Heat Transfer Analysis of High Temperature Coke Oven Carbonisation Process

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Heat transfer in a high temperature coke oven
Thesis September 1973
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Hassan Al-Haj Ibrahim

Al-Baath University
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1
Heat transfer in a high
Temperature coke oven
A thesis submitted to the
University of Leeds for the degree of
Doctor of Philosophy
By
Hassan Al-Haj Ibrahim, B.Sc.

Under the supervision of
B. A. Lilley, B.Sc., Ph.D.
Department of Fuel and Combustion Science

Houldsworth School of Applied Science,
Leeds University September 1973
2
Summary
Measurements of thermal conductivity were made for coke lumps carbonised at

different temperatures. The measurements were made at temperatures ranging
from 300 to 1050C. It was found that the conductivity/temperature curve
passed through a peak at about 500C, before the conductivity settled to a
value of about 15010 -3 W.cm-1C-1 at temperatures above about 900-1000C. The
appearance of this peak was explained in terms of the structural changes that
take place on heating the coke to temperatures beyond 500C.
In the second part of the thesis, use was made of thermal conductivity
values and their variation with temperature in order to solve the problem of
temperature distribution in a high temperature coke oven during the
carbonisation process. Many assumptions had to be made. Initially heat
generation/absorption in the coal charge was neglected. This was found to
have a significant effect on the calculated temperature field. A heat
generation/absorption term was, therefore, introduced and the calculated
temperature/time curve for the charge centre was found to agree closely with
the measured temperature curve. The calculation was found to give valuable
insight into the heating situation in coke ovens, and more work has been
suggested in order to achieve a more satisfactory solution to the problem.
3
Acknowledgements
I take the opportunity here of expressing my gratitude to Dr. Lilley

who supervised this project, and whose advice and help were indispensable
throughout the three-year period of this research.
I wish also to express my sincere thanks to Mrs. Lilley who helped in

translating a number of German papers.
The financial support of the British Coke Research Association is

gratefully acknowledged. My trips to the B.C.R.A. Centre at Chesterfield were
instructive and useful. I wish to thank all those who helped in making the
coke samples that were used for this work.
Last, but not least, are my thanks to Miss Toon who undertook the
typing of this thesis.
4
Table of contents
Summary
Acknowledgements
1. Introduction
1.1 The importance of heat transfer in coke ovens
1.2 Thermal conductivity of coke
1.3 Extra high temperature carbonisation
Part 1: The thermal conductivity of coke
2. Literature Survey
2.1 The thermal conductivity of crushed coal at room temperature
2.2 The thermal conductivity of coal on being carbonised
2.3 The thermal conductivity of lump coke measured at room temperature
2.4 The thermal conductivity of reheated coke lumps measured at high
temperatures
3. Measurement of thermal conductivity

3.1 Introduction
3.2 Apparatus used for measurement
3.3 Consideration of error
3.4 Using the apparatus to measure the thermal conductivity of a
standard material
4. Results of the thermal conductivity measurement

4.1 Preparation of the samples
4.2 Results
4.3 Discussion
Part 2: Analysis of heat transfer in a coke oven
5. Literature survey
6. Analysis of heat transfer in coke ovens

6.1 Carbonisation in coke ovens
6.2 Assumptions made for the heat transfer analysis
6.3 The first trial solution
6.4 The second trial solution
6.5 The third solution
7. Conclusions
References
Appendix
5
Chapter one
Introduction
This thesis is concerned with heat transfer in coke ovens. Knowledge of
thermal conductivity of coke is basic to such a study and appropriate
experimental measurements are made. In addition, the temperature distribution
within the extra high temperature coke oven built and operated at
Chesterfield by the British Coke Research Association (B.C.R.A.) is
calculated.
By way of introduction the background will be discussed under the

following headings:
1.1 The importance of heat transfer in coke ovens.

1.2 Thermal conductivity of coke.
1.3 Extra high temperature carbonisation.
1.1 The importance of heat transfer in coke ovens.

The problem of heat transfer in coke ovens involves four steps:
a. Heat transfer from the heating flues to oven wall,

b. Heat transfer across the oven wall,
c. Heat transfer from the inside surface of the oven wall to the oven
charge, and
d. Heat transfer across the oven charge itself.
This thesis will be concerned with this last step, namely heat transfer
across the oven charge.
To study the importance of the problem of heat transfer, it is

necessary to define the rate of heating and then to determine the importance
of this rate of heating for the coking industry. By rate of heating is meant
the rate of rise of temperature at a particular point across the width of the
oven. The average rate of heating for the whole charge is often defined as
the rate of temperature rise at a point at a distance of a quarter of the
width of the oven from the wall coke interface in the charge undergoing
transformation in the plastic range. The plastic temperature range is chosen
because of the particular importance of heating rate during this stage.
The study of heat transfer is important for three reasons:
a. because of the effect of the rate of heating on coke properties and

yield,
b. also, understanding the heat transfer conditions in coke ovens will
help in the efficient running and control of the ovens; control here
means manipulating the 'controlled factors' of the carbonisation
process to achieve a coke of specified qualities, and
c. because of the importance of the heating conditions towards a better
understanding of the carbonisation mechanism.
a. The effect of the rate of heating on coke properties and yield

It is widely accepted that in the process of formation of coke from coal,
the reactions which occur whilst the coal is in the plastic state are of
considerable importance. Echterhoff [1] concluded that a decisive change in
6
coke quality is possible only if one succeeded in influencing the

transformations taking place in the plastic zone. It is also accepted that
the rate of heating of the charge during this plastic stage will exert some
influence on the properties of the resulting coke. On the other hand, at
temperatures above about 650C (i.e. after the end of the plastic stage), and
at low heating rates (1-8C/min.) the heating rate appeared not to affect the
quality of the coke [1,2].
For a given coal the coking power depends mainly on the heating rate
during the plastic stage, the poorer the coking power, the greater the
heating rate required [2, 17, 18]. Strong cokes can be made from weakly-
coking coals by carbonisation at higher heating rates ranging from 200C/min.
near the wall to about 40C/min. at the centre, although each coal will have
an optimum rate of heating corresponding to maximum strength of the coke [2].
Before going on to discuss the effects of changing the heating rate on the
various properties of coke, it may be worthwhile to give a brief summary of
those properties of coke that are most important for blast furnaces, seeing
that the major use of coke is in blast furnaces. This would give a better
appreciation of the importance of varying the heating rate and its effects on
the coke properties.
Summary of the properties of coke desirable for blast furnaces
Coke fulfils four functions in blast furnaces:
i. It provides the necessary heat for the process,

ii. It acts as a source of reductant,
iii. It supplies carbon which is an essential ingredient of pig iron, and
iv. It acts as a skeleton which carries the rest of the charge easily
and regularly down the furnace [4].
From consideration of these functions an estimate of the coke qualities

that may affect the blast furnace performance can be made. Blast furnace
performance can be measured either by the carbon rate or by the permeability.
The carbon rate is the amount of coke needed for every ton of iron. The
(Blast volume) 2
permeability = 2 K
Blast pressure Top pressure 10 6
where K is a constant for a given working volume. Some early investigators of

the blast volume/blast pressure relationship indicated that for normal
operation the permeability of the burden column should have a value above 5.
Disturbed operation could be expected if the permeability is decreased to
about 4. [3].
The properties of coke that are important in affecting the performance

of blast furnaces are:
(i) Moisture content
(ii) Ash content
(iii) Sulphur content
(iv) Size range
(v) Strength
Before considering these qualities, however, it must be stressed that
consistency of coke quality is as important, if not more so, than the
absolute levels of any particular property.
7
i. Moisture Content
Although the absolute level of moisture content does not matter, high coke
moisture is invariably associated with high variability in the moisture
content. The undesirability of moisture content variability is due to the
fact that unless the moisture content can be closely monitored and the
necessary adjustments made, large and unknown variations in the quantity of
carbon charged may result. This adversely affects the smooth running of the
furnace [3].
ii. Ash Content

Ash, like moisture, being inert, is undesirable. High ash is also
undesirable because it costs money, requires limestone to flux it, and coke
is required to fuse the slag so formed [3].
iii. Sulphur Content

High coke sulphur is undesirable because coke is usually the major source
of sulphur in the furnace, and increased slag volume is required to
compensate for increased sulphur.
In general, coke must have a low level of chemical impurities.
iv. Size Range

Coke size range appears to be the predominant factor influencing burden
permeability. Size range should be narrow with a top size less than that of
the fissure-free coke. Voidage increases when a narrower size range of coke
is used. The most suitable size range, however, cannot be determined in
isolation from the prevailing blast furnace practice.
v. Strength
a. Resistance to degradation. Coke should be of high strength to resist
degradation.
b. Resistance to abrasion. This should be high, as abrasion leads to coke
fines which are undesirable.
Nixon concluded that the deterioration in the permeability of the
weaker coke due to breakdown was much greater than that of the strong
coke [4].
Other, less important, coke properties include:
vi. Volatile Content

No statistically significant effect has been found. Its increase may,
however, increase the carbon rate of the blast furnace.
vii. Bulk density

The permeability of the furnace is proportional to the fourth power of the
voidage. Therefore, increasing the voidage is beneficial. Low bulk density
will result in the coke occupying more furnace volume and offering high
voidage. There is no experimental evidence to support this claim [3].
viii. Absolute Particle size

This should have little direct effect on permeability when the coke size
is larger than in. Below in. the permeability is dependent on the n th
power of the particle size, where n is equal to or greater than 1. Hence,
larger coke particle size is desirable.
8
ix. Particle Shape

Particles should have rough surfaces with high prismatic ratio in order to
give high voidage. At the same time particles should be as near spherical as
possible in order to give the best effect of shape on permeability.
B.C.R.A. concluded that the imprecise relationship between voidage and

permeability observed with coke may be due to changes in the shape of the
voids and hence the shape and orientation of particles in the bed [4].
x. Reactivity
This must not be high.
Summary of desirable coke properties
Moisture content : Low

Ash content : Low
Sulphur content : Low
Size range : Narrow
Strength : High and uniform
Particle shape : Rough surfaces, high prismatic ratio, near
Spherical
Reactivity : Low
Now we come back to consideration of the effect of the rate of heating

upon the various coke properties.
i. Sulphur Content
It seems evident that at very slow heating rates (about 1C/min. or
less) the sulphur retained by the coke is substantially reduced, particularly
during the early stages of carbonisation [5,6].
ii. Strength and hardness

Results obtained by different workers suggest that there is an optimum
rate of heating foe every particular coal, corresponding to maximum hardness
and strength of the resulting coke. Increasing the heating rate seems to
improve the strength of cokes made from weakly-coking coals [7-10, 18]. On
the other hand, the hardness of the coke is reduced [18].
iii. Mean size and size range

Increasing the heating rate produces a coke of smaller mean size; it
also reduces the size range giving a coke more uniform in size [9, 10, 11].
iv. Bulk density

It appears that with ordinary coking blends the faster rates of heating
yield cokes of lower apparent density and higher real specific gravity [9].
However, opposite results were also reported by Gryaznov [18].
v. Oxygen content
Refractories of high thermal conductivity are used allowing the rate of
heating to be increased, and there was a reduction of the oxygen content of
coke [2]. (But cf. with Riley [13] where the oxygen content of chars obtained
by carbonising organic substances containing oxygen was reduced with slower
rates of heating).
9
vi. Porosity and fissuring

Faster rates of heating yield cokes of higher total percentage
porosity; the percentage of open pores, however being reduced [9]. Pashkevich
[14] and Dorofeev [15] reported that fissuring of coke is reduced by slow
heating up to about 600C followed by an increased rate of heating above about
700C. Gryaznov [18] reported a reduction in the porosity as the heating rate
is increased.
vii. Reactivity
The faster rates of heating yield more reactive coke [9]. Mller [16]
found that reactivity increases up to a maximum then decreases as the heating
rate is increased.
viii. Specific heat

Specific heats of cokes produced at lower rates of heating are higher,
e.g. The specific heats measured at 900C of cokes produced from two coals at
a heating rate of 2C/min. were 0.41 and 0.45 cal/gm.C; the corresponding
specific heats obtained by heating the coals at 4.1C/min. were 0.395 and
0.428 cal/gm.C respectively [12].
ix. Yield
Increasing the heating rate has the effect of lowering the coke yield
and increasing the chemical carbonisation product yields [19].
x. Uniformity
Coke uniformity, as has been pointed out above, may be more important
than the absolute value of any particular property. At different zones of the
oven charge there is a different rate of temperature rise and a different
rate of total heat supplied. This is particularly so at lower rates of
heating. Hence increasing the heating rate improves the coke uniformity.
From the above summary it can be readily seen that the rate of heating
is an important factor in determining the coke quality. The table below
compares the effects of the rate of heating and the desirable coke
properties.
Coke property Effect of increasing the Desirable property for
heating rate blast furnace coke
Sulphur content Reduced Low
Strength and hardness Depends on the coal High
Mean size Reduced
Size range Reduced Narrow
Specific heat Reduced
Oxygen content Reduced
Porosity
Reactivity Increased Low
Uniformity Improved High
Thus it can be seen that the overall effect of increasing the heating
rate is to improve the coke for better blast furnace performance,
particularly if the appropriate heating rate for maximum strength is taken
into account.
10
b. The importance of heat transfer conditions for the efficient running

and control of coke ovens
For the efficient running and control of the coke oven, a study of the
'controlled factors' of the carbonisation process is necessary. The
controlled factors are those factors that can be varied independently, or
controlled, to vary the 'carbonisation conditions' of the coking process.
These controlled factors include:
i. The oven factors (e.g. dimensions and in particular oven width,

refractories used, and all such factors that are related to the
design of the oven),
ii. The coal charge quality (e.g. ash content, moisture content, rank
and size range),
iii. Residence and soaking time,
iv. The rate of heat transfer from the oven flues to the coal charge.
All these factors affect to some extent the 'carbonisation conditions' of

the coal charge. The carbonisation conditions are: rate of heating, final
carbonisation temperature, carbonisation time, coking rate, coking heat and
coking pressure. By determining the effect of every factor of the 'controlled
factors' on the carbonisation conditions, and hence on the coke properties
and yield, a more efficient running and control of the carbonisation process
can be achieved.
From its effects on the coke properties, as discussed briefly above, it

can be seen that the rate of heating is an important condition of the
carbonisation process. This rate of heating can be changed by:
i. Changing the flue temperature,
ii. Changing the oven width, the wall refractories, etc., or
iii. Changing the rate of heat transfer from the flues to the oven
charge, e.g. by changing the flue gases or the combustion conditions
of the fuel.
By any or all such means, the rate of heating can be varied in order to
obtain a coke with the desired properties.
The rate of heating affects also the other carbonisation conditions, e.g.
the carbonisation time which can be reduced by improving the heating rate,
and also the coking rate and the coking heat, both of which are affected by
any changes in the rate of heating. Coking pressure is also increased when
the heating rate is increased [2].
c. Understanding of the mechanism of carbonisation

The rate of heating has an important influence on the mechanism and
process of carbonisation. Its effects on for example the thickness of the
plastic layer [18] and the coking capacity, discussed above, have been
studied for a better understanding of the mechanism of carbonisation, and
hence a more efficient running and control of it.
1.2 Thermal conductivity of coke and its importance with regard

to heat transfer
The thermal conductivity of the coal charge changes considerably as
carbonisation proceeds. Measurement of this thermal conductivity at different
points in the coke oven throughout the whole carbonisation period is
11
necessary if we are to obtain by calculation an accurate temperature

distribution throughout the oven. Comparison of this calculated temperature
distribution with that observed in practice could give further information
about the process.
Measuring the thermal conductivity of the oven charge in situ is not,

however, an easy task. It is generally necessary to measure the conductivity
of the resultant coke, discharged at different temperatures. What can be
measured, however, is not the true conductivity but rather an effective
conductivity. For coke is a porous material and heat transfer will take place
by convection and radiation through the pores as well as by conduction
through the solid mass. If such measurements of the thermal conductivity at
different temperatures can be included in the heat transfer equation for the
coke oven, it is to be hoped that improved results will be obtained.
1.4 Extra high temperature carbonisation, and its relevance

B.C.R.A.'s survey led to the conclusion that the extra high temperature
carbonisation of coal appeared to have the best potential value of any method
of desulphurisation of the resultant coke. A number of experimental ovens
were built, the latest of which is the model on which the heat transfer
calculations in this study are based. Also, the coke samples used for the
thermal conductivity measurements were carbonised in the same oven. Below is
a brief summary of the extra high temperature carbonisation process.
By extra high temperature (E.H.T.) carbonisation is meant carbonisation

at flue temperatures higher than normal. This may give a coke either of
normal final centre-of-charge temperature of about 900C or of higher final
temperature. In each case the coke properties will be affected by the higher
temperature. A brief examination of such effects will be outlined below,
followed by the actual results as found by carbonisation in EHT ovens.
a. The probable effects of raising the flue temperature on the coke

properties
Raising the flue temperature causes the carbonisation process to be
completed in a shorter period of time, at higher heating and coking rates.
The coking rate is defined as the oven width (in inches) divided by the
carbonisation time (in hours). An almost linear relationship was found
between the flue temperature and the coking rate up to a final temperature of
900C [26]. The final temperature may also be allowed to rise. Each of these
carbonisation conditions will have some effect on the coke properties. The
effect of raising the flue temperature will be the sum total of all such
effects. A brief outline of such effects is given below.
i. The effect of increasing the rate of heating

This has been discussed previously (Section 1.1a).
ii. The effect of increasing the coking rate

(1) Higher coking rates cause the resultant coke to be of smaller and more
uniform size [1,2].
(2) The strength seems to drop for strongly-coking coals when the coking
rate is increased, although as in the case of the heating rate there
is an optimum rate corresponding to maximum strength of the coke (see
1,22). According to Kammers [22] strong cokes could be made from
weakly-coking coals by higher rates of carbonisation, but the
12
improvement is not indefinite, and the best coke from weakly-coking

coals is not so strong as metallurgical coke.
(3) Resistance to abrasion was not affected markedly by changes in the
coking rate.
(4) According to Eddy [1] the apparent specific gravity, for cokes made
from strongly-coking coals, showed no change with increasing coking
rates. With less-strongly coking coals the specific gravity increased.
It was suggested that each coal might have its own individual
sensitivity to changes in carbonisation rates.
iii. The effect of reducing the carbonisation time

(1) Rapid carbonisation led to greater desulphurisation [20].
(2) The coke strength was increased by increasing the carbonisation time
up to a final centre-of-charge temperature of 900C, the magnitude of
the increase depending on the coal [7].
(3) The coke yield was essentially constant.
(4) Coke size was smaller on rapid carbonisation [24].
(5) The porosity increased.
iv. The effect of raising the final centre-of-charge temperature

This has a small effect on the coke properties.
(1) The coke strength generally decreased as the final temperature
increased when the coke was tested at atmospheric temperature, but
when the coke was tested at higher temperatures the effect of higher
final temperature on strength was not significant [2].
(2) The specific gravity depended on the final temperature. As the final
temperature increased the true specific gravity of coke generally
increased, but the reverse was true of the apparent specific gravity,
although in this case the effect of the final temperature was less
evident {1, 23].
(3) There is a trend of decreasing coke yield with increasing final charge
temperature.
(4) Sulphur content tends to be eliminated at higher temperatures, the
process being a gradual one depending on temperature. B.C.R.A.
research demonstrated that a substantial reduction in the sulphur
content of cokes and sulphur carbons could be obtained by heat
treatment at 1300C, but in general temperatures of the order of 1900C
were necessary for the complete elimination of sulphur. The presence
of mineral sulphur had no effect on the temperature required for
complete desulphurisation [2, 56].
Investigating forms of sulphur for coals and cokes led to the
following conclusion: at a final charge temperature of 1430C an entry
had just been made into the zone in which reduction of total sulphur
by release of either carbon complex or sulphide sulphur or both might
be expected [2].
(5) Oxygen content was reduced as the temperature increased. Where both
oxygen and nitrogen atoms are present, it is the nitrogen atoms which
are preferentially retained at high temperatures.
(6) The proportion of large coke was reduced at higher temperatures, hence
the mean coke size was reduced [1, 2].
The following table is a summary of the effects on the various coke

properties.
13
Effect of Effect of
Effect of Effect of
reducing the raising the
Property increasing the increasing the
carbonisation final
heating rate coking rate
temperature temperature
Sulphur
Reduced Reduced Reduced
content
Strength Depends on Depends on
Increased Reduced
coal coal
Hardness Depends on
Not affected
coal
Mean size Reduced Reduced Reduced Reduced
Size range Reduced Reduced
Real density Increased
Bulk density Depends on
Reduced
coal
Porosity and
Increased
fissuring
Specific heat Reduced
Oxygen content Reduced Reduced
Reactivity Increased
Yield Reduced Constant Reduced
Uniformity Improved
From the above table it is to be expected that EHT carbonisation would

give a coke of reduced sulphur content, smaller mean size and a narrower size
range, and somewhat decreased coke yield.
b. Results using experimental EHT carbonisation ovens

A study of coke making at EHT was undertaken by a number of researchers at
B.C.R.A., Chesterfield. For this end a number of experimental ovens were
built where coke could be made at nominal flue temperatures up to 1700C.
Their main interest in the process was, as was pointed out above, the
expected reduction of sulphur content in coke. A summary of their results is
given below [1, 23, 25].
i. Effects of EHT carbonisation when the final centre-of-charge

temperature was at about 900C
As the flue temperature is raised, pushing the coke at this low final
temperature may not be acceptable, as the temperature gradient across the
half-oven width will become increasingly severe.
Different coals were found to be affected differently depending on

their rank. For higher rank coals the resultant coke was larger, with
sulphur reduction, strength impaired and the reactivity reduced. Lower
rank coals, on the other hand, gave smaller coke of improved strength and
a slightly reduced reactivity. There was no marked change in the sulphur
content however.
ii. Effects of EHT carbonisation when the final temperature was allowed
to rise
1. A general trend towards a decrease in coke size was clearly
established. Wenger [26] found an increase of 500F in the flue
temperature reduces the +2 in. Size by about 34% on average or about 7%
per 100F of flue temperature increase. This relationship was found to
14
be linear regardless of flue temperature level. The percentage of coke

breeze was not influenced by changes in the oven flue temperature.
In general, higher flue temperature narrows the size range of coke and
reduces the amount of larger coke. These were expected (see above).
2. Coke strength was reduced. This reduction was markedly less with the
lower rank than with the higher rank coking coals.
3. The results of the apparent specific gravity were somewhat scattered,
but there appeared to be some indication that a maximum occurred at a
flue temperature of 1350C (final temperature of about 1200C). Wenger
[26] found that the apparent specific gravity, and hence porosity, and
the bulk density were not affected by changes in the flue temperature.
4. Reactivity was reduced.
5. There was some reduction in sulphur content. Echterhoff reported a
reduction in sulphur content from 0.08 to 0.04% at a flue temperature
of 1550C (final temperature 1230C).
15
Part 1. The thermal conductivity of coke
Chapter Two
Literature survey
Much work has been done on measurements of the thermal conductivities

of coals and cokes. These conductivities vary, not only with such properties
as ash content, rank, etc., but also with the temperature of measurement. It
is important to differentiate between the actual temperature of the
measurement and the temperature to which the coal/coke may have been treated
prior to the measurement. The value of the thermal conductivity of a coal
that has been heat-treated to a certain temperature will depend to a great
extent on whether the thermal conductivity was measured while the coal was at
this high temperature, or whether it was measured in fact after cooling it
down to room temperature. Most data given in the literature are concerned
with the conductivities of coals and cokes as measured at low temperatures,
regardless of the temperature to which the coal or coke has been heated
previously. In this thesis the main interest is in the thermal conductivities
of coals being carbonised measured at the actual temperature of the coals.
Such measurements are not easy in the coke oven situation. Instead, the
thermal conductivity of the coke has been measured on reheating the coke to
about the same temperature at which it was discharged. Hence the main object
of this chapter, apart from summarising such data on the conductivity of
coals and cokes as exist, is to compare the values of the conductivities of
the coal charge when it is being carbonised and of the reheated coke.
Now coal is charged into the oven in the form of a bed of particles. It
is then heated up to the final carbonisation temperature and discharged as
lumps of coke. This coke is quenched and then reheated for the purpose of
measuring its thermal conductivity. Thus it becomes apparent that four types
of conductivity measurement are relevant, namely:
1. Measurement of the conductivity of crushed coke at room temperature;

2. Measurement of the conductivity of the coal charge at different stages
of its carbonisation;
3. Measurement of the conductivity of coke lumps at room temperature;
4. Measurement of the conductivity of the coke on its being reheated to
different temperatures.
2.1 The thermal conductivity of crushed coal at room temperature
The conductivity of crushed coal has been studied extensively. This is

in essence the conductivity of a gas-coal system. Such systems have been
studied with reference to powders, cellular and fibrous substances. Heat
passing through such systems may be transferred either by conduction through
the solid, or through the gaseous phase by convection and radiation as well
as by conduction.
As far as convection through the gaseous phase is concerned, this

contributes only a small fraction of the total heat transferred and can
16
therefore be safely neglected for packed systems with particles smaller than
0.5 cm in diameter [28]. This is due mainly to two factors [27]: the decrease
in the forces which set up the currents of convection by reason of the
subdivision of the gas into small volumes, and secondly by reason of the
increased friction which accompanies the great increase in the area of the
solid surfaces in contact with the gas.
Radiation contribution on the other hand becomes important only at

temperatures exceeding about 300C [28].
Conduction through the gas phase will depend on the thermal resistance
of the gas and its pressure. But even at small pressures some heat conduction
will take place through the gas. Heat will also be transferred through the
solid itself. The relative importance of this part of the heat transfer
depends on the voidage or the bulk density of the system. At low bulk
densities when the void fraction is large, the conductivities of all powders
will be similar depending only on the gas and the geometry of the voids. But
as the bulk density increases and approaches the true specific gravity, the
thermal conductivity will depend more and more on the solid substance itself
[29]. According to Schumann and Voss the voids are of minor importance in the
case of porous sponge-like materials where the heat has a continuous passage
through the solid [31].
Several formulae have been proposed for estimating thermal

conductivities from those of the solid and gas. However, our concern here is
with the practical measurements of the conductivity.
a. Variation of the conductivity with bulk density

Zubilin [29] used the steady state method developed by Kondratev to
measure the conductivity of four different coals, one of which was a blend.
The results he obtained are given in Table 2.1. From these results he
concluded that the thermal conductivity increases linearly with the coal
density. By extrapolating these results to the value of the true specific
gravity of the coal material for the purpose of assessing the relationship
between the coefficient of thermal conductivity and the properties of the
coal material, he showed that the thermal conductivity increases with
increasing rank. The coefficients obtained for the blend suggest that over
the density range investigated these indices are additive to a first
approximation.
Table 2.1 (After Zubilin [29])
Thermal conductivity k
10-3 W.cm-1.C-1
Coals of different
ranks Charge density
gm/cm3
0.8 0.9 1.0
a 0.95 1.16 1.34
b (blend) 1.09 1.22 1.35
C 1.09 1.23 1.37
d 1.09 1.24 1.39
17
Fritz and Diemke have found the thermal conductivity of 32 coal samples to
lie between 1.94 and 3.62 10-3 W.cm-1.C-1 at 30C. The observed values seemed
to be positively correlated with density regardless of the source of the
sample [30].
According to Agroskin the thermal conductivity increased substantially

linearly from a low value (about 1.26 10 -3 -1
W.cm .C -1
or less) for loose
3
packings (0.7 gm/cm or less) to approximately double this value for
monolithic coals at room temperature [28].
b. Variation of the conductivity with type of gas filling the pores

Schumann and Voss [31] found the conductivity at room temperature with
hydrogen filling the pores to be equal to about 2.94, while with air it was
found to be equal to 1.37 10-3 W.cm-1.C-1, hydrogen being of course more
conductive than air.
c. Variation of conductivity with coal rank

As has been pointed out above, the effective conductivity of crushed coal
will depend more and more on the coal substance as the voidage decreases.
Zubilin [29] concluded that the conductivity of coal increases with rank
increase.
d. Variation of conductivity with moisture content

According to Agroskin et al. [32] the conductivity increases as the
moisture content increases. Their values of the thermal conductivity are
given in Table 2.2.
Table 2.2 (After Agroskin [32])
Moisture content % Conductivity K

10-3 W.cm-1.C-1
0 1.16
10 1.66
15 2.09
20 2.55
25 2.79
30 2.90
Similar results were given by Kegal and Matschak [30] for brown coal.
According to them powder bed containing particles about 2 mm in top size were
found to have conductivities for conditions of 0, 15, 35 and 50% moisture of
about 0.76, 0.87, 1.34 and 1.97 10-3 W.cm-1.C-1 respectively. This is to be
expected as water has a much higher thermal conductivity than coal.
e. Variation of conductivity with volatile matter content

Pomerantsev [32] found that the conductivity decreases with volatile
content increase (Table 2.3).
f. Variation of conductivity with particle size

Terres and his associates [30] found that for beds containing four
different sizes of particles, ranging up to 6 mm, of brown coal the thermal
conductivities were similar at 20C and equal to about 0.80 10-3 W.cm-1.C-1.
18
g. Variation of conductivity with the direction of heat flow

According to Scherban et al. the value of the thermal conductivity is
smaller by 51 and 85% in cases where the heat flow is transverse to banding
than in a heat flow parallel to banding [32]. Tsyrul'nikov [32] found that
the conductivity parallel to banding was equal to 3.19 as compared with 2.05
10-3 W.cm-1.C-1 if measured transverse to banding.
Table 2.3 (After Pomerantsev [32])
Volatiles % Conductivity k
10-3 W.cm-1.C-1
0 1.50
10 1.26
20 1.18
25 1.16
30 1.17
Other references
Terres, using a method in which time-temperature curves are taken at

two or more points in the direction of the flow of heat, reported that masses
of closely-sized coal grains ranging up to 5 mm had thermal conductivities of
the order of 1.26 and 1.68 10-3 W.cm-1.C-1 between temperatures of 25 and
130C [30]. A similar value (1.26 10-3 W.cm-1.C-1) was computed by Burke et.
al. for two dried crushed coals by measuring the diffusivity and assuming
some values for the specific heats and the density [30].
Comparison with the conductivity of coal lumps
Values of conductivity similar to those mentioned above for crushed

coal were reported for coal lumps, although much less work has been done on
these, because for most practical purposes coal is used in the form of a bed
of crushed particles. Some of the values reported in the literature are
summarised below.
Godridge [33] measured the conductivity for two coal lumps ay room
temperature. His values were 3.77 and 2.81 10-3 W.cm-1.C-1. Fritz et. al.
gives the following equation for the conductivity of coal lumps:
K = {3.55 + 0.01 t + 0.065 (VMd 15) + 6.6 (R 1.20)} 10-4 cal.Sec-1.cm-1.C-1
for t < 100C.
where VMd is the percentage of volatile matter (dry basis), and R is the
apparent density (gm/cm3).
A similar equation is given for anthracite. Both of these equations

agree reasonably well with measured data [28]. The value supplied by the
Research Board of Great Britain for bituminous coal was 2.26 10-3 W.cm-1.C-1
[30]. The thermal conductivity of the coal substance was also investigated by
Sinnatt et al. Using the compound bar method, they found indications of a
linear variation of conductivity with ash content. For eight coals of 30 to
35 percent volatile matter and less than 10% ash, the reported values for
conductivity ranged from 1.55 to 2.31 10-3 W.cm-1.C-1 [30, 34]. Terres has
19
reported the thermal conductivity of a single piece of coal of unreported

kind as a bout 2.51 10-3 W.cm-1.C-1 [35].
2.2 The thermal conductivity of crushed coal on being carbonised
The contribution of radiation becomes more significant as the

temperature of the coal increase. Also, heat will be transferred by
convection irrespective of the particle size by virtue of the flow of
volatiles through the voids.
Terres [35] suggested that during the progressive heating and

transformation of coal into coke, the thermal conductivity increases without
a sharp break from approximately 1.26 at 0C to values at 1000C between 11.3
and 15.2 10-3 W.cm-1.C-1 depending upon the type of coke produced. The
highest values were associated with the densest cokes. Fritz et. al. found
that the thermal conductivity of coal rose linearly with increasing test
temperature from 2.62 10-3 W.cm-1.C-1 at 20C, the rate of rise being of the
order of 0.005 for each degree rise. Three coke samples gave widely varying
results by the same method [30]. In Table 2.4 below, the conductivities at
higher temperatures were calculated assuming a rate of rise of 0.005 per
degree centigrade.
Table 2.4
Temperature C Conductivity
K/10-3 W.cm-1.C-1
20 2.62
100 3.02
200 3.52
300 4.02
400 4.52
500 5.02
600 5.52
700 6.02
800 6.52
900 7.02
1000 7,52
Wicke et al. investigated the thermal conductivity of two bituminous

coals, one being of high volatile content and the other of low volatile
content, using a two-plate apparatus [36] (Table 2.5).
Table 2.5 (After Wicke et al. [36])
Temperature Thermal conductivity k/10-3 W.cm-1.C-1

C High volatile coal Low volatile coal
Size 3-5 mm 0.3-0.5 mm Size 3-5 mm 0.3-0.5 mm
50 1.05 0.81 1.16 1.05
100 1.28 1.04 1.40 1.16
150 1.40 1.16 1.50 1.28 at 175C
200 1.63 1.40 1.63 -
20
Other measurements of thermal conductivities were also reported by

Agroskin [37], Priestley [38], Pomerantsev [32], Batchelor [39] and Millard
[40]. Their values are given in Tables 2.6, 2.7, 2.8, 2.9 and 2.10
respectively.
Temperature C True conductivity Effective

Corrected for conductivity
weight loss k/10-3 W.cm-1.C-1
200 1.51 1.51
300 1.65 1.65
400 1.79 1.87
500 2.00 2.10
600 2.15 2.34
700 2.32 3.51
800 2.46 3.96
Table 2.7 (After Priestley [38])
k/10-3 W.cm-1.C-1
100 2.09
200 2.09
300 2.09
400 2.09
500 3.35
600 5.86
700 8.79
Table 2.8 (After Pomerantsev [32])
Temperature Conductivity k/10-3 W.cm-1.C-1

C Pulverised coals of different ranks
a b c d
300 1.27 1.28 1.57 1.63
500 1.49 1.53 1.84
700 1.73 1.77 1.79 1.86
900 2.07 2.33 2.44
Table 2.9 (After Batchelor [39])
Conductivity of briquettes made from coal, char and pitch
Temperature C k/10-3 W.cm-1.C-1

200 4.33
400 6.92
700 13.16
900 19.04
21
Table 2.10 (After Millard [40])
Conductivity of packings
Temperature of 2 coals
C k/10-3 W.cm-1.C-1
a b
0 1.05 1.05
200 1.57 2.62
400 1.83 3.40
700 4.19 8.37
800 10.75 26.19
Measurements for coal lumps being carbonised were reported by Badzioch

[41] and Agroskin [28] (Tables 2.11 and 2.12 respectively).
Table 2.11 (After Badzioch [41])

Coal assumed to be chemically inert,
Heated in nitrogen atmosphere
Temperature C k/10-3 W.cm-1.C-1
20 2.76
100 2.30
200 2.34
300 2.38
400 2.14
500 3.35
600 5.35
700 8.88
800 11.98
900 17.84

Values calculated by Badzioch from values given by Agroskin
k/10-3 W.cm-1.C-1
a b
200 1.88 1.84
300 1.97 1.88
400 2.51 2.34
500 3.52 3.18
600 5.02 4.40
Rohde et al. estimated values of thermal conductivity through

comparison of measured and calculated temperature fields in the coke oven
[42] (Table 2.13). Similar values to those of Rohde were also reported by
other German workers [78].
The difference between the values of thermal conductivity quoted above

is not surprising in view of the great number of variables that affect the
thermal conductivity including the coal properties, the carbonisation
conditions and the methods used for the measurements. The values given in
this section have been measured during the carbonisation process at the
temperatures stated.
22
Table 2.13 (After Rohde [42])
Temperature Conductivity
C k/10-3 W.cm-1.C-1
100 1.75
200 1.75
300 1.75
400 2.10
500 3.14
600 5.24
700 9.31
800 17.50
850 32.6
900 58.2
950 104.9
1000 175
1050 291
1100 407
2.3 The thermal conductivity of lump coke measured at room temperature
Rohde [43] heated coal compacts to different temperatures, and then

measured their conductivities at room temperature (Table 2.14).
Table 2.14 (After Honda [43])
C k/10-3 W.cm-1.C-1
200 83.74
1000 136.08
2000 167.48
3000 355.90
Belatskaya [28] measured the conductivities of lumps of coke at room

temperature (Table 2.15). Terres [35] used compact pieces of coke carbonised
at different temperatures (Table 2.16).
Table 2.15 (After Belatskaya [28])
Temperature of Conductivity of different coals

carbonisation k/10-3 W.cm-1.C-1
C a b c d (blend)
200 1.55 1.47
500 1.84
550 2.18
600 2.38 3.10
700 4.90 4.48
800 4.44 3.64 6.28 5.82
23
Table 2.16 (After Terres [35])
C k/10-3 W.cm-1.C-1
200 2.09
400 4.19
500 5.44
600 6.70
700 8.36
900 10.90
1000 12.58
2.4 The thermal conductivity of reheated coke lumps measured at the high
temperatures
Very little work has been done on measuring the conductivity of the
reheated coke at the high temperatures. Batchelor [39] made some measurements
on briquettes made from coal, char and pitch at different temperatures (Table
2.17).
Table 2.17 (After Batchelor [39])
Conductivity, k/10-3 W.cm-1.C-1

Coke Coking Temperature of measurement C
Temp. C 205 427 650 872
A 427 1.73 2.60
B 650 2.60 2.60 6.92
C 816 3.30 2.60 6.92 15.58 *
d 983 4.33 6.92 13.16 19.04
* Extrapolated value
Terres conducted a number of experiments with granulated cokes, from

which he concluded that the conductivity was linearly related to the
temperature of test, the rate of increase being about 4.2 10-3 W.cm-1.C-1 per
100C increase in test temperature. The temperature range of the tests was
between about 180 and 620C, the values of thermal conductivity at the higher
temperature being 8.4 and 12.6 10-3 W.cm-1.C-1 for beds containing particles
of 1 and 2 mm size respectively [30, 35]. Wicke et al. measured the
conductivities of high carbon coke, of low porosity, and of a normal
metallurgical coke at temperatures up to 200C [36] (Table 2.18).
Table 2.18 (After Wicke [36])
Temperature Conductivity k/10-3 W.cm-1.C-1

C High carbon coke Normal coke
50 6.4 9.0
100 7.2 9.9
150 8.0 10.8
200 8.8 11.6
24
All The reported values have been plotted (Fig. 2.1), from which it is
evident that most of the reported conductivity values lie between 1 and 30
10-3 W.cm-1.C-1. Some values, particularly those of Rohde [42] and Honda [43]
are considerably higher (not shown in Fig. 2.1).
25
Chapter Three
Measurement of thermal conductivity

3.1 Introduction
In principle there are three possible ways of obtaining a value for

thermal conductivity.
a. It can be calculated from formulae based on the physical properties of the

material. This, however, is usually unpractical and difficult, particularly
in the case of materials such as coal or coke which are by no means
homogeneous.
Mention has already been made of some empirical formulae for

calculating the thermal conductivity of coal at room temperature. Although
some of these formulae give results that agree reasonably with measured data,
they can not be very reliable due to the many variables in the coal
substance. In any case, our main concern is with the thermal conductivity at
higher temperatures. The values reported by the different workers for the
thermal conductivity at the higher temperatures are so varied that to deduce
a general empirical formula may not be worthwhile or even possible; and
whereas most reported values are quite low, some workers have reported
relatively very high values.
b. Alternatively, the thermal conductivity can be calculated by establishing

a relationship between it and some other physical property that can be
measured easily. But because of the meagre information on the thermal
conductivity of coke at the higher temperatures, no such empirical
relationship has been established. Any empirical relationship that may be
arrived at will be too uncertain for it to be of much use. Some workers have
tried to correlate the thermal and electrical conductivities for metals, and
a reasonably well-supported relationship has been deduced. An attempt will be
made later to compare the measured thermal and electrical conductivities of
coke.
c. Meanwhile, one is left with the only practical method of obtaining a value
for the thermal conductivity and that is by using direct heat transfer
measurements. Such measurements are not always accurate. One major source of
inaccuracy in such measurements is the extreme difficulty of insulating the
heat flow completely, particularly in the case of such poor conductors as
coke. Another method of measuring the thermal conductivity would be to
measure the thermal diffusivity, and then calculate the conductivity from it.
This method is not however as attractive as it may seem despite the relative
ease and accuracy of measuring the diffusivity because in it is required
knowledge of the specific heat and the density, and their variation with
temperature.
The method chosen for measurement
After deciding upon using heat transfer measurements, the next step was
to choose a suitable technique for lump coke.
26
Any technique to be selected for measuring the thermal conductivity of a

material will depend on:
i. The thermal conductivity of the material,

ii. The physical nature of the material,
iii. The temperature range, and also
iv. The cost, the availability of equipment, accuracy required, etc.
With coke, especially when made at EHT, the sample to be used for
measurement must not be too large. The technique must not require that the
material be, for example, electrically conductive.
After due consideration of the many techniques available for measuring the
thermal conductivity for poor conductors at high temperatures, one method was
chosen, chiefly for its simplicity and convenience. There is a very good
survey of techniques for measuring thermal conductivities in a paper by Flynn
[44] for ceramic materials, and in a book edited by Tye on thermal
conductivity [46].
3.2 Apparatus used for measurement
The method of measurement chosen is based on an apparatus described by

Neel et al. [45]. It is a radial heat flow apparatus, where the measurements
are made at steady conditions. Heat is induced to flow from the outside
diameter of the specimen inward to a water calorimeter positioned axially. A
schematic dross-section of the apparatus is shown in Fig. 3.1.
27
The coke specimens are cut in the form of small cylinders of about 1.2
in. diameter and 1.2 in. long. The water calorimeter is positioned axially
through the central hole which is in. in diameter in the coke specimen.
This water calorimeter performs as a heat sink and provides a means of
measuring the heat flow through the specimen length. The temperature rise of
the metered water flow is measured using chromel-alumel thermocouples in the
calorimeter tube located about in. apart. The calorimeter must be
positioned so that this in. length is axially in the centre of the
specimen.
The coke specimen is guarded on both sides with two rings of coke about
in. length each. These are followed by carbon tubes that are packed with
carbon powder to insulate the heat flow in the specimen.
Two holes are made in the specimen (see

Fig. 3.2), through which two platinum/platinum-
rhodium thermocouples are inserted to measure
the temperature difference across the coke
specimen. The thermocouples pass through two
tubes that extend from the coke specimen
through the carbon tube and then through a
copper tube which is water-cooled as is shown
in Fig. 3.1.
The whole apparatus is placed inside an

alumina tube to enable a controlled atmosphere
to be maintained during the measurements.
The specimen is heated by means of an

electrically-heated furnace, using Crusilite
hot rods which can be raised up to a
temperature of 1500.
For the calculation of the thermal

conductivity, Fourier's equation was used:

K =
.
Where Q = the rate of heat transfer, calculated by measuring the rate of

water flow in the calorimeter tube and the water temperature rise,
L = the radial distance between the two measuring points in the coke
specimen,
A = the log mean cylindrical area through which the heat Q is flowing;
and is equal to
1 2
A = 1
ln
2
Where A1 and A2 are the cylindrical areas at the two measurement points.
T = the temperature difference across the specimen.
The mean temperature was calculated as follows (refer to Fig. 3.3):

28
Let T = T1 T2
R = r1 r2
A = AL.M.(r2 r1)
= log mean
cylindrical area
between r1 and r2.
T1 = To.f. TL.M.
R1 = ro.f. rL.M.
A1 = AL.M. (ro.f. rL.M.)
From Fourier's equation:
1
K.A. = K. A1
1
.1
or T1 = T
1 .
.1
or TL.M. = To.f. - T
1 .
where TL.M. is the log mean temperature taken as the mean temperature of the
measurements. This is the temperature which has been specified as the
temperature at which the measurement was made.
3.3 Consideration of error
A number of errors, both determinate and indeterminate, are involved in

the measurement of the thermal conductivity. There are first of all errors
connected with deviation from the conditions assumed for deriving the
equation used for the calculation. One assumption is that longitudinal heat
flow is negligible.
Another error can be caused by the perturbation of heat flow by the

thermocouples and the temperature-measuring holes. Powell [47] showed that
the presence of holes (2 millimeters in diameter and 8 mm deep, spaced 40 mm
apart in rods of 14 cm diameter and 100 mm length, is likely to give thermal
conductivity values which are low by some 2 percent.
The determinate error can be determined by a partial differentiation of

the equation used for calculation [48].

i.e. K = (1)
.
1 2 2
but A = 1 =
ln ln 12
2
where l is the longitudinal length.
Substituting back in eq. 1 we get:

29

1
2
K = (2)
2 (1 2 )
By differentiation and dividing the result by eq. 1 we get:
1 2 ( 2 )
| | = = + + + + ( 1 (3)
1 ln 1 2 ln 1 1 2 )
2 2
Errors, calculated on the basis of equation 3, were found to be of the order

of 15%. Despite this large error, it was felt that the values for the thermal
conductivity obtained were useful if only as indicators of the order of
magnitude. As has been pointed out previously, little work has been done on
measuring the coke conductivity at high temperatures.
There is no need to correct for changes in the dimensions due to

1
heating, because it is only the ratio which is used in the calculation
2
(equation 1). Another source of error is due to the anisotropic nature of
coke, where the heat flow is not uniform in all directions.
3.4 Using the apparatus to measure the thermal conductivity of a standard

material
Alumina was chosen as the standard material because of its availability

and also because its thermal conductivity is of the same order as that of
coke in the temperature range studied. The results of the measurements are
shown in Fig. 3.4 along with two recommended curves given by Powell [49] and
Goldsmith [50]. Measured values of the thermal conductivity at temperatures
above about 400C are much closer to the recommended curves than those values
below 400C. There is, however, good agreement between the values of Powell,
Goldsmith and the present measurements in the region above 400C, which is the
one of primary interest. It must also be borne in mind that the two
recommended curves are mean curves and do not represent actually-measured
values.
30
Chapter Four
Results and discussion

4.1 Results of measurement
Preparation of the samples
Crushed coal was carbonised in the EHT coke oven built at B.C.R.A.,
Chesterfield, for the purpose of investigating the effects of higher flue
temperatures on coke-making. Different flue temperatures, up to 1700C, were
used to make coke at different final temperatures. In most cases 100 per cent
Maltby coal was used but other coals and blends were also used. When the coke
charge was pushed half-way at the end of carbonisation, a sample was picked,
large enough to cover as much of the oven half-width as possible. It was not
always easy, however, to get samples large enough for the conductivity
measurement. This was particularly so at the higher flue temperatures when
the coke produced tended to be of smaller size. The coke was then either wet-
quenched or dry-cooled. Cylinders for the conductivity measurement were
drilled, using diamond drills, from the coke samples collected. Some of these
samples had large surface cracks that extended well into the interior of the
sample. Such samples usually gave higher values of conductivity, as will be
seen later.
The cylinders were then heated, either in air or in a nitrogen

atmosphere with a nitrogen stream flowing at a small pressure. A thin outside
layer of the sample was burnt away; it was expected that this should have no
effect on the conductivity measured. The heat liberated on combustion could
be considered as another source of heating the sample. Weight loss on heating
was relatively small and it varied between two and four per cent of the
original weight. Little or no difference was found in this respect with
samples heated in air or in nitrogen. This may indicate that this weight loss
is not due to combustion, but is rather associated with the evolution of
volatiles observed on heating coke.
The EHT coke oven has the following dimensions:
Oven width = 16 in.

Width of flues = 12 in.
Width of wall = 3 in.
Useful height of oven = 3 ft., 4 in.
Length of oven = 3 ft., 3 in.
Results
A summary of the results obtained are presented below, arranged

according to the various conditions of the coke sample preparation.
a. Measurements of the conductivity of coke carbonised at different

temperatures, wet-quenched, and reheated in air for the conductivity
tests
31
In Test 1, measurements were made on coke carbonised from 100% Maltby

coal. Table 4.1 summarises the coal properties and its conditions of
carbonisation. The sample used was chosen near the centre of the charge. The
results are shown in Fig. 4.1. Only three measurements were made. The only
thing that can be deduced from them is the order of magnitude of the
effective thermal conductivity, of about 50-100 10-3 W.cm-1.C-1. This is
considerably higher than values quoted in the literature for coals and cokes,
although some such reported values (e.g. by Rhode [42]) are comparable. This
same observation was noted with all subsequent measurements.
Table 4.1. Coal properties and carbonisation conditions.

Test No. 1
Moisture content, as charged 9.3 %
Ash (d.b.) 4.8 %
Volatile matter (d.a.f.b.) 36.2 %
Carbon (d.a.f.b.) 84.8 %
Mean flue temperature 1085C
Final charge centre temperature 1055C
Carbonisation rate (to 900C) 1.27 in./h
In Test 2 measurements were made on coke carbonised from Brookhouse blend.

Table 4.2 summarises the coal properties and the conditions of carbonisation.
Two samples were used, one of which was broken and the outer
platinum/platinum-rhodium thermocouple exposed. This may explain the higher
32
conductivity values obtained in that the heat flux measured is falsely high.
The results are shown in Fig. 4.2.

Test No. 2
Ash (d.b.) 8.3 %
Volatile matter (d.a.f.b.) 35 %
Carbon (d.a.f.b.) 85 %
Carbonisation rate 1.11 in./h
It can be seen that as the temperature of measurement increases, the

conductivity increases up to a maximum at about 300C and then decreases again
to settle at an approximately constant value of 150-160 10-3 W.cm-1.C-1. The
conductivity on the whole ranges from about 150 to 250 10-3 W.cm-1.C-1. It is
significant that the curve for the broken sample also showed a peak at about
550C.
In Test 3 measurements were made on coke carbonised from 100% Brookhouse

blend. Table 4.3 summarises the coal properties and its carbonisation
conditions.

Test No. 3
Ash (d.b.) 8.0 %
The results are shown in Fig. 4.3. Two peaks can be noted here, one at
about 450C similar to the one noted above (Test 2) and a second one at about
750C. The conductivity varies from 100 to 200 10-3 W.cm-1.C-1.
In Test 4 measurements were made on coke carbonised from 100% Maltby coal.
Table 4.4 summarises the coal properties and its carbonisation conditions.
The results are shown in Fig. 4.4. A peak is indicated at about 550C. The
conductivity varies between 100 and 200 10-3 W.cm-1.C-1.
33

Test No. 4
Ash (d.b.) 4.4 %
The coal properties and its carbonisation conditions are shown in Table 4.5.
The sample used had a number of large cracks.

Test No. 5

Ash (d.b.) 4.6 %
34
The results are shown in Fig. 4.5. The conductivity here also increases
with temperature up to a maximum at about 400C, and it seems to settle after
that at about 150-170 10-3 W.cm-1.C-1 at the higher temperatures. The average
conductivity varies from 150 to 250 10-3 W.cm-1.C-1. The presence of large
radial cracks may have contributed to a falsely higher value of the
conductivity.
b. Measurements of the conductivity of coke carbonised at different

temperatures, wet-quenched, and reheated in a nitrogen atmosphere for
the conductivity tests
In Test 6 measurements were made on another sample of the same coke

described earlier (see Table 4.3). The results are shown in Fig. 4.6. As was
found in the earlier test in air (Test 3) two peaks are observed, a smaller
one at about 350C and a much larger one at about 800C. Although in both
cases the conductivity starts at about the same value, in the case of the
nitrogen test it increases to a higher level than it does in the air test.
In Test 7 measurements were made on coal carbonised from Brookhouse blend.

Table 4.6 summarises its properties and the carbonisation conditions. The
results are shown in Fig. 4.7. The conductivity shows a small maximum at
about 450C then after decreasing a while, it starts to increase again to a
second maximum at about 700C, and then it settles at a constant value of
about 160 10-3 W.cm-1.C-1. The curve is similar to that of test 6 with both
having a second peak in the region of 700C.

Test No. 7

Ash (d.b.) 7.8 %
a. Measurements of the conductivity of coke carbonised at different

temperatures, dry-cooled, and reheated in air for the conductivity
tests
In Test 8 measurements were made on coke carbonised from a Scottish blend.

The coal properties and its carbonisation conditions are summarised in Table
4.7. The sample had big cracks. At the end of the test the sample was found
to be broken and the outer platinum/platinum-rhodium thermocouple was
exposed.
35
The results are shown in Fig. 4.8. A second test was made with another
sample that appeared to be free of big cracks. There is a significant
difference between the two conductivity curves. In the second test two peaks
are evident, one at about 450C and the second at about 650C. The
conductivity varies from 50 to 100 10-3 W.cm-1.C-1. The only peak shown on
the curve for the sample with the cracks is at about the same temperature as
that for the second peak, but at a much higher value.

Test No. 8
Ash (d.b.) 9.8 %
b. Measurements of the conductivity of wet-quenched, reheated coke that is

heated in air for the conductivity tests
Its properties and carbonisation conditions are summarised in Table 4.8.
36

Test No. 9
Ash (d.b.) 4.7 %
Carbon (d.a.f.b.) 85.4 %
The coke was wet-quenched, reheated to a temperature of 1535C and wet-

quenched again. The sample was reheated in air for the conductivity
measurements. The sample used looked very porous, with large pores. The
results are shown in Fig. 4.9. The curve does not show any marked peak. The
conductivity increases smoothly from about 50 at 300C to about 140 10-3
W.cm-1.C-1 in the temperature range 600-800C.
c. Measurements of the conductivity of coke carbonised at different

temperatures, wet-quenched, reheated in air and then cooled for the
conductivity measurements
In Test 10 measurements were made on coke carbonised from Maltby coal (at
the same conditions as in Test 4). The coke was heated to 620C and the
conductivity was measured on cooling. The results are shown in Fig. 4.10. The
conductivity values seem to be larger on the whole than the corresponding
values for the coke measured on heating.
37
In Test 11 measurements were made on the same coke as in Test 5. The

sample had a number of large cracks. It was heated to a temperature of 1055C
and the conductivity was measured on cooling. The results are shown in Fig.
4.11. The value of the conductivity rises as the temperature falls to 300C,
but since no measurement was made at a lower temperature the existence of a
maximum could not be confirmed. The results are however perfectly consistent
with a peak in the region of 350C. A steady value varying between 160 and 180
10-3 W.cm-1.C-1 is indicated in the temperature range 600-950C. The curve
closely resembles that obtained on heating.
In Test 12 measurements were made on the same coke as in Test No. 2. The
sample was found to be broken at the end of the test. It was heated to a
temperature of 970C and the conductivity measured on cooling. The results are
shown in Fig. 4.12. Conductivity values are slightly less than those obtained
on heating.
d. Measurement of the conductivity of dry-cooled coke on heating in air
Measurements of the conductivity of coke made from a Scottish blend (the

same as in test 8) were made. The coke was dry-cooled, reheated in air to a
temperature of 920C and the conductivity was measured on cooling. The results
of this test (Test 13) are shown in Fig. 4.13. The values obtained are
slightly higher than the corresponding ones obtained on heating. A small peak
is indicated at about the same temperature as on heating (about 650C).
38
e. Measurement of the conductivity of reheated coke on cooling
Measurements of the conductivity of reheated coke of the same properties

as Test 9 were made. The sample was heated in air to a temperature of about
780C, and the conductivity measured on cooling. The results are shown in Fig.
4.14. The conductivity values are higher than those obtained on heating for
the same sample. The curve is not as smooth as it was on heating. A minimum
is indicated at about 450C. This may have followed a maximum at a temperature
below 450C comparable to the maximum obtained with the other tests (Fig.
4.9), but unfortunately no measurements were made below 300C. Also at
temperatures above about 600C a peak is possible corresponding to the small
peak at 600C for the conductivity measured on heating (Fig. 4.9).
Summary of observations
1. Conductivity values are higher than expected. They are of the order of
100-150 10-3 W.cm-1.C-1.
2. For most wet-quenched coke samples, a a maximum was observed in the
temperature range 300-550C.
3. The conductivity curves for the dry-cooled coke, and the reheated coke
are smooth, and do not show marked peaks.
4. Conductivity values at the lower temperatures are very different for
the different cokes, but all curves seem to converge at higher
temperatures on a value of about 150 10-3 W.cm-1.C-1 (see Fig. 4.15).
Also, for all curves, the conductivity does not show much variation at
the higher temperatures, the variation being within experimental error.
The conductivity can be averaged out at about 150 10-3 W.cm-1.C-1.
4.2 Discussion of results
Coal as charged into the coke oven consists of a bed of particles. On

being heated, these particles of coal fuse and swell to form eventually a
solid mass of coke containing micropores and with cracks running through it.
The mechanism of heat transfer through a packed bed of particles is

closely similar to that of heat transfer through a porous solid such as coke.
Before going on to discuss conduction in the coke oven and the effective
thermal conductivity of coal and coke, a brief look at conduction in porous
systems in general is necessary here.
The effective thermal conductivity of porous systems
A porous system consists of a solid mass or a bed of particles with gaps

or pores filled with a fluid. But, although both porous solids and packed
beds of particles behave similarly in regard to heat transfer, there is an
important difference between them. This is due to the thermal resistance at
the points of contact between the different particles, where no such
resistance exists in the continuous mass of the porous solid.
39
Heat transfer in porous systems takes place by means of four modes:
1. Heat transfer by conduction through the solid or through the points of

contact of the particles.
2. Heat transfer by conduction through the gas.
3. Heat transfer by radiation in the pores.
4. Heat transfer by convection through the pores.
The effective thermal conductivity of such systems will depend therefore,

not only on the true thermal conductivity of the solid material, but also on
the conductivity of the gas medium in the pores, and on the volume and
geometry of the pores.
A number of equations have been derived for calculating the effective

conductivity of porous systems.
An equation derived by Maxwell [51] is:

1 1

= (1)
1+ (1)
3
=
2 +

=
+
Where K = the effective thermal conductivity of the system,

Ks = the true conductivity of the solid,
40
Vs = the total volume,

Vp = the volume of the pores,
Kp = the effective conductivity of the fluid in the pores (taking all
modes of heat transfer into account).
Assuming Kp to be small relative to Ks for extended, more or less plane

parallel sided gaps and assuming that one third of all fissures extend
perpendicular to the direction of heat flow, Eucken [51] arrived at the
following equation:
1 1
= + (2)
3
Similar formulae were derived by other workers. One such formula was derived
by Nusselt [51]. Assuming plane parallel sided gaps extending perpendicular
to the direction of heat flow, he found that:
1 12
= + (3)
13
Kp being the effective conductivity in the gas filling the pores, where heat
is transferred by conduction and radiation, convection being neglected. L12,
L13 and L23 are dimensions as indicated in the diagram.
Comparing equations 2 and 3 it can be seen that the factor 3 in the

denominator of the second term of equation 2 is missing in equation 3. This
factor was in Eucken's equation because the gap was assumed to cover only a
third of the cross-section and not all through the body.
By rearranging equation 3, replacing Kp by Kg (for conduction) and

introducing a radiation component (4T3), Nusselt found:
13
= 12 1 (4)
+

+ 4 3
23
From the above brief analysis it can be concluded that the effective thermal
conductivity depends on porosity. From equations 2 and 3 it is obvious that
the conductivity increases as the porosity decreases, Kp being << Kg.
41
The dependence of the effective thermal conductivity on the different

modes of heat transfer depends on temperature. The convection can be
neglected for most systems with particles larger than 4-5 mm in diameter. The
limited size of the pores and the micropores impedes the onset of convective
gas flow caused by the temperature gradient [52]. Radiation is not important
at low temperatures.
Neglecting the radiation term in equation 4 we get:
13
= 12 23
+

13
Or =
12 + 23
Assuming Kg << Ks this reduces to:
13
= (5)
23
i.e. the effective thermal conductivity depends principally on the

conductivity of the gas medium.
On the other hand, radiation becomes very important at high

temperatures. In equation 4, as the temperature T increases, the second term
in the denominator approaches zero, and
13
= (6)
12
with K becoming a function of Ks only. This means that at very high

temperatures the pores themselves present no resistance at all, but the
porous body conducts as though the pores were filled with solid substance
[51].
To sum up, therefore, it seems that the conductivity of a porous solid

depends on the porosity and the conductivity of the gas medium at low
temperatures; with very large values of voidage the effective conductivity
becomes very small and approaches that of the gas. That is why at low
temperatures and high voidage the conductivities of most porous systems are
similar. At high temperatures, on the other hand, the effective conductivity
depends on the true conductivity of the solid material.
A consideration of the thermal resistance at the points of contact of

the particles is given in many references [52], but will be left out here,
for it is not important for our purposes.
The thermal conductivity of amorphous and crystalline materials
Up till now we have assumed the solid material to be homogeneous. Many

porous solids, however, consist of crystallites embedded in a matrix of
amorphous substance. Coke is such a solid.
Eucken seems to have been the first to state that the conductivity of
amorphous solids is small at low temperatures and increases with temperature,
whereas that of crystals is high and decreases with increasing temperature
[51]. Eucken, assuming that composite materials can be considered as an
42
aggregate of heat resistors of crystalline and amorphous kinds, connected in

series, obtained the following equation:
1
= . (7)
++

where T = Temperature, a, b and c are constants.
This equation leads to an increase of conductivity with increasing

temperature if T is small, and to a decrease of K with increasing temperature
if T is high. If the material contains only a little amorphous substance, the
maximum occurs at low temperatures; if it contains not much crystalline
substance, the maximum occurs at high temperatures, becomes less distinct and
possibly disappears entirely [51].
a. The effective thermal conductivity of crushed coal at room temperature

Coal, as charged to the coke oven, is an amorphous material in the form of
packed particles with gaps and pores in between filled with air or moisture.
As we have seen the effective thermal conductivity of such a system at low
temperature will depend on its porosity and on the conductivity of the gas
medium. It will also depend to some extent on the true conductivity of the
coal, which is expected to be of low value with coal being an amorphous
material. The true conductivity of coal will depend on its composition and on
such variables as ash content and volatile content. Emphasis will be given,
however, to factors that affect the effective conductivity significantly.
A further factor on which the effective conductivity depends is the

moisture content. Coal, unless it is preheated, is charged wet into the oven.
The moisture plays an important role in transmitting heat across the oven
charge. As water is a much more conductive material than either air or coal,
it is evident that the effective conductivity will increase significantly as
the moisture content increases.
All these conclusions are in fact borne out by experimental work as has
been shown before (Chapter 2).
b. The effective thermal conductivity of crushed coal on being carbonised

As the coal is heated, it undergoes decomposition and after passing
through a plastic stage it solidifies into semi-coke and then coke. Thus two
main stages cab be recognised:
1. The pre-plastic stage where coal is dried, and the absorbed gases are
expelled, with a certain amount of decomposition. This stage may last
up to a temperature of about 400C. The conductivity during this stage
is expected to rise slowly with temperature.
2. With the onset of volatile evolution, the plastic stage begins. The
coal mass is fluidised and behaves very much like a fluid. After
solidification the charge forms a porous solid mass of semi-coke, and
later, after further decomposition, coke is formed.
Throughout this period the coal structure undergoes great changes,

particularly during the plastic stage where orientation of the carbon atoms
towards the graphitic form occurs. Above 800C there is also an increase in
the size of the crystals, and their growth could be recognised under the
microscope using polarised light [10].
43
Mantell [61] summarises the crystallite growth on carbonisation; Berry

and Edgeworth-Johnstone state that: From a physical standpoint, it appears
that all cokes are essentially disperse systems composed of minute
crystallites embedded in a matrix of highly-condensed aromatic compounds. The
crystallites consist of either graphite or closely-related substances. Such
crystallites have been reported to exist even in asphalt. As carbonisation
proceeds, the crystallites grow at the expense of the matrix, which also
loses volatile matter and changes in character. The hydrogen content of the
system naturally decreases as the temperature rises. Above 1100C, the
hydrocarbon matrix has practically disappeared, but the crystallites continue
to grow at higher temperatures, and conversion to massive graphite is not
complete below about 2500C.
From what has been said so far it is clear that raising the temperature of
coal affects its effective conductivity in three main ways:
1. Due to the evolution of volatiles some heat transfer will take place by
convection irrespective of particle size. In a coke oven the heat
transferred by volatiles is of considerable significance. A fuller
discussion of this phenomenon will be left to the second section of
this thesis.
2. With the increase in temperature, radiation starts to play a more
significant part in heat transfer. As we have seen earlier the
effective conductivity of porous systems increases with temperature
increase, and becomes more and more dependent on the true conductivity
of the solid material. This leads us to the third main effect of
raising the coal temperature on its conductivity, and that is the
growth of crystallites. Before discussing this it should be noted first
that at the higher temperatures, with the effective conductivity
dependent on the true conductivity of the solid mass, different coals
will have widely different conductivities depending on such factors as
rate of heating, final carbonising temperature and rank.
3. As mentioned above, carbonisation is accompanied by growth of
crystallites, particularly above 800C where their growth proceeds
rapidly. This growth of crystals is expected to affect the conductivity
in two ways. Firstly, as the conductivity of crystalline materials is
in general higher than that of amorphous material, the conductivity
will increase with temperature. Secondly, as the system becomes more
and more crystalline, a temperature will be reached at which the
conductivity will start to decrease with further increase of
temperature. This maximum, from what has been said on the
conductivities of crystalline and amorphous materials, will occur at a
high temperature, and may not be apparent for systems with not much
crystalline substance.
In conclusion we may say that the effective conductivity of coal being

carbonised increases slowly with temperature up to about 400C. It further
increases at a faster rate as the coal temperature is raised to about
800C. Above 800C the conductivity is expected to rise very rapidly up to
a maximum in the region of 1000-1100C. It may decrease slightly after that
temperature or remain steady at an approximately constant value.
Keeping in mind what has been mentioned above about the variations
expected in the value of conductivities of different coals or cokes, and
making use of the above conclusions and of the data reported in the
44
literature, these values for the effective conductivity are suggested.

They are to be understood as indicating the order of magnitude of the
conductivity of coal; they are not meant to represent actual values (see
Table 4.9 and Fig. 4.16).
Table 4.9. Suggested values for the effective thermal

conductivity of coal on carbonisation
Temperature Effective conductivity
C 10-3 W.cm-1.C-1
Room Temp. 1
400 2
700 9
800 15
900 50
1000 150
A similar trend has been observed for the variation of electrical

conductivity with the increase of the temperature of carbonisation.
Sinkinson's work indicated that conduction in coal on being heated is due
to free carbon liberated by the thermal decomposition of the hydrocarbon
gases evolved during heating [62]; which conclusion could lead one to
expect only a small increase with temperature of the conductivity in the
first stage of carbonisation, similar in fact to what we have found in the
case of thermal conductivity. This is further supported by the work done
by Koppers and his associates [63]. Investigating the possibility of using
the property of the electrical conductivity as a measure of the degree of
45
carbonisation of coke, they found that the conductivity increases markedly

with carbonisation temperature from about 400C to 1200C. The results
expressed as resistivity ranged from 0.0403 to 0.1561 cm, the lower
values being associated with the better cokes. It was concluded that ash
content, within its usual limits, is of slight importance only.
Similar results were found by Myer [64]; the resistance was found to
decrease as carbonisation proceeds.
Davis and Auvil [65] determined the electrical resistance of cokes

carbonised at temperatures ranging from 600 to 1100C. They found the
electrical resistance to decrease with temperature, with a marked change
between 700-800C. The average value for coke made at 600C was about
370,000 times that for coke made at 1100C. A logarithmic relationship fits
the data fairly well, although the constants of the expression for
carbonisation temperatures at and above 800c are different from those
below 800C. They also showed that the electrical resistance was not
directly proportional to volatile content, but was influenced by the
quality of the volatile matter. The volatile quantity changes between 700
and 800C. A rapid fall in resistance begins above 800C, which Davis and
Auvil considered to be in keeping with the conclusion of Koppers et al.
that the growth of graphite crystals proceeded rapidly at temperatures
above 800C.
From the above summary it is clear that a relationship between the

thermal and electrical conductivities of coal on carbonisation may exist.
Both vary in a similar manner with temperature increase, with 3 stages
recognised:
1. An early stage (up to about 400C) with the conductivities at low value,
the values increasing slowly with temperature.
2. Between 400 and 800C, both conductivities increase markedly with
temperature.
3. Above 800C the rate of increase becomes extremely high for both
conductivities. This is consistent with the rapid rate of crystallite
growth observed at about this temperature.
c. The effective thermal conductivity of coal carbonised to EHT

EHT as was defined above (Chapter 1) involves heating the coal charge
at higher flue temperatures, with the result that the rate of heating
increases, and the coke is heated to higher final temperatures. Both these
factors are expected to affect the structure of the coke and hence
influence its conductivity.
According to Mott [10] rapid heating, which extends the temperature

range of plasticity, probably enables crystallisation to proceed to a
greater extent, i.e. the conductivity would be of a higher value than it
would have been, had the coal been heated at the lower rates of heating.
Although, by a temperature of about 1100C, most of the amorphous

matrix would have disappeared, the crystallites continue to grow at higher
46
temperatures. From evidence shown by work on reheating coke (see below) it

seems that the growth of the crystallites can continue up to a temperature
of 1500C due to coalescing of the crystallites. We have already suggested
that beyond the temperature range 1000-1100C, the effective conductivity
of coke would decrease slightly or remain at an approximately constant
value. The natural increase of the effective conductivity due to the
continuous growth of the crystallites with temperature is offset by the
decrease of conductivity in the case of crystalline substances. Concluding
therefore we may say that the likely effect of EHT is to raise the general
level of the conductivity value.
Unfortunately, we have not been able to find any reported data relating
to the conductivity of EHT coke at the higher temperatures. The only
reported values above 1000C that could be found are those reported by
Rohde [42] which indicate a tremendous increase above 1000C. The
significance of these values is uncertain. In any case they do not go
beyond 1200C.
d. Effects of quenching on normal metallurgical coke

Coke, when discharged, is either wet-quenched with cold water, or
allowed to cool in an inert atmosphere. It is only to be expected that
subjecting the red-hot coke to the cold water or gas will have an effect
on its structure that may be irreversible.
The effects of wet-quenching will be discussed below and this will be

followed by a study of the effects of dry cooling.
Effects of wet-quenching on coke
Porosity is affected by wet-quenching. It seems evident, however, that

wet-quenching does not create new pores, but only enlarges existing ones. On
the other hand the micropores are hardly affected by water-quenching. A brief
outline of the cause of this effect of water-quenching on coke porosity is
given below.
We know from our laboratory experience that it is very difficult

thoroughly to penetrate a piece of coke with water. That the hot coke is able
to take up high percentages of water in the short quenching period is easily
explained by the fact that in cooling down, the gases contract thus sucking
the water into the innermost pores [66]. The water penetrates the pores, its
temperature rises rapidly to the point where steam is formed under pressure,
with the obvious result of serious fractures. Such fractures, however, are
not complete with the result that the coke will ride over the screens without
further disintegration [66. 67]. Hard metallurgical cokes are better able to
resist the thermal shock of wet-quenching and the stresses caused by it in
the coke lumps, as their lower porosity tends to minimise this effect [68].
The second important factor that was found to affect the effective
conductivity was the type of gas filling the pores. As water penetrates into
the coke pores, steam is formed which will have a serious effect on any
conductivity measurement of coke at low temperatures.
The effect of moisture on the conductivity is due to the fact that the
body's capillaries and pores are filled with water. In the presence of a
47
temperature gradient additional transport of heat will take place due to

migration of water (thermal moisture conductivity).
Sulphurous and sulphuric acid gases are liberated during wet quenching as
may be ascertained not only by smell, but by determining the sulphur content
of coke before and after wet-quenching [69, 70]. Deposits of salts of
alkaline metals at the surface of the coke are also eliminated on wet-
quenching [71].
Crystallinity may also be affected by quenching, and internal stresses may

be set up in the coke structure. According to Vikharev [59], if we assume
that, at the termination of the coking process, the coke possesses a
structure which is very nearly in a state of equilibrium, then as the result
of sudden cooling brought about by wet-quenching, a spontaneous tempering of
the given structure takes place. Consequently the structure can not possibly
regain the equilibrium corresponding to its normal temperature. As a
consequence of the cooling of the coke, a temperature gradient is set up
therein, and this introduces internal stresses, giving a residual supply of
strain energy.
Effect of wet-quenching on EHT coke
Raising the carbonisation temperature, and hence the temperature of the

coke when discharged decreases the moisture content of coke on quenching.
Apart from this it does not seem that raising the coke temperature has any
additional effect on the coke on wet-quenching.
The effective conductivity of coke at room temperature
The conductivity of coke at room temperature would be lower than the

conductivity of hot coke before quenching. At low temperature as we know, the
conductivity is dependent on the type of fluid in the pores and on the
porosity. Both of these are affected on quenching. The decrease in the
conductivity due to the increase in porosity is counterbalanced by the
increase due to the moisture conductivity.
The thermal conductivity as measured at room temperature would be lower

because of the lower temperature and hence the absence of any radiation
effects. Also, some reduction in crystallinity is possible on quenching.
Honda [43] reported a value of 136 10-3 W.cm-1.C-1 for compacts of coal
heated to 1000C, and measured at room temperature. Terres [35], on the other
hand, found the effective conductivity for his coke to be about 13 10-3
W.cm-1.C-1 at room temperature. This value is probably too low, and it does
not fit in with the values recommended for coke at high temperatures. It is
felt that 136 is of the right order of magnitude, though it may be slightly
on the high side.
1 1
A good correlation between and for a weakly-coking coal was found by

Honda [43], K being the thermal conductivity and La the crystallite size. The
coal compacts were heated up to a temperature of 3000C before the
conductivity was measured. A good correlation was also found between the
48
thermal and electrical conductivities of these same compacts. The value of

K/E (where E is the electrical conductivity) was about 0.0004 above 2000C and
about 0.0003-0.00034 below heat treatment temperature of about 2000C.
Effects of dry-cooling on coke
It has been claimed that dry-cooled coke is stronger than the normal wet-
quenched coke. Some experimental evidence has been found in support of this
claim. In any case it is well known that gas media possess far less tempering
or annealing properties than liquids, hence with dry-quenching the tempering
of the coke material is less likely to take place.
As the coke is of a hygroscopic nature, the dry-cooled coke will not be

free from moisture. Some moisture will be adsorbed by the coke. This however
does not penetrate the pores and can be driven off easily as steam [66, 72].
Other effects of dry-cooling include the removal of the sources of

incompletely-burnt material from the coke [71, 72].
When CO2 was used for cooling in the type of plant used at Ford's, the
coke appeared to suffer from the reversible reaction
CO2 + C 2 CO
the decomposition of the amorphous carbon on the surface of the coke

vitiating its appearance [69].
We have not been able to find any reference to measurement at room

temperature of the conductivity of coke that has been dry-cooled. As far as
the EHT coke is concerned, it is not expected that it will be affected on
dry-cooling in any way other than is expected for normal coke.
e. Effects of reheating the wet-quenched coke

As the coke is reheated to higher temperatures, its thermal conductivity,
as can be seen from equation 6, will depend on the porosity and the true
conductivity of the solid, which in turn depends on the structure of the
coke.
Below is a summary of the effects observed, on reheating normal wet-

quenched coke, on its structure and properties. Variations introduced by dry-
cooling and/or EHT coking will be dealt with later.
Porosity
Reheated coke was found by B.C.R.A. to have either the same apparent
density as the normal coke (as in the case of Maltby coal) or slightly lower.
The coke was discharged at 1000C, quenched and reheated to 1700C.
Measurements were made after wet-quenching it [56]. Polish workers found that
in general the total volume of micropores was reduced by the secondary
heating process [53]. Changes in surface area were reported by Erkin [54].
According to him the surface area of the coke at first increases and then
decreases, the turning point being the temperature at which the coke was
made. If such changes in surface area are taken to indicate expansion or
contraction, then it is to be expected that the bulk density will decrease at
49
first, taking into account also the loss of weight on heating, up to a

certain temperature, then it may either remain steady or start to increase
again. As will be seen later, weight is lost mainly between temperatures of
600 and 800C. Reactivity evidence also suggests that the porosity increases
to a maximum then it decreases again. Reactivity is closely related to
porosity.
From the above-mentioned observations it can be concluded that the

porosity increases with the temperature of reheat up to a maximum in the
region of 800C for normal high-temperature coke and then it decreases again.
The lower porosity observed by B.C.R.A. and the Polish workers is that of the
coke after having passed the porosity peak; the B.C.R.A. sample was heated up
to 1700C.
Such changes in the coke porosity will have an influence on the

effective thermal conductivity, but the effect of secondary heating on the
coke structure may be the more important factor. Coke, as we have seen,
consists chiefly of crystalline particles contaminated with and cemented
together by a hydrocarbon matrix. On heating such a material, it would be
expected that the effective thermal conductivity would increase with
temperature up to a maximum then decrease again. The temperature of this
maximum will depend on the relative amount of the amorphous material in the
system (see above, section 4.2a). The problem is further complicated in the
case of coke by the structural changes including the growth of crystals as
the heating progresses.
After considering the various changes on reheating, we came to the

conclusion that this maximum is in the temperature region of 450C. Two points
must be noted, however, before going on to discuss these changes. One is that
the rate of heating as well the temperature of the secondary heating may
influence the coke properties; in other words the time taken to reach the
desired temperature may affect the coke properties. Fair [55] reported that
both the interlayer spacing and the resistivity decreased with increasing
temperature or increased residence time. Secondly the thermal history of a
piece of coke is very important regarding the effects of reheating on it. A
piece of coke that is left at room temperature for sufficient time will not
be affected by secondary heating.
Coke strength
B.C.R.A. research found that the impact strength indices of the

reheated coke were lower than those of the normal high temperature coke. The
abrasion strength of the reheated coke, on the other hand, was not materially
different from that of the normal coke [56]. The compressive strength was
found to increase up to a temperature of 600-700C, then decreases up to the
final coking temperature of 1000C. Up to this temperature the variations in
strength are small. Above 1100C and up to 1300C a greater decrease in
strength results. Much greater decrease is also observed above 1300 and up to
1600C. The absolute value of the compressive strength becomes less than the
corresponding initial value for the unheated coke only at temperatures higher
than the final coking temperature. The compressive strength of a body
50
decreases as the crystal size increases. A correlation between the

compressive strength and the crystal size was found [59, 73, 74, 75].
The structural strength (or abrasion resistance) was found to behave

similarly on heating. It increased slightly with temperature up to about
600C, and then it decreased again up to 1000-1100C, the final coking
temperature. The absolute value becomes less than the initial value at
temperatures higher than the final coking temperature. Above 1200C there was
a greater decrease in strength up to 1700C, above which temperature the
decrease became much greater, In the range 1500-1700C the decrease was small
[58, 59, 73, 74, 75].
Theoretically the strength of a solid substance, in which there does

not take place any chemical reaction nor any structural changes, must
steadily decline when its temperature is raised. Tempering of the coke at the
moment of its wet-quenching causes the transition of the system into a
metastable state. The reheating of such a system gives, at the initial
moment, a picture of the algebraic sum of two opposed processes: that of
relaxation leading to an increase in the strength, and the natural reduction
in the strength of a solid body when the temperature is raised. This creates
a condition whereby the maximum strength of the body on reheating occurs
after the passing of a certain interval in the temperature scale [59].
A significant correlation between the strength and the crystal size was
observed (58, 74). Also, the structural strength, as measured by abradability
tests, was found to be influenced by the physical properties of coke such as
porosity and density [74].
Thus the strength after an initial increase up to a temperature of 600-

700C decreases again, the rate of decrease becoming faster above about 1000-
1100C, when the strength becomes lower than that of the ordinary coke.
Porosity also was found to pass through a peak in the temperature

region of about 800C.
Weight loss
Some weight loss was found on reheating the coke. Bogoyavlenskii [57]
reported values of weight loss varying from 1.1% at 1100C to 9.6% at 1700C.
Slightly higher values were found when the coke was heated up to 1100c (see
above). Part of the weight loss would consist of ash (Table 4.10). All the
mineral contents of coke are reduced on heating, some of them (P, K, Na, Mg)
become negligible. Iron is halved, others (Si, Al, Ca) decrease but not
greatly [58]. Sulphur was also found to be reduced after heating (Table
4.11). Some volatiles evolve on heating. This evolution begins intensively at
a temperature of 600C and reaches its maximum rate of change in weight at the
moment of incidence of the endothermic effect (about 820-860C) [59].
51
Table 4.10
Ash % on reheating coke

Temp. C
Bogoyavlenskii [57] Fukuyama [58]
Initial sample 10.0 9.6
1100 9.8
1300 9.1
1500 8.4 9.0
1700 7.0 9.4
2000 6.7
Table 4.11
Temp. C Sulphur % on reheating coke

Bogoyavlenskii [57] Fukuyama [58]
Initial sample 1.57 0.49
1100 1.55
1300 1.26 0.45
1500 1.05 0.42
1700 0.73
Above the carbonisation temperature (1000C) it seems likely, from

considering the weight losses as reported in [57, 58], that an evolution of
volatile matter takes place which continues up to 2000C, which is the highest
temperature of secondary heating studied.
So, again in the temperature region of 600-800C, changes in the coke

are indicated. (See also Ref. 59, and Mott [10] who found that on reheating
coke there was some gas evolution at the same decomposition temperature as on
the first heating, but the rate was lower. It is not clear to what
temperature the heating was taken, but it appears to be a relatively low
one.)
Crystallinity
According to Bogoyavlenskii [57] the ordered carbon content is

increased to 90-95% by heat treating to 1300C and it reaches one hundred per
cent in the case of heat treatment to 1500C. Below about 1300-1500C there is
a growth of the crystallites, which is to a considerable extent due to the
transition of the unordered part into a condensed aromatic, two-dimensionally
ordered form. Above 1300-1500C there is a further growth of the crystallites
which is due this time to their joining together (coalescing). The
interplanar spacing, calculated from the Woolf-Bragg equation, decreases as
the temperature increases. The change can be expressed approximately by the
straight line equation:
D002 = 3.57 0.00007 T,
where T is the temperature in C. True graphite is not formed at the

temperatures investigated. It requires temperatures above 2100C.
Vikharev [59] reported that the distance between the crystal faces
(d002) increases up to 400C then decreases up to 1000C. Immediately after
1000C the temperature of coking, the sharpest reduction in the distance
52
between the crystal faces is observed, and this continues up to 1300C. This
distance becomes constant after 1300C and up to 1500C.
Fukuyama [58] found that the thickness of the crystallites along the C-
axis increases with temperature. This increase continues up to 1500C. Above
1500C the rate of increase slows down, but after 1700C the increase in
crystalline thickness proceeds very fast.
In Table 4.12 a summary is given of these observations. Particular

attention should be paid to the change round about 400C reported by Fukuyama
[58].
Table 4.12
Temp. c Reference
57 59 58
-400
400-1000
1000-1300 90-95%
1300-1500 100%
1500-1700
1700-2000
Growth of crystallites with temperature of reheat
decrease, increase, greater increase, no change
Electrical resistance
This is a very sensitive property which reacts to the slightest change

in the coke structure. It decreased as the temperature increased up to about
350C. This was followed by a slight increase in the range 350-550C. This
anomaly undoubtedly points towards occurrence of structural changes in coke.
Above 550C the resistance continues to decrease. At about 1100C a
commencement of greater decrease of resistance was observed. Tests were done
up to 1200C [59]. Again, changes are indicated in the region 350-550C.
Moisture
Surface moisture is expelled early in the secondary heating process as

steam. Water in the interior of the coke is more difficult to expel.
According to Beebee [66] over-quenched coke charged into the furnace

must retain its moisture until the coke gets into fairly hot zones. When this
moisture is driven out of the interior of the coke pieces, it is heated to a
point where, in the presence of so much red-hot carbon, it is instantly
dissociated. That this takes place we know from the increased hydrogen in the
gases when using over-quenched coke. The nascent oxygen, just liberated,
eagerly combines with carbon to form CO or CO2 depending on the local
temperature.
The reactivity was measured for coke heated to high temperatures [58]. Kimura
[60, 60a] measured it by gas chromatography and found that it tends to rise
with temperature of reheat; he also found it to be closely related to
porosity.
53
Thermal effects
The stored residual energy, due to wet-quenching, is dissipated as

heat, as coke is heated in the temperature range 350-550C. An endothermic
effect is observed in the range 820-860C. This effect is characteristic of
all wet-quenched cokes coked at 1000C [59].
In addition to the above-mentioned effects, secondary heating causes an

increase in the extent of cracking. Zaslavskaya indicated that during the
heating of coke, the quantity of long cracks increased by 14-20%, with a
simultaneous increase in the total extent of cracking [73]. A piece of coke,
on being heated, becomes hotter at the outer surface than at the centre, so
that stresses leading to the disintegration of the lump could be set up. This
breakdown might be overcome by reducing the lump size of coke [54].
It was suggested that such increased breakage arose from the

variability of the thermal expansion properties within the coke pieces, and
that it becomes less pronounced with increasing temperature [73].
Summary of the secondary heating effects:
Property Temperature range where structural changes are indicated

Strength 600-700C
Porosity 800C
Volatile evolution 600-800C
Crystallinity 400C
Electrical resistance 350-550C
Exothermic effects 350-550C
Endothermic effects 820-860C
The close correspondence in the case of the exothermic release of heat

and the anomaly in the electrical resistance, both of which take place in the
temperature range 350-550C, is quite significant. In view of this and the
variation of crystallinity at 400C, it would be reasonable to suggest 450C
as the temperature for the effective conductivity peak of the reheated coke.
Other changes are also indicated around about 700C, including the start of
the decrease in porosity. Some anomaly in the thermal conductivity curve may
be noticeable at about 700C.
Consideration of the present thermal conductivity measurements
(See section 4.1 above)
No measurements were made below 200C, as the apparatus used for

measurement was designed for higher temperatures only. For the conductivity
of the reheated coke at low temperatures below 300Cthe values reported by
Wicke [36] and Batchelor [39] seem to be too low.
The conductivity of normal wet-quenched coke
For coke made at a temperature of 1050C, a peak was observed in the

conductivity versus temperature curve (Test 2) at about 300C, which is lower
54
than the temperature range expected. After increasing to a value of ~ 260

10-3 W.cm-1.C-1 the conductivity decreased to a steady value of the order of
150 10-3 W.cm-1.C-1. A higher average value (~ 200) was obtained on cooling
the sample (Test 12).
For Test 3 the coke was discharged at a final temperature of 1050C but
the rate of heating was faster than in the previous case. The conductivity
peak was at about 450C. But there was in addition to this peak a second peak
at about 770C. We have not been able to account for this second peak. But it
is well to remember that the electrical resistance curve with temperature
shows two peaks also, the second one being at 550C. Attention has already
been focussed on the changes around 700C which takes place on reheating the
coke (see above). But why this second peak should be observed only in this
case and not in the earlier tests cannot be explained at the moment. When the
sample was heated in nitrogen the first peak was less evident than before,
whereas the second peak became more conspicuous (Test 6).
The only possible effect of introducing the nitrogen stream is to drive

out the volatiles that may evolve. We know that the volatile evolution is at
its maximum around 800C. This is possibly accompanied by some heat
absorption.
The conductivity of dry-cooled coke
It is expected that the energy release, observed on reheating wet-

quenched coke, will be absent on this case of reheating dry-cooled coke. This
may reduce the prominence of the peak observed in the region 350-550C.
The peak observed at 430C (Test 8) is indeed of moderate prominence,

and the conductivity rises to about 100 10-3 W.cm-1.C-1. A similar small peak
is also observed at 670C. The curve on the whole is smoother than those
obtained on heating wet-quenched coke. On cooling the same general
observations are true (Test 13).
The conductivity of reheated coke
This is coke that has been reheated after being quenched, quenched
again, then reheated for the purpose of measuring its conductivity at the
various temperatures. The coke sample of Test 9 had been heated to about
1550C. It is interesting to note that the conductivity curve is smooth
showing almost no peaks, and the conductivity increases from about 50 at 270C
to about 150 10-3 W.cm-1.C-1 at 800C. This is quite consistent with the fact
noted before of the importance of the thermal history of a piece of coke
regarding the effects of reheating on it. It is to be expected that a piece
of coke that is reheated once and cooled is not affected on its being
reheated again.
The conductivity of EHT coke
The fact that the conductivity curves of EHT cokes that had been wet-
quenched show peaks similar to those observed for the wet-quenched normal
cokes, but absent from the curves of the dry-cooled and the reheated cokes,
indicates the connection between the tempering of the coke on wet quenching
55
and the appearance of such peaks. Test 4 shows a peak at 550C. A similar peak
is shown by Test 5 at about 400C, and the conductivity then settles to an
approximately constant value of about 150 10-3 W.cm-1.C-1. Similar results
were obtained on cooling the coke, with the peak at about 350C (Test 11).
In conclusion, it is clear from what has been said above, that the
conductivity of wet-quenched coke, both normal and EHT, increases with
temperature up to a maximum then decreases again to settle at a constant
value. The peak was observed in the region of 300-500C.
Average values of the effective conductivity at different temperatures

of reheat are suggested below:
Suggested value
Temperature C K/10-3 W.cm-1.C-1
200 80
300 90
400 125
500 160
550 180
650 160
700 155
900 160
1000 160
For dry-cooled coke the value of the conductivity varies between 50 and
100 10-3 W.cm-1.C-1.
For reheated coke there was a continuous increase:
300C 75 10-3 W.cm-1.C-1

400 100
500 125
600 140
800 150
It is quite evident that the value of the conductivity is at
approximately 150 10 -3
W.cm .C -1 -1
for all cokes at the higher temperatures.
The conductivity of graphite is much greater than that of coke. For
comparison the following values are taken from Jakob [51]. They refer to
Acheson graphite.
150 1680 10-3 W.cm-1.C-1
300 1541
500 1264
700 934
with the conductivity decreasing with temperature, as for any crystalline
material.
Fig. 4.17 shows the recommended curve for the conductivity of reheated
wet-quenched coke and the experimental results obtained.
The values suggested for use in the oven heat transfer calculations are
the same as those suggested for the coal being carbonised (see above). The
56
results obtained using such values will be considered in the second part of
this thesis.
57
Part 2. Analysis of heat transfer in a coke oven
Chapter Five
Literature survey
Despite the increasing importance of heat transfer analysis in coke
ovens, little work has been done up to date on it.
Millard [40] seems to have been the first to attempt a complete

analysis of the heat transfer in coke ovens. His aim was to determine whether
Fourier's heat flow equation provides an adequate description of the
temperature conditions in a coke oven. The equation he used for the
calculation was:

+ =

Where T is the temperature, x is a space co-ordinate, is time, K is the

thermal conductivity, R is the density and C is the specific heat at constant
pressure. The assumptions made for the calculation were:
1. That the heat transfer is one-dimensional. This is reasonable "as the

dimensions of the walls are large with respect to their spacing". The
oven width was 16 inch.
2. Unsteady conditions were assumed.
3. Heat transfer was assumed to take place through the charge by
conduction rather than radiation or mass transfer.
4. The charge was assumed to be homogeneous and isotropic throughout the
whole carbonisation period.
5. The thermal properties. The effective conductivity was deduced from
measurement of the temperature-difference between the inside and the
outside of hollow cylindrical specimen for a known heat flux. The
results were shown in Table 2.10, Chapter 2. The value for the volume
specific heat (RC) used in the calculation below 450C was that measured
for coal. Above 450C the value used was that measured for the resultant
coke. The specific heats were determined at room temperature only and
no account was taken of the increase of specific heat with temperature.
6. In a first trial, the rate of heat generation (Q) in the oven was
neglected. The results obtained for the temperature distribution in the
oven did not match the measured values. In a second trial the rates of
heat generation (or absorption) were estimated from a detailed study of
a pair of adjacent points in the coke oven. Heat absorption was assumed
below 700C, and heat liberation above 700C.
7. The water in the green coal provides a heat transfer medium at low
temperatures. It evaporates from hot regions and condenses in the
nearest region at a temperature of less than 100C. As soon as the
entire oven is at or above 100C water is regarded as only delaying
heating in the region in which it occurs until its latent heat of
evaporation has been supplied by conduction from hotter parts of the
charge.
An analogue technique of solution due to Liebmann was used where an

electric model is made of the system to be studied and conditions in the
analogue are varied to correspond to changing conditions in the system being
studied. The calculation was carried out over half of the oven and the
experimentally-observed temperature histories of two points, one at the oven
58
wall and the other at the centre, were used as boundary conditions to the
heat flow equation. The results reported closely agreed with the measured
data. It is to be noted that the values that it was necessary to postulate
for the rate of heat generation were very large. Apart from the reasons that
the author suggested for this, namely the effects of heat transfer by
convection and radiation, an underestimation of the effective conductivity at
the higher temperatures may have also been part of the reason.
Some work on similar lines has been done by Japanese workers. Their main
interest, however, seems to lie more in the heat transfer to the charge from
the flues rather than in the heat transfer across the charge.
Suga {76} and his associates calculated the temperature distribution in a

small test coke oven. The simplified Fourier equation was used for the
calculation:
2
= .
2
where D is the thermal diffusivity.
The assumptions made for the calculation were:
1. Heat transfer in the heating walls and in the oven charge in both the
vertical and in the chamber-length directions were ignored, i.e. the
problem was simplified, as in Millard's solution, to a one-dimensional
problem.
2. Unsteady conditions were assumed.
3. Heat transfer through the oven charge was assumed to take place by
conduction only. The charge itself was assumed to be homogeneous and
isotropic.
4. Heat generation and absorption were neglected.
5. The thermal properties were assumed to be constant.
6. Heat transfer to the charge from the flues was calculated.
The Schmidt graphical method was used for the calculations. The results
were in fair agreement with the measured values.
A similar approach was undertaken by Tashiro [77]. According to him

there was a considerable gap between the calculated values and the absolute
values, although the essence of the heat transfer was adequately
reconstructed. It was suggested that improving the accuracy of the
calculation, for example by assuming temperature-dependent thermal
properties, may lead to results that approximate even more closely to the
conditions in the coke ovens.
German workers seem to have done some work on this problem also. Rohde
[42] calculated temperature-time curves at different positions for a
commercial oven with the aid of an extended Fourier differential equation,
and matched them with the measured temperature-time curves at different
positions during the carbonisation of coal in practice.
Hofherr and Simonis [78] assumed for the purpose of their calculation
that the coal charge in an oven is a homogeneous isotropic body and that the
departures from this assumption are expressed in changes in the temperature-
dependent thermal properties. They also assumed the heat transfer process to
be one-dimensional and that heat transfer takes place by conduction only. All
other modes of heat transfer are to be taken into account in the value used
for the effective thermal conductivity. Unsteady conditions were assumed. The
thermal properties, and the rate of heat generation or absorption, were
assumed to be temperature-dependent. The equation used for the calculation
was based on the difference method:
59
1 1( ) 1( +1) 1( )+ 1( 1) .1( ) 1( 1) 1( 1)
2() = + + 1 () +
1( ) 1( ) 2 2 2
1() (1)
Where: T1 and T2 are the temperatures at times and +.
J represents the position, where T(J+1) is the temperature at distance

x from T(J).
Q is the rate of heat generation or absorption per one heat source or

sink and n is the number of these sources or sinks.
For the boundary conditions the wall temperature was measured and
different formulae were suggested for its variation with time depending on
the flue temperature. The drying of the coal was represented in the
differential equation by a heat sink.
The heat generation or absorption terms based on chemical and physical

reactions apply over quite definite temperature ranges. The initial and final
temperatures of these ranges were determined from the results of
devolatilisation tests. A net endothermic reaction was assumed in the
temperature range 400 (start of softening) to 650C (end of semi-coke
formation) and a net exothermic reaction in the temperature range 650-950C.
The endothermic heat, on the other hand, was supposed to be dependent on the
carbonisation conditions. The change in the bulk density with temperature was
determined from the weight loss during devolatilisation of the coal and from
the shrinkage of the charge. The specific heat was calculated from formulae
given by Fritz and Kasperczyk. It was found that beyond 1100C the value
remains constant.
The results calculated were in good agreement with the measured values.
As the carbonisation advanced, the calculated temperatures in the charge were
lower than those measured until equality was attained again at the end of the
carbonisation.
Very similar treatments were reported by Kasperczyk and Simonis [79],

and by Rohde and Kasperczyk [80]. Because the coal charge was neither solid
nor homogeneous the simple conduction equation was not applicable. For
simplicity it was assumed that an infinitesimally small element of volume of
the charge behaves as a solid homogeneous body; heat transfer in the charge
can then be described by:
()
= () + 1 () (2)
()
where the subscript K refers to the charge. This equation was used by Rohde
[42]. It was solved to give equation 1, given above, using the same
differential method.
The boundary conditions were given by the heating wall temperature and
the centre-of-charge temperature [79]. As has been noted by Rohde [80] the
calculated temperature fields depend on the boundary conditions used.
Litterscheid [81] in his calculations did not use the oven wall temperature
as the boundary condition; instead he used the flue temperature because it is
more accessible to measurements and subject to such great fluctuations during
the coking process.
In conclusion, it is clear from what work that has been done, that good
results are obtained for the temperature distribution curves in coke ovens
using the Fourier differential equation for heat conduction. Our aim in this
60
part of the thesis is to examine the effects of introducing temperature

dependence of the thermal properties, and particularly of the thermal
conductivity, into the heat flow equation.
61
Chapter Six
Analysis of heat transfer in coke ovens

The heat transfer situation can be described adequately, as we have
seen in Chapter 5, by the differential Fourier equation. The accuracy and the
reliability of the temperature distribution calculated from this equation
will depend on the assumptions made for the calculation. The problem is in
fact so complex that it can not be solved at all without making a good many
assumptions and simplifications.
Coke ovens, as is well known, are rectangular

chambers of narrow width L (see Fig. 6.1). A fuel gas
is burnt in flues adjacent to the walls. Heat is
transferred by radiation and convection to the oven
walls; then it is conducted across the walls, and is
eventually radiated to the coal charge. The coal is
charged into the oven from the top. Just before
charging the wall temperature would be at its highest
value, but immediately thereafter it drops down to a
low value. As the charge is heated from both walls at
the same time, it is dried and then slowly decomposes
to form semi-coke and later coke. The isotherms are
more or less parallel to the walls and they move
towards each other and towards the centre of the oven
as the heating proceeds. At any one time during
carbonisation the coal charge will consist of a number
of adjacent and parallel layers with different
properties and characteristics.
This is in brief what takes place essentially on carbonisation of coal

in coke ovens. During the carbonisation the coal charge changes from being a
packed bed of particles into a continuous and viscous fluid that is in turn
transferred into a porous solid. At no time during the carbonisation would
conduction be the only mode of heat transfer. But in order to use the Fourier
differential equation this assumption must be made, that conduction is the
only mechanism of heat transfer. Hence, accepting this assumption, the most
general equation for three-dimensional unsteady conduction is [82]:

+ + + = (, , , ) (1)

Where: R is the density

C is the specific heat
x, y, z, are space coordinates
is time
T is temperature
fx, fy, fz are the heat fluxes across three planes perpendicular
to the axes of the coordinates.
This is the equation for heat conduction in a solid (implying

conduction only) that is isotropic, homogeneous (i.e. with position-dependent
thermal properties) with heat generation (Q) and variable (temperature-
dependent) thermal properties.
62
The assumptions made in order to simplify and hence be able to solve

this equation are:
1. That heat transfer takes place by conduction only, i.e. the coal charge
is assumed to be a continuous solid.
2. That it is one-dimensional heat conduction flow.
3. That the charge is isotropic and homogenous.
4. That expansion or contraction of the charge during heating is
negligible.
Two further assumptions will be made in the first trial solution, namely
that there is no heat generation or absorption, and that the thermal
properties are constant and independent of temperature.
These assumptions will be dealt with in more detail later, but first a
brief look at the carbonisation process in coke ovens.
6.1 Carbonisation in coke ovens
As the wet coal charge is heated, it passes through five stages before
being fully carbonised:
1. The coal is first dried (up to 100C). The adsorbed gases and water
vapour are also expelled.
2. The dry coal decomposes slightly on further heating, softens and
swells.
3. At above 400C the decomposition is at its maximum, and the coal fuses
to form a swelled plastic mass.
4. At about 470C the plastic mass begins to re-solidify emitting some
volatile matter all the time.
5. A solid dull black semi-coke is formed, which decomposes from about
600C, decomposition reaching a maximum at 700C, shrinking, hardening
and fissuring meanwhile to form true coke.
1. The wet green coal: Coal as charged up to a temperature of 100C.

During this stage the coal charge is dried, and it may also expand
thermally. Most of the expelled moisture passes inwards towards the centre
of the charge where some condenses. Some surface moisture will be retained
to high temperatures during rapid heating of the coal. During slower
heating dewatering takes place at the lower temperatures [83].
Some carbon dioxide and methane will also be expelled during this
stage. These were probably adsorbed on the coal and escape on heating
[84].
2. The dry coal charge: From 100C up to the first critical temperature of
decomposition Tc at about 400C.
During this stage the coal decomposes slightly, this being possibly
accompanied by some softening. No decomposition, however, is noted below
about 200C [10]. According to Davis [88] this initial carbonisation stage
appears to continue the natural process of coalification by concentrating
the carbon and eliminating the oxygen. At temperatures up to 300C, carbon
63
dioxide and water vapour are almost the only products which distil from
the coal.
The major part of the free hydrocarbons is liberated between 220C and
300C. According to Mott [10] occluded oil vapours are liberated at
temperatures below Tc and are adsorbed on the surfaces of coal particles,
whence they are removed by entrainment when the rate of gas evolution
becomes sufficiently rapid (see also [85]).
Solvent analysis of a coking coal that has been heated to about 325C
(i.e. below its critical temperature Tc) shows that from 2 to 4 percent of
an oily extract can be obtained with ethyl ether, whereas the unheated
coal yields but a trace of extract to that solvent. This oily extract
comprises resins and hydrocarbons liberated from the coal but adsorbed
within it [10]. King and Willgress [86] also distilled small quantities of
oils from coking coals at 215C.
It is likely that the initial softening of the coal follows an initial

decomposition. This initial softening may also be preceded by some
contraction which continues up to the temperature of first fusion or
swelling.
3. The plastic stage:
During the preceding two stages, no major changes in the chemical and
physical properties of the coal take place. But with the onset of
maximum volatile evolution at Tc such changes occur and the coal
structure is markedly affected. Hence it is this stage of structural
changes that is the most important of the carbonisation process. This
stage continues up to the temperature of re-solidification (Ts) at about
470C. During this stage the coal decomposes rapidly with copious
evolution of volatiles; it is also fluidised to form a plastic layer,
which is eventually re-solidified at Ts.
Volatile evolution:
Paraffins and olefins, with some hydrogen, are evolved. Later,

naphthenes evolve also. Roberts [85] found that ethane, propane, butane and
higher members of the paraffin series formed a large proportion of the gases
evolved below 450C. The plastic stage is also marked by the appearance of
phenolic and aromatic compounds in the oils. These are re-adsorbed, partly on
the surfaces of the particles from which they have been evolved, but mainly
on the surfaces of adjacent particles [10].
The larger portions of the volatile products evolved passes upwards

through the hot coke rather than through the cold coal, and is decomposed:
naphthenes and paraffins are converted to aromatic compounds; higher boiling
hydrocarbons are cracked down to more volatile ones, the permanent gases,
hydrogen and methane, and carbon which accumulates as a thin cemented layer
on the exposed surfaces of the coke. This carbon is a hard graphitic form
which imparts a silvery sheen to high temperature coke.
The smaller amount of gas evolved on the coal side of the plastic zone
finds its way up through the cooler inner layers of the coal. It consists
essentially of the primary decomposition products of coal, which are formed
up to its temperature of fusion, and a considerable proportion of steam. The
sensible heat in this gas is consumed in heating the coal and evaporating the
moisture from it. Since the temperature of the coal is lower than that of the
plastic zone, some volatile products are condensed. The uncondensed gas
64
emerges from the top into the heated space below the oven roof. There
cracking reactions commence [84].
According to Ellis [87] the activation energy for the coal

decomposition during the plastic stage was found to be about 50 k cals per
mole. This same value was found by two different methods. Van Krevelen
measured the volatile matter emitted from coal over a wide range of
temperatures, and Bronowski et al. measured the production of semi-coke in
the fluid range. This value found for the activation energy is about the same
value as that quoted for breaking the carbon-carbon bond in the thermal
decomposition of mineral oils, and it seems reasonable to assume that this is
what is happening in the coal decomposition reaction when large molecular
complexes break away from the coal substance.
Some of these complexes of low molecular weight volatilize and appear

as gaseous and liquid products, and those that remain again polymerise,
although there is little tendency to fusion of the aromatic rings until the
temperature rises above 600C [88].
According to Brown [89] the aliphatic or alicyclic material is removed

most probably by simple distillation and chemical decomposition. Hydrogen-
bonded phenolic groups are also eliminated, the change being most marked in
the temperature range 460-550C. The data suggest that the formation of
carbon-carbon cross links between the aromatic systems accompanies the loss
of aliphatic groups.
Softening and swelling of the coal particles:
There is no agreement among authors on carbonisation on whether the

softening of coal particles precedes decomposition, accompanies it, or
follows it. According to Fitzgerald [90] the initial softening follows an
initial decomposition. Softening itself may be due to a chemical reaction in
which part of the solid coal is decomposed into a fluid product. Mott [10]
also maintains that the softening of coal does not precede the evolution of
gas. Porter claims that decomposition with most coals, whether coking or non-
coking, appears to begin coincidentally with softening [91]. Finlayson, on
the other hand, assumes fluidisation to precede active decomposition [92].
The theories advanced to explain the plastic behaviour of coking coals

are not less contradictory. But it seems, in general, true to say that the
coal particles, after some initial decomposition, swell and soften. The pores
between the particles will be filled, but the total volume being constant in
a coke oven, pressure is built up which may cause surface flow and further
fluidisation. The swelling of the particles may be due to their being
inflated by gases evolving within them.
At one time it was believed that coal melts homogeneously on

carbonisation. This view is rejected nowadays. It is now accepted instead
that only a fraction of the coal causes softening and that the fluidisation
phenomena is that of plastic surface flow rather than of true fusion. There
is no agreement, however, on whether this fraction is a carbonisation product
or exists as such in the coal.
65
According to the coking principle theory there is present in coking

coals a specific coking principle which is responsible for the coke
formation. This coking principle may be composed of bitumens and has the
property of melting when heated. During carbonisation it melts and fills in
the void space in the coal charge. Also decomposition of the coal sets in
with the melting of these bitumens. The gases and vapours which are evolved
are prevented from escaping by the viscous condition of the fluid mass. Thus
a pressure is generated inside the coal charge which depends on the character
of the bitumens present and the coal structure. The internal pressure
produced in the fluid mass assists in its consolidation into the voids
between the coal particles. The swelling observed is an index of this effect
[93]. Dryden [94] suggested that lower molecular-weight polymers in a coking
coal achieve mobility without decomposition on being heated, and his
experiments indicate that only some 10 per cent of the coal material behaves
in this way. This small fraction of fusible material is insufficient to act
as a continuous fluid in which the remainder of the coal is dispersed. It is
therefore presumed that the fusible fraction acts as a lubricant of the
infusible structures.
According to Finlayson [92] the initial consequence of heating is a

degradation process which produces a small quantity of material of molecular
weight low in relation to the coal , little of which evaporates at 381C. This
degradation product is formed largely within the microporous structure of the
coal particles, through which it diffuses to the exterior surface. Its
presence within coal particles renders them deformable, and its eventual
accumulation on their external surfaces plasicizes the mass. Slow
accumulation of the fusible material results in local envelopment of small
groups of particles in continuous liquid. A slow evaporation of low
molecular-weight material within such a group results in the formation of a
bubble. This process continuing, colonies of expanding bubbles are formed, so
that eventually the entire coal mass is a foam comprising an increasing
number of bubbles whose cell dimension increases, and whose cell-wall
thickness decreases with time.
According to Mott [10] the swelling of a piece of coal is effected by

the evolution of volatile matter from it whilst it is plastic. The plasticity
appears to be induced primarily by the pressure of the gases causing surface
flow at the moment when, under the action of heat, the molecules at the
surface have attained a degree of freedom comparable with that obtaining in a
liquid. Sufficient resistance must be offered to the escape of the volatiles
to develop a pressure high enough to cause surface flow and to form a porous
structure. Such a resistance is afforded mainly by films of oil and tar (part
of the volatile matter) adsorbed at cracks and partly-formed pores so as to
seal them.
In coke ovens, within the plastic layer, the tendency for coal
particles to expand (beyond the range given by the void spaces in the charge)
is checked by the same tendency of the surrounding particles. Only in the
uppermost layer of the charge, therefore, is there full freedom for upward
movement, and the spongy coke formed in consequence is but a thin layer on
the top of the charge. This upward movement is small, and broadly-speaking
the formation of coke can be considered to be taking place at a constant
66
volume. A swelling pressure thus develops which may affect the coal
plasticity [10].
At the end of the plastic state there is a sudden release of the

imprisoned volatiles when the seals are ruptured.
A more quantitative description of the changes in the plastic stage has

been given by Van Krevelen and others. They proceeded from earlier
suppositions that the decomposition may be distinguished by three successive
reactions: formation of an unstable intermediate phase (metaplast) which is
partly responsible for the plastification, and transformation of this
intermediary into semi-coke and finally into coke:
where K1, K2 and K3 denote the respective reaction velocity constants.

Reaction 2 (Metaplast semi-coke) describes the re-solidification of the
plastic system. The evolution of gas causes the coal to swell.
Naturally, such an interpretation is much too simple to provide a

complete description of the complicated decomposition process. It is more
appropriate to regard it as a mathematical record [95].
Crystallisation:
We have already (in Chapter 4) referred to the crystallisation which

takes place during this plastic stage. This crystallisation is favoured by
the coal fluidisation where orientation of the carbon atoms towards the
graphitic form occurs [10].
With further heating the plastic zones move inward. The volatile
products which were condensed on the coal are partly re-vaporised and partly
fused into the plastic mass [84]. Finally the two plastic zones meet forming
a plastic envelop. This prevents further escape of gas evolved by the coal
lying within the envelope and a gas pressure is built up which is eventually
released suddenly by its rupture [96].
4. The semi-coke stage

At about 470c the coke starts to solidify to form eventually a black
dull solid with a bubble structure known as semi-coke. The solidification
is achieved by a process of nucleation and growth of spherical bodies in
the plastic layer [97]. It is widely believed that the medium-sized
molecules forming the plastic phase are cracked, and the heavier fractions
link together to form the larger molecules of which semi-coke is formed
[96].
5. The coke stage

The semi-coke formed after solidification begins to decompose, the
gases evolving escaping through the network of open pores. There is a
considerable loss of volatile matter, mostly gaseous, and this loss causes
the structure to shrink. Cracks are formed which may weaken the coke.
67
Eventually at about 900-1000C true coke is formed, which is less reactive

and much harder than semi-coke.
Volatile evolution:
Volatiles continue to evolve from the coal after its solidification. At

about 700C, however, there appears a very definite change over from the
evolution of hydrocarbon gases to the evolution of hydrogen and some carbon
monoxide.
At temperatures above 1000C there is still a certain amount of

hydrogen emitted, the main phenomena in this stage however is concerned with
changes in the layer structure of coke [87]. Graphitisation continues after
solidification, with an increase in the size of the crystals above 800C.
According to Davis [88], there is during this stage a large evolution of free
hydrogen, representing that which has formerly held the carbon rings separate
from one another. With the removal of hydrogen these carbon rings condense,
and X-ray diffraction studies have shown how this condensation has built up
plate-like crystals which, if carbonisation is sufficiently prolonged,
develop into a graphitic structure.
The continuous loss of volatiles results in continuous shrinking of the

solid which may amount to 10% in linear measure. This contraction causes the
fissuring of coke. The temperature drop from the walls of the oven to the
centre results in a considerable differential shrinking, and it is this,
under the conditions of restraint, which causes the fissuring [87]. With the
loss of volatiles and the shrinkage the specific gravity of the coke
increases.
With increasing temperature the coke tends to pull away from the oven
walls, and shrinkage cracks develop, which run from the oven walls inward
towards the centre of the coke mass. The junction, where the two plastic
zones meet, appears as a vertical crack running lengthwise through the oven
at the centre of the charge. When an oven is pushed, the coke divides
vertically at this crack [84].
Thus, during carbonisation of coal, three major stages can be

recognised:
1. The coal stage, consisting of a bed of coal particles.

2. Plastic stage, where the coal behaves as a viscous fluid.
3. Coke stage, where the coal becomes a porous solid.
Carbonisation stages in the coke oven:
The different stages of carbonisation at any one time in the oven

depend on factors such as the rate of heating and the flue temperature.
What follows below is an attempt to draw the general picture of what

goes on in a coke oven step by step during the carbonisation process (See
Fig. 6.2):
In Step (1) the oven immediately after charging is represented. The charge
consists of wet coal.
68
69
In Step (2) the charge is represented just before the formation of a plastic
layer. The moisture expelled from the wet coal passes inwards to the cooler
parts of the charge and can be considered as another mode of heat transfer.
In Step (3) the charge is represented just before the formation of semi-coke.
In Step (4) the charge is represented just before the formation of coke. The
temperature at the centre starts rising above 100C with the complete drying
of the charge. Volatiles evolved from the plastic layer pass to the semi-coke
layer where they decompose or crack. Some volatiles pass to the coal side
where they assist in heating it.
In Step (5) the charge is represented at the time of the joining of the two
plastic zones. Coke is formed near the walls.
In Step (6) the plastic layer is completely

transformed into semi-coke.
In Step (7) the carbonisation is complete and the

charge becomes true coke.
6.2 Assumptions made for the heat transfer analysis
1. Heat transfer is one-dimensional
Apart from the main flow of heat in the coke

oven, i.e. from wall to charge (A direction), there
may be some heat flow in the vertical direction (B
direction) or along the length of the oven (C
direction). The average temperature difference in these two directions (B and
C) is quite small compared with the main temperature difference (along the A
direction). According to Tashiro [77] this is about 25C/m (n B direction )
and about 5C/m (C direction) as compared to 3000C/m for the A direction.
According to Suga [76] the temperature difference in the vertical (B)

direction varies from about 10C to about 120C per (3m) in the charge centre
(or about 36C/m); near the wall it varies from about 60C to about 130C per
3m of oven height (or about 23C/m). It was predicted by the same writer
(Suga [76]) that the vertical temperature difference was even less for actual
commercial-type ovens.
Because of this insignificant heat flow in both directions (B and C) as

compared to heat flow in the A direction, workers on heat transfer in coke
ovens assume the heat flow to be one-dimensional (Chapter 5).
The relative importance of heat flow in the two directions depends to a

great extent on the carbonisation conditions. In order to estimate the error
of making the one-dimensional heat flow assumption in our calculation, some
measurements of temperature in the various directions need to be made in the
oven. Unfortunately such measurements are not available.
Factors on which the vertical (B) temperature difference depends:
a. Position of burners, etc.

70
b. Effect of refractory. Suga [76] found the vertical temperature

difference along the surface of the oven wall to vary from 100c using
silica brick to 70C when fireclay castable mortar was used.
c. Effect of oven height. Suga [76] found that with a flame length of
6.9m, the vertical temperature difference along the wall surface varied
from 140C with a chamber height of 4.6, to 350C with a height of
9.0m. Similar results were reported by Tashiro [77].
d. Effect of using a recirculation system to reduce the vertical
temperature difference. According to Suga [76] and Tashiro [77], for a
flame length of 6.9m, the vertical temperature difference in a 6.8m
oven is 240C, while this suddenly changes to 40C when 15% combustion
gas is recirculated, i.e. circulation reduces the vertical temperature
difference considerably.
e. Effect of reversing time. Shortening the reversing cycle causes the
vertical temperature difference to increase [76, 77].
Reversing time Vertical temp. Difference
10 mins 200C
30 mins 100C
f. Effect of wall thickness. Wall thickness was found not to affect the
vertical temperature difference [76].
g. Effect of carbonisation time. Fig. 6.3 shows the variation of vertical
temperature difference with time. On the wall surfaces the difference
reaches a maximum before the end of coking (after four to six hours, a
result which is similar to commercial data), whereas at the centre it
has been observed not to reach the maximum value even at the end of the
coking period. Fig. 6.4 shows the temperature in the centre of the oven
after 11, 13 and 16 hours. There are some strange irregularities which
can be ignored as they may have resulted from the unevenness of the
charge density, but the early coking of the bottom of the charge is
clearly shown [107]. This observation that the temperature at the
bottom is higher than at the top, and the fact that the bottom of the
charge is coked earlier on in the carbonisation process, can both be
confirmed by the observation that, up to six hours, the transferred
heat quantity is more in the lower part of the heating wall; but after
this the upper part has been observed to catch up gradually with the
lower part. This is apparently because at the initial stage of coking,
the wall temperature is low and heat is transferred before the
generated heat reaches the upper part of the flue.
There are a number of different methods which have been used as means
of achieving uniform heating. Taylor [107] mentioned among them:
1. Using stepped thickness of the oven wall bricks.

2. Using better-conducting dense silica in different areas.
3. Control of the rich gas calorific value by external dilution.
4. Vertical taper of the oven width.
C direction:
Barker [2], in an attempt to assess the uniformity of heating, carried

out a survey of temperatures along the centre line of the charge. It was
found that the temperature changed in a regular manner between C (the centre)
and C+6 (6 beyond the centre); the C+6 temperature being higher. This effect
became more pronounced as the (nominal) flue temperature increased. To offset
this effect, at higher flue temperatures, the temperatures in the outer flues
were lowered. At still higher flue temperatures (above 1350C), the
temperatures were lowered in two other flues also. But at flue temperatures
above 1350C the difference between the temperatures measured at points C+6
71
and C in the charge increased and persisted even when the flue temperatures
were adjusted as mentioned above.
72
2. Heat transfer takes place by conduction only, or the coal charge is

considered a solid body
We have already seen that coal on carbonisation passes through three

main stages: pre-plastic, plastic and a coke stage. In all these stages heat
is transferred not only by conduction, but also by radiation and convection.
Something has already been said about the effective conductivity of porous
systems (Chapter 4). Using the effective conductivity takes account of part
of the error involved in assuming conduction to be the only mode of heat
transfer.
Below we will consider in some detail the other modes of heat transfer
through the three main stages of carbonisation.
1. The pre-plastic stage: This stage has already been considered in

Chapter 4 when the effective conductivity of coal was discussed. As we
have seen, at the lower temperatures, for small particle size, both
radiation and convection play a small part only in the overall heat
transfer.
2. The plastic stage: As the coal is plasticized, convection will start to
play a more important role in the heat flow.
Pore formation during the plastic stage has been studied by Mackowsky
and Wolff [99]. On devolatilisation if the mass of gas formed in a
particle at a given temperature and in unit time is greater than that
transported by diffusion, the resulting pressure inside the particle
will cause both pore-formation (the so-called devolatilisation pores)
and simultaneous deformation of the particle into the available void
volumes, which is accompanied by a simultaneous increase of the
particle volume. For particles of decreasing size, the pressure drop
from the inside toward the outside of the particle decreases until
finally there is no pore formation. Thus smaller particles will have
considerably fewer pores per particle than larger particles. Thus,
depending on the particle size and hence on the size and number of
pores formed, convection and radiation will take place during this
plastic stage.
3. The final stage is when the coal has solidified into a porous solid. As
the carbonisation proceeds further this solid shrinks and a number of
large cracks are formed in it. As we have seen a large crack develops
in the centre of the oven at the point where the two plastic zones
meet. Through the pores and the cracks both convection and radiation
are expected at the higher temperatures. These may be of major
importance as the temperature increases.
In a coke oven, apart from the modes of heat transfer discussed so far,
heat is transformed with the volatile compounds and steam given off as
carbonisation proceeds. This heat transfer can be very significant. It will
be discussed below as we follow the carbonisation process step by step (see
Fig. 6.2).
Step (1) where the coal is in the wet stage, steam is expelled, and it passes
inwards to the cooler parts of the oven charge and thus improves the rate of
heat transfer. This continues during steps (2) and (3) also.
In step (4) the gases released in the plastic zone leave the oven via the
coke rather than via the pre-plastic coal. These gases moving from a colder
region constitute a cooling breeze through the oven. Some of these gases,
73
however, pass through the coal side and assist in heating it. A similar
situation exists during step (5) up to the time of the disappearance of the
plastic zone.
Some attempts have been made to estimate theoretically the radiation

contribution regarded as conductivity. The few available expressions [100]
have in common a dependence on the absolute temperature and the path length
from particle to particle. The theory given in terms of finite difference
equations was tested using alumina spheres. The ratio of heat transfer by
radiation to heat transfer by conduction increased from 0.1 at 100C to 1.2
at 1000C. Badzioch [28] concluded, however, that the possibility of
successful application of the theoretical expression for the radiation
contribution to the heat transfer appears to be doubtful. The expressions
involve the knowledge of the sizes of pores which is a formidable problem for
a packing of particles of a wide range of sizes. He further concluded that a
prudent approach is to rely on empirical data [28].
Some expressions have also been derived to account for the convective
heat transfer. However, because of the convection due to the volatiles and
steam the problem becomes more complicated and would involve knowledge of the
rate of evolution of volatile matter. Again reliance on empirical data seems
to be the best approach [28]. Burke [109] claims however that convection is
of minor importance, as far as the transfer of heat in the coking process is
concerned. He reached this conclusion by supposing that the transfer of heat
were due to convection only, conduction playing no part whatsoever. The laws
of convection state that the amount of heat transfer is directly proportional
to the area of the heated surface. This means that the rise in temperature
will be directly proportional to the area and inversely to the volume. Thus
the heating time of a cylinder, for example, will no longer be proportional
to the square of the radius but simply to the first power of its radius. If,
therefore, experiment shows that the heating time is directly proportional to
some linear dimension to a power less than the second, it will be safe to
conclude that convection plays an important part in the transfer of heat. He
further claims that his experiments showed that the square law holds with
precision, indicating a minor importance for convection.
3. Another assumption that must be made is that the coal charge is isotropic
throughout the whole carbonisation period. Although this assumption is not
true, as will be seen later, the fact that only one-dimensional heat flow is
considered should reduce the error involved in making it.
Pre-plastic coal is anisotropic. According to Taylor [101] all the vitrinite

in a given seam at one locality is usually optically anisotropic in the same
sense and at about the same degree. This optical anisotropy in bituminous
coals and anthracite is readily detected in both reflected and transmitted
light.
The importance of the optical anisotropy stems from the fact that it is
always the expression of structural anisotropy [101]. This optical anisotropy
is a result of the orientation of the aromatic clusters being parallel to the
bedding plane as an effect of the unidirectional overburden pressure during
coalification. Folding pressure may occasionally change the orientation which
is oblique to the bedding plane [102]. As coal is charged crushed into the
74
oven, the orientation of the aromatic clusters will be in all directions.

On carbonisation, no optical changes occur until the temperature approaches
that at which the coal becomes plastic [101].
Plastic coal is isotropic. The change to isotropic coal takes place over a
range of about 10C and occurs at slightly different temperatures for
different coals, usually being higher for coals of higher rank. It was
suggested by Taylor [101] that the loss of optical anisotropy, rather than
other measurements, marks the true onset of plasticity. He concluded that the
loss of structural anisotropy, which is indicated by the loss of optical
anisotropy, must almost certainly be due to incipient mobility of the ordered
units rather than to chemical changes [101]. Once this isotropic state is
achieved, it was found to persist throughout the plastic stage [101].
Semi-coke and coke are anisotropic. Some 10 to 15C before the onset of
resolidification the microscope indicates that only plastic isotropic coal is
present [101]. As the temperature is increased slightly minute anisotropic
spheres are formed which increase in size at the expense of the isotropic
matrix. When these spheres begin to interfere with each others growth, their
shapes become progressively less uniform. The growth of these anisotropic
areas proceeds until the isotropic plastic coal disappears. At the same time
and temperature resolidification is also complete and the coal is transformed
into semi-coke [101].
This semi-coke has a three-dimensional mosaic structure comprising

anisotropic units, often ill-defined, which differ from one another in
optical orientation. These units commonly measure from less than one to
several microns across [97, 101, 103]. The formation of texture of this type
can be compared to the crystallisation of a supersaturated solution.
With further heating , even up to 1500C, the appearance visible through

the microscope undergoes little further change while carbonisation takes
place, except for a minor shrinkage [97, 101, 103]. Up to 1000C, however,
the optical anisotropy increases steadily with temperature [97, 101].
Abramski and Mackowsky claimed that the size of the mosaic units is
related to the degree of plasticity developed on carbonisation, the higher
the plasticity developed, the greater the possibility of obtaining order over
large areas, resulting in larger mosaic units. Thus coal with more than about
35% volatile matter forms coke which is essentially isotropic [101].
4. A further assumption is that the coal charge is homogeneous throughout the

carbonisation process.
This means that the thermal properties are independent of position.

Most workers, as we have seen (Chapter 5), make this assumption.
The variation of the thermal properties with position in the coke oven
may be a result of the non-uniform heating of the charge, but also it may be
a result of charging the oven unevenly, especially with regard to density.
According to Rembashevskii [104] the density of coke depends on its

position in the oven. For example the density is greatest at the bottom and
near the walls, whereas the coke at the top has lower density.
75
Barman [93] investigated the variation of coke strength and other

properties with the coke position in the oven. He found that the strength
improved as the distance from the wall decreased. He further concluded that
the variation in coke properties with position in the oven is due to
variations in the thermal treatment of the coke at these locations.
Zubilin, on the other hand, investigated the density distribution in a

coke oven after charging. According to him [106] the lack of uniformity in
the density of the charge over the cross-section of the oven chamber arises
from the densification of the charge when it is dropped, and the spreading
out of the stream of charge as it slides along the generatrix of the cone. No
noticeable segregation of charge during filling was found.
Similar investigations were also reported by Wenger [108] for tall

ovens. It was found that the pattern of vertical density distribution was
essentially the same in tall and normal column heights, with the density
lowest in the uppermost form and highest at about one third of the distance
up the column.
Having considered the above assumptions, two more assumptions will be

made here for the first trial solution, namely: the independence of the
thermal properties of temperature and the neglect of the heat generation
term. Making use of all these assumptions, the differential Fourier equation
(1) will be simplified to the following equation:
2 1
=0 (2)
2
Where D is the average diffusivity assumed constant with temperature.
6.3 The first trial solution
Maltby 100% coal was carbonised at different flue temperatures in the

EHT B.C.R.A. coke oven.
In case one the coke was discharged at a final charge-centre

temperature of 1055C, the flue temperature being at 1085c. The coal
properties and other carbonisation conditions were shown in Table 4.1.
In case two the coke was discharged at a final charge-centre

temperature of 1255C, the flue temperature being at 1300C. The coal
properties and other carbonisation conditions were given in Table 4.4.
In case three the final temperature was 1520C and the flue temperature
being at 1590C. The coal properties were given in Table 4.5.
The same procedure was used for the solution of all three cases.
In the B.C.R.A. coke oven the temperatures were measured continually

during carbonisation at the wall, at the centre of the charge, and at a point
1
inch distance from the wall (1 ).
4 4
Equation (2) was used. It was solved by a numerical method based on

Schmidt, in which the coke oven was divided into a number of sections of
76
thickness x each. The calculation was carried out in steps of seconds

each [106].
Using the finite difference method, equation (2) simplifies to:
1 + 3 20 1 0 +1 0
= (3)

Where refers to the time, and the subscripts 0,1,3 refer to the relative
position across the oven width.
Hence from (3):
1 1
1 + 3 20 = 2 +1 0
0
2
Let =

1 2
0 +1 = 1 + 3 + 1 0

1 2
or +1 = (+1 + 1 ) + 1 (4)

with M 2 for a convergent solution.
A computer programme was written to solve this equation . For the

initial conditions the temperature was assumed to be uniform at 20C
throughout the oven chamber immediately after charging.
For the boundary conditions the measured wall temperature was assumed
to represent boundary temperature. The solution obtained thus for the centre-
of-charge temperature was quite different from the measured values (see
below). It was found that by making the boundary condition equal to the
measured 1 a much better solution was obtained.
4
It is expected that a better solution for the temperature distribution

in the coke oven can be obtained using the measured charge-centre temperature
as the other boundary condition. But then we will not have any measured data
to compare with the calculated values.
The average diffusivity:
The thermal diffusivity of coal has been measured at temperatures up to

1100C. No measurements at higher temperatures were available to us. From the
curve of average diffusivity versus the final coking temperature (Fig. 6.15)
(see later), it can be deduced that the average diffusivity of a coal charge
heated to 1055C (case one) is about 10610-4cm2sec-1.
77
Virozub [28] carried out some investigations on the average thermal

diffusivity of a coal charge heated to different temperatures. He arrived at
the following expression, with the average diffusivity a function of the
final coking temperature:
1000 1000 2
= 92.2 + 25.3 + 7.2 104 2 1 (5)
100 100
This expression seems to give values of average diffusivity similar to

reported values in the temperature range 800-1100C. Its validity above
1100C is doubtful. Using this expression, we can find that the average
diffusivity for the three cases is:
Case one: D = 92.2 + 25.3(0.55) + 7.2(0.55)2 = 108.310-4 cm2sec-1.
Where tc = 1055C. This value is slightly higher than the average quoted
above.
Case two: with tc = 1255C.
D = 92.2 + 25.3(2.55) + 7.2(2.55)2 = 203.510-4 cm2sec-1.
which seems to be high.
Case three: with tc = 1520C.
D = 92.2 + 25.3(5.2) + 7.2(5.2)2 = 418.310-4 cm2sec-1.
which is also very high.
78
An approximate method of estimating the average thermal diffusivity is

to assume the coke oven to be a slab with zero initial temperature and whose
ends are kept at a constant temperature (assumed equal to the nominal flue
temperature). Solutions for the temperature distribution in such a slab based
on the differential conduction equation have been worked out, and the
temperatures at different distances from the ends were plotted (See Fig. 6.5,
after Carslaw [82]).
Using the final centre-of-charge temperature for the three cases we

find:

For case one: = 0.972

where t = the final coking temperature = 1055C
T = the flue temperature considered as the constant surface temperature

= 1085C.

From Fig. 6.5 at = 0 where x denotes the distance from the centre, and l the

half-width of the slab (oven) = 8 inch.

= 1.5 from Fig. 6.5.
2
is, in this case, the total carbonisation time.
= 16.3 hours.
16.3 3600
= = 1.5
2 (8 2.54)2
And D = 105.510-4 cm2sec-1, which compares well with the earlier values found
(see above).
By similar calculations for case two, D was found to be 134.910-4 cm2sec-1;
and D for case three = 208.610-4 cm2sec-1.
These values seemed to give best results, and were therefore used in the
calculations.
CASE ONE
1. A solution was attempted using the wall temperature as the boundary

conditions.
The oven was divided into 10 sections, with x, the thickness of a
162.54
section = =4.064 cm.
10
was chosen to be 305.7 secs.
2 (4.064 )2
= = = 5.121
105 .510 4 305 .7
16.33600
Number of steps = = 193 steps
305 .7
The results are shown in Fig. 6.6, Curve No. 2 compared with curve No.
1 for the charge-centre temperature.
It is clear that there is a wide divergence between the two.
2. When 1 was used for the boundary condition, Curve No. 3 was obtained
4
for the charge-centre temperature (Fig. 6.6).
79
CASE TWO
1 was used for the boundary condition.

4
D = 134.910-4 cm2sec-1.
No. of sections = 10
x = 3.937 cm
= 250 secs.
M = 4.6
No. of steps = 180.
The results are shown in Fig. 6.7 for the charge-centre temperature.
CASE THREE
Again 1 was used for the boundary condition.

4
D = 208.610-4 cm2sec-1.
No. of sections = 10
x = 3.937 cm
= 180 secs.
M = 4.13
No. of steps = 156.
The results for the centre-of-charge temperature are shown in Fig. 6.8.
All the above results show some deviation from the measured data. In
case one the calculated temperature is always less than the actual measured
one, with the difference becoming greater after about eleven hours of
carbonisation in the temperature range 550150C. At about the same
temperature (550C) for cases two and three the difference between the
80
measured and the calculated temperatures changes from being a positive one
below 550C (where the calculated temperature is larger than the measured ),
to a negative one above 550C.
81
This difference could be explained by the fact that the rate of heat
generation was neglected. This rate of heat generation may be endothermic
below 550C and exothermic above this temperature. It is surprising, however,
that the carbonisation process seems to be exothermic throughout for case one
(Fig 6.6, curve 3). After considering the problem we came to the obvious
conclusion that the average diffusivity affects greatly the difference
between the measured and the calculated curves for the charge-centre
temperature. For, increasing the diffusivity D reduces the value of M, all
2
other conditions remaining constant, as M equals . And from equation (4) it

is evident that if M decreases +1
increases, with the result that the
calculated charge-centre temperature curve will be raised up relative to the
measured value.
In order therefore to arrive at a curve similar to the curves obtained

for cases two and three, the diffusivity for the first case was increased to
23010-4 cm2sec-1, and the calculations were carried out as before. The results
are shown in Fig. 6.6 (curve 4).
This step is justified in view of the conclusion, arrived at later,

that the carbonisation process is in fact endothermic below about 500C and
exothermic above that temperature. This also means that the values quoted for
the average diffusivity in the literature , for a coke heated to about 1000C,
are too low. This conclusion seems to fit in with our recommended
conductivity values (above 800C), which were much higher than is found in
the literature, the diffusivity being of course directly proportional to the
conductivity.
Increasing the diffusivity for the other two cases has one effect only
and that is to raise both calculated curves relative to the measured ones,
indicating higher endothermic effects and less exothermic effects. The change
was found to be small, however, even when the diffusivity was increased
considerably (Fig. 6.7, curve 3).
In the second trial solution, the rate of heat generation was

introduced into the heat flow equation in order to see what effect this has
on the solution. This was done for all three cases.
6.4 The second trial solution (Introducing the rate of heat generation)
Much of the heat supplied to the coal charge in a coke oven is not
spent in raising the temperature. A part of it is spent on latent heat and
thermal decomposition reactions. The heat, which is associated with the
decomposition reactions, can be endothermic (absorption) or exothermic
(generation).
Although much work has been done on estimating the total coking heat or
the total heat of reaction in a coke oven from observed thermal balances
etc., little work has been done on investigating the heats generated at
particular stages during the carbonisation of coal. All we have consists of
averages of all the endothermic and exothermic processes that take place
during carbonisation up to a certain temperature.
82
Below is an attempt to discuss the thermal effects associated with the

different carbonisation stages:
In the wet stage heat is needed to evaporate the water of the coal
charge, and therefore this stage is endothermic.
In the dry stage heat is absorbed first, then with the onset of
decomposition the process starts to become exothermic. This is evident from
the calculations carried out by Littlechild [110] and Barman [93]. Their
results confirm the earlier work of J. D. Davis [112, 113] who concluded that
all the coals showed endothermic reactions up to about 300Cm followed by a
rapid evolution of heat. Barkowitz [115] also found that following an
endothermic response , exothermic reactions appear to commence near 200C and
to reach a maximum intensity between 260 and 280C. The overall effect during
this stage may therefore be slightly exothermic.
According to J. E. Davis [88] the chemical substances evolved from the

coal in this stage are all stable bodies such as water and carbon dioxide, or
are of greater chemical stability than the material of the original coal, and
with this liberation there is some energy release.
Parr [111] also observed, on preheating coal before charging it into a

retort, that the exothermic reactions which occurred were sufficient to
maintain a rapid progress of coking in the preheated charge. Agroskin [37]
found the rate of heat generation endothermic up to about 350C for brown
coal and exothermic above this temperature. For gas coals, however, the
endothermicity seems to have continued up to a temperature of 660-700C.
On the whole it seems that the thermal effects during this stage are
small with a slightly exothermic net effect. Dryden [114] reported the
absence below 400C of significant effects exceeding 1 cal.gm-1.
During the plastic stage depolymerisation and hydrogenation exothermic

reactions take place, followed by condensation reactions, which are all
exothermic. Si it would appear that the plastic stage will be accompanied by
heat liberation. This was borne out in fact by the calculations carried out
by Littlechild [110] and Barman [93], the exothermic effect increasing with
temperature to reach a maximum at about 500C near the end of the plastic
stage. Similar conclusions were arrived at by Davis [88]. According to him
the substances produced during the plastic stage are of greater chemical
stability than the material of the original coal and hence their separation
must be accompanied by heat liberation.
Agroskin [37] also found evidence of exothermic heat effects during the
plastic stage for brown coal. Similarly Hollings [116] reported heat
liberation in the temperature range 420-460C. On the other hand, Burkes
calculation indicated that coals showed pronounced endothermic reactions of
decomposition in the plastic coal layer [109]. Trefny has also found that
decomposition starts with endothermic reactions; and when the decomposition
was greatest, the heat consumption was greatest also [117].
This contradiction is difficult to explain, unless one remembers that

in most cases of reported rate of heat generation values, these do not
represent true rates of heat generation but may include such effects as the
83
convective heat transfer and the variation of the diffusivity with

temperature.
Trefny [117] found that the joining of the two plastic zones at the
centre of the oven coincided with strong exothermic reactions so that a net
flow of heat flowed from the oven centre to the walls. This may explain the
higher exothermic heat value obtained by Littlechild at the centre of the
oven [110]. This could be a result of the inability of the volatiles to
escape from the plastic envelope formed by joining the two plastic zones.
Thus it is possible for the heat generation to be thought positive at a
certain location in the oven and negative at a different location. Thus while
at step 3 (refer to Fig. 6.2) the plastic layer may be endothermic, it is
possible that it becomes exothermic at step 5.
Concluding we may suggest therefore that the reactions during the

plastic stage are endothermic in general. The exothermic effects observed may
be due to factors other than the reactions as suggested above.
In the semi-coke stage most workers agree that there is a net

exothermic heat effect [88, 93, 110], although others reported haet
absorption [116].
In the coke stage endothermic reactions are reported. This is indicated by

the minimum at about 850C obtained by both Barman [93] and Littlechild
[110]. Davis [88] explains this endothermic effect by stating that this stage
involves the breaking down of molecules which have a high rate of formation,
e.g. hydrocarbons are decomposed to carbon and hydrogen and the sum total of
these reactions is endothermic.
After the formation of coke there is evidence to indicate exothermic

reactions which take place in the final stage of coke formation [118].
The values quoted for the heat generated/absorbed during the different
stages vary considerably. They average between 20 and 80 cals.gm-1, although
some authors quoted much larger values.
So far we have been concerned with the heat generated/absorbed in one

layer at a time. As has been pointed out before, a number of layers exist in
the oven at any one time. The overall rate of heat generation is an average
of all the layers rates of heat generation. There is some work on the
average rate of heat generation for the whole coke oven at different charge-
centre temperatures. Let us now follow the carbonisation steps (see Fig. 6.2)
and see what average thermal effects to expect at each step.
Step 1 is endothermic.
Step 2: as the coal is dried, and the dry coal is heated, heat is absorbed.
Hence the overall thermal effect is endothermic.
Step 3: towards the end of the dry stage exothermic effects are observed.
Endothermic effects, however, are in the other two layers and hence the
overall effect is likely to be endothermic.
84
Step 4: the semi-coke stage is exothermic. This is counterbalanced by

endothermic reactions in the other two layers. The overall effect may be
endothermic.
As was noted by Millard [40] the volatiles evolving in the plastic

layer pass through the coke and form a cooling breeze. These volatiles, on
reaching a hotter part of the oven, may crack into secondary products. It is
not certain, however, whether this would absorb or liberate heat.
Step 5: endothermic reactions occur near the walls (coke stage) and in the
centre. There are exothermic reactions elsewhere. The overall effect may be
endothermic.
Step 6: with endothermic and exothermic layers, with possibly an overall

exothermic effect.
Step 7 is exothermic.
Thus it can be concluded that the overall thermal effects in a coke

oven are endothermic up to the time of the formation of a semi-coke layer in
the centre of the oven , i.e. at a charge -centre temperature of about 500c,
above which the thermal effects are likely to become exothermic. This seems
to fit in with what was observed before, of the change from a positive
difference between the measured charge-centre temperature and the calculated
(trial solution one) below about 550C, to a negative difference above it
(Figs 6.6, 6.7 and 6.8). Millard [40] for his calculations assumed the heat
generation to be endothermic up to a charge -centre temperature of 700C and
exothermic above that temperature. His values which were not meant to
represent true rates of heat generation were quite high and varied between
200 and 800 cals/gm. Leibovich [119] measured the specific heat consumption
during coking. He found a maximum consumption (about 130 cals/gm) in the
temperature range 20-400C. This he took to indicate heat absorption . Above a
charge-centre temperature of 400C he found minimum heat consumption (about
30 cal/gm), indicating heat evolution.
Derivation of the rate of heat generation
In the absence of any consistent and reliable data on the rate of heat
generation at different temperatures and positions in the coke oven, one is
left with one choice only, and that is to derive a formula for the rate of
heat generation, and this despite the obvious shortcomings of any such
formula.
For one thing heat generation is a function of time as well as

temperature. But as the coking time is a matter of hours, while the bulk of
any chemical change can be measured in minutes and possibly in seconds,
therefore, there is reason to believe, according to Burke [109], that the
time factor will not be of great significance. On the other hand, most
estimated rates of heat generation include the effects of convection and
diffusivity changes. These factors may mask and distort the true effect of
exothermic or endothermic phenomena [109].
85
Added to this is the fact that often the same equation is used to
derive the rate of heat generation and for the heat transfer analysis (see
for example Millard [40]).
With these reservations in mind, the following heat generation formula

was used. It was derived by P. H. Price and quoted by Littlechild [110] and
Barman [93]. The thermal diffusivity was assumed constant throughout and
equals D.
Let the rate of heat generation per unit volume be q. Then the heat
flow equation (2) becomes:
2
= +
2
2
=
2
2 2
So 0 = 0 +1 0 1 3 + 1 0
2
2
Put =
2
2
Then 0 = 0 +1 0 1 3 + 1 20 = 0 (say)

Let Q be the rate of heat generation per unit mass
0
0 = =
2

0 = 0 +1 0 1 3 + 1 20 (6)
2
By means of equation (6) the rate of heat generation at position 0 at

time per unit mass (0 ) can be calculated. The procedure followed was to
estimate from the difference in the calculated and measured curves an average
temperature (T1) to be subtracted from the calculated temperatures below
about 500C, and another temperature (T2) to be added above 500C. From these
average temperatures, the rates of heat generation/absorption were estimated
as will be explained below.
Solution of the heat transfer equation in the coke oven after introducing the
heat generation term:
Equation (2) becomes:
2
= (7)
2
Using the same finite difference method used above, we get eventually:
1 2 0 2
0 +1 = 1 3 + 1 0 + (8)

2
Now =

86
0
And 0 =
2
By substituting these in the last term of equation (8) we get:
1 2 0
0 +1 = 1 + 3 + 1 0 +
2
Below about 500C we have:
1 2
0 +1 = 1 + 3 + 1 0 1

0
Where = 1
2
And 0 = 21
21 1
Or 0 = = (9)
2
This means an endothermic heat effect.
Similarly above 500C we get:
2
0 = (10)

with an exothermic heat effect.
Results of the calculations:
A computer programme was written to solve the heat flow equation. 1 was
4
used, as before, for the boundary condition. The oven was also divided into
ten sections of thickness 3.937 cm each. The diffusivity values used were the
same as used in the first solution, except in case one where the modified
diffusivity was used.
CASE ONE
D = 23010-4 cm2sec-1
= 360 secs
Total carbonisation time = 16.5 hours
No. of calculation steps = 165
2
= = 2.805

x = 39.37/8 cm.
Temperature of charge = 580C (from curve 4, Fig. 6.6)
The results are shown in Fig. 6.9. From these results it is obvious that a
variable heat generation term must be assumed in order to get exact
conformity between the measured and calculated temperatures.
87
No heat absorption was assumed below 580C. This means negligible heat
absorption. Above 580C an average T1= 6 was used in a first attempt. Later
variable values of heat generation were used (see Table below).
Temp. Range T C Q
C C cal.gm-1C-1 cal.gm-1C-1
20-580 - Negligible
580-720 +6 0.545 0.009
720-990 +19 0.615 0.0324
990-1030 +6 0.663 0.0111
1030-1050 +3 0.671 0.0056
C, the specific heat, was calculated by means of equation (11) given later.
These values of Q, if multiplied by the time period for any temperature

range, give the heat liberated or absorbed during that particular range. For
example, in the temperature range 580-720C, the time taken at the charge
centre equals about 1.1 hours (Fig. 6.9),
= 1.1 3600 0.0093 37 . 1
For other temperature ranges the calculation was also carried out.
88
0 Time Q
cal.gm-1C-1 h cal.gm-1
0.0093 1.1 +37
0.0324 1.3 +152
0.0111 1.1 +44
0.0056 3.0 +61
= 294
CASE TWO
The same conditions as were used in the first trail solution. The table
below shows the values used for the rates of heat generation, the temperature
of charge being equal to 540C. The results are shown in Fig. 6.10.
Temp. Range T C 0 Time Q

C C cal.gm-1C-1 cal.gm-1sec-1 h cal.gm-1
20-100 0 - -
100-540 -5 0.419 0.0084 3.2 -97
540-728 +12 0.542 0.0260 0.3 +28
728-850 +30 0.597 0.0716 0.2 +52
850-1120 +60 0.660 0.1583 0.3 +171
1120-1259 +5 0.694 0.0139 1.5 +75
1259-1265 0 - -
= 229
These results are quite comparable to the results of case one.

89
CASE THREE
The same conditions as in the first trial solution were used. The table
below shows the values used for the rates of heat generation. The temperature
of charge was equal to 400C. The results are shown in Fig. 6.11.
Temp. Range T C 0 Time Q

C C cal.gm-1C-1 cal.gm-1sec-1 h cal.gm-1
20-100 0
100-400 -10 0.390 -0.0216 0.80 -54
400-700 5 0.511 0.0142 0.40 +20
700-1050 40 0.626 0.1390 0.45 +225
1050-1190 20 0.700 0.0780 0.25 +70
1190-1450 10 0.695 0.0386 1.15 +160
1450-1510 5 0.695 0.0193 0.95 +66
1510-end 0
= 487
The total heat generated is about double the value found for the earlier two
cases.
In conclusion it can be seen that there is a great interdependence

between the diffusivity and the rate of heat generation that must be assumed
to get a close correspondence between the measured and calculated
temperatures. In these calculations the values of the diffusivities used were
rough approximations only, and hence not much can be learnt from the rates of
90
heat generation values obtained unless better values for the diffusivity are
used. The values of the rates of heat generation obtained are better
understood as correction factors necessary to correct for all the assumptions
involved in solving the heat flow equation including the error involved in
neglecting the heat generation term itself, and also the error involved in
using an average diffusivity value.
In the third solution below more accurate values of the diffusivity

were used. Also, the diffusivity variation with temperature was considered.
6.5 The third solution:
The thermal diffusivity of coal is not constant with temperature

increase. All three terms involved in its calculation are in fact affected by
heating, namely the thermal conductivity, the specific heat and the bulk
density. In the first part of this thesis, the effect of temperature on the
thermal conductivity has already been considered in detail. Although the
thermal conductivity has the greatest effect on the shape of the diffusivity
temperature curve, the other two properties can also be important.
Before attempting to consider the possible variations of the

diffusivity with temperature, a brief examination of the effect of
temperature increase on the two properties, density and specific heat, will
be made.
The specific heat of coal on heating
Two approaches to the problem of the specific heat of coal are

possible. A theoretical one based on the considerations of the coal molecular
structure, which is, however, of doubtful value in view of the heterogeneous
and complex nature of coal [28, 95]. The second approach is an empirical one
based on formulae derived from experimental measurements of the coal specific
heat. The specific heats of coals at low temperatures (i.e. below the
decomposition temperature) have been measured by a number of workers. Three
variables were found important regarding their effects on the specific heat.
These are the moisture content, the volatile matter and the ash content.
The presence, at temperatures below the decomposition temperature, of

structures giving rise to volatile matter leads to a substantial increase in
the specific heat, the increase being approximately proportional to the
volatile matter content [28]. Also, at temperatures below 100C, the specific
heats of coals are affected considerably by the moisture content. The
moisture contribution to the specific heat was found to be additive, assuming
a specific heat of 1 cal.gm-1C-1 for the moisture.
The presence of ash in coal has some effect on the specific heat,
though a small one. The specific heat of ash is much lower than that of coal.
The contribution of ash was also found to be additive. Gladkov (quoted in
[28]) suggested an empirical relation for the variation of the specific heat
of ash (CA) with temperature (t):
CA = 0.17 + 0.00012 t (cal.gm-1C-1)
Where 0 < t < 500C

91
Above the decomposition temperature it is very difficult, however, to

measure the true specific heat because of the heats of reactions involved
during the carbonisation process. For this reason only practical specific
heats are in fact measured. A number of formulae have been suggested for the
calculation of the specific heat at different temperatures. One such formula,
based on the principle of additive contributions from the derivatives
obtained in carbonisation, is given by Kirov [120]:
= [(1 1 )(0.165 + 3.4 104 1.4 107 2 ) + (1 0.1)(0.395 + 8.1 104 ) + 0.1(0.71 + 6.1

104 )] 1 + (0.18 + 7 105 ) (cal.gm-1C-1) (11)
100 100
Where C is the specific heat for the dry coal and W1 is the volatile matter
(d.a.f.b.). At temperatures below 100C, the moisture (additive) contribution
to the specific heat is to be added. It was claimed by Kirov that the
specific heat values obtained using this equation agreed well with the
empirical data. The equation was used up to a temperature of 1100C. Above
this temperature there is evidence to indicate that the specific heat remains
approximately constant. The Kirov formula was chosen to be used in the
calculation for the third solution here.
Other formulae are also available. Gladkov [28] derived one such
formula for the temperature range 0-250C. This seems to give comparable
results to those obtained using the Kirov formula. Badzioch, however,
recommended its use in the 100-250C range only. Clendenin [28}, after
compiling an extensive amount of information on the specific heats of coals
below 100C, obtained an equation for bituminous coals . Hofherr [78] for his
calculations used a formula derived by Fritz and Moser in the temperature
range 100-300C. For the temperature range 300-1100C a formula given by
Kasperczyk was used . It was assumed that beyond 1100C the value of the
specific heat remains constant at 0.495 cal.gm-1C-1 for a coal with 22%
volatile matter (d.a.f.b.).
Bulk density on heating
Bulk density changes considerably with temperature. Hofherr [78] used a

method given by Kasperczyk to determine the change in density with
temperature, from the weight loss during devolatilisation of the coal and
from the shrinkage of the reactor contents. The density change was
characterised by a factor (F3). Its variation with temperature is shown in
Fig. 6.12.
In the present calculation the density of the coal was used in the
temperature region 20-600C. Above 600C the density of coke was used.
By using the recommended conductivity values, as was suggested before,

and by calculating the specific heats, using equation (11), the diffusivity
of coal at different temperatures was obtained. The results are shown in Fig.
6.13 (See Table below).
92
Calculated diffusivity values D (10-4 cm2 sec-1)
Temperature, C Case one Case two Case three

100 13.15 12.79 13.25
200 13.86 13.48 13.97
300 14.48 14.08 14.58
400 15.03 14.61 15.14
500 29.95 29.11 30.15
600 42.79 43.06
700 51.67 51.32 51.28
800 81.18 80.61 80.54
900 256.59 254.75 254.49
1000 733.79 728.35 727.54
1050 717.72
1100 697.38 696.54
These values, as expected, fall in the same range as the reported values at
low temperatures, but as the temperature is increased above 800C there is a
marked difference, with the calculated values becoming much greater than most
reported ones.
Literature survey of the thermal diffusivity data
1. Values for powdered, briquetted or compacts of coal measured at room

temperature:
The table below summarises some reported values.

93
Material Diffusivity Ref. Date

10-4 cm2 sec-1
1. Packing of powdered coals 11 to 13 Beletskaya [28] 1940-48
2. Cylindrical briquettes of (i) 14.5 Kusakin [28] 1959
three coals, measured at 15- (ii) 13.6
40C (iii) 14.6
3. Packing of coal, with air Air : 14 Schumann [31] 1934
or hydrogen filling the pores Hydrogen : 30
4. A packing 0f -3 mm coal Air : 11 Kusakin [28] 1959
particles with different gases Hydrogen : 17
filling the pores CO2 : 9
5. spherical briquettes of (i) about 10 Agroskin [28] 1957-9
Moscow district brown coal (at (ii) about 12.5
about 10C)
6. Crushed coal of varying 10.8 to 11.7 Zubilin 1961
densities
Conclusions
1. From 3 and 4 it seems that the thermal diffusivity of packings is affected

considerably by the nature of the gas in the interstices. The diffusivity is
dependent on the thermal conductivity of the gas in the pores.
The gas Its thermal conductivity Coal diffusivity

10-4 W.cm-1.C-1 10-4 cm2 sec-1
Carbon dioxide 1.454 9
Air 2.423 11 to 14
Hydrogen 16.721 17 to 30
94
2. The table below gives some reported values of the diffusivity of lumps of
coal, also measured at room temperature.

10-4 cm2 sec-1
1. monolithic German coals 14 to 17 Clendenin [28] 1949
2. monolithic German anthracite 15 to 24 Clendenin [28] 1949
3. British coals Similar to Clendenin [28] 1949
above values
4. Solid anthracite, with Air : 27 Kusakin [28] 1959
different gases in the pores Hydrogen : 37
CO2 : 24
5. anthracite Average = 19.4 Tsyrulnikov 1964
approx. [32]
6. Solid coal (The coal sample Parallel to Tsyrulnikov 1964
used here is assumed to have been banding: 24.6 [32]
solid because the effects of Transverse:
banding cannot be studied with 16.4
powdered coal) Parallel and
transverse:
20.5
7. Lump coal Average 16-17 Badzioch [41] 1964
3. From Kiegel [32] it can be seen that the diffusivity depends on the
moisture content, with the diffusivity increasing as the moisture content
increases. It also depends on the volatile content, the diffusivity decreases
with volatile content increase, and on the ash content with the diffusivity
becoming higher with ash inclusion. Badzioch [41] concluded that the
variability in crack formation of different coal lumps entirely obscures any
correlation which may exist between the diffusivity and such parameters as
carbon content and swelling number. The conclusions reached by Kiegel (see
above) may have been from measurements on powdered coal, seemingly at room
temperature.
4. Preheating the coal and then measuring its thermal diffusivity at room
temperature seems to have little effect on the diffusivity. Beletskaya [28]
found that the values of diffusivity are approximately 3.5% higher when coal
was preheated to 300C. Agroskin [28] showed that up to 200c the values of
the diffusivity were similar to those found on measurements after cooling to
room temperature . But above 200C the values determined at the actual high
temperatures were higher than those determined at room temperature. For a
coal preheated to 300C the diffusivity was found to be 12.6 when measured at
room temperature compared to 1510-4 cm2 sec-1 when measured at 300C.
To sum up, the thermal diffusivity of coal packing is approximately

1310 cm2 sec-1, compared to about 20 for monolithic coal. It depends on such
-4
factors as moisture content, ash content, volatility, the gas filling the
pores and , to a small extent , on the degree of preheat particularly above
200C.
95
2. Values for powdered, briquetted or compacts of coal measured at

temperatures up to 400C (before the plastic stage sets in):

10-4 cm2 sec-1
1. Spherical briquettes of brown 1 2 Agroskin 1957-9
coal 100: 11 13 [28]
200: 12 15
300: 15 19.5
400: 20 25
2. Packing of -16 mesh coal Average over the Burke [28] 1930-1
range 15-370C = 17.5
3. Pulverised coals of different Value at 300C Pomerantsev 1948
ranks (particle size to 0.5 mm) (i) 11.7 [32]
(ii) 11.7
(iii) 16.1
(iv) 19.5
4. Coal, packed in the same way 100 : 12.5 Priestley 1968
as a briquette 200 : 11.0 [38]
300 : 11
400 : 11.5
5. Gas coal, heating rate Temp. Effective True Agroskin 1968
10C/min. 100 17.5 17.5 [37]
200 16.7 16.7
300 16.1 15.3
400 16.4 13.6
6. Coal being carbonised Temp. C Rohde [42} 1969
100 8.34
200 9.44
300 10.56
400 9.44
Thus in the pre-plastic stage, it seems that the diffusivity doesnt vary
much with temperature. There may be a slight decrease up to a minimum (at
about 300C) as in 5 and 4 or a slight increase as in 1.
3. Values for plastic range (400-500C)

10-4 cm2 sec-1
1. Packing of coal heated at a Average = 15 Virozub 1941
rate of 5C/min. [28]
2. Pulverised coals of different (i) 16 Pomerantsev 1948
ranks (Particle size to 0.5 mm), (ii) 15 [32]
measured at 500C. (iii) 19.5
3. Gas coal. Heating rate Temp. Effective True Agroskin 1968
10C/min. 400 13.6 16.1 [37]
500 13.1 16.7
4. Coal, packed in the same way 400 11.5 Priestley 1968
as a briquette 500 16.5 [38]
5. Lump coal carbonised. 400 12 to 14 Badzioch 1964
450 12 to 18 [41]
500 13 to 28
6. Coal being carbonised. 400 9.44 Rohde [42] 1969
500 11.11
96
4. Values for monolithic semi-coke (500-500C)

10-4 cm2 sec-1
1. Packing of coal heated at a 500 16.5 Virozub 1941
rate of 5C/min. 600 22.5 [28]
2. Pulverised coals of different (i) 16 Pomerantsev 1948
ranks (Particle size to 0.5 mm), (ii) 15 [32]
measured at 500C. (iii) 19.5
3. Gas coal. Heating rate Temp. Effective True Agroskin 1968
10C/min. 500 13.1 16.7 [37]
600 16.1 17.2
4. Coal, packed in the same way 500 16.5 Priestley 1968
as a briquette 600 25.5 [38]
550 16 to 31 [41]
600 21 to 39
500 27.8
In Badzioch [28] values for the diffusivity of semi-coke measured at room

temperature were quoted after different authors. These range from 18 to
3010-4 cm2 sec-1.
5. Values for lump coke (over 600C)

10-4 cm2 sec-1
1. Spherical briquettes of brown 1 2 Agroskin 1957-9
coal 600: 30 46 [28]
700: 36 55
800: 40
900: 46
2. Packing of coal in the process 600 23 Virozub 1941
of decomposition, heating rate 700 43 [28]
5C/min.
3. Pulverised coals of different 1 2 3 4 Pomerantsev 1948
ranks (Particle size to 0.5 mm). 700: 51 18.9 20.8 4.2 [32]
900:27 31.6 - 33
4. Coal carbonised, heating rate Temp. Effective True Agroskin 1968
10C/min. 700 30.6 17.8 [37]
600 18.1 18.9
5. Coal packed in the same way as 700: 60 Priestley 1968
a briquette. [38]
700 81 to 75 [41]
750 147 to 200
800 210 to 271
850 384 to 415
700 38.4
800 197.3
850 270
900 358.2
950 556
1000 972
1050 1667
1100 3196
97
6. Average thermal diffusivity over the whole carbonisation range
1. Burke [28], 1931: Range 15-540C, average diffusivity = 3910-4 cm2 sec-1.
2. Millard [40], 1955, Range 100-(900 to 1060C), average diffusivity at flue

temperature of 1000C = 37, and of 1500C = 70.
3. Littlechild [28], 1934, Range up to final coking temperature of 900C:

-4 2 -1 -4 2 -1
7410 cm sec , and 950C: 8110 cm sec , and 1050: 107, 1100: 125.
4. Kylakov [28], 1955, at a flue temperature of 1284C:
Final charge-centre temperature, C Average diffusivity, 10-4 cm2 sec-1

264 24.4
385 28.4
515 34.2
It seems likely that the diffusivity depends on the rate of heating,

increasing as the rate increases.
The reported values for the diffusivity at different temperatures are plotted
in Fig. 6.14. Fig. 6.15 shows the reported average diffusivity over the
carbonisation range.
98
Solution of the heat transfer equation in the coke oven, with the diffusivity
assumed dependent on temperature
Using the finite difference method the following equation was derived
by Kasperczyk and used by the German workers in their calculations [78, 79,
80) (See also Ch. 5).
1
0 +1 = 0 3 0 + 1 0 + 1 1 + 0 (12)
0 0 2
Where T is a term added to correct the calculated temperatures and bring it

into closer agreement with the measured temperatures, and as with the second
solution this should be interpreted as a correction factor rather than true
rate of heat generation. However, after introducing the variable, and more
reliable, diffusivity values, this term is expected to come nearer to
representing the true rate of heat generation.
Equation (12) was solved, using a computer, for all three cases. The
results of the temperature calculations are shown in Figs. 6.16, 6.17 and
6.18. The rates of heat generation assumed are given below.
Case one
Temperature range, C T, C Q, cal.gm-1

100-150 +1 17
150-end +7 570
600
99
Case two

110-600 8 99
600-900 12 67
900-1250 22 323
500
Case three

110-980 7 144
980-1200 3 26
1200-1500 8 185
360
From these values it is apparent that despite the use of variable and
more reliable diffusivity values the rates of heat generation that had to
assumed were large. This shows that the errors introduced by the various
assumptions made including the assumption of heat transfer by conduction
only, are not negligible.
100
101
In conclusion, therefore, it can be said that calculations based on the

differential Fourier equation give only tentative solutions. For more
accurate results more work needs to be done, particularly on the part played
by the heat generation and the transfer of heat by volatiles.
The accuracy attained may be, however, sufficient for most practical
purposes. The general trend of the progress of heat through the oven can thus
be drawn.
102
Chapter Seven
Conclusions
The aim of this research was partly to investigate the variation of the
thermal conductivity of coal on being carbonised to extra high temperatures;
and also to use this knowledge of the variation of the conductivity with
temperature in order to obtain a better solution of the problem of heat
transfer in coke ovens.
However, in view of the difficulties pertaining to measuring the

conductivity in situ, it was decided upon heating the discharged coke to
various temperatures and making the conductivity measurements at these
temperatures. This was duly done, and a number of conclusions were reached:
1. The conductivity of the reheated coke was found not to be comparable to

the conductivity of coal being carbonised, even if measurements were made at
the same temperatures. Coal, on being carbonised, undergoes significant
structural changes that are irreversible. The conductivity values, however,
at the higher temperatures (1000C and above) seem to be similar, and are of
the order of 15010-3 W.cm-1.C-1. This value is much greater than values
reported in the literature for coal being carbonised or for coke. The coal
conductivity increases rapidly above about 800C. Part of the confusion was
caused by not differentiating clearly between values of conductivity measured
at high and at room temperatures. The heat treatment temperature was often
confused with the temperature of measurement.
2. The conductivity of the reheated coke was found to increase with

temperature up to about 500C and then decrease to settle eventually at a
value of about 15010 W.cm-1.C-1 at temperatures in the range 900-1000C and
-3
above.
3. Previous work on reheating coke was examined, and it was concluded that
significant changes in the coke structure take place in the temperature range
400-500C. The appearance of a peak in the conductivity/temperature curve was
explained with reference to these structural changes.
4. The conductivity measurements were made up to a temperature of reheat of

1050C. It was not possible to make measurements at higher temperatures
because of the heat losses from the furnace at these high temperatures. It
was, however, concluded, by reference to earlier work and to the pattern of
the conductivity/temperature curve established below 1050C, that the
conductivity of the coke will only rise slowly, if at all, above 1050c. No
major changes were expected. However, experimental measurements at
temperatures above 1100C would be necessary to confirm this.
As far as the second part of this work is concerned, it was not

possible to use the measured conductivity values to solve the heat transfer
equation in the coke oven. Instead, previous work was analysed, and making
use of the knowledge of the order of magnitude of the conductivity of coke,
based on the practical measurements, some recommended values for the
103
conductivity of coal on being carbonised were suggested. These were then used
to solve the heat transfer equation. A number of assumptions had to be made
before this equation was solved. The solution was obtained for three cases
with different carbonisation conditions in each case. The solutions were
found to be closely in agreement with measured data only after introducing a
term for the rate of heat generation/absorption.
It is suggested that further work is necessary on the heats of reaction

before a satisfactory solution of the heat transfer problem in coke ovens can
be obtained. A great interdependence between the diffusivity values used and
the temperature distribution obtained was found. This indicates the
significance of accurate measurements of the thermal properties, particularly
the thermal conductivity.
104
References
1. Coke Research Report 41, B.C.R.A., July 1966.
2. Barker, J.E., et al., Year Book of C.O.M.A., 1968, p.260.
3. Coke in iron making, ISI Publication 127, 1970, pp.105-112, 123-134 and
141-153.
4. Milson, A., Year Book of C.O.M.A., 1965, p.360.
5. Coke Research Report 57, B.C.R.A., February 1970.
6. Patrick, J.W., Influence of carbonisation conditions on some properties
of sulphur-carbons, reprint, Soc. Of Chemical Industry.
7. Coke Research Report 31, B.C.R.A., November 1964.
8. Gagarina, M.I. et al., abstract in Coke Review, vol. 7, No. 4.
9. Mott, R.A. and Wheeler, R.V., Coke for blast furnaces, London, 1930.
10. Mott, R.A. and Wheeler, R.V., The quality of coke, London, 1939.
11. Riley, H.L., Year Book of C.O.M.A., 1966, p.336.
12. Sanyal, A., quoted in (28), below.
13. Riley, H.L., Year Book of C.O.M.A., 1962, p.286.
14. Pashkevich, A.Z., Coke Chem. U.S.S.R., vol. 6, No. 8, 1936, p. 37.
15. Dorofeev, D.S., Coke Chem. U.S.S.R., vol. 9, No. 6, 1939, p.21.
16. Mller, W.W. et al., Brennstoff. Chem., vol. 14, 1933, p. 341.
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21. Shoenberger, R.W. et al., Iron making Proc., vol. 28, 1969, p. 145.
22. Kramers et al., Fuel, vol. 29, 1950, p. 184.
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University, June 1966.
24. Brady, E.A., Blast furnace and Steel Plant, vol. 46, 1958, p.54.
25. Coke Research Report 54, B.C.R.A., October 1969.
26. Wenger, R.O. et al., J. of Metals, vol. 22, 1970, p. 55.
27. Aberdeen, J. et al., Proc. Royal Soc., London, vol. 113A, 1927, p.459.
28. Badzioch, S., B.C.U.R.A. Month. Bull., vol.24, No. 11, Part II, Oct.-
Nov. 1960, p.485.
29. Zubilin, I.G., Coke Chem. U.S.S.R., No. 8, 1961, p.19.
30. McCabe, L.C. et al., Chem. Of coal utilisation, ed. H. H. Lowry, 1945,
p.310.
31. Schumann, et al., Fuel, vol. 13, 1934, p.249.
32. Kiegel, T.B., Heat transfer- soviet Research, vol. 2, No. 1, 1970, p.12
33. Godridge, Fuel, vol. 35, 1956, p.379.
34. Sinnatt, F.S. et al., Fuel, vol. 3, 1924, p.12.
35. Terres, E., Proc. 2nd Intern. Conf. Bituminous Coal, 1928, p.657.
36. Wicke, M. et al., Brennstoff. Chemk., vol. 49, 1968, p.97.
37. Agroskin, A.A. et al., Coke Chem. U.S.S.R., No. 11, 1968, p.3.
38. Priestley, A.M. et al., BHP Tech. Bull., vol. 12, part 3, No. 33, 1968,
p.36.
39. Batchelor, J.D. et al., J. Chem. Engng. Data, vol. 4, 1959, p.241.
40. Millard, D.J., J. Inst. Fuel, vol. 28, 1955, p.345.
41. Badzioch, S. et al., Fuel, vol. 43, 1964, p.267.
42. Rohde, von W., et al., Brennstoff. Chem., vol. 50, 1969, p.1.
43. Honda, H. et al., Carbon, vol. 3, 1966, p.421.
44. Flynn, D.R., Thermal conductivity of ceramics.
45. Neel, D.S. et al., Progress in International Research on Thermodynamic
and Transport Properties, A.S.M.E., New York, 1962, p.500.
46. Tye, R.P. (ed.), Thermal conductivity, vol. 1, London, 1969.
47. Powell, R.W., Proc. Phys. Soc., vol. 51, 1939, p.407.
48. McElroy, D.L. et al., Thermal conductivity (ed. R.P. Tye), vol. 1,
1969, p.185.
49. Powell, R.W., Thermal Conductivity of selected Materials, NSRDS-NBS-8,
November 1966.
105
50. Goldsmith, A. et al., Handbook of Thermophysical Properties of Solid

Materials, McMillan Co., 1961.
51. Jakob, M., Heat transfer, vol. 1, New York, 1964.
52. Luikov, A.V. et al., Int. J. Heat Mass Transfer, vol. 11, 1968, p.117.
53. Heilpern, S., Abstract in Coke Review, vol. 8, No. 4, p.116.
54. Erkin, L.I., Abstract in Coke Review, vol. 7, No. 2, item 291.
55. Fair, F.V. et al., 5th Carbon Conf., vol. 1, 1961, p.503.
56. Coke Research Report 63, B.C.R.A., December 1970.
57. Bogoyavlenskii, K.A., Coke Chem. U.S.S.R., No. 8, 1962, p.21.
58. Fukuyama, T., J. Fuel Soc. Japan, vol. 47 (8), 1968, p.607.
59. Vikharev, A.V., Khimiya tverd Topl., vol. 3, 1968, p.85.
60. Kimura, H. et al., J. Fuel Soc. Japan, vol. 47 (8), 1968, p. 653.
60a. Kimura, H. et al., J. Fuel Soc. Japan, vol. 46 (8), 1967, p. 630.
61. Mantell, C.L., Carbon and Graphite Handbook.
62. Sinkinson, E., Ind. Eng. Chem., Ind. Ed., vol. 17, 1925, p.27.
63. Koppers, H. et al., Arch. Eisenhttenw., vol. 5, 1932, p.543.
64. Myer, J.L. et al., Am. Inst. Mining Met. Engrs., Tech. Pub. 482, 1932.
65. Davis, J.D. et al., Ind. Eng. Chem., vol. 27, 1935, p.1196.
66. Beebee, A.M., The Gas World Coking section, vol. 87, August 1927,
p.83.
67. Pearson, F., Year Book of C.O.M.A., 1948, p.95.
68. Myhill, A.R. et al., Mech. World, vol. 137, 1957, p.367.
69. Boon, W.L., Trans. Inst. Gas Eng., vol. 84, 1934-35, p.980.
70. Coke and Gas, vol. 11, 1949, p.429.
71. Kruchinin, M.S. et al., Coke Chem. U.S.S.R., No. 3, 1968, p.18.
72. Akulov, P.S. et al., Coke Chem. U.S.S.R., No. 9, 1968, p.18.
73. Coke Research Report, 38, B.C.R.A.
74. Smolyaninova, N.M. et al., Coke Chem. U.S.S.R., No. 5, 1961, p.24.
75. Bradshaw, K. et al., J. Inst. Fuel, vol. 42, 1969, p.112.
76. Suga, Z. et al., AIME Iron Making Proc., vol. 29, 1970, p.9.
77. Tashiro, K. et al., Tech. Rep. Fuji Steel, vol. 17, 1969, p.353.
78. Hofherr, K. et al., Glckauf. Forschungshefte, vol. 32, No. 1, 1971,
p.35.
79. Kaspercyzk, J. et al., Glckauf. Forschungshefte, vol. 32, No. 1, 1971,
p.23.
80. Rohde, W. et al., Glckauf., vol. 107 (26), 1971, p.986.
81. Litterscheidt, W., Glckauf., vol. 71, 1935, p.173.
82. Carslaw, H.S. et al., Conduction of heat in solids, Oxford, 1959.
83. Gauger, P.J., Chemistry of coal utilisation, vol. 1 (ed. H.H. Lowry),
1945, p.600.
84. Wilson, P.J., Coal, coke and coal chemicals, 1950.
85. Roberts, J. et al., Int. Coal Carbonisation, London, 1934.
86. King et al., Dept. Sci. Ind. Research, Fuel Research Board, Tech.
Paper, 16, 1927.
87. Ellis, C., Inst. Gas Engrs., Pub. No. 436, 1953.
88. Davis, J.E. et al., Inst. Fuel, Conf. on science in the use of coal,
1958, p.C1.
89. Brown, J.K., J. Chem. Soc., 1955, Part 1, p.752.
90. Fitzgerald, D., Trans. Faraday Soc., vol. 52 (i), 1956, p.362.
91. Porter, H.C., Coal carbonisation, Am. Chem. Soc., New York, 1924.
92. Finlayson, P.C. et al., Residential Conf. on science in the use of
coal, Inst. of Fuel, London, 1958, p.C-15.
93. Barman, B.K., Thermoplastic properties of coal in relation to
carbonisation conditions, Ph.D. Thesis, Sheffield University, 1953.
94. Dryden, I.G.C., Fuel, vol. 34, 1955, p.363.
95. Van Krevelen, D.W., Coal, 1961.
96. McKee, J.H., B.C.U.R.A., Month. Bull., vol. 16, No. 2, 1952, p.41.
97. Brooks, J.D. et al., Coal Science, Advances in Chem. Series 55, Am.
Chem. Soc., 1966, p.549.
98. Gibson, J. et al., Carbonisation of coal, London, 1971.
106
99. Mackowsky, M. et al., Advances in Chem. Series 55, Am. Chem. Soc.,
1966, p.527.
100. Hill, F.B. et al., Am. Inst. Chem. Eng. J., vol. 5, 1959, p. 486.
101. Taylor, G.H., Fuel, vol. 40, 1961, p.465.
102. Teichmller, M., Coal Science, Advances in Chem. Series 55, Am. Chem.
Soc., 1966, p.133.
103. Pregermain, S. et al., ibid, p. 248.
104. Rembashevskii, A.G. et al., Coke Chem. U.S.S.R., No. 9, 1960, p.23.
105. Zubilin, I.G., ibid, No. 6, 1961, p.22.
106. Kreith, F., Principles of heat transfer, 1965.
107. Taylor, A., Year Book of C.O.M.A., 1971, p.114.
108. Wenger, R.O., Iron Making Proc. A.I.M.E., vol. 30, 1970, p.382.
109. Burke, S.P. et al., proc. Am. Gas Assoc., 1930, p.820.
110. Littlechild, J.E., Coke properties in relation to carbonisation
conditions, Ph.D. Thesis, Sheffield University, 1950.
111. Parr, S.W. et al., Ind. Eng. Chem., vol. 13, 1921, p.14.
112. Davis, J.D. et al., ibid, vol. 16, 1924, p.589.
113. Davis, J.D. et al., Fuel, vol. 4, 1925, p.286.
114. Dryden, I.G.C., Coal Research, 1946 (June), p.60.
115. Berkowitz, N., Fuel, vol. 36,1957, p.355.
116. Hollings, H. et al., ibid, vol. 2, 1923, p.322.
117. Trefny, F., Brennstoff. Chem., vol. 43, 1962, p.251.
118. Raskin, V.Z. et al., Coke Chem. U.S.S.R., No. 2, 1965, p.18.
119. Leibovich, R.E. et al., ibid, No. 7, 1961, p.22.
120. Kirov, N.Y. et al., Physical aspects of coal carbonisation, Australia,
1967.
107
APPENDIX
Typical computer programme
(Solution three, case one)
LIST
0010 LET N=7
0020 DIM T[7],P[7],C[7],R[7],K[7],I[7]
0030 FOR J=1 TO N
0040 LET T[J]=20
0050 NEXT J
0060 PRINT TIME TEMP DEG C
0070 FOR M=1 TO 208
0080 LET Z=(16.3/208)*M
0090 FOR J=1 TO N
0100 IF T[J]=<600 THEN GOTO 0120
0110 IF t[J]>600 THEN GOTO 0140
0120 LET R[J]=44.2*.016
0130 GOTO 0145
0140 LET R[J]=.74
0145 LET C[J]=.638*(.165+0.00034*T[J]-1.4E-7*T[J]2)
0146 LET C[J]=C[J]+.262*(.395+.00081*T[J])
0147 LET C[J]=C[J]+.1*(.71+.00061*T[J])
0148 LET C[J]=C[J]*.952+.048*(.18+.00007*T[J])
0150 IF T[J]=<100 THEN GOTO 0180
0160 IF T[J]>100 THEN IF T[J]=<1100 THEN GOTO 0200
0170 IF T[J]>1100 THEN GOTO 0220
0180 LET C[J]=(C[J]*90.7+9.3)/100
0190 GOTO 0230
0200 LET C[J]=C[J]

108
0210 GOTO 0230
0220 LET C[J]= .673
0230 IF T[J]=<400 THEN GOTO 0290
0280 IF T[J]>1000 THEN GOTO 0390
0290 LET K[J]=(1+T[J]/400)/1000
0300 GOTO 0400
0310 LET K[J](2+(T[J]-400)*7/300)/1000
0320 GOTO 0400
0330 LET K[J]=(9+(T[J]-700)*.06)/1000
0340 GOTO 0400
0350 LET K[J]=(15+(T[J]-800)*.35)/1000
0360 GOTO 0400
0370 LET K[J]=(50+T[J]-900)/1000
0380 GOTO 0400
0390 LET K[J]=150/1000
0400 LET K[J]=K[J]/4.186
0405 NEXT J
0410 FOR J=2 TO N-1
0420 LET P[J]=282.5/(R[J]*C[J])
0430 LET P[J]=P[J]*((K[J]*T[J+1])/6.562-(K[J]+K[J-1]*T[J]/6.562)
0431 LET P[J]=P[J]+282.5/(R[J]*C[J])*((K[J-1]*T[J-1])/6.562)+T[J]
0432 IF T[J]=<100 THEN GOTO 0440
0433 IF T[J]>100 THEN IF T[J]=<100.5 THEN GOTO 0442
0434 IF T[J}>100.5 THEN IF T[J]=<150 THEN GOTO 0444
0435 IF T[J]>150 THEN GOTO 0446
0440 LET P[J]=P[J]+5

109
0441 GOTO 0448
0442 LET P[J]=P[J]
0443 GOTO 0448
0444 LET P[J]=P[J]+1
0445 GOTO 0448
0446 LET P[J]=P[J}+7
0448 NEXT J
0449 FOR J=2 TO N-1
0450 LET T[J]=P[J]
0460 NEXT J
0470 READ I[1]
0480 LET T[1]=I[1]
0490 LET T[N]=I[1]
0500 PRINT Z,T[1],T[2],T[3],T[4]
0510 NEXT M
0520 DATA 0,20,90,95,95,95,100,100,100,100,100,100,100,100,100,100,100
0521 DATA 100,100,100,100,100,100,100,100,100,100,100,100,100,100,102
0522 DATA 102,104,106,108,110,112,115,120,125,125,130,135,140,145,145
0523 DATA 155,165,175,175,180,180,195,200,218,220,230,230,235,240,275
0524 DATA 275,285,285,300,310,315,318,322,325,352,355,360,360,360,360
0525 DATA 375,385,396,410,415,425,425,430,450,480,480,490,506,506,530
0526 DATA 550,560,575,590,590,598,608,610,610,615,625,645,655,655,655
0527 DATA 660,666,674,680,684,685,692,698,704,710,716,718,721,724,730
0528 DATA 734,739,740,740,742,747,748,753,760,760,766,774,780,788,795
0529 DATA 795,800,810,816,825,835,835,850,860,875,885,900,900,900,918
0530 DATA 925,932,940,950,950,955,958,960,965,970,870,972,973,976,978
0531 DATA 980,980,982,984,986,988,990,990,990,990,990,990,990,990,990
0532 DATA 991,992,993,993,993,993,993,994,994,995,995,995,995,996,996
0533 DATA 997,997,998,1000,1000,1000,1000,1000,1000,1000
0540 END
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Heat transfer in a high temperature coke oven

Thesis September 1973

Hassan Al-Haj Ibrahim

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Heat transfer in a high

Temperature coke oven

A thesis submitted to the

University of Leeds for the degree of

Hassan Al-Haj Ibrahim, B.Sc.

B. A. Lilley, B.Sc., Ph.D.

Department of Fuel and Combustion Science

Measurements of thermal conductivity were made for coke lumps carbonised at

I take the opportunity here of expressing my gratitude to Dr. Lilley

I wish also to express my sincere thanks to Mrs. Lilley who helped in

The financial support of the British Coke Research Association is

Part 1: The thermal conductivity of coke

3. Measurement of thermal conductivity

4. Results of the thermal conductivity measurement

Part 2: Analysis of heat transfer in a coke oven

6. Analysis of heat transfer in coke ovens

By way of introduction the background will be discussed under the

1.1 The importance of heat transfer in coke ovens.

1.1 The importance of heat transfer in coke ovens.

a. Heat transfer from the heating flues to oven wall,

To study the importance of the problem of heat transfer, it is

The study of heat transfer is important for three reasons:

a. because of the effect of the rate of heating on coke properties and

a. The effect of the rate of heating on coke properties and yield

coke quality is possible only if one succeeded in influencing the

Summary of the properties of coke desirable for blast furnaces

Coke fulfils four functions in blast furnaces:

i. It provides the necessary heat for the process,

From consideration of these functions an estimate of the coke qualities

where K is a constant for a given working volume. Some early investigators of

The properties of coke that are important in affecting the performance

ii. Ash Content

iii. Sulphur Content

In general, coke must have a low level of chemical impurities.

iv. Size Range

Other, less important, coke properties include:

vi. Volatile Content

vii. Bulk density

viii. Absolute Particle size

ix. Particle Shape

B.C.R.A. concluded that the imprecise relationship between voidage and

Summary of desirable coke properties

Moisture content : Low

Now we come back to consideration of the effect of the rate of heating

ii. Strength and hardness

iii. Mean size and size range

iv. Bulk density

vi. Porosity and fissuring

viii. Specific heat

b. The importance of heat transfer conditions for the efficient running

i. The oven factors (e.g. dimensions and in particular oven width,

All these factors affect to some extent the 'carbonisation conditions' of

From its effects on the coke properties, as discussed briefly above, it

c. Understanding of the mechanism of carbonisation

1.2 Thermal conductivity of coke and its importance with regard

necessary if we are to obtain by calculation an accurate temperature