Activated carbons are widely used as commercial adsorbents. Thermal or chemical activation creates a pore system and functional groups on the inner surface which may significantly change adsorption properties. Therefore, in addition to knowledge of the structural properties, a sound understanding of surface chemistry is indispensable. This paper summarizes the state of art as well as new developments in both fields. Standardized methods for characterizing structural properties are volumetric measurements and mercury porosimetry. To get a more detailed insight into the region of micropores, a probe molecule method was developed. For characterization of surface chemistry, methods such as IR spectroscopy, temperature-programmed desorption, and Boehm titration are subject of research. Novel methods were developed such as measuring of excess isotherms and calorimetric measurement of heat of adsorption, which are presented and discussed in greater detail in this paper. As each single method can only provide limited information, a better description of surface chemistry requires combination and careful interpretation of complementary information from different methods. Property Standard Limitation Apparent density ASTM D 2854-09 Total ash content ASTM D 2866-11 Moisture ASTM D 2867-17 Ball-pan hardness ASTM D 3802-16 pH-value ASTM D 3838-05 Electrical conductivity ASTM D 1125-14 Water soluble components ASTM D 5029-98 Volatile matter content ASTM D 5832-98 Acid extractable content ASTM D 6385-99 Particle size distribution ASTM D 2862-16 granular activated carbon ASTM D 5158-98 powdered activated carbon Ignition temperature ASTM D 3466-06 granular activated carbon Dusting attrition ASTM D 5159-04 granular activated carbon www.ChemBioEngRev.de
Hydrogen sulfide is removed from natural gas via adsorption on zeolites. The process operates very effectively, but there is still potential for improvement. Therefore, in this article, the adsorption of hydrogen sulfide was investigated on eight LTA zeolites with different cation compositions. Starting with the zeolite NaA (4 A), which contains only Na+ cations, the Ca2+ cation content was gradually increased by ion exchange. Equilibrium isotherms from cumulative breakthrough curve experiments in a fixed-bed adsorber at 25°C and 85°C at 1.3 bar (abs.) were determined in the trace range up to a concentration of 2000 ppmmol. From a comparison of the isotherms of the different materials, a mechanistic proposal for the adsorption is developed, taking into account the specific positions of the cations in the zeolite lattice when the degree of exchange is increased. The shape of the isotherms indicates two energetically different types of adsorption sites. It is assumed that two mechanisms are superimposed: a chemisorptive mechanism with dissociation of hydrogen sulfide and covalent bonding of the proton and the hydrogen sulfide ion to the zeolite lattice and a physisorptive mechanism by electrostatic interaction with the cations in the lattice. As the degree of exchange increases, the proportion of chemisorption sites seems to decrease. Above an exchange degree of 50%, only evidence of physisorption can be found. It is shown that this finding points to the involvement of weakly bound sodium cations at cation position III in the chemisorption of hydrogen sulfide.
Since the recent discovery of the template-free synthesis
of porous
boron nitride, research on the synthesis and application of the material
has steadily increased. Nevertheless, the formation mechanism of boron
nitride is not yet fully understood. Especially for the complex precursor
decomposition of urea-based turbostratic boron nitride (t-BN), a profound
understanding is still lacking. Therefore, in this publication, we
investigate the influence of different common pre-heating temperatures
of 100, 200, 300, and 400 °C on the subsequent properties of
t-BN. We show that the structure and porosity of t-BN can be changed
by preheating, where a predominantly mesoporous material can be obtained.
Within these investigations, the sample BN-300/2 depicts the highest
mesopore surface area of 242 m
2
g
–1
with
a low amount of micropores compared to other BNs. By thermal gravimetric
analysis, X-ray photoelectron spectroscopy, and Raman spectroscopy,
valid details about the formation of intermediates, types of chemical
bonds, and the generation of t-BN are delivered. Hence, we conclude
that the formation of a mesoporous material arises due to a more complete
decomposition of the urea precursor by pre-heating.
In addition to the adsorption mechanism, the heat released during exothermic adsorption influences the chemical reactions that follow during heterogeneous catalysis. Both steps depend on the structure and surface chemistry of the catalyst. An example of a typical catalyst is the faujasite zeolite. For faujasite zeolites, the influence of the Si/Al ratio and the number of Na+ and Ca2+ cations on the heat of adsorption was therefore investigated in a systematic study. A comparison between a NaX (Sodium type X faujasite) and a NaY (Sodium type Y faujasite) zeolite reveals that a higher Si/Al ratio and therefore a smaller number of the cations in faujasite zeolites leads to lower loadings and heats. The exchange of Na+ cations for Ca2+ cations also has an influence on the adsorption process. Loadings and heats first decrease slightly at a low degree of exchange and increase significantly with higher calcium contents. If stronger interactions are required for heterogeneous catalysis, then the CaNaX zeolites must have a degree of exchange above 53%. The energetic contributions show that the highest-quality adsorption sites III and III’ make a contribution to the load-dependent heat of adsorption, which is about 1.4 times (site III) and about 1.8 times (site III’) larger than that of adsorption site II.
Development of a Device for Coupling of Calorimetric and Volumetric Sorption MeasurementsA new measuring device for the simultaneous measurement of heat of adsorption and load has been developed. A volumetric adsorption measurement device is extended by a calorimetric unit which measures the pressure difference between two identical sensor gas volumes surrounding a sample cell and a reference cell. Due to the exothermic adsorption a pressure rise in the gas volume around the sample cell is induced. After calibration the heat of adsorption can be calculated from the pressure difference curve. First results of the measurement of the adsorption enthalpy of CO 2 on 13X zeolite are shown.
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