Adsorption Experiments For Continuous Adsorption Of Carbon Dioxide (Co2) By Delonix Regia Fruit Powder (Drf) And Carbon Produced From Delonix Regia Fruit(Drf) Powder

The adsorption experiments were carried out for continuous adsorption of carbon dioxide (CO2) by Delonix Regia Fruit powder (DRF) and carbon produced from Delonix Regia Fruit(DRF) powder. The experiments were conducted to characterize the breakthrough characteristics of CO2 in fixed bed reactor for different gas flow rates and different weight of powder. EDAX analysis showed presence of carbon original DRF powder and presence of titania(1.216%),alumina(3.739%) and magnesia(9.271%) in XRF analysis showed high affinity towards CO2 molecules. For 5gm DRF powder adsorption capacity was found more for 10 LPH flow rate than carbon made from DRF powder .The trend for adsorption capacities was decreasing with increasing flow rates.

Keywords: Carbon dioxide, Delonix Regia Fruit .
Introduction
The increase of greenhouse gases in atmosphere induced the global warming due to the rise of global temperature that causes severe impacts to the environment. The abundance of CO2 come from the main emissions of combustion of fossil fuels such as coal, natural gas or petroleum, and industrial processes such as oil refinement and the production of cement, iron ,steel and aluminum . The issues of climate change can be solved by enhancing the removal of CO2 from the industrial emissions and decrease the atmospheric concentration level of it. One of the major solutions in CO2 removal is from the emergence modification of activated carbon that was considered as highly potential adsorbent for CO2 [1]. Many industrial environmental methods used to decrease the emissions and concentrations of CO2 such as improving the fuel used or technological methods or using of renewable energies. Many industries concerned and become a necessarily in removal of carbon dioxide (CO2) from air or gas streams for different purposes. For an example in fuel production industries, the removing of carbon dioxide could enrich methane in biogas to have fuel of higher calorific value. Furthermore, elimination of carbon dioxide from the flue gas could also prevent the greenhouse gasses effects as well. [2]. Carbonaceous material is any types of substances that can produce activated carbon such as wood, lignite, anthracite or bone. This adsorbent involved in small cost, currently easy to found from the agricultural wastes, by-products and other types of materials as well as can reduce the waste disposal. Thus, modifying of activated carbon has been focused by researchers in order to enhance effectiveness of its specific properties in capturing CO2[3]. Modified activated carbon was considered to be a potential adsorbent due to its better selectivity. Several method have been done in modifying activated carbon for producing effective activated carbon for gases adsorption and most common methods are by using physical treatment such as heat treatment, and chemical treatment like ammonia treatment and impregnation of chemicals[4].Specific modification techniques on activated carbon for carbon dioxide adsorption could give some beneficial effects and the efficiency of adsorption is depending on the technique used [5].For CO2 concentrations such as found in the flue gas, a chemical solvent such as mono-ethanolamine or a solid sorbent such as solid phase amine, silver oxide, or lithium hydroxide is preferred; for higher CO2 concentration, e.g. CO2 rejection from natural gas , a physical solvent is favored . Chakravarti et.al carried out high surface area adsorbent, using zeolite, alumina or activated carbon in chemical adsorption Cost effective carbon sequestration schemes have been identified as a key need for dealing with carbon dioxide's impact on global climate change. Two main approaches are being pursued for sequestration: the enhancement of biological carbon sinks, and the capture and storage of CO2. Since the bulk of the cost in a capture and storage sequestration scheme stems from CO2 separation and compression, Praxair has focused on substantially reducing these costs through technology advances. CO2 capture from flue gases emitted from the existing energy infrastructure was studied. Such large point sources account for nearly sixty percent of global CO2 emissions. Praxair has developed advanced amine absorption processes that can separate CO2 from flue gases at much lower costs than current commercial alternatives. These significant capital and operating cost savings have been achieved by developing an oxygen tolerant amine absorption process, and by the application of amine blends. [6].Rao and Rubin studied Low temperature (cryogenic) distillation by liquefaction and purification of CO2 from high concentration (>90%). Capture and sequestration of CO2 from fossil fuel power plants is gaining widespread interest as a potential method of controlling greenhouse gas emissions. Performance and cost models of an amine based CO2 absorption system for post combustion flue gas applications have been developed and integrated with an existing power plant modeling framework that includes multipollutant control technologies for other regulated emissions. The integrated model has been applied to study the feasibility and cost of carbon capture and sequestration at both new and existing coal-burning power plants. The cost of carbon avoidance was shown to depend strongly on assumptions about the reference plant design, details of the CO2 capture system design, interactions with other pollution control systems, and method of CO2 storage. The CO2 avoidance cost for retrofit systems was found to be generally higher than for new plants, mainly because of the higher energy penalty resulting from less efficient heat integration as well as site specific difficulties typically encountered in retrofit applications. For all cases, a small reduction in CO2 capture cost was afforded by SO2 emission trading credits generated by amine-based capture systems. Efforts are underway to model a broader suite of carbon capture and sequestration technologies for more comprehensive assessments in the context of multipollutant environmental management. [7]. Gas separation membranes were developed by J.J. Spivey using solubility-selective polymers for low temperature separation and ceramics for high-temperature separation [8]. Bates, Eleanor D, suggested advanced processes such as CO2 capture by an ionic liquids Reaction of 1-butyl imidazole with 3-bromopropylamine hydrobromide, followed by workup and anion exchange, yields a new room temperature ionic liquid incorporating a cation with an appended amine group. The new ionic liquid reacts reversibly with CO2, reversibly sequestering the gas as a carbamate salt. The new ionic liquid, which can be repeatedly recycled in this role, is comparable in efficiency for CO2 capture to commercial amine sequestering reagents, and yet is nonvolatile and does not require water to function [9].The carbon dioxide storage capacity of magnesium oxide (MgO) particles was examined as a function of particle size, shape, and surface area. Two types of MgO nanocrystals (5 nm spheres and 23 nm disks) were synthesized and compared against commercially available MgO (325 mesh/44 mm and 40 mesh/420 mm). The surface area of the four types of particles was determined by N2 gas adsorption. Carbon dioxide capture was measured at 60 'C and 600 'C using thermogravimetric analysis, with results indicating enhanced CO2 capacity correlating with increased surface area. [10]. Molecular sieves were used to remove CO2 by adsorption in the space station, but their high cost limits their usage for CO2 capture form flue gas mitigating the global warming greenhouse effect while maintaining a fossil fuel economy, requires improving efficiency of utilization of fossil fuels, use of high hydrogen content fossil fuels, decarbonization of fossil fuels, and sequestering of carbon and CO2 applied to all the sectors of the economy, electric power generation, transportation, and industrial, and domestic power and heat generation. Decarbonization means removal of carbon as C or CO2 either before or after fossil fuel combustion and sequestration means disposal of the recovered C or CO2 including its utilization. Removal and recovery of CO2 from power generation plants and sequestration in the ocean represents one possibility of making a major impact on reducing CO2 emissions to the atmosphere[11].Cryogenic processes can produce liquid CO2 ready for transportation prior to use or sequestration, but is only worth considering when the CO2 concentration in flue gas is high [12]. Activated carbon was produced from banana empty fruit bunch (BEFB) and Delonix regia fruit pod (DRFP) through single step chemical activation process. As both the lignocellulosic wastes showed maximum weight loss at temperatures lower than 500??C, they were carbonized at 450??C and 400??C respectively after impregnating with H3PO4 and KOH. Highest yield of 41.09% was recorded in DRFP treated with H3PO4.. The KOH treated DRFP recorded maximum bulk density of 0.46 g/ml followed by H3PO4 treated DRFP. The BEFP carbons displayed lower attrition values than DRFP carbons. While the H3PO4 treated DRFP carbon sample showed higher surface area, the untreated DRFP registered higher pore volume [13]. Aime?? Serge Ello, Luiz K.C. de Souza , Albert Trokourey, Mietek Jaroniec carried work on Microporous carbons prepared from African palm shells by carbonization and KOH activation were examined as adsorbents for CO2 capture. The micropore volume and specific surface area of the resulting carbons varied from 0.16 cm3/g (365 m2/g) to 0.82 cm3/g (1890 m2/g), respectively, depending on the KOH/char ratio used in the activation process. These carbons showed high CO2 adsorption capacities. [14].U.S. Department of Energy, National Energy Technology Laboratory carried work on Fossil fuels supply more than 98% of the world's energy needs. However, the combustion of fossil fuels is one of the major sources of the green house gas CO2 . It is necessary to develop technologies that will allow us to utilize the fossil fuels while reducing the emissions of greenhouse gases. Commercial CO2capture technology that exists today is very expensive and energy intensive. Improved technologies for CO2 capture are necessary to achieve low energy penalties. Pressure swing adsorption (PSA) is one of the potential techniques that could be applicable for removal of CO2 from high pressure gas streams such as those encountered in Integrated Gasification Combined Cycle (IGCC) systems [15].Graphite nanoplatets were prepared by acid intercalation followed by exfoliation technique. These graphite nanoplatelets were further functionalized and characterized by different characterization techniques. The CO2 adsorption capacity was measured by high pressure Seiverts' apparatus using vander Waals equation. Maximum adsorption capacity of 0.0036, 0.004 and 0.0049 mol/g was observed at 12 bar equilibrium pressure and at 100, 50 and 25 ??C temperature respectively [16]. Study of the adsorption of carbon dioxide on hydrotalcite-likecompounds was done by Zou Yong and, Al_??rio E. Rodrigues. They found that there is an optimum aluminum content and heat treatment temperature for the adsorption capacity; the larger and/or higher is the charge of the anion, the more is the adsorption capacity of carbon dioxide [17]. Novel CO2 ''molecular basket'' adsorbents were prepared by synthesizing and modifying the mesoporous molecular sieve of MCM-41 type with polyethylenimine (PEI) by Chunshan Song and etal. The adsorbent prepared by a one-step impregnation method had a higher CO2 adsorption capacity than that of prepared by a two-step impregnation method [18].
The feasibility of a CO2 capture system based on sodium carbonate'bicarbonate slurry and its integration with a power plant was studied. Formation of solid bicarbonate is allowed, thus forming slurry, which can increase the capacity of the solvent. With this the energy requirement of stripping of the solvent could potentially be around 3.22 MJ/kg of captured CO2 which is significantly lower than with MEA based systems which typically have energy consumption around 3.8 MJ/kg of captured CO2[19].Daniel J. FauthT and etal ,studied a number of binary and ternary eutectic salt-modified lithium zirconate (Li2ZrO3) sorbents and evaluated for high temperature CO2 capture. The ternary K2CO3/NaF/Na2CO3 eutectic and Li2ZrO3 combination at 600 and 700 0C produces the fastest CO2 uptake rate and highest CO2 capacity [20]. Solid solutions of lithium and potassium meta zirconates Li2_xKxZrO3 were prepared by co precipitation. Thermal analyses into a CO2 flux showed that Li2_xKxZr2O3 solid solutions present a better CO2 absorption than Li2ZrO3 pure. The differences observed in the CO2 sorption processes were explained with thermodynamic data [21].
Experimental
Materials and Method
Delonix regia fruit powder (DRF) was selected as adsorbent for carbon dioxide. Delonix fruit was collected from local forests, washed thoroughly to remove dirt, dried and powdered. The powder was sieved through 106 micron Mesh sieve. The powder was analyzed for chemical composition, structure and surface area.
Original powder used for the capture of carbon dioxide. Carbon was made from the powder with the help of 98% H2SO4.Yield was 70.98%. Carbon was used for adsorption of carbon dioxide.Both continuous and batch experiments were carried out for different weight of the material, different pressure and different flow rate.
Continuous Experiment: Mixture of carbon dioxide (20%) and Argon (80%) was taken for the continuous experiments. Height of the column for continuous experiments was 60cm and diameter 1cm with inlet at bottom and outlet at the top of the column. 5gm of original DRF filled into column and height was measured. The empty space filled with glass beads. The mixture of CO2 and Argon passed through the inlet at the different flow rate i.e. 10, 15 and 20 LPH. Outlet of the column was connected to the CO2 analyzer. (CO2 Analyzer (NUCON MODEL: 2007P Carbon Dioxide (CO2) Analyser .PRINCIPLE: Non Dispersive Infra Red. RANGE : 0 to20%) With the help of CO2 analyzer the quantity of CO2 adsorbed in the material was calculated. Same procedure followed for the 6 and 7gm of original DRF and carbon made from DRF at different flow rate.
Result and Discussion:
Scanning electron microscopy (SEM) was used to visualize the surface morphology of DRF and carbon made from DRF. The original DRF samples showed the hollow channel type structure. While DRF treated with H2SO4 (carbon made from DRF) showed porous structure and many layers surface with broken edges. The H2SO4 treated sampled showed good porous structure than the original one. Elemental analysis of the original and carbon is as shown in table 1 and 2.
Analysis of both the samples was done like EDAX, XRF and Scanning electron microscopy. CO2 adsorption capacity was found more in DRF original sample than carbon made from DRF. CO2 molecule was strongly bound on titania, alumina and magnesia (22). In DRF original sample availability of titania(1.216%),alumina(3.739%) and magnesia(9.271%) was found and in carbon made from DRF powder availability of titania(3.743%),alumina(1.561%) and magnesia(1.398%) was found.
For 5gm DRF original sample adsorption capacity was found 4.71211 mmol/g at 10 LPH flow rate. It was found that when quantity of sample increased with increasing flow rates as (quantity 6g and 7g and flow rates 15,20 LPH) then adsorption capacities was decreased.
For carbon made from Delonix Regia Fruit adsorption capacity of 6g sample was found more at 10,15 and 20 LPH than 5g and 7g samples.
Elemental analysis showed that presence of more carbon may be responsible for more adsorption capacity of carbon dioxide.

Fig.1. Scanning electron microscopy of
powder of Delonix Regia fruit Fig.2. Scanning electron microscopy of carbon
made Delonix Regia fruit powder

Table.1. EDAX Analysis of Delonix Regia Table.2.EDAX Analysis of carbon made from
Element Wt%
Carbon 67.68
Oxygen 21.41
Sulfur 7.88
Platinum 1.47
fruit powder Delonix Regia fruit powder
Element Wt.%
Carbon 56.77
Oxygen 37.71
Platinum 2.03
Calcium 1.55
Potassium 1.41
Magnesium 0.53

Table.3.XRF Analysis of original Table 4.XRF Analysis of carbon made from Delonix Regia fruit powder Delonix Regia fruit powder
Element Wt %
Silicon 52.376
Aluminum 1.561
Potassium 1.459
Calcium 17.987
Titanium 3.743
Sodium 0.407
Magnesium 1.398
Phosphorus 1.084
Manganese 0.239
Iron 8.751
Element Wt %
Silicon 17.602
Aluminum 3.739
Potassium 16.649
Calcium 13.958
Titanium 1.216
Sodium 0.205
Magnesium 9.271
Phosphorus 4.169
Manganese 0.153
Iron 7.053

.

Table 5.CO2 adsorption capacities of Delonix Regia fruit powder
1)5gm DRF original
.Sr.No Sr Flow rate(LPH) Adsorption capacity(m mole/gm) LMTZ(cm)
1 10 4.71211 22.3626
2 15 1.1167 17.4
3 20 0.248 25.779

2)6gm DRF original
Sr.No Flow rate(LPH) Adsorption capacity(m mole/gm) LMTZ(cm)
1 10 1.24 19.872
2 15 0.3101 31.39
3 20 0.41168 30.14

3)7gm DRF original
Sr.No Flow rate(LPH) Adsorption capacity(m mole/gm) LMTZ(cm)
1 10 0.70858 21.239
2 15 0.93058 28.654
3 20 0.531428 34.833


Table 6. CO2 adsorption capacities of carbon made from Delonix Regia fruit powder
1) 5gm DRFC
Sr.No Flow rate(LPH) Adsorption capacity(m mole/gm) L tmz(cm)
1 10 2.356 7.1296
2 15 1.3028 10.2965
3 20 0.744 9.7338

2) 6gm DRFC
Sr.No Flow rate(LPH) Adsorption capacity(m mole/gm) L tmz(cm)
1 10 2.5833 8.6684
2 15 2.48156 7.9473
3 20 3.3066 8.39

3) 7gm DRFC
Sr.No Flow rate(LPH) Adsorption capacity(m mole/gm) L tmz(cm)
1 10 1.1514 10.75
2 15 0.26588 17.21
3 20 0.70857 13.69

Fig 3.Breathrough curve for Delonix Regia fruit powder (5g)

Fig4.Breathrough curve for Delonix Regia fruit powder (6g)

Fig 5.Breathrough curve for Delonix Regia fruit powder (7g)

Fig.6. Breakthrough curve for carbon made from Delonix Regia fruit powder (5g)

Fig.7. Breakthrough curve for carbon made from Delonix Regia fruit powder (6g)

Fig.8. Breakthrough curve for carbon made from Delonix Regia fruit powder (7g)

Conclusion
From above results we can predict that CO2 adsorption was more in DRF original sample than carbon made from DRF because of high affinity of CO2 molecules towards the titania, alumina and magnesia. The adsorption capacities for this adsorbent is less but in future since it is waste and readily available , if the surface area of the same adsorbent can be increased by different methods the adsorption capacity will be increased.

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