Praveen Bollini

Dramatic Enhancement of CO2 Uptake by Poly(ethyleneimine) Using Zirconosilicate Supports

The CO(2) adsorption characteristics of prototypical poly(ethyleneimine)/silica composite adsorbents can be drastically enhanced by altering the acid/base properties of the oxide support via incorporation of Zr into the silica support. Introduction of an optimal amount of Zr resulted in a significant improvement in the CO(2) capacity and amine efficiency under dilute (simulated flue gas) and ultradilute (simulated ambient air) conditions. Adsorption experiments combined with detailed characterization by thermogravimetric analysis, temperature-programmed desorption, and in situ FT-IR spectroscopy clearly demonstrate a stabilizing effect of amphoteric Zr sites that enhances the adsorbent capacity, regenerability, and stability over continued recycling. It is suggested that the important role of the surface properties of the oxide support in these polymer/oxide composite adsorbents has been largely overlooked and that the properties may be even further enhanced in the future by tuning the acid/base properties of the support.

Structural changes of silica mesocellular foam supported amine-functionalized CO2 adsorbents upon exposure to steam

Three classes of amine-functionalized mesocellular foam (MCF) materials are prepared and evaluated as CO(2) adsorbents. The stability of the adsorbents under steam/air and steam/nitrogen conditions is investigated using a Parr autoclave reactor to simulate, in an accelerated manner, the exposure that such adsorbents will see under steam stripping regeneration conditions at various temperatures. The CO(2) capacity and organic content of all adsorbents decrease after steam treatment under both steam/air and steam/nitrogen conditions, primarily due to structural collapse of the MCF framework, but with additional contributions likely associated with amine degradation during treatment under harsh conditions. Treatment with steam/air is found to have stronger effect on the CO(2) capacity of the adsorbents compared to steam/nitrogen.

Enhanced CO2 adsorption over polymeric amines supported on heteroatom-incorporated SBA-15 silica: impact of heteroatom type and loading on sorbent structure and adsorption performance.

Silica supported amine materials are promising compositions that can be used to effectively remove CO(2) from large stationary sources, such as flue gas generated from coal-fired power plants (ca. 10 % CO(2)) and potentially from ambient air (ca. 400 ppm CO(2)). The CO(2) adsorption characteristics of prototypical poly(ethyleneimine)-silica composite adsorbents can be significantly enhanced by altering the acid/base properties of the silica support by heteroatom incorporation into the silica matrix. In this study, an array of poly(ethyleneimine)-impregnated mesoporous silica SBA-15 materials containing heteroatoms (Al, Ti, Zr, and Ce) in their silica matrices are prepared and examined in adsorption experiments under conditions simulating flue gas (10 % CO(2) in Ar) and ambient air (400 ppm CO(2) in Ar) to assess the effects of heteroatom incorporation on the CO(2) adsorption properties. The structure of the composite adsorbents, including local information concerning the state of the incorporated heteroatoms and the overall surface properties of the silicate supports, are investigated in detail to draw a relationship between the adsorbent structure and CO(2) adsorption/desorption performance. The CO(2) adsorption/desorption kinetics are assessed by thermogravimetric analysis and in situ FT-IR measurements. These combined results, coupled with data on adsorbent regenerability, demonstrate a stabilizing effect of the heteroatoms on the poly(ethyleneimine), enhancing adsorbent capacity, adsorption kinetics, regenerability, and stability of the supported aminopolymers over continued cycling. It is suggested that the CO(2) adsorption performance of silica-aminopolymer composites may be further enhanced in the future by more precisely tuning the acid/base properties of the support.

Important Roles of Enthalpic and Entropic Contributions to CO2 Capture from Simulated Flue Gas and Ambient Air Using Mesoporous Silica Grafted Amines

The measurement of isosteric heats of adsorption of silica supported amine materials in the low pressure range (0-0.1 bar) is critical for understanding the interactions between CO2 and amine sites at low coverage and hence to the development of efficient amine adsorbents for CO2 capture from flue gas and ambient air. Heats of adsorption for an array of silica-supported amine materials are experimentally measured at low coverage using a Calvet calorimeter equipped with a customized dosing manifold. In a series of 3-aminopropyl-functionalized silica materials, higher amine densities resulted in higher isosteric heats of adsorption, clearly showing that the density/proximity of amine sites can influence the amine efficiency of adsorbents. In a series of materials with fixed amine loading but different amine types, strongly basic primary and secondary amine materials are shown to have essentially identical heats of adsorption near 90 kJ/mol. However, the adsorption uptakes vary substantially as a function of CO2 partial pressure for different primary and secondary amines, demonstrating that entropic contributions to adsorption may play a key role in adsorption at secondary amine sites, making adsorption at these sites less efficient at the low coverages that are important to the direct capture of CO2 from ambient air. Thus, while primary amines are confirmed to be the most effective amine types for CO2 capture from ambient air, this is not due to enhanced enthalpic contributions associated with primary amines over secondary amines, but may be due to unfavorable entropic factors associated with organization of the second alkyl chain on the secondary amine during CO2 adsorption. Given this hypothesis, favorable entropic factors may be the main reason primary amine based adsorbents are more effective under air capture conditions.