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This paper presents breakthrough curves and isotherms of the adsorption of sulfur compounds, carbon dioxide, and water from a carrier gas (methane) on a fixed solid bed at 298 K and 1.3 bar. For the investigation two industrial adsorbents (silica−alumina gel, zeolite 5A) were used. The adsorptives were prepared in trace level concentrations up to 2000 mol-ppm. Common isotherm equations were fitted to the adsorption capacities which were obtained from breakthrough curves by mass balances. Binary systems (one adsorptive in methane) and ternary systems (two adsorptives in methane) are included. Methane is used to duplicate conditions of industrial scale natural gas treatment as far as possible. Though methane is a very weak adsorptive on oxidic adsorbents the reported adsorptive capacities might be slightly lower than pure component loadings accessible from a volumetric or gravimetric method. The adsorption isotherms of the binary systems show distinctly different capacities depending on the polarity of the adsorptive and the structure of the adsorbent. The investigation of the ternary systems reveals significant coadsorption and displacement as well as kinetic effects due to the presence of competing adsorptives.

Removing of trace-leveled light hydrocarbons from exhaust air or gas streams becomes an increasingly important issue in the field of process and environmental technology, e.g., storage and transport of liquefied natural gas. Adsorption processes at temperatures below 0 °C have great potential to meet process specifications or environmental regulatory limits. Designing of such adsorption processes requires a profound insight into the thermodynamics of adsorption at low temperatures, which is not available yet. Therefore, this work provides adsorption isotherms of ethane, propane, and n-butane on microporous activated carbon and zeolite 13X in a temperature range from −40 to +60 °C and at partial pressures from 5 to 1000 Pa. The influence of temperature on the adsorbed amount on activated carbon and zeolite 13X is discussed for each adsorptive considering isosteric heats of adsorption and specific interactions between the adsorptive and the adsorbent surface.

Adsorption is one of the key technologies for the removal of sulfur compounds in trace levels from natural gas prior to a technical utilization. To improve the design of these coupled adsorption–desorption processes a profound insight into the thermodynamics of adsorption is necessary. Therefore, this article provides adsorption isotherms of ethyl mercaptan, methyl mercaptan, hydrogen sulfide, water, and carbon dioxide on a commercial silica–alumina gel used in natural gas purification. The experimental data spans a temperature range between 25 and 300 °C at concentrations between 0 and 2000 mol-ppm at total pressure of 1.3 bar. Equilibrium capacities and isosteric heats of adsorption are compared and discussed based on an analysis of specific interactions between the adsorptives and the adsorbent’s chemical surface functionality.

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

The separation of short-chained alkanes and alkenes is challenging because of their chemical similarity and thus being costly in energy. The implementation of a cryogenic adsorption process may overcome this problem, but systematic studies on light hydrocarbon adsorption at low temperatures are virtually lacking. Therefore, as a first step, in this paper, we present single-component adsorption isotherms of ethane, ethylene, propane, and propylene on activated carbon (AC) and zeolite 13X for temperatures of −80 to +20 °C and partial pressures of 5–1250 Pa. Based on these experimental data, the interactions of the adsorptives with the chemically different surfaces and their temperature dependence are discussed. Results show a strong increase in capacity with decreasing temperature for both AC and zeolite 13X. Cryogenic adsorption increases the overall (calculated) selectivity of alkane–alkene separation, especially for the zeolite 13X.

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.

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