadiene and cyclopentane oxidation reactions. In the previous phase of the work [12,13], the role of alkali promoters on the catalyst selectivity was examined. The catalysts were reduced in situ at different temperatures and the effect of pre-reduction temperature was investigated. Controlled-atmosphere characterization of pre-reduction, post-reduction, and post-reaction catalysts were performed using X-ray diffraction. X-ray photoelectron spectroscopy, laser Raman spectroscopy and temperature-programmed desorption experiments. The objectives of this study were to determine the activity and selectivity of different suboxides of vanadia in... 

Further infonnatioii on the catalytic properties of stoichiometric and nonstoichiometric CaHAp may be obtained from studies on the adsorption and dehydrogenation of methanol. WiA stoichiometric CaHAp methanol decomposes at 600°C to produce predominantly carbon monoxide (Table 1) whose selectivity diminishes as the Ca/P ratio decreases while those to formaldehyde and dimethyl ether increase. Infrared spectra show that methoxy groups are formed on the surface of both the stoichiometric and nonstoichiometric catalysts. The results from temperature-programmed desorption experiments together with those from infrared spectroscopy suggest that the acidic sites found on the nonstoichiometric CaHAp catalyze the dissociative adsorption whereas the basic sites on the stoichiometric analogue catalyze the C-H bond scission and formation of CO and H. ... 

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