Minggu, 16 November 2014

Utilization of Coal Fly Ash as CO Gas Adsorbent - ICCME 2012 Paper

Utilization of  Coal Fly Ash as CO Gas Adsorbent 

Ayu Lasryzaa, Dyah Sawitria
a Department of Engineering Physics, Faculty of Industrial Technology,Institut Teknologi Sepuluh Nopember,
Kampus Keputih ITS Sukolilo Surabaya 60111 INDONESIA


Abstract :
This research focused on coal fly ash fabricated as CO adsorbent. Coal fly ash having grain size of 325 mesh was characterized by XRF, XRD and SEM-EDX. Physical activation was done at temperatures of 500 0C, 520 0C, 540 0C, 560 0C, 580 0C and 600 0C. Chemical activation was undertaken by mixing between fly ash and NaOH with mass ratio of 1: 1.2 with subsequent heating at 7500C for 1 h and followed by washing the specimens until pH=7. The samples were dried at 1000C for 1 h. The major constituents of unactivated coal fly ash are Fe, Ca, K, Si and Al in the form of quatz and anorthite. The chemical activation led to reduce the amount of quartz or increase the amount of anorthite. Physical activation does not affect the amount of minerals.
Keywords: fly ash, adsorbent, activation, characterization

1.    Introduction
Coal is one of alternative energy resources. In term of price coal is cheaper than natural oil. Indonesia has a lot of coal resources, and the utilization of coal  in Indonesia increases every years. It attains 14,1% from total of other energy resources. It is expected that coal usage will increase until 34,6% at 2025[1]. Utilization of coal produces waste that can contaminate environment such as   CO2, NOX, CO, SO2, hydrocarbon dan  solid waste. The solid waste is in the form of ash, i.e  fly ash and  bottom ash. According to data of Ministry of Environment in 2006, fly ash production reaches 52,2 ton per day, whereas bottom ash waste production reaches 5,8 ton per day[1].
Coal fly ash is exhaust waste was usually released to air without control. Actually fly ash waste is a kind of hazardous waste. Generally, fly ash can be temporary saved at coal power plant and further thrown in landfill. Accumulation of this coal fly ash may raise environment al problem[2]. Coal fly ash can be used for raw material of cement and construction material[2]. Another utilization of coal is as adsorbent[3]. As adsorbent, fly ash has advantage in term of economical prices and good for gas and liquid waste management[4]. Physical and chemical activation is required to allow coal fly ash for being use as adsorbent. Physical activation is done by heating at high temperature, whereas chemical activation is done by mixing of fly ash and acid liquid or alkali.

2.    Materials and Methods

2.1 Materials
Coal fly ash is exhaust result of kiln I process in PT. Semen Gresik. It has grain size of 325 mesh. Coal fly ash have dark brown colour. This colour depend on type of coal, too. In this research the type of coal is lignite whose quality is the lowest among other type of coals.

2.2 Methods
Two activations were used in this research, namely physical and chemical activations. The physical activation was done by heating the sample at  temperatures of 500°C, 520°C, 540°C, 560°C, 580°C, and 600°C for 1 hour. Chemical activation was done by mixing fly ash and NaOH with the mass fractions of fly ash and NaOH are 1 : 1.2. The mixtures were heated at temperature of 7500C for 1 hour followed by grinding process. Then, the samples were mixed with distilled water with L/S of 1/5 in a constant stirring of 400 rpm for 30 minutes. Finally leaching was done until pH = 7, the samples were then subsequently dried at temperature of 1000C for 1 hour.
Raw material coal fly ash was characterized by X-Ray Fluorescence (Minipal4 PanAlytical), X-Ray Diffraction (Brücker AXS D8 Focus) Cu K-α with λ = 1,5418 Å, and Scanning Electron Microscopy (SEM) Zeiss-EVO MA 10 equipped with Electron Diffraction-X (EDX) of Brücker.

3.    Results and Discussion
3.1 Unactivated Coal Fly Ash Characterization
Table 1 shows composition in unactivated fly ash. From Table 1 it is known that the highest contents in the fly ash are Fe, Ca, K, Si and Al, and the highest oxide are Fe2O3, CaO, SiO2, Al2O3 and K2O. The important substance for adsorbent are Si and Al, while Ca is the substance that has to be remove. Ca can disturb the adsorption process because it may lead the reaction to become unstable.

Table 1. XRF analysis of unactivated coal fly ash
No.
Substance
Concentrate (%)
Oxide
Concentration (%)
1.
Al
1,8
Al2O3
2,9
2.
Si
9,3
SiO2
14
3.
P
0,64
P2O5
1,0
4.
K
2,19
K2O
1,84
5.
Ca
30,0
CaO
29,2
6.
Ti
1,79
TiO2
2,9
7.
Mn
0,60
MnO
0,49
8.
Fe
51,23
Fe2O3
46,51
9.
Ba
0,76
BaO
0,61

Table 2 is mineral composition of unactivated coal fly ash from XRD analysis. XRD analysis shows that the most dominant minerals are amorphous structure and crystalline phase of quartz (SiO2). Fly ash samples consist mainly amorphous aluminosilicate with a less number of iron-rich part. It is likely that the iron oxide bounds with aluminosilicate to form amorphous phase. While aluminum and silicon form either as sillimanite, quartz, or binds with Ca to form anorthite. Calcium was associated with oxygen, sulfur or with silicon or aluminum. The calcium-rich material is different in elemental composition from the amorphous alumino-silicate parts. It is clearly a non-silicate mineral possibly calcite, lime, gypsum or anhydrite[5].

Table 2. XRD analysis of unactivated coal fly ash
No.
Mineral
Formula
Konsentrasi (%)
1.
Quartz
21,1
2.
Sillimanite
Al2SiO5
1,6
3.
Anhydrite
CaSO4
0,7
4.
Magnetite
Fe3O4
3,3
5.
Anorthite
Ca3SiO5
1,7
6.
Siderite
FeCO3
1,1
7.
Arcanite
K2SO4
2,4
8.
Periclase
MgO
6,2
9.
Hematite
Fe2O3
0,5
10.
Maghemite
Fe2O3
3,9
11.
Wuestite
FeO
1,2
12.
Amorphous
-
54,9

Figure 1 shows elemental mapping of unactivated fly ash. EDX analysis indicates that the big particle contains a lot of Si while Fe and Al distribute evenly in all particles. This evidence indicates intermixing of Fe and Si-Al mineral phases while Ca may in form non-silicate minerals[5]. These results are supported with XRD data.

Figure 1 Result SEM of unactivation coal fly ash

3.2 Activation Coal Fly Ash Characterization

Table 3. XRD Quantitative Data of Coal Fly Ash with Physical Activation  
CRYSTAL/MINERAL
FORMULATION
UNIT
PHYSICAL ACTIVATION
500
520
540
560
580
600
Quartz
SiO2
%
20,0
21,1
22,0
22,2
22,3
21,0
Sillimanite
Al2SiO5
%
4,2
2,8
3,2
2,5
3,1
2,8
Anhydrite
CaSO4
%
0,4
0,6
0,4
0,8
1,0
0,4
Magnetite
Fe3O4
%
2,9
3,2
3,6
3,9
3,2
3,5
Anorthite
Ca3SiO5
%
1,6
2,1
2,3
2,7
1,4
1,7
Siderite
FeCO3
%
1,1
0,9
1,4
1,1
1,2
1,3
Arcanite
K2SO4
%
2,7
2,8
2,4
2,1
2,8
3,1
Periclase
MgO
%
6,7
6,3
5,9
7,4
6,6
6,4
Hematite
Fe2O3
%
0,5
0,6
0,5
0,6
0,6
0,6
Maghemite
Fe2O3
%
3,5
3,4
2,7
2,8
3,4
3,0
Wuestite
FeO
%
0,5
1,2
0,8
0,6
0,9
0,9
Amorphous
-
%
54,0
53,7
54,1
52,5
52,7
54,3
R_wp
-
%
2,9
2,9
2,9
2,9
2,9
2,9

Table 4. XRD Quantitative Data of Coal Fly Ash with Chemical Activation  
CRYSTAL/MINERAL
FORMULATON
UNIT
CHEMICAL ACTIVATION
500
520
540
560
580
600
Quartz
SiO2
%
13,2
1,0
0,5
5,1
0,2
3,3
Sillimanite
Al2SiO5
%
0,0
2,6
4,0
2,5
4,3
8,4
Anhydrite
CaSO4
%
0,0
0,0
0,1
1,2
0,3
0,0
Magnetite
Fe3O4
%
3,1
3,4
0,1
0,0
4,3
3,5
Anorthite
Ca3SiO5
%
35,6
14,2
7,1
20,8
17,1
24,0
Siderite
FeCO3
%
1,3
0,0
0,0
0,2
0,2
0,2
Arcanite
K2SO4
%
14,1
18,0
16,9
18,6
15,3
14,8
Periclase
MgO
%
11,9
15,3
22,5
12,2
9,9
6,5
Hematite
Fe2O3
%
0,2
0,0
1,4
0,1
0,1
0,1
Maghemite
Fe2O3
%
0,0
0,0
3,0
0,0
0,0
0,0
Wuestite
FeO
%
1,0
2,8
6,2
2,7
4,6
2,0
Amorphous
-
%
15,2
41,1
38,3
34,5
42,7
35,4
R_wp
-
%
5,1
9,6
8,5
7,2
8,5
6,9

From Table 3 and 4 one can observe that amorphous phase and quartz crystalline still dominate in fly ash after physical activation. There is little changes of mineral composition after physical activation. On the other hand, the chemical activation changed the amount of minerals in fly ash. For example, after chemical activation the amount of quartz decreases while the amount of anorthite increases. Figure 2 exemplifies the change in the amount of mineral of fly ash after physical and chemical activation. From figure 2 it is known that chemical activation plays an important in changing the amount of minerals, while the physical activation does not affect significantly.

Figure 2. Comparison of quartz contents after physical and chemical activation
 
Physical activation causes losing water content (intercrystalline water) in fly ash as indicated by thermogravimetry experiments[6]. Whereas chemical activation may active the unactivated  substances, and finally aids the adsorption process.

4.     Conclusions
Unactivated coal fly ash consist mainly of Fe, ca, K, Si, and Al, in the form of quartz and amorphous. The mineral contents were found to change after chemical activation e.g. quartz was reduced, anorthite was increased. Physical activation does not affect it.

5.     Acknowledgement
The authors would like to thank to DITJEN DIKTI as organizer of Program Kreativitas Mahasiswa for funding this research, Mr. Heri Purnomo, ST from PT. Semen Gresik for his assistanship in XRD analysis, Ninit Martianingsih, S.Si who helps the SEM-EDX characterization, Nurul Faradillah Said, S.Si who helps the XRF characterization.

6.     References
[1] Setiaka, Juniawan, Ita Ulfin, Nurul Widiastuti. 2011. Adsorpsi Ion Logam Cu(ii) dalam Larutan pada Abu Dasar Batubara Menggunakan Metode Kolom. Prosiding Tugas Akhir. Jurusan Kimia, Institut Teknologi Sepuluh Nopember. Surabaya
[2] Jumaeri,dkk. 2007. Preparasi dan Karakterisasi Zeolit dari Abu Layang Batubara secara Alkali Hidrotermal.  Reaktor, Vol. 11 No.1, Juni 2007, Hal. : 38-44
[3] Ahmaruzzaman M. 2010. A review on the utilization of fly ash. Progress in Energy and Combustion Science, 36: 327–363
[4] Mohan S,  Gandhimathi R. 2009. Removal of heavy metal ions from municipal solid waste leachate using coal fly ash as an adsorbent. Sience Direct. Journal of Hazardous Materials, 169: 351-359
[5] Barbara G, Kutcko, Ann G. Kim. 2006. Fly Ash Characterization by SEM-EDS. Fuel, 85: 2537-2544
[6] Lasryza, Ayu. 2012. Pemanfaatan Fly Ash Batubara sebagai Adsorben Emisi Gas Buang CO pada Kendaraan Bermotor. Tugas Akhir. Jurusan Teknik Fisika, Institut Teknologi Sepuluh Nopember. Surabaya

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