Massoud Rostam-Abadi

Activity and stability of immobilized carbonic anhydrase for promoting CO2 absorption into a carbonate solution for post-combustion CO2 capture

An Integrated Vacuum Carbonate Absorption Process (IVCAP) currently under development could significantly reduce the energy consumed when capturing CO2 from the flue gases of coal-fired power plants. The biocatalyst carbonic anhydrase (CA) has been found to effectively promote the absorption of CO2 into the potassium carbonate solution that would be used in the IVCAP. Two CA enzymes were immobilized onto three selected support materials having different pore structures. The thermal stability of the immobilized CA enzymes was significantly greater than their free counterparts. For example, the immobilized enzymes retained at least 60% of their initial activities after 90 days at 50 °C compared to about 30% for their free counterparts under the same conditions. The immobilized CA also had significantly improved resistance to concentrations of sulfate (0.4 M), nitrate (0.05 M) and chloride (0.3 M) typically found in flue gas scrubbing liquids than their free counterparts.

Applications for activated carbons from waste tires: natural gas storage and air pollution control

Natural gas storage for natural gas vehicles and the separation and removal of gaseous contaminants from gas streams represent two emerging applications for carbon adsorbents. A possible precursor for such adsorbents is waste tires. In this study, activated carbon has been developed from waste tires and tested for its methane storage capacity and S02 removal from a simulated flue-gas. Tire-derived carbons exhibit methane adsorption capacities (g/g) within 10% of a relatively expensive commercial activated carbon; however, their methane storage capacities (VmVs) are almost 60% lower. The unactivated tire char exhibits SO2 adsorption kinetics similar to a commercial carbon used for flue-gas clean-up.

Natural gas storage with activated carbon from a bituminous coal

Abstract Granular activated carbons (−20 + 100 mesh; 0.149−0.84 mm) were produced by physical activation and chemical activation with KOH from an Illinois bituminous coal (IBC-106) for natural gas storage. The products were characterized by BET surface area, micropore volume, bulk density, and methane adsorption capacities. Volumetric methane adsorption capacities ( V m V s ) of some of the granular carbons produced by physical activation are about 70 cm 3 /cm 3 which is comparable to that of BPL, a commercial activated carbon. ( V m V s ) values above 100 cm 3 /cm 3 are obtainable by grinding the granular products to −325 mesh ( V m V s ) is due to the increase in bulk density of the carbons. Volumetric methane adsorption capacity increases with increasing pore surface area and micropore volume when normalizing with respect to sample bulk volume. Compared with steam-activated carbons, granular carbons produced by KOH activation have higher micropore volume and higher methane adsorption capacities (g/g). Their volumetric methane adsorption capacities are lower due to their lower bulk densities.

A new mathematical solution for predicting char activation reactions

Abstract The differential conservation equations that describe typical gas–solid reactions, such as activation of coal chars, yield a set of coupled second-order partial differential equations. The solution of these coupled equations by exact analytical methods is impossible. In addition, an approximate or exact solution only provides predictions for either reaction- or diffusion-controlling cases. A new mathematical solution, the quantize method (QM), was applied to predict the gasification rates of coal char when both chemical reaction and diffusion through the porous char are present. Carbon conversion rates predicted by the QM were in closer agreement with the experimental data than those predicted by the random pore model and the simple particle model.

Sintering of calcium oxide (CaO) during CO2 chemisorption: a reactive molecular dynamics study

Reactive dynamics simulations with the reactive force field (ReaxFF) were performed in NVE ensembles to study the sintering of two solid calcium oxide (CaO) particles with and without CO(2) chemisorption. The simulated sintering conditions included starting adsorption temperatures at 1000 K and 1500 K and particle separation distances of 0.3 and 0.5 nm. The results revealed that the expansion of sorbent particles during CO(2) chemisorption was attributed to the sintering of two CaO-CaO particles. Increasing the adsorption temperature resulted in more particle expansion and sintering. The shorter the distance between two particles, the faster the rate of sintering during CO(2) adsorption. A detailed analysis on atom spatial variations revealed that the sorbent particles with a larger separation distance had a larger CO(2) uptake because of less sintering incurred. The chemisorptions of CO(2) on CaO particles sintered at high adsorption temperatures were also simulated to mimic the process of sorbent regeneration. It was found that regeneration would be more difficult for sintered particles than for fresh particles. In addition, a possible sintering barrier, magnesium oxide (MgO), was introduced to prevent CaO particles from sintering during CO(2) chemisorption. It was found that the MgO particles could reduce the sintering of CaO particles during CO(2) chemisorption. Simulation results from this study provided some guidelines on synthesizing or selecting sorbents with less sintering effect for multiple CO(2) adsorption-regeneration cycles.

Production of carbon molecular sieves from Illinois coal

Abstract Carbon molecular sieves (CMS) have become an increasingly important class of adsorbents for application in the separation of gas molecules that vary in size and shape. A study is in progress at the Illinois State Geological Survey to determine whether Illinois basin coals are suitable feedstocks for the production of CMS and to evaluate their potential application in gas separation processes of commercial importance. Chars were prepared from Illinois coal in a fixed-bed reactor under a wide range of heat treatment and activation conditions. The effects of various coal/char pretreatments, including coal demineralization, preoxidation, char activation, and carbon deposition, on the molecular sieve properties of the chars were also investigated. Chars with commercially significant BET surface areas of 1500 m2/g were produced by chemical activation using potassium hydroxide as the activant. These high-surface-area (HSA) chars had more than twice the adsorption capacity of commercial carbon and zeolite molecular sieves. The kinetics of adsorption of various gases, e.g., N2, O2, CO2, CH4, CO and H2, on these chars at 25°C was measured. The O2/N2 molecular sieve properties of one char prepared without chemical activation were similar to those of a commercial CMS. On the other hand, the O2/N2 selectivity of the HSA char was comparable to that of a commercial activated carbon, i.e., essentially unity. Carbon deposition, using methane as the cracking gas, increased the O2/N2 selectivity of the HSA char, but significantly decreased its adsorption capacity. Several chars showed good potential for efficient CO2/CH4 separation; both a relatively high CO2 adsorption capacity and CO2/CH4 selectivity were achieved. The micropore size distribution of selected chars was estimated by equilibrium adsorption of carbon dioxide, n-butane and iso-butane at O°C. The extent of adsorption of each gas corresponded to the effective surface area contained in pores with diameters greater than 3.3, 4.3 and 5.0 A, respectively. Kinetic and equilibrium adsorption data provided complementary information on the molecular sieving capabilities and microstructure of the prepared chars.

Development of carbon-based adsorbents for removal of mercury emissions from coal combustion flue gas

Publisher Summary This chapter illustrates that the minimum amount of carbon needed to achieve specific mercury removal efficiency by sorbent injection into a flue gas stream can be predicted by assuming mass transfer limitations. Mercury removal effectiveness can be increased by decreasing the size of the carbon injected, increasing the residence time, or the amount of carbon injected. If mercury removal is limited by the reactivity and capacity of the carbon (i.e. not mass transfer limited), then significantly more carbon than the amount predicted by mass transfer limitations may be needed for effective mercury removal unless the reactivity and capacity of the carbon can be improved through structural and surface chemistry changes. Intra particle diffusion is not important because of the small carbon sizes normally used for injection.

Evaluation of Dry Sorbent Injection Technology for Pre-Combustion CO{sub 2} Capture

This document summarizes the work performed on Cooperative Agreement DE-FE0000465, “Evaluation of Dry Sorbent Technology for Pre-Combustion CO{sub 2} Capture,” during the period of performance of January 1, 2010 through September 30, 2013. This project involves the development of a novel technology that combines a dry sorbent-based carbon capture process with the water-gas-shift reaction for separating CO{sub 2} from syngas. The project objectives were to model, develop, synthesize and screen sorbents for CO{sub 2} capture from gasified coal streams. The project was funded by the DOE National Energy Technology Laboratory with URS as the prime contractor. Illinois Clean Coal Institute and The University of Illinois Urbana-Champaign were project co-funders. The objectives of this project were to identify and evaluate sorbent materials and concepts that were suitable for capturing carbon dioxide (CO{sub 2}) from warm/hot water-gas-shift (WGS) systems under conditions that minimize energy penalties and provide continuous gas flow to advanced synthesis gas combustion and processing systems. Objectives included identifying and evaluating sorbents that efficiently capture CO{sub 2} from a gas stream containing CO{sub 2}, carbon monoxide (CO), and hydrogen (H{sub 2}) at temperatures as high as 650 °C and pressures of 400-600 psi. After capturing the CO{sub 2}, the sorbents would ideally be regenerated using steam, or other condensable purge vapors. Results from the adsorption and regeneration testing were used to determine an optimal design scheme for a sorbent enhanced water gas shift (SEWGS) process and evaluate the technical and economic viability of the dry sorbent approach for CO{sub 2} capture. Project work included computational modeling, which was performed to identify key sorbent properties for the SEWGS process. Thermodynamic modeling was used to identify optimal physical properties for sorbents and helped down-select from the universe of possible sorbent materials to seven that were deemed thermodynamically viable for the process. Molecular modeling was used to guide sorbent synthesis through first principles simulations of adsorption and regeneration. Molecular dynamics simulations also modeled the impact of gas phase impurities common in gasified coal streams (e.g., H{sub 2}S) on the adsorption process. The role of inert dopants added for mechanical durability to active sorbent materials was also investigated through molecular simulations. Process simulations were conducted throughout the project to help determine the overall feasibility of the process and to help guide laboratory operating conditions. A large component of the program was the development of sorbent synthesis methods. Three different approaches were used: mechanical alloying (MA), flame spray pyrolysis (FSP), and ultrasonic spray pyrolysis (USP). Sorbents were characterized by a host of analytical techniques and screened for SEWGS performance using a thermogravimetric analyzer (TGA). A feedback loop from screening efforts to sorbent synthesis was established and used throughout the project lifetime. High temperature, high pressure reactor (HTPR) systems were constructed to test the sorbents at conditions mimicking the SEWGS process as identified through process modeling. These experiments were conducted at the laboratory scale to examine sorbents for their CO{sub 2} capacity, conversion of CO to CO{sub 2}, and impacts of adsorption and regeneration conditions, and syngas composition (including impurities and H2O:CO ratio). Results from the HTPR testing showed sorbents with as high as 0.4 g{sub CO{sub 2}}/g{sub sorbent} capacity with the ability to initially shift the WGS completely towards CO{sub 2}/H{sub 2}. A longer term experiment with a simple syngas matrix and N{sub 2}/steam regeneration stream showed a USP sorbent to be stable through 50 adsorption-regeneration cycles, though the sorbent tested had a somewhat diminished initial capacity. The program culminated in a technoeconomic assessment in which two different approaches were taken; one approach was intended to be technically conservative while the second required several key engineering challenges to be met in order to succeed. The project team is confident that, with the proper support, those challenges could be met. The second approach relies on a slipstream of H{sub 2} from the shifted syngas and O{sub 2} from an air separation unit (ASU) to be combusted in the presence of the sorbent for regeneration; termed a regenerating boiler. The approach also makes use of the heat of adsorption to generate >400 MW of turbine quality steam; total plant gross energy output as high as 1 GW was estimated for an IGCC with an initial gross energy output of 737 MW, without any additional coal usage. The regenerating boiler concept could benefit further from additional heat integration, but the results of this effort show a COE of

Adsorption equilibrium of organic vapors on single-walled carbon nanotubes

97.50 per MWh for a rational combination of operating parameters and sorbent lifetime as well as conservative estimates for steam turbines, gas turbine, and ASU. If the COE of CO{sub 2} transmission, storage and monitoring (