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This journal is The Royal Society of Chemistry 201315 Analytical Methods, 2014, 1-5 |1



Cite this: DOI: 10.1039/x0xx00000x


















Received 00th January 2012,
Accepted 00th January 2012
DOI: 10.1039/x0xx00000x
www.rsc.org/


Optimisation and Determination of Sulphur
content in coal
D. Dabuleanu
a
, S. T. Lancaster
a
and J. R. Hutcheson
a


In this present study a multiple variable optimisations process was conducted to
ensure that the setup provides the best possible case for trapping sulphur dioxide,
released from the burning of coal, with also the aid of chromatographic and
meteorological techniques that provided the quantitative analysis required for this
experiment. The method was optimised first in a controlled setting by the use of
permeation tube containing SO
2
, with a release rate determined by daily weighing of
0.2826 mg min
-1
.The variable that were put through the process of optimisation were:
flow rate of gas into impinger, time given for uptake of SO
2
, mass of the coal sample,
time of burning, and temperature variation for the burning process. The results
demonstrated that Sulphur content of coal is elevated with an average of 0.80% and
0.75% by titration and 1.61% and 1.54% using Ion Chromatography(IC) with
temperatures of the system at 500
o
C and 600
o
C respectively but further investigation
with regards to its impact on the environment must be performed.


1. Introduction
Determination of Sulphur content in coal is essential as it can
easily enter the environment by converting it into a more
volatile compound namly SO
2
through the process of
burning the coal as a means of of converting its chemical
energy in electricity via coal burning power plants; thus
devising a method of capturing SO
2
from burning coal and
obtaining the highest possible efficiency in trapping it is vital
to maintaining a balanced environment.
As sulphur dioxide enters the atmosphere its hygroscopic
properties become evident as it is absorbed into the
atmospheric humidity where it forms sulphuric and
sulphurous acid which are part of the phenomena called acid
rain. Its effects range from dissolving mineral into water
bodies to having detrimental effect to human health, by
inducing corneal haze, difficulty breathing, airways
inflammation and in some more extreme cases pulmonary
edema and even heart failure
[1][2]
.
In the atmosphere SO
2
is oxidized by reaction with hydroxyl
radical, which is present in lowest part of the atmosphere
(the troposphere)
[3]
, to form sulphur trioxide which is finally
2. Experimental

2.1 Materials and methods
The SO
2
was solubilized by using an oxidative method ,similar
to the natural process previously mentioned, which required
that the sources of the gas be pushed through a solution
comprised of Hydrogen peroxide (H2O2) of 30 %
concentration .The aforementioned solution was prepared by
diluting 10 mL of Hydrogen Peroxide in 1L of distilled water
and acidified to a pH value of 4.5 with Hydrochloric acid.The
indicator used to signal the 4.5 pH was BDH 4.5 indicator.As
the samples was passed through the capturing solution it now
contains sulphur in the form of sulfate ions ( SO
4
-2
) and also
being very acidic ,it was then titrated with titrant solution
composing of 0.01M sodium carbonate, Na
2
CO
3
The precision
of the titrations was determined by titrating multiple separate
solutions composed of a dilute solution of sulfuric acid of 2M
(approximately). The control samples were produced by a
permeation tube that released a constant, temperature
dependent, quantity of SO
2
.As for the sample, a British coal,
was ground to a coarse powder, which concentration of

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converted into sulfuric acid when interacting with water
molecules.
[4]

Another factor adding to the environmental impact of having
a high concentration of sulphur in coal is that the potential
quantity of sulphur dioxide released by burning coal would
be in the range of tens of thousands of tones to even millions
of tons, values were extrapolated from the total world coal
production that reached a record level in 2013 of 7822 Mt
[5]
.
Therefore, utmost care was in devising an analytical process
that could give accurate and precise measurements sulphur
content in coal was made .

SO
2
,with a release rate determined by daily weighing . The
setup involved maintaining the permeation tube at a constant
30
o
C with the use of a temperature controlled water jacket
around it, to maintain a constant rate of elimination of
sulphur dioxide from the tube as it has its rate dependent on
the temperature; then air was passed over the outlet of the
permeation tube to collect the SO
2
and bubbled through the
hydrogen peroxide solution mentioned in the section 2.1 of
this paper, through the use of a Dreschel bottle with an
impinger.
The Drescher bottle was chosen from a selection of six
125mL such bottles that were fitted each with an impinger.
The choice of bottle was based on the size of bubbles it
produced as the smaller the bubbles the more surface area for
a given flow rate. All other parameters were optimised
around the chosen impinger.
The next parameter to be optimised was the flowrate of the
air/SO
2
mixture through the impinger. This was done by
varying the flow rate but keeping the uptake time constant,
and after each sample was collected it was subsequently
titrated to determine if there is a change in the concentration
of SO
2
in the solution with regards to the expected value
dictated by the rate of the permeation tube. Once a suitable
flow rate was determined, the uptake time was the next
variable to be optimised by varying the duration of the
uptake time while at a constant flow rate. After the
optimisations with regard to flowrate, time and impinger
were done a 40 mL aliquot of the optimised captured SO
2

was titrated and a 1 mL of the solution was diluted by a
factor of 50 and its concentration of sulphate was measured
using IC.
The second part of the optimisation was done on the
collection of the sample, in which the mass of the coal,
particle size and time of burning were taken in account all of
which done at two temperature 500
o
C and 600
o
C. The
quality of the burn was determined from the remnant let in
the crucible inserted in the furnace.

2.3 Sample collection and analysis of processed coal

The optimised mass of the coal sample was determined to
range from 95-100 mg was placed in a ceramic crucible that
was then inserted into a temperature controlled furnace set at
500
o
C. The construction of the furnace permitted a
connection at one end of the heating chamber to an air
supply at in turn was controlled by a flow meter and set at
0.6 L min
-1
while at the other end of the chamber the
sulphur was unknown. The sample was later processed in
different ways for optimisation purposes for optimal results
during the burning procedure.
As for the chromatographic method using an Ion
Chromatograph, it used a pre-prepared calibration solutions of
1 to 10 mgL
-1
.

2.1 Capturing method optimisation

The optimisation process was firstly applied with regards to
the controlled system,that used a permeation tube containing
3.1 Optimisation results

Table 1. Concentrations determined for replicates of the dilute H2SO4
standard. Used to test the reproducibility of the method.


Volume of Titrated
Volume
H
2
SO
4

Run H
2
SO
4
(mL)
(mL)

Conc.
(mgL
-1)

1 50 8.7 166
2 20 3.4 162
3 20 3.4 162
4 20 3.2 153
5 20 3.4 162
6 30 5.0 159
7 30 5.1 162
8 30 5.1 162
9 30 5.1 162
The data in Table 1 shows that the titration process produces
reproducible data ,with a standard deviation of 3.66 mg L
-1

and a RSD of 2.3%.
Fig. 1. Variation of the mass loss of SO
2
from the permeation tube
with time.
The graph shows the linearity of the mass loss of the SO
2

permeation tube, indicated by an R
2
value of 0.99374. As the
graph indicates by its gradient, the rate of mass loss of SO
2
is -
2.826*10
-4
g min
-1
, or -0.2826 mg min
-1
, thus if the trapping
efficiency is 100% the uptake rate of SO
2
should be 0.2826
min
-1
.
The effect of flow rate on the trapping efficiency SO
2
was
determined by titration with the results being shown in Fig.2.



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exhaust was being sent through the impinger of the the
optimised Drescher bottle (see section 2.1 in this paper) that
contained 50 mL of prepared H
2
O
2
absorption solution.The
uptake time of the exhaust from the furnace was set at an
optimal 30 min. After the combustion has finished (i.e. the
uptake time has run out), 40 mL were removed and titrated
with a 0.01M Na
2
CO
3
titrant solution, while the remainder of
10 mL was prepared for IC measurements, by diluting 1 mL
aliquot from it with 25 ml of distilled water. The same
procedure was executed again at 500
o
C and another two
times at 600
o
C.

3. Results and Discussion

Fig. 2. Variation of the SO2 trapping efficiency with flow rate. The
time for uptake remained consistent at 5 minutes.
As the graph exhibits a polynomial trend its peak can be
determined by using simple mathematics .When the
derivative of the function with respect to its variable y/x is
0, it marks the change in slope giving the peak flow rate at
0.576 L min
-1


.
Fig. 3. Variation of the sulphate concentration in the H2O2 solution
with the time the air/SO2 mixture was bubbled through it. The flow
rate remained constant at 5.8 L min
-1
.
Fig 3 portraits that the system doesn't seem to attain a
maximum efficiency or doesn't have variation in efficiency
for reasonable amounts of time.From the available data ,
Table 2. Determined sulphur contents of the coal sample with
changing mass of coal and burning time. The descriptions of the
condition of the coal after burning are also included. During this
process the flow rate remained consistent at 6.0 L min
-1

mass of
coal
Time
burned
Sulphur
content

g min % Description
0.1590 10 04' 0.64 chucky
remnant
that looked
combusted
0.2010 10 02' 0.62 no obviuos
sings of
total
combustion
0.2290 15 01' 0.75 top layer
charred
0.2136 20 00' 0.69 top layer
greatly
charred
0.0636 15 02' 0.65 light
charring
0.0651 10 00' 0.64 minimal
residue

3.3 Comparison of Methods

In Table 3 the results of the two methods used in the
determination of sulphur content of sample (i.e. titration and
IC )as they were compared by analysing the samples prepared
using SO
2
generated by the permeation tube at optimum
conditions and comparing with the mass loss of the

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time doesn't seem to be a variable that affects efficiency.

3.2 Optimisation results of coal analysis

The results of the optimisation of the temperature at which
the burning occurs seem to indicate that there is no
significant difference on a 95% confidence level (result
made clear by a 2 tailed, unpaired t-test of equal variance).
Granulation of the coal seem to affect the most the behaviour
of the coal during burning so it was decided that the coal
would be ground to a powder .Time of exposure to the
furnace was correlated to the other factors like granulation
factors and mass of the sample.But the optimum
performance was obtained at 30 min for 500
o
C respectively
25 for 600
o
C both with masses ranging from 95-100 mg of
coal sample.
make up the H
2
O
2
solution, although this is a very small
contribution to the error, a more likely scenario could be
standard solutions were not made properly as there was no
control on the quality of said standards(see section 2.1).

3.4 Determination of Sulphur Content of the Coal

Literature values indicate that coal content should not exide
0.7%
[6]
which is a similar value to what the titration as it can
be seen from table 4. but as there was no teste done on a
CRM during the experimental phase of this project the
values obtained can not be relied on.Although accuracy was
determined through a meteorological system explained
previously in this paper ,it is not a perfect method for doing
so.

Table 4. Sulphur content of the coal sample determined by titration
and IC. The sulphur content was determined for coal burning at
500
o
C and at 600
o
C.
temperature Sulphur Content %
o
C titration IC
500 0.80 1.61
600 0.75 1.54

4.Conclusions

The optimum flow rate for the experiment was 0.576 L min-
1.There were no defined optimum time for uptake within a
reasonable time limit.
The sulphur content of the coal sample was found to be an
average of 0.80% and 0.75% by titration and 1.61% and
1.54% using IC when burning the coal at 500oC and 600oC
respectively.
The titration method was found to be more accurate than the
IC method.In future, determine the recovery of SO2 using a
coal CRM.

permeation tube.

Concentration of Trapping
Method Sulphate (mg L
-
1
)
Efficiency %
Titration 112 103
IC 247 226

Although the trapping efficiencies might seem not in
accordance with reality (as they are more than 100% efficient)
,the titration method seems to be a more accurate than the IC
as a resonable 5% error margin make the result of the titration
trapping efficiency more feasible , and thus making it a good
candidate for determining the concentration of SO
4
-2
ions
created after bubbling SO
2
through a acidic H
2
O
2
.The
measurements of the IC are too high compared to the expected
concentrations and thus it can not be considered a viable
method.The errors in the IC measurements could be traced
back to trace levels of sulphate in the distilled water use to
spending less time in the capturing solution and also creating
bigger bubbles , which have a smaller surface as a big bubble
then if the same volume of gas would be separated into
smaller bubbles. These two factors could be at play in
decreasing the overall efficiency at higher flow rates. At lower
flow rate the effect could have been that as the speed of the
gas is small the bubbles coalesce in bigger spheres thus
decreasing the surface of interaction between the capturing
fluid and SO
2
. As said at the beginning of this footnote these
statements are just hypothesis and were not tested during this
experiment.

[1]Pollutant Realise and Transfer Register
http://www.mma.gob.cl/retc_ingles/1316/w3-article-
51518.html
[2] Sulpher dioxide ,Air fact sheets ,16 Oct 2014
http://www.environment.gov.au/protection/publications/factsh
eet-sulfur-dioxide-so2
[3] Montzka, S.A.; M. Krol; E. Dlugokencky; B. Hall; P.
Jckel; J. Lelieveld (2011)."Small interannual variability of
global atmospheric hydroxyl". Science 331(6013): 67
69.Bibcode:2011Sci...331...67M.doi:10.1126/science.1197640
.PMID 21212353. Retrieved 2011-01-09.
[4] Seinfeld, John H.; Pandis, Spyros N (1998). Atmospheric
Chemistry and Physics From Air Pollution to Climate
Change. John Wiley and Sons, Inc. ISBN 978-0-471-17816-3
[5] World Coal Assosiation , 16 Oct 2014 :
http://www.worldcoal.org/resources/coal-statistics/
[6] Departament of the Enviroment community and local
government ,16 Oct 2014
http://www.environ.ie/en/Environment/Atmosphere/AirQualit
y/SulphurinCoal/





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5.Acknowledgements

First and foremost, we would like to thank our supervisors
of this project, Prof. Joerg Feldmann, Dr. Andy Kindness,
Dr. Eva Krupp and all other staff members of the chemistry
department of Aberdeen University that made this project
possible.Also I would like to thank my project colleagues
for their contribution of to the project.

6.Notes and references

a
University of Aberdeen , Chemistry Department
The following statements are just a hypothesis about why
does the behaviour of the optimisation of the flow rate has a
parabolic shape to it .As the flow rate increases the gas that
flows through the impinger comes at much higher speed thus

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