Professional Documents
Culture Documents
+
r
c
) (CO
2
,
where U
r
mineral part, free from mineral CO
2
,
r
c
) (CO
2
- amount of mineral CO
2
,
r
K
-
carbonate free from mineral CO
2
.
At ashing of oil shale, gaseous carbon dioxide is related due to thermal decomposition of
carbonate minerals, and amount of the ash formed does not correspond to the amount of the
mineral matter. Therefore, the amount of mineral carbon dioxide must be given separately.
3.1. Organic and combustible matter
The elemental composition of the organic matter of oil shale is given in Table 1.
Table 1. Elemental composition of organic matter of oil shale, %.
Element C H O N S Cl
Range 77.11-77.80 9.49-9.82 9.68-10.22 0.30-0.44 1.68-1.95 0.60-0.96
Average 77.45 9.70 10.01 0.33 1.76 0.75
The main characteristics of the organic matter of oil shale are: high hydrogen and oxygen
content, and low nitrogen percent. The mass ratio of C/H is 8, which is similar to the values
found in liquid fuels. Oil shale organic matter contains in average about 1.8 % of organic
sulfur. An important characteristic of the organic matter is a high chlorine content.
One of the combustible component of oil shale is marcasite (pyrite) with general chemical
formula FeS
2
. The sum of organic and pyretic sulfur is called combustible or volatile sulfur:
S
V
= S
o
+ S
p .
Organic matter together with pyretic sulfur is considered combustible matter of oil shale.
Oil shale also contains a small amount of sulfate sulfur whose content does not exceed 10 %.
Figure 5 present the thermal decomposition characteristics of oil shale as the release of
different components during devolatilization.
The first signs of the thermal decomposition of organic matter appear at 150
0
C. Visible
decomposition starts at 200 250
0
C. One feature in decomposition process of oil shale
organic matter is thermobitumen formation on temperature between 250 425
0
C. It is also
characteristic that the proportion of the condensing phase in volatile matter decreases with
temperature, which is accompanied by increase in the gaseous phase.
Because the devolatilization process of fuel depends on many parameters, the amount of
realized volatile matter can be determined only in fixed (standard) conditions. Due to the low
ratio of C/H, oil shale has very high volatile matter content. Its standard value is 85 90 %.
6
Figure 5. Material balance of oil shale organic matter as a function of temperature.
The higher heating value (HHV ) of oil shale organic matter is 36.68 MJ/kg and lower heating
value (LHV) is 34.56 MJ/kg. The LHV of volatile matter is approximately 34 MJ/kg.
The properties of oil shale char depend on organic matter decomposition conditions or C/H
ratio in the char. Figure 6 depicts the relationship between the C/H ratio and the carbonizing
temperature. The C/H ratio in oil shale char rises uniformly with an increase in the
carbonizing temperature. In oil shale, the ratio C/H is 8, in the char formed at 900
0
C, the
average C/H ratio is 25. The activation energy of oil shale char oxidation also depends
strongly on the ratio C/H in the char.
Figure 6. Dependence of C/H ratio in oil shale char on carbonizing temperature.
3.2. Mineral matter
Mineral matter is an association of minerals compounds initially present in fuel.
The mineral matter of oil shale can be divided into two large groups: a sandy-clay or
terrigenous part and carbonate part. The sandy-clay part is densely interwind with organic
matter and can be considered as an inherent mineral impurity. Carbonate minerals in oil shale
deposit occur as separate layers or are distributed as limestone concretions in oil shale seams.
The carbonate part can be considered extraneous mineral matter.
Table 2 presents the chemical composition of the sandy-clay and carbonate parts of oil shale.
The main component of the oil shale carbonate part is calcium oxide (48.1 %), followed by
magnesium oxide (6.6 %). Their ratio corresponds to the average oil shale carbonate part
CaO/MgO = 7.3.
7
The average ratio of oxides and CO
2
in oil shale carbonate part is MO
c
/CO
2
= 1.217, where
MO
c
and CO
2
denote content of oxides in carbonate minerals and mineral CO
2
content in
mineral matter, respectively.
The main components in the sandy-clay part are SiO
2
, Al
2
O
3
, and K
2
O. The content of
potassium (given as K
2
O) exceeds that of Na
2
O by about 8 to 12 times.
Table 2. Chemical composition of oil shale mineral matter, %.
Sandy-clay part Carbonate part
Component Content Component Content
SiO
2
59.8 CaO 48.1
CaO 0.7 MgO 6.6
Al
2
O
3
16.1 FeO 0.2
Fe
2
O
3
2.8 CO
2
45.1
TiO
2
0.7
MgO 0.4
Na
2
O 0.8
K
2
O 6.3
FeS
2
9.3
SO
3
0.5
H
2
O 2.6
Total 100.0 Total 100.0
Table 3 give the mineralogical composition of oil shale mineral matter.
Table 3. Mineralogical composition of oil shale mineral matter, %.
Group of minerals Mineral Formula Content
Carbonate minerals
Calcite CaCO
3
69.1
Dolomite CaMg(CO
3
)
2
30.6
Siderite FeCO
3
0.3
Total 100.0
Sandy-clay minerals
Quartz SiO
2
23.9
Rutile TiO
2
0.7
Orthoclase K
2
OAl
2
O
3
6SiO
2
29.0
Albite Na
2
OAl
2
O
3
6SiO
2
6.0
Anorthite CaOAl
2
O
3
2SiO
2
1.4
Muskovite [K
1-x
(H
2
O)
x
Al
3
Si
3
O
10
(OH)
2
]
2
23.7
Amphipole [NaCa
2
Mg
4
)Fe,Al)Si
8
O
22
(OH)
2
] 2.1
Markasite FeS
2
9.3
Limonite Fe
2
O
3
H
2
O 2.9
Gypsum CaSO
4
2H
2
O 1.0
Total 100.0
The main minerals in carbonate part are calcite and dolomite.
The main minerals in the oil shale sandy-clay part are quartz, feldspars (mainly as orthoclase),
and micas (mainly as muscovite). Iron present in the oil shale sandy-clay part is bound mainly
to marcasite sulfur, but, to a limited extent, also to siderite.
8
Because carbonate minerals are present as independent components of oil shale mineral
matter, and does not bind with organic part, then the content of SiO
2
decreases and CaO
content increases as a function of amount of ash. Figure 7 shows the content of CaO and
SiO
2
in oil shale laboratory ash as a function of the amount of ash.
Figure 7. CaO and SiO
2
content of laboratory ash depending on the amount of ash formed
from dry matter of oil shale.
3.3. Formation of ash
The content of combustible matter is usually determined by using standard amount of ash.
For oil shale, one also has to take into account the content of mineral CO
2
which is realized
during ashing from calcite and dolomite by the following dissociation reactions:
CaCO
3
CaO + CO
2
,
CaMg(CO
3
)
2
CaO + MgO + 2CO
2
.
Reactions between pyrite (marcasite) and oxygen proceeds according to the following
reaction:
4FeS
2
+ 11O
2
2Fe
2
O
3
+ 8SO
2
.
In principle, SO
2
can also be formed at oxidation of organic sulfur.
Formed CaO react with sulfur dioxide and oxygen:
CaO + SO
2
+O
2
CaSO
4
.
During the formation of laboratory ash, crystal water is released from minerals of the oil shale
sandy-clay part.
Due to mentioned reactions oil shale mineral matter content always lower than sum of ash and
mineral CO
2
. Therefore, in the case of oil shale, establishing the content of combustible
matter by amount of laboratory ash, yields a marked error. The difference between the actual
and apparent content of combustible matter depends on the extent on the mentioned reactions.
3.4. Heating value
The heating value of fuel is primarily determined on the basis of experiments in fixed
conditions. Usually, the heat released during the combustion of a fuel sample is measured in a
calorimetric bomb in standard conditions.
Oil shale as fuel with complicated composition of organic and mineral matter heating value
determined in a calorimetric bomb does not coincide with the actual amount of heat released
during the combustion of fuel in the combustion chamber. This is caused by differences in the
combustion processes in a calorimetric bomb and in the furnace, which are greatly influenced
9
by the behavior of fuel mineral matter. Therefore, one should know the phenomena
influencing thermal effects in a calorimetric bomb and in the combustion chamber.
Heat is released mainly during combustion of organic matter, but during the burning of oil
shale, it must be taken into account the thermal effects associated with the decomposition of
carbonate minerals and the behavior of sulfur.
The relationships between thermal effects and the heating value measured in a calorimetric
bomb are presented on Figure 8, as well as the sum of thermal effects Q. There are: Q
C
thermal effect due to incomplete combustion of carbon, Q
c
- thermal effect due to
incomplete decomposition of carbonaceous minerals, Q
S-D
- thermal effect due to
incomplete oxidation of sulfides,
4 2
SO H
Q
- thermal effect due to formation of sulfuric acid, -
Q
S-T
- thermal effect due to formation of sulfate.
Figure 8. Thermal effects occurring during combustion of oil shale in a calorimetric bomb.
When oil shale heating value is low, thermal effect from partial decomposition of carbonate
minerals have a significant influence. Similarly, thermal effects due to sulfation of calcium
oxide in the range of heating value
d
B
Q = 10 MJ/kg, and thermal effects due to formation of
sulfuric acid over this value are also important. The sum of heat effects Q decreases with
an increase in heating value.
Heat released during oil shale combustion is dependent on the combustion technology used.
The most important factor is the influence on the behavior of carbonate minerals. The
behavior of carbonate minerals is expressed as the extent of carbonate decomposition
2
CO
k .
This is the ratio of the amount of CO
2
released from carbonate minerals to the total content of
mineral CO
2
in the initial material.
The average extent of decomposition of carbonate minerals during high-temperature
pulverized firing of oil shale is 0.97. However, in the case of low-temperature fluidized
combustion, the extent of decomposition of carbonates remains in the range of 0.7 to 0.8.
Figure 9 shows the influence of the decomposition extent of carbonates on heat release from
oil shales of various heating values. On the vertical axis, there is
10
( )
( )
1
r
L
1
r
L
r
L
L
2
CO
2
CO
=
=
=
k
k
Q
Q Q
q
and on the horizontal axis, there is the decomposition extent of carbonates.
Figure 9. Influence of decomposition extent of carbonates on heat release during oil shale
combustion.
In the first approximation, the dependence between heat release from oil shale and
decomposition extent of carbonates can be viewed as linear. As oil shale with smaller heating
value contains more carbonate compounds, the influence of the decomposition extent of
carbonates on heat release increases with a decrease in heating value. This reflects, in
principle, the influence of the absolute amount of carbonate minerals on heat release.
Figure 10. Relationship between LHV of oil shale and ash content, amount of mineral carbon
dioxide, and moisture.
Oil shale heating value is the main integral indicator of oil shale quality from the firing
technology point of view. Despite the varying ratio of oil shale components, a strong
relationship exists between oil shale technical characteristics and heating value. Statistical data
offer the possibility of linking the amount of ash, mineral CO
2
content, and moisture with oil
shale heating value. The results are presented on Figure 10. The data include oil shale
analyses from underground and opencast mines. The results show that the amount of ash and
mineral CO
2
content decrease, but moisture content increases with a decrease in oil shale
11
heating value. The dependence presented in Figure 10 can also be expressed by the analytical
Formulas.
3.5. Fusion characteristics
The fusion characteristics of ash at three temperatures are as follows: t
A
(or t
1
) - initial
deformation temperature, t
B
(or t
2
). - softening temperature, and t
C
(or t
3
) - fusion temperature.
The fusion temperatures of ash depend on the chemical and mineralogical composition of the
ash. Fusion temperatures are generally considered to depend on the sum of the basic
components, the CaO content of ash, and the ratio of basic components to acidic ones. Ash
fusion temperatures also influenced, to a certain extent, on the composition of the surrounding
gaseous medium. In a reducing and partly reducing atmosphere, fusion temperatures are lower
than in an oxidizing one. The influence of the composition of the surrounding atmosphere is
related primarily to the behavior of iron compounds. In a reducing atmosphere, iron oxides of
higher oxidation numbers are converted to lower oxides and, therefore, they reduce the ash
fusion temperature.
The main components in oil shale ash that influence ash fusibility are CaO, SiO
2
, and Al
2
O
3
.
During the burning of oil shale, ash forms primarily from the carbonate and sandy-clay matter
of a stable chemical composition. This allows one to follow the relationship of the fusion
temperatures of oil shale ash as a function on calcium oxide content in the ash.
Figure 11 presents the relationship of temperatures t
A
, t
B
, and t
C
to the amount of calcium
oxide in oil shale ash. The fusion temperatures are lowest when the CaO content is 25 to 40
%, and they correlate well with the liquidus curve of CaO-SiO
2
-Al
2
O
3
. The absolute values of
fusion temperatures in this region are relatively high and do not differ by more than 70 to
80 K. The value of t
A
is between 1,170 and 1,190 C.
In the region CaO > 40 %, ash fusion temperatures increase quickly, and temperature t
C
reaches 1,750 to 1,850 C at a CaO content of 65 to 70 %. The difference between
temperatures t
C
and t
A
is substantial, and can reach 400 to 450 K.
Figure 11. Fusion temperatures of oil shale ash as a function of CaO content.
Oil shale mineral matter is a heterogeneous system containing minerals of carbonate and
sandy-clay parts. Therefore, different ash particles have different fusion temperatures
depending on the proportions of the mentioned components. Consequently, ash as whole
12
consists of mixture of particles of different phase state. Integral fusion characteristics of oil
shale ash as a function of temperature are shown on Figure 12. The vertical axis represents the
share of the corresponding phase in ash.
The curves show the proportion of ash components in different states. The first signs of
deformation of oil shale ash appear at about 1,050 C; the fusion temperature is close to
1,150 C. At higher temperatures, the amount of the liquid phase in the system increases
rapidly.
Figure 12. Integral fusion characteristics of oil shale ash. Sl solid state, D deformed state, Sf
softened state, L liquid state.
4. Size distribution characteristics of ground oil shale
The fuel preparation system is an integral part of the essential operations of a power plant.
The polyfractional particles system that is formed during different fuel pretreatment process
(for instance, blasting in mines, crushing, grinding in mills, etc.) is subject to a certain
principles of the distribution law. The grind oil shale polyfractional particles system is
described well by Kolmogorov logarithmic-normal distribution law. According this law the
mass of particles passing through the sieve:
(
(
|
|
.
|
\
|
= =
m
M
ln ) ( R 1 ) D( ,
where R() mass of particles remaining on the sieve, particle size,
*
M
- particle median
size, m uniformity factor of polyfractional system.
The Kolmogorov-Fay-Zselew (K-F-Z) diagram is widely used in practice for representation
(visualization) of oil shale particle size distribution. The horizontal axis of the K-F-Z diagram
represents the particle size, and the vertical axis represents the relative amount of the particles
in the system according to Kolmogorov distribution law.
For example, the particle size distribution of oil shale prepared in mills with a gravitational
and an inertial classifier is shown on Figure 13. The median size of pulverized oil shale
13
burned in industrial boilers is between
*
M
= 35 60 m, and sieve residues are R
90
= 20-45%
and R
200
= 10-25%.
Figure 13. Particle size distribution of pulverized oil shale on K-F-Z diagram. 1 MV-
1050/400/1470 (ventilator mill), 2 MMT-1500/2510/735 hammer mill (inertial classifier, 3
MT-1300/2564/740 hammer mill (gravitational classifier, cylindrical shaft), 4 MT-
1300/2564/740 hammer mill (inertial classifier), 5 without blowing ball-tube mill, 6 ball-tube
mill BM-280/600, 7 laboratory ball-tube mill.
Figure 14. Content of organic (R), sandy-clay (T), and carbonate (K) matter in different
fractions of oil shale in the K-F-Z diagram.
As was mentioned before, dry matter of oil shale is heterogeneous material consisting of three
components. These components differ in their behavior at grinding and, therefore, the share of
those components in fractions of different particle size differs from that in oil shale before
14
grinding. Fractions of ground oil shale yield different amounts of ash, mineral CO
2
, and
organic compounds. Similarly, various oil shale fractions are characterized by different
heating values, density, and other parameters.
Figure 14 gives the content of organic (R), sandy-clay (T), and carbonate (K) matter in oil
shale as a function of particle size. The carbonate part predominates in coarser fractions, but
the sandy-clay matter concentrates in finer particles. The distribution of organic matter is
characterized by the line between those representing carbonate and sandy-clay matter.
5. Combustion and mineral matter behavior characteristics
In the classical sense, combustion means chemical reactions between components of fuel
organic matter and oxygen, which results in the formation of gaseous combustion products or
flue gas. In flue gas environment takes place fuel mineral matter conversion processes and ash
formation. The composition of flue gas environment (for instance, oxygen-, carbon dioxide-,
and sulfur dioxide partial pressure) strongly influenced on formed ash physic-chemical
properties, because ash properties determined ash fouling intensity of boiler heat transfer
surfaces, extent of boiler tubs corrosion, thermal resistance of ash deposits on heat transfer
surfaces, etc.
Figure 15 shows the dynamics of the combustion of polyfractional pulverized oil shale at two
different excess air factors. The vertical axis represents the temperature and volumetric
concentration of flue gas components along the axis of the combustion chamber. The
horizontal axis represents time. The figure also expresses the extent of fuel combustion.
An intensive heat release (combustion) and a rapid rise in temperature start after a short
period of 0.02 to 0.04 s. Intensive combustion demonstrated a rapid decrease in oxygen
concentration and an increase in CO
2
concentration. Particles burn with particular intensity
within 0.25 to 0.35 s.
Figure 15. Combustion characteristics of polyfractional pulverized oil shale.
The value of combustion extent 0.8 (zone of combustion of volatile matter) depending upon
the combustion regime, corresponds to the combustion time 0.12 to 0.20 s. The volumetric
heat release rate in the zone of combustion of volatile matter is high and can reach 1.5 to
15
2.5 MW/m
3
. Beginning from the value 0.8, slower char burning dominates, and heat release
diminishes rapidly. The extent of combustion starts to approach asymptotically to one. The
time required for complete combustion of pulverized oil shale is in the range of 1.0 to 1.5 s.
Flue gas in the region of a rapid decrease in oxygen concentration also contains small
amounts of components of incomplete combustion, CO being the most important one.
Carbon dioxide released during oil shale combustion forms both from organic carbon (CO
2C
)
and through the thermal decomposition of carbonate minerals (CO
2CC
). The ratio =
CO
2CC
/(CO
2C
+ CO
2CC
) indicates the share of mineral CO
2
in the amount of total CO
2
formed.
Dissociation of carbonate minerals is a dynamic process, and increases over time. The
maximum value of , is determined by the ratio of mineral to organic carbon content in the
fuel and by the extent of decomposition of carbonate minerals. The time dependence of is
influenced by the parameters affecting the thermal decomposition of carbonate minerals. For
oil shale burned at power plants during the complete combustion of organic carbon ( = 1)
and during the complete decomposition of carbonate minerals (
2
CO
k
= 1), the maximum possible
ratio is = 0.18-0.22. One can see on Figure 16 that the amount of mineral CO
2
increases the
absolute concentration of CO
2
in flue gas by 2.5 to 3.0 %; the total concentration of CO
2
in
the flue gas is 15 to 16 %.
The phenomena occurring during the combustion of oil shale mineral matter can be divided
into four groups:
1. Thermal decomposition of the initial minerals into simpler compounds.
2. Full or partial volatilization and sublimation of minerals. Formation of superfine
particles (aerosols).
3. Formation of novel minerals through the chemical reactions taking place in mineral
and organic matter during contact within particles and between particles.
4. Change in the phase state (solid, plastic, liquid, etc.) of ash particles.
One of the most reactive ash components with respect to ash fouling, sulfate-rich deposits
formation, and heat exchange intensity is calcium oxide. The reactivity of calcium oxide
depends on CaO form in ash.
The dynamics of calcium oxide conversion in gaseous atmosphere corresponding on Figure
15 is shown on Figure 16. The vertical axis represents the amounts of the different forms of
calcium oxide in sulfur free ash. CaO
c
- calcium oxide that is bound to carbonate minerals,
CaO
b
- bound calcium oxide, CaO
f
- calcium oxide that stays in free form. Dimensionless
values k
c
= CaO
c
/CaO, k
b
= CaO
b
/CaO, k
f
= CaO
f
/CaO, where:CaO = CaO
c
+ CaO
b
+ CaO
f
.
The horizontal axis represents time.
It can be seen that the decomposition of carbonates starts immediately after pulverized fuel
has entered the combustion chamber. The dissociation of carbonates is slightly slower at
lower values of excess air factor.
The formation of free calcium oxide is immediately followed by the intensive formation of
novel minerals from sandy-clay minerals in reactions with CaO. The primary minerals that
form from free calcium oxide in an oxygen-containing medium are -2CaOSiO
2
, CaOAl
2
O
3
,
2CaOFe
2
O
3
, and CaSO
4
. In a reducing atmosphere, calcium sulfide can also form. All these
minerals form when there is an excess of free calcium oxide (k
f
> 0). Therefore, the thermal
decomposition of carbonates does not limit the presence of free CaO in ash or the formation
of novel minerals. It is clear that the rate of formation of minerals depends on temperature. At
higher temperatures, the amount of novel minerals in ash is greater. Temperature also
determines their phase state.
16
Figure 16. Dynamics of calcium oxide conversion.
Oil shale ash is characterized by the ability to react with gaseous sulfur compounds present in
flue gas. This phenomenon is known as ash sulfation.
Sulfation takes place in boiler gas passes through reactions between fly ash components and
sulfur containing gaseous compounds, either in the space of the boiler gas pass or on the heat
exchange surfaces during formation of the ash deposit. In the first case, the concentration of
SO
2
in the flue gas and the SO
2
emissions into the atmosphere diminish. In the second case, a
sulfate ash deposit forms on boiler heat transfer surfaces, and SO
2
concentration in the flue
gas also somewhat decreases.
The main sulfur compound present in flue gas is SO
2
. Flue gas can contain small amounts of
SO
3
. Flue gas can also contain hydrogen sulfide, which is formed during the decomposition of
fuel organic matter. H
2
S is more often present during the incomplete combustion of fuel.
Calcium oxide is the major component in oil shale ash that is subject to sulfation. The
sulfation ability of CaO depends on its form in ash. Calcium oxide is present in free and
bound forms. Free CaO is chemically more active. Free calcium oxide sulfates according to
the formula CaO + SO
2
+ O
2
CaSO
4
. Bound calcium oxide is also able to react with SO
2
,
for instance, according to the following reactions:
2CaOSiO
2
+ SO
2
+ O
2
2CaSO
4
+ SiO
2
.
Oil shale ash sulfation intensity depends on temperature, partial pressures of SO
2
and oxygen,
and particle sizes. The dynamics of the sulfation of oil shale fly ash at two different
17
temperatures and values of
2 2
O SO
p p is shown on Figure 17. Value of m on the vertical axis
denotes mass increas; the horizontal axis denotes time.
Figure 17. Dynamics of sulfation of oil shale ash.
Sulfation of oil shale ash is possible at relatively low partial pressures of SO
2
, as proved by a
significant increase in the ash mass during the sulfation process, even at a low concentration
of SO
2
in the surrounding medium. Figure also shows that at the same temperature (1,000 C),
but at lower values of
6. Oil shale firing power plants
The chief aim of oil shale mining today is to obtain source material for the production of
electrical energy.
Until between 1920 and 1925, the main fuel resource in Estonia was wood, which provided
more than 90 % of the energy requirements. Imported coal was the second most widely
consumed fuel.
Initially, oil shale was used as a fuel in locomotives. Thereafter, more and more lump oil shale
was burned in industrial boilers.
An important milestone in the history of the oil shale power industry was the switch to oil
shale firing at the Tallinn Power Plant in 1924. The electrical capacity of Tallinn power plant
was 23 MW. This year can be considered the start of the oil shale power industry. Thereafter,
many oil shale-fired power plants were built in north Estonia: Pssi, Kohtla, Kunda, and
Kivili.
At that time, a steam boiler with a grate-firing furnace was typical. The key problem with
firing oil shale rich in volatile matter is ensuring soot-free combustion. This issue was
successfully solved.
The next stage was introducing oil shale pulverized firing technology. The first power plants
using oil shale pulverized technology were the Kohtla-Jrve Power Plant, which began
operation in 1949, and had designed electrical capacity 48 MW, and Ahtme Power Plant,
which began operation in 1951 and had an electrical capacity of 75.5 MW. Steam boilers at
18
these power plants were slightly modified medium-pressure boilers initially designed for
pulverized firing of coal or brown coal. Operational experience showed that these boilers on
oil shale could be operated only at loads considerably below the design value, because ash
deposits caused fouling of radiant and convection heat transfer surfaces and high-temperature
corrosive-erosive wear of the boiler tubes. These experience indicated for the first time
specific problems with fouling of heat transfer surfaces, high-temperature corrosion and wear
of boiler tubes, cleaning of heating surfaces from ash deposits, and heat transfer. It became
evident that boilers designed for burning coal or brown coal cannot work satisfactorily with
pulverized oil shale due to the very specific and complex composition of oil shale mineral and
organic matter. Systematic application of the results of scientific studies allowed the
operational capacity of medium-pressure boilers to increase, which formed a basis for
designing of original construction of oil shale boilers.
The next stages in development of oil shale power engineering industry started in 1959, when
the first high-pressure pulverized firing boilers specially designed for firing of oil shale were
launched at Balti Power Plant. The designed electrical capacity of Balti Power Plant was 1624
MW.
The first power unit at Eesti Power Plant was inaugurated in 1969. The design capacity of the
power plant was 1610 MW.
At the beginning of 2004, a power unit of electrical capacity of 215 MW with two circulating
fluidized bed combustion boilers was put into operation at Eesti Power Plant. Some months
later, a power unit of the same type was put into operation at Balti Power Plant.
Burned in power plants oil shale has the following proximate characteristics W
r
= 11-13 %, A
r
= 45-57 %,
r
c
) (CO
2
= 16-19 %, and
r
L
Q = 8.3-8.7 MJ/kg
Profile drawing of Eesti Power plant is shown in Figure 18.
Figure 18. Profile drawing of Eesti Power Plant. 1 fuel conveyer, 2 fuel hopper, 3 fuel
feeder, 4 mill with classifier, 5 boiler, 6 ash cyclones, 7 electrostatic ash precipitator, 8
flue gas fan, 9 stack, 10 deaerator, 11 steam turbine.
7. Oil shale firing technologies
19
7.1. Pulverized firing
Today, pulverized firing is the most widely used combustion technology for solid fuels. This is
true in oil shale fired-power plants by installed power.
Pulverized firing of solid fuels is a high-temperature combustion technology. Maximum flame
temperature in the furnace chamber by burning of pulverized oil shale reach to 1400- 1450
0
C.
Medium-pressure pulverized oil shale boilers in Kohtla-Jrve and Ahtme Power Plant have
played an important role in studying the processes occurring during oil shale combustion. The
scientific results obtained have formed the basis for more advanced designs of high-pressure
boilers for Balti and Eesti power plant.
The conceptual solutions of the boilers designed with cooperation of Thermal Engineering
Department of Tallinn University of Technology (STI TTU) and built at the Taganrog Boiler
Factory for Balti and Eesti power plant differ from those typical pulverized firing boilers. The
designers have taken into account the experience gained from the operation and reconstruction
of medium-pressure boilers for pulverized firing of oil shale and also research results.
The main issues which must be taken account by designing of oil shale firing boilers are
following:
1. Ash fouling mechanism and ash deposits formation dynamics of boiler heat transfer
surfaces.
2. Arrangement of boiler gas passes and heat exchange surfaces according to ash fouling
mechanism.
3. Influence of ash fouling mechanism on heat transfer on boiler heat exchange surfaces.
4. Heat transfer in heat exchange surfaces as transient process due to unlimited growth of
ash deposits.
5. Boiler heat exchange surface ash deposits cleaning technology.
6. Influence of boiler heat exchange surface cleaning technology on heat transfer
conditions.
7. High-temperature corrosion of boiler tube metal under the influence of ash deposits.
8. Influence of heat exchange surface cleaning technology on corrosive-erosive wear
intensity of boiler tubes.
The longitudinal section of the high-pressure pulverized oil shale firing TP-101 boiler
mounted at Eesti Power Plant is shown on Figure 19.
TP-101 is a balanced-draft, natural-circulation, single-drum boiler with a superheater and
reheater. The steam capacity of the boiler is 320 t/h. The pressure in the drum is 15.3 MPa.
Pressure and temperature of the superheated steam after the boiler are 13.8 MPa and 520 C.
Steam pressure and temperature at the reheater inlet and outlet are 2.5 MPa/330 C and
2.2 MPa/525 C, respectively.
The boiler has four vertical gas passes. The first (rising) gas pass is the furnace chamber. In
the second (downflow) gas pass, there are hanging platen-type superheaters. In the third
(rising) gas pass, there is an economizer, and in the fourth (downflow) gas pass, an air
preheater.
Rear and side walls of the furnace are screened by water tubes. Radiant superheater panels
cover the front wall.
20
In the front wall of the furnace, two rows of eight turbulent burners are placed. Oil shale fed
into the boiler is pulverized in four hammer mills with an inertial classifier. The particle size
distribution of the pulverized oil shale is characterized by the following residues in the sieves:
R
90
= 25-35 % and R
200
= 17-22 %. The median size of pulverized fuel
M
= 45-55 m.
Figure 19. Boiler TP-101. 1 burners, 2 furnace, 3 outlet screen, 4 furnace platen
superheater, 5 intermediate platen superheater, 6 hanging platens of primary superheater,
7 hanging platens of reheater, 8 economizer, 9 air preheater.
The primary superheater consists of the located in the front wall and on the ceiling of the
furnace chamber, 16 crossflow platens (furnace platens), panels placed on the ceiling of the
upper reversing chamber after the furnace, 32 crossflow platens in the upper reversing
chamber in the horizontal gas pass after outlet screen (intermediate platens), panels in the
ceiling of the downflow gas pass, and 32 long hanging platens in the first row of the
downflow gas pass. Thirty-two long platens of the reheater hang in the second row of the
downflow gas pass.
Ash deposits are cleaned from furnace platens and the platens in reversing chamber by
vibration. In addition to vibrators, long-distance retraceable water blowers are used for
cleaning crossflow platens
In the third (rising) gas pass, there is a economizer. It consists of two sections: lower platens
and upper convection tube bundles. Ash deposit is cleaned from the economizer by vibration.
For additional cleaning of the economizer platens, long-distance water blowers are also used
periodically.
An air preheater is located in the fourth (downflow) gas pass. It is a three-story heat
exchanger made from smooth tubes.
21
7.2. Fluidized combustion
Fluidized bed combustion of solid fuels, a technology that still in the development stage, is the
newest trend in the thermal power plants. It is very prospective also for firing of oil shale.
A fluidized bed is a floating aerodynamic system of fine inert solid particles in gas flow. If fuel
particles are fed into the fluidized bed, where the temperature is at least equal to the ignition
temperature, continuous combustion without the need for high temperature take place.
Combustion temperature is typically between 800-900
0
C. Consequently, fluidized bed
combustion is low-temperature firing technology.
There are currently three fluidized bed combustion technologies in use: stationary or bubbling
fluidized bed, circulating fluidized bed, and pressurized fluidized bed.
Estonian Power plants has more than two years experience of burning of oil shale in circulating
fluidized boilers.
Figure 20 shows the circulating oil shale boiler designed from Foster Wheeler for burning of oil
shale in Eesti and Balti power plant. The power unit, with an electrical capacity of 215 MW, has
two boilers. The main parameters of the boiler are follows: steam capacity, 342/272 t/h;
primary/reheated steam pressure, 12.7/2.4 MPa; and primary/reheated steam temperature,
535/535
0
C.
Figure 20. Oil shale fired CFB boiler. 1 raw fuel bunker, 2 fuel feeder, 3 grate, 4 furnace
chamber, 5 separating chamber, 6 fluidized bed internal heat exchanger, 7 separator, 8
superheater, 9 economizer, 10 air preheater.
The circulating fluidized bed loop consists of the following items making up the solid particles
recirculation system: furnace, gas-solid separator, loop-seal and internal heat exchanger. The
back-pass consists of: superteater, reheater, economizer and air preheater.
The inertial bed material is usually sand. However, if high mineral matter content oil shale is
burned, the bed material forms ash during the fuel combustion process.
The concentration of fuel in a circulating fluidized combustor is very small (usually 0.5 to 2
22
%); heat release is dissipated over the entire combustion chamber and balanced by the
uniform energy absorption of the heat transfer surfaces on the furnace wall. Therefore, flue
gas temperature is not dramatically changed along the furnace height, and there is no need to
add tube bundles into the bed.
Modern circulating fluidized boilers are equipped with an external or internal air fluidized bed
heat exchanger in the back pass after the separator. In this heat exchanger, intensive heat
transfer from the fluidized bed to the heating surface takes place.
When oil shale is burned, sulfur is completely captured by ash, and the concentration of SO
2
in the flue gas is almost negligible. There is no need to add sorbent (limestone) into the
fluidized bed for sulfur capture. The Ca/S molar ratio in oil shale is high, and free lime forms
during thermal decomposition of carbonate minerals.
7.3. Ash fouling
Important issues in design and exploration oil shale firing boiler are: ash fouling and high-
temperature corrosion of heat transfer surfaces, and transient heat exchange.
During the firing of a solid fuel, the flue gas passing through the convective heat transfer
surface always contains ash particles; therefore, the boiler tubes inevitably become covered
with an ash deposit. Ash fouling of the heat exchange surface decreases the heat transfer rate
and also influences boiler tube corrosion.
These processes in oil shale firing boilers related with very complicated composition of oil shale
organic and mineral matter, and also with combustion technology.
Ash fouling of heat transfer surfaces in a boiler is a complex phenomenon; it is a result of
several physical and chemical processes. Composition of the ash deposit on a boiler tube in an
oil shale boiler usually differs significantly from the composition of fly ash passing through heat
transfer surface. This difference is caused by selective deposition of ash particles on the surface,
condensation vapor phase components from flue gas, chemical reactions, sintering, and others
processes within the deposit layer. Therefore, ash deposits of different structure, chemical and
mineralogical composition, strength, thermophysical properties, can be found on heat transfer
surface tubes.
In oil shale pulverized firing boilers, the highest ash fouling rate can be observed in
superheaters and in the economizer located in the high-temperature region of the flue gas.
For oil shale boiler is specify formation of bound ash deposit. A bound deposits forms on the
tubes as result of the transfer of particles onto it and by the condensation of vapors of flue gas
components and through the chemical reactions in deposit. Deposits formed on can vary in
structure and mechanical strength. According to these characteristics, bound deposits can be
divided into two categories: hard deposits of dense structure and high compression strength
and friable deposits of porous structure and low compression strength. The compression
strength of the friable-type and the hard-type deposit is usually 0.1 to 0.5 MN/m
2
and 5 to
20 MN/m
2
, respectively.
Both mechanical and chemical processes influence the formation of the bound deposit. The
growth rate and strength of the bound deposit are influenced primarily by composition of ash
particles, flue gas temperature, composition, velocity, and particle size distribution of the ash.
Photos on Figure 21 provides an overview of the fouled convective heat transfer surfaces of oil
shale fired boilers.
23
Loose deposits on boiler tubes surfaces.
Bounded ash deposits on boiler tubes surfaces.
Figure 21. Ash deposits on heat transfer surface tubes.
24
The typical characteristics shapes of bound ash deposits that form on boiler tube surface are
shown on Figure 22. The deposit shapes mainly depends on flue gas temperature and velocity.
A weakly bound friable deposit forms on the front side of the tube at low gas velocity. The
formation of a hard deposit is associated with a higher gas velocity. The strongly bound
deposit consists of a bottom layer, thin middle crest, and the tops of lower side crests, which
all grow together. The weakly bound friable deposit is wedge-shaped and resembles a loose
deposit; however, it is much more massive.
Figure 22. Shape of a bound deposit formed on a boiler tube. a) hard deposit on the front side
of the tube, b) friable deposit on the front side of the tube. 1 base, 2 middle crest, 3 side
crest, 4 loose crest, 5 friable deposit on the back side of the tube, 1- thin hard side layer. I-
IV stages of formation of the hard deposit.
Figure 23 depicts the growth rate of the ash deposit formed on a boiler tube as a function of
particles velocity and the flue gas temperature. The curves correspond to the temperature
range of flue gas at 560 to 700 C. The concentration of fly ash in the flue gas was 10 g/m
3
,
the median size of fly ash particles