CHAPTER 3

METHODOLOGY
This chapter describes the details of the experimental procedure followed
in this study. Also, the methods in obtaining data as well as brief discussions on
the theoretical framework of the study are presented.
3.1 Determination of Process Temperature and Pressure
The process temperature can be calculated theoretically using equation
2.24. Equilibrium temperature is the temperature in which the formation of
products is equal to formation of reactants. Equilibrium temperatures occurs at a
certain pressure and this happens when

is zero (0). Enthalpies and

entropies are needed to calculate the equilibrium temperature. Table 3.1 shows the
H and
f

S magnesium, calcium and iron (II) carbonates. The

symbol indicates that the conditions are at STP.

H
f

Reaction
CaO(s) + CO2 (g)
MgO(s) + CO2 (g)
FeO(s) + CO2 (g)

CaCO3 (s)
MgCO3 (s)
FeCO3 (s)

cal/mol-K
-38560
-27800
-19790

cal/mol
-32.6
-21.45
-43.10

Table 3.1. Enthalpy and Entropy of magnesium, calcium and iron (II) Carbonates

From the data given above, equilibrium temperatures can then be

calculated. Consider the formation of calcium carbonate:

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CaO(s) + CO2 (g)

CaCO3 (s)

Eqn. 2.17

Using equation 2.21, we can derive an empirical equation for the

calculation of Gibbs free energy.
G = Hf - TS

Eqn.

2.21
Substituting the values in the table,
G=38560+32.6 T

(CaCO3 (s))

G=27800+ 41.45T

(MgCO3 (s))

G=19790+ 43.1T

(FeCO3 (s))

To calculate for the equilibrium temperature, equation 2.24 is used.

T=

Hf
S

Eqn. 2.24

Substituting the data given in the table, we obtain the following equilibrium
temperatures:
Reaction
CaO(s) + CO2 (g)
MgO(s) + CO2 (g)
FeO(s) + CO2 (g)

CaCO3 (s)
MgCO3 (s)
FeCO3 (s)

Temperature ,

909.67
397.54
186.01

Table 3.2 Equilibrium Temperature of magnesium, calcium and iron (II) Carbonates

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Since magnesium silicate is the major component of the Ferronickel slag

from PGMC, the equilibrium temperature of magnesium carbonate is observed.
Since at this temperature, the formation of products is equal to the formation of
reactants, any temperature below the equilibrium temperature can be used.
However partial pressure of CO2 is another consideration. To determine the partial
pressure of CO2 we used equation 2.26. From our experimental design, adding
pressure is not possible, a standard pressure will be assumed (1 atm).

k =e

G
RT

Eqn. 2.26

The temperature that can be used is 350 C, with partial pressure of

0.68 atm and a

of -1970 J/mol which indicates that the reaction is

possible.
3.2 Materials and Equipment
The Ferronickel slag from PGMC in Iligan City was used as a medium in
sequestering carbon dioxide in this study. Chemical composition of the slag prior
to the carbon dioxide sequestration was determined using XRF.
The carbon dioxide used in this experiment was purchased from Sugeco
with at least 95% purity and zero moisture.
The experiment was conducted using a fixed bed reactor having a vertical
electric resistance furnace with an alumina working tube allowed for heating
samples. Thermocouples of either type A or C was equipped for measurement of

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temperatures. The furnace could be set at different temperatures, ranging from 0

to 1200C. A manometer was used to primarily measure the pressure of carbon
dioxide and regulate its flowrate. The flowrate of the carbon dioxide was
determined using bubble test experiment. A ball mill grinder (pulverizer) was used
in reducing the particle size to increase the surface area of the slag. Tyler mesh
screens and a mechanical shaker was used in separating t he different particle
sizes of the ground slag. The different samples were weighed using analytical
balance. XRD was used to quantify the amounts of carbonates formed in the slag.
Samples were sent to National Institute of Geosciences (NIGS) in University of
the Philippines-Diliman for the XRD Analysis.
3.3 Ferronickel Slag Preparations
The Ferro-Nickel slags are of large or bulk sizes, hard, and dark gray in
color. First, the slag was sun-dried to remove some of the moisture before
grinding to increase the efficiency of obtaining fine particles. Particle size was
reduced using a ball mill to increase the slag surface area. The ground slag was
screened to obtain the desired particle sizes of 1.41mm, 0.177mm, 0.149mm, and
0.074mm using Tyler mesh screens with mesh numbers 12, 80, 100 and 200,
respectively. The Tyler mesh screens were shaken using mechanical shaker to
obtain efficient screening of the slag. After sieving, the pulverized samples were
placed in an oven for two (2) hours at about 200 5

to remove the

remaining moisture. Prepared ferronickel slag samples were placed in resealable

plastics and kept in desiccators.
3.4 Calibration of Instruments

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The instruments used in the study were calibrated prior to using. The
muffle furnaces temperature was checked by placing a standard thermocouple
inside the furnace and a calibrated testometer was used in reading the temperature
outside. The temperatures obtained were compared to the displayed temperature.
The analytical balance was calibrated by first checking the spirit or bubble
of the balance and ensuring that it is on the center. Test weights were used to
check the accuracy and reproducibility of the balance.
3.5 Experimental Set-up

Figure 3.1: Experimental Design Set-up

Optimal Carbon dioxide gas flowrate and pressure stored in CO 2 gas

cylinder was regulated by the manometer. Then the regulated CO2 gas (5 MPa;
2L/minute gas flowrate) was allowed to flow into a braided chemical hose leading
to -diameter copper tube and finally into the muffle furnace. The braided

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chemical hose and the copper tube were fitted to connect together using stainless
steel hose clamp and were tied sealed with thread seal tape to ensure no leaks. The
copper tube encased in a ceramic tube was connected to the exhaust of the muffle
furnace serving as an entry point for the CO 2 gas; leaks were sealed using clay.
Another diameter copper tube was installed in the experimental set-up which
served as exhaust to excess gas. Stainless steel plate was used as the fixed bed for
the 3g ferronickel slag sample since it is non-reactive to CO 2 gas and can resist
temperature up to 1510 C.
3.6 Bubble Test Method
To determine the optimal gas flowrate of the carbon dioxide, bubble test
experiment was prepared. A burette was filled with water until the 50-mL. The
outlet of the cylinder (braided chemical hose) was placed under the tip of the
burette. The appearance of the first bubble was timed until it reaches the 50-mL
mark of the burette that is filled water. The test was performed in triplicates.

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Figure 3.2. Bubble Test Experiment Set-up

3.7 Carbon Dioxide Sequestration

Three (3) grams of pulverized slag will be obtained having different
particle sizes and was placed in the muffle furnace injected with 2L/minute of
CO2 gas. The calibrated muffle furnace will be heated at 200 10C, 300 10C,
and 400 10C, for 30 minutes, 60 minutes, and 120 minutes reaction time,
respectively with the 3g ferronickel slag sample inside. The carbon dioxide
released from the gas cylinder through a braided chemical hose was regulated by
the manometer and its flowrate was determined using bubble test method. When

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the temperature reached 200 10C, the slag and carbon dioxide was made to
react in the muffle furnace for 30 minutes. After 30 minutes contact time, the
furnace allowed to cooled down to 70C before the slag was removed from the
furnace. The slags was stored in a desiccator for about ten (10) minutes and
allowed cool. The slag was weighed after cooling. The same procedure was
employed for the samples with different particle sizes, reaction time, and
temperature. During the whole experiment, temperature fluctuating is under
controlled within 10C difference from the settings.

3.8 XRD Analysis

After the sequestration process, the slag samples were kept in resealable
bags and were sent to National Institute of Geological Sciences (NIGS), UP
Diliman for XRD analysis to verify the presence of carbonates specifically
magnesium carbonate (magnesite) that were formed. Microsoft Excel was used to
plot and analyze the recorded intensity. The software Mineral Database from
International Center for Diffraction Data (ICDD) was used to identify the peaks.