Ammonia, adsorption

Turner, L., Improvement of activated charcoal-ammonia adsorption heat pumping/refrigeration cycles. Investigation of porosity and heat/mass transfer characteristics. Ph.D. Thesis, University of Warwick, UK, 1992. 

Postcombustion processes are designed to capture NO, after it has been produced. In a selective catalytic reduction (SCR) system, ammonia is mixed with flue gas in the presence of a catalyst to transform the NO, into molecular nitrogen and water. In a selective noncatalytic reduction (SNCR) system, a reducing agent, such as ammonia or urea, is injected into the furnace above the combustion zone where it reacts with the NO, to form nitrogen gas and water vapor. Existing postcombustion processes are costly and each has drawbacks. SCR relies on expensive catalysts and experiences problems with ammonia adsorption on the fly ash. SNCR systems have not been proven for boilers larger than 300 MW. 

We have also tried the trapping reactor system, in which ammonia is trapped on the catalyst/adsorbent and microwave is irradiated intermittently. However, due to the small specific surface area and the small ammonia adsorption capacity on the employed CuO, the trapping system was not effective compared to the continuous irradiation. Further study should be made to develop a material having high ammonia adsorption capacity and high efficiency for microwave absorption. Supported CuO on high surface area material or preparation of high surface area CuO can be effective. 

Analysis of the dynamics of SCR catalysts is also very important. It has been shown that surface heterogeneity must be considered to describe transient kinetics of NH3 adsorption-desorption and that the rate of NO conversion does not depend on the ammonia surface coverage above a critical value [79], There is probably a reservoir of adsorbed species which may migrate during the catalytic reaction to the active vanadium sites. It was also noted in these studies that ammonia desorption is a much slower process than ammonia adsorption, the rate of the latter being comparable to that of the surface reaction. In the S02 oxidation on the same catalysts, it was also noted in transient experiments [80] that the build up/depletion of sulphates at the catalyst surface is rate controlling in S02 oxidation. 

Figure 9.15. Comparison of the total ammonia adsorption of coated and extruded V2O5/WO3—Ti02 catalysts. Catalyst volume = 7 cm3. Model gas for loading 10% 02, 5% H20, NH3 = 1000ppm, and balance N2. GHSV = 52000h 1. Model gas for temperature-programmed desorption (TPD) experiment 10% 02, 5% H20, NO = 1000 ppm, NH3 = 1000 ppm, and balance N2. NH3 desorbed is calculated as the sum of thermally desorbed NH3, directly measured at the catalyst outlet, and chemically desorbed NH3, measured by the reduction of the NO concentration due to the SCR reaction.

Kleemann, M., Elsener, M., Koebel, M., et al. (2000) Investigation of the Ammonia Adsorption on Monolithic SCR Catalysts by Transient Response Analysis, Appl. Catal. B, 27, 231. 

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. 

A-CAT [Activity adjustment by ammonia adsorption] A method for pre-sulfiding and passivating hydrocracking catalysts. Developed by EUROCAT in 1989. 

Prior to solving the structure for SSZ-31, the catalytic conversion of hydrocarbons provided information about the pore structure such as the constraint index that was determined to be between 0.9 and 1.0 (45, 46). Additionally, the conversion of m-xylene over SSZ-31 resulted in a para/ortho selectivity of <1 consistent with a ID channel-type zeolite (47). The acidic NCL-1 has also been found to catalyze the Fries rearrangement of phenyl acetate (48). The nature of the acid sites has recently been evaluated using pyridine and ammonia adsorption (49). Both Br0nsted and Lewis acid sites are observed where Fourier transform-infrared (FT IR) spectra show the hydroxyl groups associated with the Brpnsted acid sites are at 3628 and 3598 cm-1. The SSZ-31 structure has also been modified with platinum metal and found to be a good reforming catalyst. 

Another thermal analysis method available for catalyst characterization is microcalorimetiy, which is based on the measurement of the heat generated or consumed when a gas adsorbs and reacts on the surface of a solid [66-68], This information can be used, for instance, to determine the relative stability among different phases of a solid [69], Microcalorimetiy is also applicable in the measurement of the strengths and distribution of acidic or basic sites as well as for the characterization of metal-based catalysts [66-68], For instance, Figure 1.10 presents microcalorimetry data for ammonia adsorption on H-ZSM-5 and H-mordenite zeolites [70], clearly illustrating the differences in both acid strength (indicated by the different initial adsorption heats) and total number of acidic sites (measured by the total ammonia uptake) between the two catalysts. 

Adsorbents (Activated carbons and charcoals) Large adsorption capacity for VOCs and odors Immediately noticeable effects Operates wall avuri uniter vary humid uundiliuris. Inefficient for removing tow molecular weight pollutants such as formaldehyde end ammonia, Adsorption decreases rapidly with time snd frequent ruplautmerit is requited. 

Fig. 10.8 Comparison of the ammonia adsorption capacities on MOF-5/GO composites and HKUST/GO composites (1-4 represent increasing GO content 1 - 5 %, 2 - 10 % ...

Fig. 10.9 Ammonia adsorption centers in M0G5-G0 [35] composite and FIKUST-l/GO composite [42].

Cu(NH3)2BTC2/3 and finally copper hydroxide in the presence of water. The formation of the BTC salts was supported by the collapse of the structure after interaction of ammonia with unsaturated copper centers. The release of BTC and copper oxide centers provides sites for reactive adsorption of ammonia during the course of the breakthrough experiments. Interestingly, even though the structure collapses, some evidence of the structural breathing of the resulting materials caused by reactions with ammonia was found, based on the ammonia adsorption at equilibrium and the analysis of the heat of interactions [51]. 

Petit C, Seredych M, Bandosz TJ. Revisiting the chemistry of graphite oxides and its effect on ammonia adsorption, J. Mater. Chem. 2009,19, 9077-9185. 

Most of the work with alumina was done, however, attempting to elucidate the nature of the catalytically active sites in dehydrated alumina. The catalytic activity of alumina is enhanced by treatment with hydrofluoric acid. Oblad et al. (319) measured a higher activity in the isomerization of 1- and 2-pentene. Webb (339) studied the effect of HF treatment on ammonia adsorption by alumina. There was no difference in the capacity. However, the ammonia was more easily desorbed at a given temperature from the untreated sample. Apparently, the adsorption sites grew more strongly acidic by the treatment. No NH4+ ions, only NHj molecules were detected by their infrared spectra, indicating that the ammonia was bound by Lewis acids rather than Bronsted acids. 

Langmuir kinetics have usually been considered for ammonia adsorption-desorption kinetics [48, 51, 52]. On the other hand, Andersson et al. ruled out that... 

Lietti and co-workers studied the kinetics of ammonia adsorption-desorption over V-Ti-O and V-W-Ti-O model catalysts in powder form by transient response methods [37, 52, 53[. Perturbations both in the ammonia concentration at constant temperature in the range 220-400 °C and in the catalyst temperature were imposed. A typical result obtained at 280 °C with a rectangular step feed of ammonia in flowing He over a V2O5-WO3/TiO2 model catalyst followed by its shut off is presented in Figure 13.5. Eventually the catalyst temperature was increased according to a linear schedule in order to complete the desorption of ammonia. 

The activation energy for ammonia desorption was found to be dose to zero and accordingly a non-activated ammonia adsorption process was considered ( a = 0) ... 

This empirical rate expression considers the active sites of the catalyst as only a fraction of the total adsorption sites for ammonia and is consistent vfith the presence of a reservoir of ammonia adsorbed species which can take part in the reaction. The ammonia reservoir is likely associated vfith poorly active but abundant W and Ti surface sites, which can strongly adsorb ammonia in fact, nhs roughly corresponds to the surface coverage of V. Once the ammonia gas-phase concentration is decreased, the desorption of ammonia species originally adsorbed at the W and Ti sites can occur followed by fast readsorption. When readsorption occurs at the reactive V sites, ammonia takes part in the reaction. Also, the analysis of the rate parameter estimates indicates that at steady state the rate of ammonia adsorption is comparable to the rate of its surface reaction with NO, whereas NH3 desorption is much slower. Accordingly, the assumption of equilibrated ammonia adsorption, which is customarily assumed in steady-state kinetics, may be incorrect, as also suggested by other authors [55]. 

To describe the NH3 + NO/NO2 reaction system over a wide range of temperatures and NO2 NOxfeed ratios in addition to ammonia adsorption-desorption, ammonia oxidation and standard SCR reaction with the associated kinetics already discussed in Section 2.3.2, the following reactions and kinetics have been considered by Chatterjee and co-workers [79] ... 

Measurement of the thermokinetic parameter can be used to provide a more detailed characterization of the acid properties of solid acid catalysts, for example, differentiate reversible and irreversible adsorption processes. For example, Auroux et al. [162] used volumetric, calorimetric, and thermokinetic data of ammonia adsorption to obtain a better definition of the acidity of decationated and boron-modified ZSM5 zeolites (Figure 13.7). 

The number of strong sites can be estimated directly from the nnmber of sorbed basic molecules defined by the peak maximum, provided that one basic molecule interacts with one acidic site. Auroux and colleagues [162] observed that ammonia adsorption shifts from strong chemisorption for H-ZSM5 to a process controlled by physisorption (shorter x) for boron-modified zeolites. 

The pretreatment temperature is an important factor that influences the acidic/ basic properties of solids. For Brpnsted sites, the differential heat is the difference between the enthalpy of dissociation of the acidic hydroxyl and the enthalpy of protonation of the probe molecule. For Lewis sites, the differential heat of adsorption represents the energy associated with the transfer of electron density toward an electron-deficient, coordinatively unsaturated site, and probably an energy term related to the relaxation of the strained surface [147,182]. Increasing the pretreatment temperature modifies the surface acidity of the solids. The influence of the pretreatment temperature, between 300 and 800°C, on the surface acidity of a transition alumina has been studied by ammonia adsorption microcalorimetry [62]. The number and strength of the strong sites, which should be mainly Lewis sites, have been found to increase when the temperature increases. This behavior can be explained by the fact that the Lewis sites are not completely free and that their electron pair attracting capacity can be partially modified by different OH group environments. The different pretreatment temperatures used affected the whole spectrum of adsorption heats... 

The amphoteric indium oxide can be considered as more basic than acidic when comparing the adsorption heats and irreversible adsorbed amounts, which are clearly higher for SO2 adsorption than for ammonia adsorption [40,47]. The heats of NH3 adsorption decreased continuously with coverage, while the SO2 adsorption heat remained constant over a wide range of coverage. 

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