H84PGC Power Generation and Carbon Capture Technology Review Carbon Capture with Activated Carbon

Name Student ID Module Conveyor Submission Date

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Wong Xing Jia 007789 Dr. Gan Suyin 10th December 2013

Technology Review: Carbon Capture with Activated Carbon

Executive Summary
Recent increase in emissions of carbon dioxide has caused the need to find a suitable method to capture and prevent further emissions to the atmosphere. The topic of interest is to use adsorption as a method for carbon capture. Activated carbon has been proposed as a potential adsorbent due to its low cost, natural affinity for carbon dioxide and the additional possibility of tailoring textural properties and surface chemistry. Studies show that activated carbon is suited to be used for carbon capture in low temperature and pressure pre-combustion processes due to the low performance of carbon capture in high temperature and pressure environments. Recent research also show that modifications to activated carbon can increase the carbon dioxide adsorption performance.

Background
The recent increasing levels of carbon dioxide (CO2) emissions from transportation and energy industries around the world has caused concern where some researches and studies pint point that CO2 is one of the main contributors to the increase of presence of greenhouse gases in the world causing side effects such as global warming. This has led to an increase of interest and research on methods to reduce CO2 emissions through carbon capture sequestration (CCS). CCS is the process of capturing CO2 from point sources, such as power plants, and transporting the gas to a storage site where it will not be released to the atmosphere. One of the methods that this technology review is interested is the use of activated carbon to capture CO2. Activated carbon (AC) is a type of non-graphite carbon which can be manufactured from any type of carbonaceous material such as coal, wood and even coconut shells. The unique point of AC is that it shows a high degree of microporosity (diameters of <2nm), high surface area (1000m2), high reactivity at surface makes it a very versatile adsorbent1. A suitable adsorbent must be cheap, selective for CO2 despite (high) process temperature, have high surface area and pore volume together with fast intraparticle diffusion and reversible adsorption (ideally upon pressure swings). AC can fulfill most of these requirements. The process of activating a carbon is using physical or chemical activation where more pore sites are activated on the carbon for adsorption.

Discussion
The manufacturing of activated carbon has been traditionally been done using charcoal and fossil fuel as raw materials2. There are recent studies3 that show the use of coconut shell can be considered a suitable substitute as a raw material due to the excellent natural structure of high number of microspores which aids adsorption and low ash content from the manufacturing process. In addition, coconut shell is renewable and sustainable since it is harvested easily compared to non-renewable materials like coal mining or fossil fuel extraction which leaves a very large carbon foot print.

Figure 1: Granular coconut activated carbon. (Eurocarb Products Ltd, 2010)

The manufacture of AC can be done via chemical or physical activation4. Chemical activation uses chemicals to activate and increase the micropore numbers but is not financially sound due to wastewater treatment and production costs (Su et al., 2006). Physical activation of the carbon through steam is preferred as it is a simple process through kilns or special designed vessels. Prior to activation, a pre-activation process of charcoaling is needed, where the original carbonaceous material is converted to charcoal through carbonization as shown in Figure 2. Most charcoaling is done through pit-charcoaling where the material is placed in a wide pit and burned under restricted oxygen conditions. This downside of this process is that it is usually occurs at uncontrolled conditions and results in large emissions of greenhouse gases. A new method is proposed whereby carbonization is called the Recogen process where charcoaling is done in special designed reactors and the gas emissions would be used is collected and combusted to generate steam and in turn electricity5. A small scale project was initiated in Badalgama, Sri Lanka by Eurocarb Products Ltd and it has a charcoal production capacity of 26,000 tons per year with electricity output of 6 megawatts.

Figure 2: Charcoaling pit (left) with traditional charcoaling of coconut shell (right). (Eurocarb Products Ltd, 2010) The use and application of AC in CCS can be seen in the possible application of AC in power generation industries. As shown in Figure 3 in the next page, there are possible three different stages of combustion in power generation that CCS can be used. These three are the pre-combustion, post-combustion and oxy-fuels. Pre-combustion seeks to remove CO2 before the fuel is combusted and the reverse is so for post-combustion. However in oxy-fuel combustion process, nitrogen is removed from input air to produce an oxygen rich stream which is mixed with the fuel to be combusted and producing a very CO2 rich flue gas easily ready for sequestration.

Figure 3: CCS at different stages (CO2CRC, 2011) The way AC functions in capturing CO2 is by the way of adsorption. The way it is adsorbed onto AC can be seen in Figure 4 as shown below. It can be seen that when the CO2 in the flue gas passes through the AC, it is adsorbed physically to the surface or pores of the AC hence captured onto the AC. The way the AC is regenerated determines what type of adsorption the process undergoes. The two main adsorption methods are pressure swing adsorption (PSA) and temperature swing adsorption (TSA).

Figure 4: Adsorption mechanism of AC with regeneration using PSA. (CO2CRC. 2011)

In PSA, the pressure of the bed is reduced to desorb the absorbed CO2 while TSA the temperature is raise while maintaining constant pressure. Interesting to note is that in a study, it was found that a combination of vacuum (pressure is reduced to below atmospheric) and temperature swing adsorption (VTSA) is the most efficient way of recovering the adsorption column without taking into consideration operational costs6. To maximize the efficiency and as well the time, a two adsorption cycle PSA setup is usually used as shown in Figure 5.

Figure 5: Two bed adsorption cycle set-up in pre-combustion CCS. (CO2CRC, 2011) As mentioned earlier that there are three stages in a power generation plant where CCS can be applied, AC was initially found to be suited for pre-combustion processes7 as some research show that physisorption (physical adsorption) tends to be insignificant at high temperatures8 and also at increasing pressures, the selectivity of CO2 adsorption over nitrogen is reduced9. Another preliminary study has shown that influence of pressure over adsorption is more significant over temperature and that general low pressures of around 5-15 bar is most suitable for best adsorption10. However recent research on postcombustion has shown that the process is possible, but not very effective at capturing CO2 with which agrees with previous statements. This is where one of the advantages of AC comes into consideration, as the nature of the surface of the carbon itself allows for possible tailoring of textual properties and surface chemistry. There is a large interest by the scientific community to experiment and research the results of modification of AC structure, with emphasis on the effects of its adsorbent properties. Some examples including impregnating the micropores of the carbon with other elements such as metals or other functional groups to modify the structure of the carbon and resulting it to have different properties and thus resulting in different CO2 capture efficiencies. There are also other methods where the physical structure of the AC is changed and researched so that the effects it has on carbon capture efficiency can be studied.

With reference to the modifications mentioned earlier, some of the results of research papers have shown positive results in modification to the AC to achieve better carbon capture efficiency. Some studies show that there is some increase in CO2 adsorption by loading nickel oxide into AC using post oxidation method11 at 298K and 1 atm while some claim of significant improvement of CO2 adsorption by functionalizing additional amine groups to AC with triethylenetetramine at 298K and 40 bar with 90% increase of CO2 adsorption compared to raw AC12. Other research on the physical modification of the AC includes manufacturing the AC into spherical shape and a relationship of AC structure-CO2 uptake performance was established whereby well-developed porous systems is key to obtain a higher CO2 capture capacity13. One more research also sees the combination of AC and zeolite to be used in a hybrid adsorption bed and reported that such hybrid set up is able to increase the amount of CO2 adsorbed even with ratio of zeolite and AC of 18%/82%14. Further research is still being carried out to determine different adsorption rates with different zeolite/AC ratios. This shows that AC can and should be used with other carbon capture methods to increase the performance of carbon capture.

Conclusions and Recommendations

Activated carbon was found to be suitable to be used as an adsorbent for carbon dioxide capture. It was concluded that AC can be used in pre-combustion carbon capture to replace other methods due to the somewhat low temperature and pressure environment where it is able adsorb carbon dioxide very efficiently. The fact that AC has low manufacturing cost suggest that it could be adapted and scaled up to industrial scale usage easily. AC is suggested to be used as a complementary system to a larger whole system of carbon capture as it itself cannot operate on its own to effectively capture carbon dioxide at all stages of process due to its own limitations at inefficient carbon uptake at high pressures and temperatures. More studies and research should be carried out to determine if any other modifications or combinations of modifications is able to allow the activated carbon to perform more efficiently at carbon uptake and also at elevated temperatures and pressures so that it may replace other expensive methods.

References and Bibliography

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12. M. Keramati, A.A. Ghoreyshi, Improving CO2 adsorption onto activated carbon through functionalization by chitosan and triethylenetetramine, Physica E: Lowdimensional Systems and Nanostructures, Volume 57, March 2014, Pages 161 168 13. N. Sun, C. Sun, H. Liu, J. Liu, L. Stevens, T. Drage, C.E. Snape, K. Li, W. Wei, Y. Sun, Synthesis, characterization and evaluation of activated spherical carbon materials for CO2 capture, Fuel, Volume 113, November 2013, Pages 854862 14. R.P.P.L. Ribeiro, C.A. Grande, A.E. Rodrigues, Activated carbon honeycomb monolith Zeolite 13X hybrid system to capture CO2 from flue gases employing Electric Swing Adsorption, Chemical Engineering Science, Volume 104, 18 December 2013, Pages 304318 15. Figure 3 to Figure 5 taken from The Cooperative Research Centre for Greenhouse Gas Technologies (CO2CRC). Website available at: http://www.co2crc.com.au/ [Accessed 9 December 2013]