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Title: Development of Superior Sorbents for Separation of CO2 from Flue Gas at a Wide Temperature Range During Coal Combustion

Abstract

In chapter 1, the studies focused on the development of novel sorbents for reducing the carbon dioxide emissions at high temperatures. Our studies focused on cesium doped CaO sorbents with respect to other major flue gas compounds in a wide temperature range. The thermo-gravimetric analysis of sorbents with loadings of CaO doped on 20 wt% cesium demonstrated high CO{sub 2} sorption uptakes (up to 66 wt% CO{sub 2}/sorbent). It is remarkable to note that zero adsorption affinity for N{sub 2}, O{sub 2}, H{sub 2}O and NO at temperatures as high as 600 C was observed. For water vapor and nitrogen oxide we observed a positive effect for CO{sub 2} adsorption. In the presence of steam, the CO{sub 2} adsorption increased to the highest adsorption capacity of 77 wt% CO{sub 2}/sorbent. In the presence of nitrogen oxide, the final CO{sub 2} uptake remained same, but the rate of adsorption was higher at the initial stages (10%) than the case where no nitrogen oxide was fed. In chapter 2, Ca(NO{sub 3}){sub 2} {center_dot} 4H{sub 2}O, CaO, Ca(OH){sub 2}, CaCO{sub 3}, and Ca(CH{sub 3}COO){sub 2} {center_dot} H{sub 2}O were used as precursors for synthesis of CaO sorbents on this work. The sorbents preparedmore » from calcium acetate (CaAc{sub 2}-CaO) resulted in the best uptake characteristics for CO{sub 2}. It possessed higher BET surface area and higher pore volume than the other sorbents. According to SEM images, this sorbent shows 'fluffy' structure, which probably contributes to its high surface area and pore volume. When temperatures were between 550 and 800 C, this sorbent could be carbonated almost completely. Moreover, the carbonation progressed dominantly at the initial short period. Under numerous adsorption-desorption cycles, the CaAc{sub 2}-CaO demonstrated the best reversibility, even under the existence of 10 vol % water vapor. In a 27 cyclic running, the sorbent sustained fairly high carbonation conversion of 62%. Pore size distributions indicate that their pore volume decreased when experimental cycles went on. Silica was doped on the CaAc{sub 2}-CaO in various weight percentages, but the resultant sorbent did not exhibit better performance under cyclic operation than those without dopant. In chapter 3, the Calcium-based carbon dioxide sorbents were made in the gas phase by flame spray pyrolysis (FSP) and compared to the ones made by standard high temperature calcination (HTC) of selected calcium precursors. The FSP-made sorbents were solid nanostructured particles having twice as large specific surface area (40-60 m{sup 2}/g) as the HTC-made sorbents (i.e. from calcium acetate monohydrate). All FSP-made sorbents showed high capacity for CO{sub 2} uptake at high temperatures (773-1073 K) while the HTC-made ones from calcium acetate monohydrate (CaAc{sub 2} {center_dot} H{sub 2}O) demonstrated the best performance for CO{sub 2} uptake among all HTC-made sorbents. At carbonation temperatures less than 773 K, FSP-made sorbents demonstrated better performance for CO{sub 2} uptake than all HTC-made sorbents. Above that, both FSP-made, and HTC-made sorbents from CaAc{sub 2} {center_dot} H{sub 2}O exhibited comparable carbonation rates and maximum conversion. In multiple carbonation/decarbonation cycles, FSP-made sorbents demonstrated stable, reversible and high CO{sub 2} uptake capacity sustaining maximum molar conversion at about 50% even after 60 such cycles indicating their potential for CO{sub 2} uptake. In chapter 4 we investigated the performance of CaO sorbents with dopant by flame spray pyrolysis at higher temperature. The results show that the sorbent with zirconia gave best performance among sorbents having different dopants. The one having Zr to Ca of 3:10 by molar gave stable performance. The calcium conversion around 64% conversion during 102-cycle operations at 973 K. When carbonation was performance at 823 K, the Zr/Ca sorbent (3:10) exhibited stable performance of 56% by calcium molar conversion, or 27% by sorbent weight, both of which are less than those at 973 K as expected. In chapter 5 we investigated the performance of CaO sorbents by flame spray pyrolysis at higher temperature with much shorter duration period. Stable high conversions were attained after 40 cycles The results show that the sorbent could reach high CO{sub 2} capture capacity, be completely regenerated in short time and be quite stable even at these severe conditions. Several studies were devoted to identify sorbents which could effectively capture CO{sub 2} while survive in SO{sub 2} atmosphere. From the group of sorbents we checked, a couple of sorbents showed very promising behavior, namely CO{sub 2} uptakes higher than 60% (wt/wt sorbent) while they acquired higher than 95% of their original activity/performance characteristics in a short period of time.« less

Authors:
Publication Date:
Research Org.:
Univ. of Cincinnati, OH (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
923327
DOE Contract Number:  
FG26-03NT41810
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
01 COAL, LIGNITE, AND PEAT; ACETATES; ADSORPTION; AFFINITY; CALCINATION; CALCIUM; CARBON DIOXIDE; CESIUM; COAL; COMBUSTION; FLAMES; FLUE GAS; NITROGEN OXIDES; PYROLYSIS; SILICA; SORPTION; SPECIFIC SURFACE AREA; STEAM; SURFACE AREA; SYNTHESIS; WATER VAPOR

Citation Formats

Smirniotis, Panagiotis G. Development of Superior Sorbents for Separation of CO2 from Flue Gas at a Wide Temperature Range During Coal Combustion. United States: N. p., 2007. Web. doi:10.2172/923327.
Smirniotis, Panagiotis G. Development of Superior Sorbents for Separation of CO2 from Flue Gas at a Wide Temperature Range During Coal Combustion. United States. doi:10.2172/923327.
Smirniotis, Panagiotis G. Sat . "Development of Superior Sorbents for Separation of CO2 from Flue Gas at a Wide Temperature Range During Coal Combustion". United States. doi:10.2172/923327. https://www.osti.gov/servlets/purl/923327.
@article{osti_923327,
title = {Development of Superior Sorbents for Separation of CO2 from Flue Gas at a Wide Temperature Range During Coal Combustion},
author = {Smirniotis, Panagiotis G},
abstractNote = {In chapter 1, the studies focused on the development of novel sorbents for reducing the carbon dioxide emissions at high temperatures. Our studies focused on cesium doped CaO sorbents with respect to other major flue gas compounds in a wide temperature range. The thermo-gravimetric analysis of sorbents with loadings of CaO doped on 20 wt% cesium demonstrated high CO{sub 2} sorption uptakes (up to 66 wt% CO{sub 2}/sorbent). It is remarkable to note that zero adsorption affinity for N{sub 2}, O{sub 2}, H{sub 2}O and NO at temperatures as high as 600 C was observed. For water vapor and nitrogen oxide we observed a positive effect for CO{sub 2} adsorption. In the presence of steam, the CO{sub 2} adsorption increased to the highest adsorption capacity of 77 wt% CO{sub 2}/sorbent. In the presence of nitrogen oxide, the final CO{sub 2} uptake remained same, but the rate of adsorption was higher at the initial stages (10%) than the case where no nitrogen oxide was fed. In chapter 2, Ca(NO{sub 3}){sub 2} {center_dot} 4H{sub 2}O, CaO, Ca(OH){sub 2}, CaCO{sub 3}, and Ca(CH{sub 3}COO){sub 2} {center_dot} H{sub 2}O were used as precursors for synthesis of CaO sorbents on this work. The sorbents prepared from calcium acetate (CaAc{sub 2}-CaO) resulted in the best uptake characteristics for CO{sub 2}. It possessed higher BET surface area and higher pore volume than the other sorbents. According to SEM images, this sorbent shows 'fluffy' structure, which probably contributes to its high surface area and pore volume. When temperatures were between 550 and 800 C, this sorbent could be carbonated almost completely. Moreover, the carbonation progressed dominantly at the initial short period. Under numerous adsorption-desorption cycles, the CaAc{sub 2}-CaO demonstrated the best reversibility, even under the existence of 10 vol % water vapor. In a 27 cyclic running, the sorbent sustained fairly high carbonation conversion of 62%. Pore size distributions indicate that their pore volume decreased when experimental cycles went on. Silica was doped on the CaAc{sub 2}-CaO in various weight percentages, but the resultant sorbent did not exhibit better performance under cyclic operation than those without dopant. In chapter 3, the Calcium-based carbon dioxide sorbents were made in the gas phase by flame spray pyrolysis (FSP) and compared to the ones made by standard high temperature calcination (HTC) of selected calcium precursors. The FSP-made sorbents were solid nanostructured particles having twice as large specific surface area (40-60 m{sup 2}/g) as the HTC-made sorbents (i.e. from calcium acetate monohydrate). All FSP-made sorbents showed high capacity for CO{sub 2} uptake at high temperatures (773-1073 K) while the HTC-made ones from calcium acetate monohydrate (CaAc{sub 2} {center_dot} H{sub 2}O) demonstrated the best performance for CO{sub 2} uptake among all HTC-made sorbents. At carbonation temperatures less than 773 K, FSP-made sorbents demonstrated better performance for CO{sub 2} uptake than all HTC-made sorbents. Above that, both FSP-made, and HTC-made sorbents from CaAc{sub 2} {center_dot} H{sub 2}O exhibited comparable carbonation rates and maximum conversion. In multiple carbonation/decarbonation cycles, FSP-made sorbents demonstrated stable, reversible and high CO{sub 2} uptake capacity sustaining maximum molar conversion at about 50% even after 60 such cycles indicating their potential for CO{sub 2} uptake. In chapter 4 we investigated the performance of CaO sorbents with dopant by flame spray pyrolysis at higher temperature. The results show that the sorbent with zirconia gave best performance among sorbents having different dopants. The one having Zr to Ca of 3:10 by molar gave stable performance. The calcium conversion around 64% conversion during 102-cycle operations at 973 K. When carbonation was performance at 823 K, the Zr/Ca sorbent (3:10) exhibited stable performance of 56% by calcium molar conversion, or 27% by sorbent weight, both of which are less than those at 973 K as expected. In chapter 5 we investigated the performance of CaO sorbents by flame spray pyrolysis at higher temperature with much shorter duration period. Stable high conversions were attained after 40 cycles The results show that the sorbent could reach high CO{sub 2} capture capacity, be completely regenerated in short time and be quite stable even at these severe conditions. Several studies were devoted to identify sorbents which could effectively capture CO{sub 2} while survive in SO{sub 2} atmosphere. From the group of sorbents we checked, a couple of sorbents showed very promising behavior, namely CO{sub 2} uptakes higher than 60% (wt/wt sorbent) while they acquired higher than 95% of their original activity/performance characteristics in a short period of time.},
doi = {10.2172/923327},
journal = {},
number = ,
volume = ,
place = {United States},
year = {2007},
month = {6}
}