Masoud Jahandar Lashaki

Effect of adsorption and regeneration temperature on irreversible adsorption of organic vapors on beaded activated carbon.

This paper investigates the effect of adsorption and regeneration temperature on the irreversible adsorption of a mixture of organic compounds typically emitted from automobile painting operations. Adsorption of the organic vapors mixture onto microporous beaded activated carbon (BAC) and regeneration of the saturated BAC were completed under different conditions. Results indicated that increasing the adsorption temperature from 25 to 35 or 45 °C increased heel buildup on BAC by about 30% irrespective of the regeneration temperature due to chemisorption. The adsorption capacity (for the first cycle) of the mixture onto the BAC at these three temperatures remained almost unchanged indicating chemisorption of some of these compounds onto the BAC. Increasing the regeneration temperature from 288 to 400 °C resulted in 61% reduction in the heel at all adsorption temperatures, possibly due to desorption of chemicals from narrow micropores. BET area and pore volumes of the BAC decreased proportionally to the cumulative heel. Pore size distribution and pore volume reduction confirmed that the heel was mainly built up in narrow micropores which can be occupied or blocked by some of the adsorbates.

Adsorption and Desorption of Mixtures of Organic Vapors on Beaded Activated Carbon

In this study, adsorption and desorption of mixtures of organic compounds commonly emitted from automotive painting operations were experimentally studied. A mixture of two alkanes and a mixture of eight organic compounds were adsorbed onto beaded activated carbon (BAC) and then thermally desorbed under nitrogen. Following both adsorption and regeneration, samples of the BAC were chemically extracted. Gas chromatography-mass spectrometry (GC-MS) was used to quantify the compounds in the adsorption and desorption gas streams and in the BAC extracts. In general, for both adsorbate mixtures, competitive adsorption resulted in displacing low boiling point compounds by high boiling point compounds during adsorption. In addition to boiling point, adsorbate structure and functionality affected adsorption dynamics. High boiling point compounds such as n-decane and 2,2-dimethylpropylbenzene were not completely desorbed after three hours regeneration at 288 °C indicating that these two compounds contributed to heel accumulation on the BAC. Additional compounds not present in the mixtures were detected in the extract of regenerated BAC possibly due to decomposition or other reactions during regeneration. Closure analysis based on breakthrough curves, solvent extraction of BAC and mass balance on the reactor provided consistent results of the amount of adsorbates on the BAC after adsorption and/or regeneration.

Effect of the adsorbate kinetic diameter on the accuracy of the Dubinin-Radushkevich equation for modeling adsorption of organic vapors on activated carbon.

This paper investigates the effect of the kinetic diameter (KD) of the reference adsorbate on the accuracy of the Dubinin-Radushkevich (D-R) equation for predicting the adsorption isotherms of organic vapors on microporous activated carbon. Adsorption isotherms for 13 organic compounds on microporous beaded activated carbon were experimentally measured, and predicted using the D-R model and affinity coefficients. The affinity coefficients calculated based on molar volumes, molecular polarizabilities, and molecular parachors were used to predict the isotherms based on four reference compounds (4.3≤KD≤6.8 Å). The results show that the affinity coefficients are independent of the calculation method if the reference and test adsorbates are from the same organic group. Choosing a reference adsorbate with a KD similar to that of the test adsorbate results in better prediction of the adsorption isotherm. The relative error between the predicted and the measured adsorption isotherms increases as the absolute difference in the kinetic diameters of the reference and test adsorbates increases. Finally, the proposed hypothesis was used to explain reports of inconsistent findings among published articles. The results from this study are important because they allow a more accurate prediction of adsorption capacities of adsorbents which allow for better design of adsorption systems.

The role of beaded activated carbon's pore size distribution on heel formation during cyclic adsorption/desorption of organic vapors

The effect of activated carbons pore size distribution (PSD) on heel formation during adsorption of organic vapors was investigated. Five commercially available beaded activated carbons (BAC) with varying PSDs (30-88% microporous) were investigated. Virgin samples had similar elemental compositions but different PSDs, which allowed for isolating the contribution of carbons microporosity to heel formation. Heel formation was linearly correlated (R(2)=0.91) with BAC micropore volume; heel for the BAC with the lowest micropore volume was 20% lower than the BAC with the highest micropore volume. Meanwhile, first cycle adsorption capacities and breakthrough times correlated linearly (R(2)=0.87 and 0.93, respectively) with BAC total pore volume. Micropore volume reduction for all BACs confirmed that heel accumulation takes place in the highest energy pores. Overall, these results show that a greater portion of adsorbed species are converted into heel on highly microporous adsorbents due to higher share of high energy adsorption sites in their structure. This differs from mesoporous adsorbents (low microporosity) in which large pores contribute to adsorption but not to heel formation, resulting in longer adsorbent lifetime. Thus, activated carbon with high adsorption capacity and high mesopore fraction is particularly desirable for organic vapor application involving extended adsorption/regeneration cycling.

Two-Dimensional Modeling of Volatile Organic Compounds Adsorption onto Beaded Activated Carbon

A two-dimensional heterogeneous computational fluid dynamics model was developed and validated to study the mass, heat, and momentum transport in a fixed-bed cylindrical adsorber during the adsorption of volatile organic compounds (VOCs) from a gas stream onto a fixed bed of beaded activated carbon (BAC). Experimental validation tests revealed that the model predicted the breakthrough curves for the studied VOCs (acetone, benzene, toluene, and 1,2,4-trimethylbenzene) as well as the pressure drop and temperature during benzene adsorption with a mean relative absolute error of 2.6, 11.8, and 0.8%, respectively. Effects of varying adsorption process variables such as carrier gas temperature, superficial velocity, VOC loading, particle size, and channelling were investigated. The results obtained from this study are encouraging because they show that the model was able to accurately simulate the transport processes in an adsorber and can potentially be used for enhancing absorber design and operation.

Microporous activated carbon from pinewood and wheat straw by microwave-assisted KOH treatment for the adsorption of toluene and acetone vapors

Pinewood and wheat straw activated carbons were prepared by KOH and microwave heating, and their adsorption properties were determined. The pinewood and wheat straw activated carbons achieved total pore volumes of 0.93 and 0.60 cm3 g−1, surface areas of 2044 and 1250 m2 g−1, as well as a high contribution of micropores of 75% and 76%, respectively, at a KOH/char ratio of 3.0, in less than 30 min at 600 W and in the presence of humidity. The adsorption properties of the activated carbons were quantified using toluene and acetone adsorption at 200 ppm and adsorption isotherms. Equilibrium isotherm data were fitted using the Dubinin–Radushkevich model.

The role of beaded activated carbon’s surface oxygen groups on irreversible adsorption of organic vapors

The objective of this study is to determine the contribution of surface oxygen groups to irreversible adsorption (aka heel formation) during cyclic adsorption/regeneration of organic vapors commonly found in industrial systems, including vehicle-painting operations. For this purpose, three chemically modified activated carbon samples, including two oxygen-deficient (hydrogen-treated and heat-treated) and one oxygen-rich sample (nitric acid-treated) were prepared. The samples were tested for 5 adsorption/regeneration cycles using a mixture of nine organic compounds. For the different samples, mass balance cumulative heel was 14 and 20% higher for oxygen functionalized and hydrogen-treated samples, respectively, relative to heat-treated sample. Thermal analysis results showed heel formation due to physisorption for the oxygen-deficient samples, and weakened physisorption combined with chemisorption for the oxygen-rich sample. Chemisorption was attributed to consumption of surface oxygen groups by adsorbed species, resulting in formation of high boiling point oxidation byproducts or bonding between the adsorbates and the surface groups. Pore size distributions indicated that different pore sizes contributed to heel formation - narrow micropores (<7Å) in the oxygen-deficient samples and midsize micropores (7-12Å) in the oxygen-rich sample. The results from this study help explain the heel formation mechanism and how it relates to chemically tailored adsorbent materials.