July, 1926 INDUSTRIAL AND ENGINEERING CHEMISTRY
Calcination Rates of Limestonel
L IME BURNING was one of the first industries to be
carried on by m!ln wherein raw materials are con-
verted into useful substances by chemical reactions.
Lime mortars were used by the Romans in the construction
of some of their buildings.
Although the lime-burning industry had such an early be-
ginning, it still presents a promising field for scientific re-
search. The calcination of limestone plays an important
part in the Portland cement industry. The powdered lime-
stone contained in the raw mix is all bmned to lime in the
upper part of the rotary kilns at a comparatively low tem-
perature. It is then necessary to raise the mixture to a much
higher temperature (about 1400° C.) until a state of incipient
fusion is obtained. The material partly fuses together to
form cement clinker.
300 r--------------------------,
~" 260
"
' i)
-e~220
..
0.
B temperatures (above 800° C.), where the rates of calcination
8 180
700 750 BOO 850 900 950
Temperatures iD dei!'ees Centicrade
Time Required for the Complete Calcination of
Santa Cruz Llmeatone at Different Temperaturea.
(Complete Calcination Taken from Prevloua
Cunu aa About 98% of lll.nltlon Loaa)
Because of the high temperature required for the clinker-
ing process and the large volume of air which rushes through
the kiln, very high stack temperatures are produced and an
enormous amount of heat is wasted. When it is considered
that the average stack temperatures in a cement kiln are from
700° to 850° C., the large amount of waste heat is realized.
A new process for burning Portland cement was under con-
sideration in which the clinkering process would be carried
out in a smaller furnace and the limestone content of the raw
mix burned to lime by the waste heat in another furnace ar-
ranged in series with the first. The important question arose
as to how fast the material could be passed through this
calcining furnace--in other words, what are the rates of cal-
cination of limestone at different temperatures? No answer
to this important question is found in the scientific literature.
Procedure
A sample of selected limestone was obtained from the
quarry of the Santa Cru.z Portland Cement Company. The
sample was of crystalline structure, varied in color from pure
white to a light gray, and had the following analysis according
to the cement company:
L Received March 11 1926.
727
By Wallace A. Gilkey
STANI"OaD UNIVJCRSlTY, CAI.D".
Per cent
SiO.
Fe.Oa
AhOo
CaO
MgO
1.26
0.48
M.50
0.21
SO,, KtO, NatO Traces
lpitioo loss 43 . 37
The crushed and ground sample was carefully separated
into sizes from 4 to 6 mesh to through 200 mesh by screening.
The sample was thoroughly dried, although only a trace of
moisture was present.
The procedure finally adopted was to heat the samples
at different constant temperatures for different intervals of
time in small porcelain crucibles in an upright, cylindrical,
4 X 4 inch Hoskins electric furnace. The per cent of calcina-
tion during any time interval was determined by the loss of
weight of the samples. Five samples could be heated at the
same time.
The temperature of the furnace could be controlled by a
rheostat connected in series with the furnace to a lighting
circuit. Very good temperature control was obtained by this
method and also by slightly raising or lowering the lid of the
furnace for a few seconds. When making runs at the higher
were very high and the t ime of heating the samples was short,
the temperature of the furn-ace was raised to a hundred de-
grees or more above that at which the rate of calcination was
to be determined before the samples were placed in the
furnace. The furnace cover was then removed and the
crucibles were quickly placed in the furnace and the furnace
cover placed in position. In this way the required tempera-
. 60
1000
0
-20
c
t:
b
II. 10
700
750 BOO 850 900 950 1000
Temperature. io degrees Centigrade
The Ratea of Calcination of Santa Cruz Lime-
atone at Dlllarent Temperatur. .
ture could be reached in a very short time compared with
the time required for t he run. At the highest temperatures
(900° to 1000° C.) it was necessary to work very rapidly.
By exercising great care the crucibles could be brought
to the required temperature in a small fraction of a minute.
At the highest temperatures the full current was turned on
and the temperature of the furnace was controlled by raising
or lowering the furnace cover. A current or air was drawn
through the furnace in order to obtain as nearly as possible
the conditions that would prevail in a cement kiln. Tem-
peratures were determined by means of a Brown nichrome
728 INDUSTRIAL AND ENGINEERLVG CHEMISTRY
thermocouple. The instrument was found to be accurate
to within 3° c. for any temperature on the scale of the gal-
vanometer, which read up to 1000° C.
Results
As might have been expected, the rates of calcination were
greatly influenced by the concentration of carbon dioxide in
the furnace atmosphere. Samples in covered and in un-
coYered crucibles were heated at the same time at the same
temperature and for the same time interval. The rate of
calcination under atmospheric pressure of carbon dioxide was
-only about 40 per cent of that obtained in uncovered crucibles
in. a current of air. There is need for more research to de-
termine the effect of the concentration of carbon dioxide upon
the rates of calcination.
It was observed that the coarser particles of limestone
would begin t<> decrepitate when heated to about 570° C.
and that some of the material would thus be thrown out of the
crucibles and lost. The crucibles could not be covered during
the calcination because the reaction would be greatly retarded
<>wing to the increased concentration of carbon dioxide.
Measurement of Surface Temperatures'
1-A Portable Thermocouple Device Compensated for H ea t Losses
By M . W. Boyer and J. Buss
MASSAcliusS:T'l'S h~STITUT& oF TscoNOLOGV . ScHOOL o P CHEMICAL E:.;crKS.ERrN.J P«ACTlCS . E.,sTERN
N 1\•I ANY problems of heat transfer, investigators
I have been confronted with the difficulty of obtaining
accurate surface temperatures. An important ex-
ample is the problem of heat ffow in pulp and paper driers,
in which the quantitative consideration of the heat transfer
coefficients necessitates the determination of the surfa.c e
temperatures not only of the rotating drier shells, but of
the mo'ving sheet as well.
Probably the most important methods in use at the present
time are the imbedded thermocouple, thermocouple and
thermometer pads, and the radiation method. The im-
bedded thermocouple is the most accurate, but is limited
in its application. The thermocouple pad usually consists
of one or more couples backed by an insulating pad. The
errors connected with this method are more or less evident.
In the first place, when applied to the surface of a. wall
through which there is a small temperature drop, the poor
heat transfer t<> the pad along with the thermal losses from
the pad may result in low values. On tb.e other hand, when
applied to a wall through which there is a large temperature
drop, there may be a building up of the surface temperature
beneath the pad. Although these errors tend to compensate
each other, their relative magnitude is unknown and there
is no assurance of obtaining the true surface temperature.
The radiation method is based upon the Stefan-Boltzmann
radiation law and depends upon the black body coefficients
of the radiating surface. The lack of accurate information
concerning these black body coefficients, or the alternative
necessity of calibrating the instrument for each surface,
renders this method of little practical value.
Since none of these methods were considered suitable
for obtaining true surface temperatures under various
conditions, it was decided to develop if possible a device
for this purpose.
Although the development of such a device was prompted
' Reooved March 12. 1926.
Vol. 18, No.7
Experiments were performed which showed that practically
all of the decrepitation could be accomplished by heating the
samples in covered crucibles for about 10 minutes at 650° C.
The very small amount of calcination at this temperature for
the short time interval could be neglected. Every sample
was heated in a covered crucible at 650° C. for 10 minutes
before being placed in the furnace.
The rates of calcination were determined at 25-degree in-
tervals between 700° and 1000° C. It would have been
practically impossible to have determined the rates of cal-
cination of the limestone with any degree of accuracy at
temperatures much above 1000° C. because of the rapidity
at which the reaction proceeds.
The accompanying graphs represent the results of deter-
minations made on over four hundred and fifty samples and
were obtained from the average results plotted on a number
of other graphs.
Acknowled~troent
The research was carried out at the suggestion of Prof.
S. \V. Young, of Stanford University.
Mvc . Co.. BAsaoa. !\.is.
by its possible use with moving surfaces, it was borne in
mind that many kinds of surfaces are encountered in practice,
such ns metallic, lagged and fibrous, either moving or sta-
tionary. As the primary instrument for the measurement
of the temperatures of these Yarious surfaces, the thermo-
couple offered the most promise because of its ruggedness,
accuracy, and ease of applicat ion. The use of the bare
thermocouple, however, results in such large heat losses
from the couple that it never reaches the temperature of
the surface to which it is applied. The use of an insulating
pad diminishes the error somewha t, but even with this,
except in the case noted above, the heat losses are usually
sufficient to prevent the couple from attaining the true
temperature of the surface. It seemed possible, however,
that these losses could be prevented by applying to the ex-
posed side of the thermocouple sufficient heat to prevent
any heat flow through the thermocouple. Under these
conditions there should be no temperature drop from the
surface to the thermocouple and the couple should indicate
the true temperature of the surface. This is the principle
of the so-called compensated thermocouple for surface
temperature measurement.
In order to apply this idea to a practical device, it was
necessary to develop a means of determining the absence
of heat flow between the surface and the couple. It was
believed that this could best be accomplished by the use of
an additional thermocouple, both couples being made in
the form of disks, placed with their surfaces adjacent. Thus,
if the disk in contact with the surface should show a higher
temperature than the inner, or regulating, disk, it would
indicate a heat flow from the surface to the disks, in which
case heat would be supplied by a heating element until the
two couples attained the same temperature. With this
condition there would be no heat flow and the tempera-
ture of either couple should be the true temperature of the
surface.