International Journal of Research in Pharmaceutical and Biomedical Sciences

ISSN: 2229-3701

_____________________________________________Research Article

Effect of Fuel Combustion in Libyan Power Stations and

Cement Industries on Environment
Iftikhar Ahmad and Mohamed Nuri Rahuma
Department of Chemistry, Faculty of Science, Benghazi University, Benghazi (Libiya).
ABSTRACT
The modern oil-fired heavy industries such as power stations and cement industries, which use heavy fuel oil
as a fuel, are highly concentrated sources of combustion gases. The flue gases comprise a combination of
gases such as carbon dioxide (CO2), sulphur dioxide (SO2), nitrogen oxides (NOx), carbon monoxide (CO),
particulate matters and others. Most of the power stations and cement factories in Libya use heavy fuel oil as
energy source while some of them are using natural gas as fuel. This paper describes the composition of heavy
fuel oil produced in different Libyan refineries and also describes the combustion chemistry of these heavy fuel
oils. The effects of flue gases generated during combustion of heavy fuel oil on environment and human health
have been discussed in this paper. The methods and techniques to minimise the impact of emissions have
been presented. The alternative fuels and their availability in Libya has been discussed.
remained in the atmosphere during the available
period of observation, the rest being absorbed by
vegetation, soil and oceans. A primary effect of
increasing the carbon dioxide concentration is to
increase the absorption of infrared radiation from
the earths surface and so lead to warming of the
atmosphere (the so-called green house effect). Such
a temperature rise would certainly cause important
climatic changes with massive consequences such
as flooding of coastal areas and major cities.
Along with the carbon dioxide as it emerges from
the stack there will be water vapour, other gases
such as sulphur dioxide, nitrogen oxides and very
fine dust carried along with the gases which will
emerge from the stack top at velocity as high as 30
m/s. The amount of pollutants from stack gases
depends upon the composition of the fuel. Most of
the Libyan power stations and cement factories use
heavy fuel oil as fuel. Table-1 shows the quality
control tests of heavy fuel oil produced in Libyan
refineries. Table-2 gives the impurities in a typical
heavy residual fuel oil3.

1. INTRODUCTION
The modern oil-fired power stations and cement
factories are source of combustion gases and
special measures have to be taken to protect the
environment from pollution by them. These
comprise a combination of control of the unwanted
emission at source, for example by dispersal of the
bulk of the flue gases from very tall stack, and by
removal of dusts. The effectiveness of tall stacks
has been discussed in detail by other workers1.
Carbon dioxide is the main discharged gas from the
stack. Carbon dioxide is the least regarded as a
pollutant, although since the early seventies the
possible long-term climatic effect, on a global
scale, of adding to the long-established atmospheric
concentration of carbon dioxide has become a
subject of speculation and inquiry2.
The principal reason is that the measured
atmospheric concentration of carbon dioxide at
different latitudes has increased and about half of
the carbon dioxide emitted appears to have

Table 1: Quality control properties of Libyan heavy fuel oils

Result
Test Method

Test Description
o

ASTM D4052
IP 170
ASTM D4007
Calculation
ASTM D189
ASTM D482
ASTM D97
IP 377 Mod

Specific gravity at 15.6/15.6 C

API gravity
Density at 15 o C, kg/l
Flash point, oC
Water and sediment content, vol.%
Calorific value (gross), kcal/kg
Conradson carbon residue, wt.%
Ash content, wt.%
Pour point, oC
Vanadium. ppm

Vol. 3 (4) Oct Dec 2012

Az-Zawiya
Refinery
0.9231
21.8
0.9225
162
<0.05
19598
5.12
<0.001
+ 36
6

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Tobruk
Refinery
0.9126
23.6
0.9121
162
<0.05
10691
9.34
<0.001`
+39
1

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International Journal of Research in Pharmaceutical and Biomedical Sciences

Sulphur is an important impurity in heavy fuel oil.
It burns to sulphur dioxide and up to one percent of
this may oxidise in the hot gases to sulphur
trioxide, which eventually unites with the water to
form sulphuric acid. Nitrogen is another important
impurity in heavy fuel oil. Much of it is oxidised
to nitric oxide, NO. At the very hottest parts of a
flame nitrogen from the air reacts with oxygen to
form the equilibrium amount of nitric oxide
appropriate to that temperature. A small but highly
variable fraction of the NO is oxidised to the
nitrogen dioxide, NO2/N2O4 that is the

ISSN: 2229-3701

physiologically active form, NO being itself inert.

This oxidation is thermodynamically favoured
when the flue gases mix with air through it occurs
extremely slowly. It has become customary to refer
to nitrogen oxides as NOx since NO is capable of
slow oxidation and can be regarded as a potential
source of the more active oxide. In this paper
references has been made very briefly to a number
of features of oil-fired factories emissions which
have clear chemical interest. A selection of these
will now be discussed in greater detail.

Table 2: Impurities in typical fuel oil

Impurity
Sulphur
Nitrogen
Silicon
Vanadium
Iron
Nickel
Calcium
Potassium
Aluminium
Sodium
Chlorine
Magnesium

Amount
(in ppm)

Impurity

Amount
(in ppm)

2700
1500
300
150
100
50
100
50
75
50
25
12

Zin
Phosphorous
Chromium
Cobalt
Manganese
Copper
Lead
Selenium
Cadmium
Antimony
Arsenic
Mercury

4
4
3
3
2.5
2.5
2
1
0.2
0.02
0.01
0.01

2. Gas Reactions in the Furnace

The gaseous species whose concentrations in
emissions are most affected by flame reactions are
sulphur trioxide (eventually sulphuric acid),
nitrogen oxides, carbon mono oxide and minor
amounts of hydrocarbon gases. The flame
parameters, which affect the concentration of these
species, are the temperature to which gas mixtures
the fuel may occur more than in other zones of the
flame where oxygen will be in excess. Such
different zones will be mixed by violent shortrange turbulence. The task of accurately modeling
such a complex process in which chemical
reactions and mixing are closely involved is a
daunting one but considerable success has been
achieved with simplified models, which assume
that the higher temperatures in a flame most of the
chemical species in dynamic equilibrium with each
other and that it is valid to apply known data for the
kinetic parameters of the reaction of interest. This
approach has made it possible to deduce the effect
of cooling and mixing processes on the final gas
composition. Thus, Billingsley et. al4 took account
of the interaction of forty six gas phase reactions
with a bearing on the formation of NO, SO3 and
CO in a combustor operating under a variety of
conditions of pressure, fuel/air ratio, fuel
composition and temperature history.
The calculations show that the way to limit the
formation of NO is so to arrange the mixing of the

Vol. 3 (4) Oct Dec 2012

are exposed and the duration of such exposure, the

gas mixing, i.e., the excess oxygen concentration
during the combustion process and finally the rate
of cooling. In a flame of particulate fuel and air the
combustion parameters will vary across the width
of the reaction zone.
Some regions will be rich, heated less by reaction
than by radiation and convention, and pyrolysis of
gases that some part-cooled combustion gas is
recycled to dilute the flame gases and diminish the
top temperature achieved. This technique has been
applied successfully to boiler plant in many
countries. It is also clear from the calculations that
SO3 can be minimised by limiting the concentration
of residual oxygen present after the flame and
during the cooling of the flue gases from say, 1650
K to 1000 K.
3. Smokes and Tarry Organic Materials
By regulation the smoke permitted from a power
station stack is severely limited. The total permitted
solids can only be achieved if plant conditions
burner efficiency, excess oxygen, gas mixing in the
furnace are such as to consume the fuel particles
and avoid the formation of soot and tars almost
entirely. The unburnt carbon particles are usually
greater than 10 m in diameter and do not emerge
from the chimney. Smaller particles, which may be
associated with the fine dust do not usually exceed
20 mg/m3 when the plant is on steady load. At

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International Journal of Research in Pharmaceutical and Biomedical Sciences

ground level this is a negligible contribution to
background smoke and soot. Attention has been
focussed upon it, however, because of the wellknown presence in such soot particles of the
carcinogenic polycyclic aromatic hydrocarbons of
which the most dangerous by far is benzo-a-pyrene.
Power stations and cement factories are not, of
course, the only sources of this type of compound.
Whenever combustion of fuel oil and fossil fuels
takes place formation and releases of these
compounds will occur, to a degree which reflects
the efficiency of the combustion process. Libya has
no data of how much benzo-a-pyrene goes to
atmosphere from power stations, cement factories
and other sources. Allen5 concluded that in USA
power stations expelled a total of 0.8 tonnes/year
whereas residential heating provided 390 tonnes
and garden refuse burning 75 tonnes. It is clear that
good flame mixing and high intensity combustion
in a power station furnace are effective in
destroying complex aromatic structures and
minimizing benzo-a-pyrenes.
4. Long Range Transport of Industries Flue
Gases
During the last decade the possibility that industrial
emissions could be transported over long distance
has become the focus of great interest both in
Europe and North America. A central feature of the
claims that have been made is that precipitation
(rain and snow) is acidic, that there is a trend of
increasing acidity and an expanding area of acidity
on a regional scale which matches the increased
emissions of sulphur dioxide and nitrogen oxides
from industry. Such claims are of major concerns
to electrical power utilities which, through
combustion of fuels, are major emitters of both SO2
and NOx . Sophisticated methods have been
successfully developed to protect the near-field
environment from these pollutants by ensuring that
the flue gases are sufficiently diluted by the air and
it has been argued that such measures are likely to
be equally effective in removing risk of pollution
from the far field.
Within the mixing layer primary pollutants can be
removed by direct contact with land or sea
surfaces, which is called dry deposition, or by
being washed out by rain or snow, i.e., by
precipitation scavenging. They can also undergo
chemical transformation into secondary products
which can then be removed by the same processes.
In the case of SO2 the dominant removal process is
directed dry deposition of the gas by oxidation to
sulphuric acid and subsequent deposition as
particles of the acid also contributes. Oxidation
involves a complex sequence of gas phase reactions
in which free radicals, generated photochemically
by sunlight, play an important role. Many of the
primary
reactions
occurring
have
been
characterized in detail in laboratory kinetic studies
so that it is now possible to model in some detail

Vol. 3 (4) Oct Dec 2012

ISSN: 2229-3701

the chemical evaluation of a plume, under

conditions
where
photochemical
reactions
predominate. The principal chemical step is the
reaction of SO2 with hydroxyl radicals:
OH + SO2

HSO3

Leading ultimately to sulphate aerosol. The major

reactions generating hydroxyl are
O3
O (D) + H2O
HNO2
O + RH

O (D) + O2
OH + OH
OH + NO
OH + R

From which it is evident that the fate of SO2 is

connected with other minor atmospheric
constituents such as ozone, hydrocarbons and
oxides of nitrogen and it is inappropriate to attempt
to describe the fate of a single pollutant in
isolation.
5. Chemical Measures to Minimize the Impact
of Emissions
(a) Combustion with additives to retain
sulphur
By adding lime or magnesium hydroxide to the
combustion gases it is possible to retain a high
proportion of sulphur as calcium or magnesium
sulphate in the solid ash. Unfortunately the short
residence time available in the boiler means that
the added lime must be in the form of very fine
(e.g., < 10 m) particles to ensure that it has time to
react to a reasonable extent. An alternative
procedure is so burn the fuel in a fluidized bed to
which the coarsely crushed lime is added.
Experience has shown that the lime stone or
dolomite can be used since there is time to
decompose the carbonate as well as for the
particles of additive to react in depth with the
sulphur oxides. A ratio of Ca/S of 2:1 is said to be
sufficient to retain nearly 90% of sulphur in the
fuel as calcium sulphate with the ash.
(b) Flue gas desulphurization
Flue gas desulphurization plants are being installed
in existing as well as new power stations
particularly in Japan, USA and Europe. The
technique most often used is to wash the flue gases
with the lime slurry. The resultant calcium sulphite
or sulphate if air is blown through it, must then be
removed. A regenerable absorbent process based
on the Na2SO3/NaHSO3 conversion is also
possible, it can be operated to produce either
sulphur or sulphuric acid as the end product.

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International Journal of Research in Pharmaceutical and Biomedical Sciences

6. Alternative Fuels
(a) Natural Gas
Natural gas is the least polluting fossil fuel per unit
of heat produced, with respect to both greenhouse
gas emissions and other combustion products. Any
market share won by natural gas from other fossil
fuels will therefore promote the cause of
environmental protection.
Resources of Natural Gas
Up-to-date proved reserves of natural gas of the
whole world comprise 15 trillion m3 and
considering current and expected levels of
production this fact provides better conditions for
reserves of natural gas compared with oil.
International Gas Union (IGU) estimates the
resources of natural gas approximately up to 400
trillion m3 though it is clear that their transfer into
the category of proved ones will require a great
scope of exploration work. Moreover, it is
important to note that international classification of
reserves takes into consideration economic
efficiency of their being recovered under
conditions of current price level. The proven gas
reserves of Libya comprise 46.4 trillion cubic feet.
Total proved gas reserve estimates are the sum of
all non associated gas, associated and dissolved
gas, plus all of the recoverable gas volumes

ISSN: 2229-3701

available in the under ground storage reservoirs.

Natural gas reserves are classified in two categories
based on the reservoir occurrence: (a) Non
associated gas it is defined as free natural gas not
in contact with crude oil in reservoirs associated,
(b) Associated gas - it occurs in crude oil reservoirs
either as free gas or in solution with crude oil.
Table 3 shows6 world gas proven reserves,
consumption and production.
Besides conventional gas resources the proved
reserves of which are sufficient for 60 year and,
taking into account new discoveries, for 90 100
year period of time there are so-called nonconventional natural gas reserves the completion of
which will secure an assured development of gas
industry beyond the limits of 21st century. They
are:
tight gas;
coalbed methane;
gas dissolved in formation waters;
gas hydrate;
deep gas.
Unconventional gas reserves are some tens and
may be even hundred thousand trillion m3.

Table 3: World gas proven reserves, production and consumption (1998)

Region
Africa
Asia/Pacific
Federation of Soviet
Union (FSU)
Latin America
Middle East
North America
Western Europe
Total

Reserves
(Trillion ft3)
361.1
359.5

Production
(Billion m3)
101.2
245.8

Consumption
(Billion m3)
48.7
259.0

P/C

R/P

2.08
0.95

>100
41.4

2002.6

643.9

529.0

1.22

83.4

2190.0
1749.6
294.6
183.9
5170.3

86.7
181.0
739.0
274.3
2271.8

86.0
171.8
718.9
927.1
2240.5

1.01
1.05
1.03
0.30
1.01

71.5
>100
11.4
18.4
63.0

(b) Dimethyl ether (DME)

DME is another type of clean fuel which can be
produced from natural gas and can be used as a
substitute for power plant fuel. The Tropsae
process is the process for direct synthesis of DME
from natural gas. It is a plant of production of
methanol and subsequent conversion into DME in
one integrated synthesis section. This process
layout eliminates the need to isolate and purify
methanol as an intermediate before further
processing into DME.
The Tropsae DME process is based on well proven
technology and process scheme, similar to the one
used for producing methanol. The plant comprises
three process sections, viz.
1. Synthesis gas preparation by Auto Thermal
Reforming (ATR)

Vol. 3 (4) Oct Dec 2012

2.

Oxygenate synthesis (combined synthesis of

methanol and DME)
3. Product separation and purification.
Production of liquid fuels from natural gas requires
very large capacities in order to benefit from
economy of scale to the maximum degree. The
most suitable reforming technology7 for this
purpose is the Topsoe ATR technology, which
permits single line production units exceeding
7,500 MTPD DME. The Topsoe ATR technology
has been developed tremendously over the last
decade, and recently it has been demonstrated
industrially at a steam/carbon ratio of only 0.6.

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International Journal of Research in Pharmaceutical and Biomedical Sciences

Combines Synthesis of Methanol and DME
The oxygenate synthesis takes place in a synthesis
loop consisting of two reactor stages over a
combination of methanol and dual function
catalysis. The reaction from synthesis gas to DME
is a sequential reaction, involving methanol as an
intermediate. The first part of the reaction from
synthesis gas to methanol is quite exothermal and it
is limited by equilibrium at a fairly low
temperature. Therefore, the first part of the reaction
takes place in a cooled reactor where the reaction
heat is continuously removed, and the equilibrium
is approached at optimum conditions. The second
part of the reaction from methanol to DME is much
less exothermal, and the equilibrium is limited at a
higher temperature. Therefore, this part of the
reaction takes place in an adiabatic fixed bed
reactor.
Consequently, the two-stage reactor concept
permits both parts of the sequential reaction to take
place at optimum conditions, while at the same
time the synthesis section becomes more similar to
a conventional methanol synthesis loop. The only
major difference between the oxygenate synthesis
and the methanol synthesis is the reactor, loaded
with the proprietary Topsae dual-function catalyst.
The dual function catalyst is a unique development
made in the early 1990s. Since then this catalyst

ISSN: 2229-3701

has been tested in excess of 30,000 hours in a

Topsae DME process demonstration unit. Due to
the extensive catalyst testing and the simple
adiabatic reactor configuration, the technology risk
in the DME synthesis is minimal.
Product Separation and Purification
The layout of the separation and purification
section depends on the specific demands for
product purity. Obviously, the lower demands for
product purity, the lower investment and energy
consumption. In fact, substantial savings are
achieved by producing fuel grade DME, i.e., DME
containing minor amounts of methanol and water.
From a reference point of view, the direct DME
purification section may be considered as a
combination of a methanol distillation section and
the purification section of a conventional DME
plant based on methanol dehydration. Fuel grade
DME to power generation will be a blend of DME
plus water, methanol and other minor oxygenates.
This is due to economies in the manufacturing
process and the incremental benefits associated
with the blend of methanol and water. The ranges
of technical specifications of the fuel grade DME
are shown in Table 4 and the physical properties in
Table 5.

Table 4: Fuel grade DME specification

Component
Water
Methanol
DME
Oxygenates, high ethers and greases
Metals, nitrogen and sulphur

Range wt.%
3.2 + 0.3
7.5 + 1.0
88.9 + 0.9
0.4 + 0.1
Nil

Table 5: Physical properties of fuel grade DME

Property
Liquid density at 25 oC
High heating value as a liquid
Low heating value as a liquid
Low heating value as a gas

DME is physically similar to liquefied natural gas

(LPG). The properties of DME are compared with

Value
0.7458 tons/m3
7.152 kcal/kg
6.449 kcal/kg
6.636 kcal/kg or 11,986 kcal/m3

those of propane and butane, the two main

components of LPG and presented in Table 6.

Table 6: Properties of DME compared with propane and butane

Property
DME*
Propane
Boiling point, o C
- 24.9
- 42.1
Vapour pressure at 20 oC, bar
5.1
.4
Liquid density at 20 oC, kg/m3
668
501
Specific density, gas
1.59
1.52
Lower heating value, kJ/kg
28,430
46,360
Ignition temperature at 1 atm., oC
235 350
70
Explosion/Flammability Limit in air, vol.%
3.4 - 17
2.1 9.4
* The properties of fuel grade DME will differ from neat DME
depending on the amount and type of other oxygenates and water.

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Butane
- 0.5
2.1
610
2.01
45,740
365
1.9 8.4

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International Journal of Research in Pharmaceutical and Biomedical Sciences

ISSN: 2229-3701

Since DME has physical characteristics similar to

LPG, it can take advantage of the vast experience
and mature technologies available for LPG
handling. DME can be transported, offered and
offloaded and stored at a receiving location using
the same conventional LPG-type unloading and
storage equipment. DME, like LPG, can be stored
onshore in either a pressurized, semi pressurized or
refrigerated condition. With respect to DME
shipping, this project can be carried in LPG tankers
that have been altered for this cargo. Some gaskets
and pump seals may need to be changed. While
LPG vessels come in many sizes and types
(pressurized, semi refrigerated refrigerated).
7. REFERENCES
1. Clarke AJ, Lucas DH and Ross FF. Proc.
2nd International Clean Air Conf.,
Washington DC. USA, 1970.
2. Keeling CP and Bacaston RB. Chapter 4
of National Academy of Sciences Report,
Energy and Climate, Washington, DC.
1977.
3. Hart AB. The Chemistry of Power Station
Emissions, The Proceedings of a
Symposium organised by The Industrial
Division of The Royal Society of
Chemistry as part of the Annual Chemical
Congress. 1981;221-251.
4. Billingsley J, Kallend AS and Marsh
ARW. CERL. Note RD/L/N 121/73, 1973.
5. Allen JM, Levy A, Jones PW and
Freudenthal RI. Polycyclic Organic
Materials and the Electric Power Industry.
EPRI. Report EA 787- SY,1978
6. El Missirie A. Natural Gas Versus
Conventional
Petroleum
Products,
Technical, Economical and Environmental
Comparison.
Presented
in
1st
Mediterranean Offshore Conference &
Exhibition MOC 2000 held at
Alexandria (Egypt), on 18-20 April (2000)
7. Jones GR, Holm-Larsen H, Romani D
and Sills RA.DME for power generation
fuel: Supplying Indias Southern Region.
Proceedings in Petrotech 2001, held at
New Delhi on 912 January, 2001.

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