July, 1926 INDUSTRIAL AND ENGINEERING CHEMISTRY 727

Calcination Rates of Limestonel

By Wallace A. Gilkey
STANI"OaD UNIVJCRSlTY, CAI.D".

Per cent

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
SiO.
Fe.Oa
AhOo
CaO
MgO
1.26
0.48
M.50
0.21
SO,, KtO, NatO Traces
of some of their buildings. lpitioo loss 43 . 37
Although the lime-burning industry had such an early be-
ginning, it still presents a promising field for scientific re- The crushed and ground sample was carefully separated
search. The calcination of limestone plays an important into sizes from 4 to 6 mesh to through 200 mesh by screening.
part in the Portland cement industry. The powdered lime- The sample was thoroughly dried, although only a trace of
stone contained in the raw mix is all bmned to lime in the moisture was present.
upper part of the rotary kilns at a comparatively low tem- The procedure finally adopted was to heat the samples
perature. It is then necessary to raise the mixture to a much at different constant temperatures for different intervals of
higher temperature (about 1400° C.) until a state of incipient time in small porcelain crucibles in an upright, cylindrical,
fusion is obtained. The material partly fuses together to 4 X 4 inch Hoskins electric furnace. The per cent of calcina-
form cement clinker. tion during any time interval was determined by the loss of
weight of the samples. Five samples could be heated at the
300 r--------------------------, same time.
The temperature of the furnace could be controlled by a
~" 260 rheostat connected in series with the furnace to a lighting
"
' i) circuit. Very good temperature control was obtained by this
-e~220 method and also by slightly raising or lowering the lid of the
..
0.
furnace for a few seconds. When making runs at the higher
B temperatures (above 800° C.), where the rates of calcination
8 180 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

700 750 BOO 850 900 950 1000

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 0
the kiln, very high stack temperatures are produced and an -20
c
enormous amount of heat is wasted. When it is considered t:
that the average stack temperatures in a cement kiln are from b
II. 10
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 700
750 BOO 850 900 950 1000
Temperature. io degrees Centigrade
mix burned to lime by the waste heat in another furnace ar- The Ratea of Calcination of Santa Cruz Lime-
ranged in series with the first. The important question arose atone at Dlllarent Temperatur. .
as to how fast the material could be passed through this
calcining furnace--in other words, what are the rates of cal- ture could be reached in a very short time compared with
cination of limestone at different temperatures? No answer the time required for t he run. At the highest temperatures
to this important question is found in the scientific literature. (900° to 1000° C.) it was necessary to work very rapidly.
By exercising great care the crucibles could be brought
Procedure to the required temperature in a small fraction of a minute.
A sample of selected limestone was obtained from the At the highest temperatures the full current was turned on
quarry of the Santa Cru.z Portland Cement Company. The and the temperature of the furnace was controlled by raising
sample was of crystalline structure, varied in color from pure or lowering the furnace cover. A current or air was drawn
white to a light gray, and had the following analysis according through the furnace in order to obtain as nearly as possible
to the cement company: the conditions that would prevail in a cement kiln. Tem-
L Received March 11 1926. peratures were determined by means of a Brown nichrome
728 INDUSTRIAL AND ENGINEERLVG CHEMISTRY Vol. 18, No.7

thermocouple. The instrument was found to be accurate Experiments were performed which showed that practically
to within 3° c. for any temperature on the scale of the gal- all of the decrepitation could be accomplished by heating the
vanometer, which read up to 1000° C. samples in covered crucibles for about 10 minutes at 650° C.
Results The very small amount of calcination at this temperature for
the short time interval could be neglected. Every sample
As might have been expected, the rates of calcination were was heated in a covered crucible at 650° C. for 10 minutes
greatly influenced by the concentration of carbon dioxide in before being placed in the furnace.
the furnace atmosphere. Samples in covered and in un- The rates of calcination were determined at 25-degree in-
coYered crucibles were heated at the same time at the same tervals between 700° and 1000° C. It would have been
temperature and for the same time interval. The rate of practically impossible to have determined the rates of cal-
calcination under atmospheric pressure of carbon dioxide was cination of the limestone with any degree of accuracy at
-only about 40 per cent of that obtained in uncovered crucibles temperatures much above 1000° C. because of the rapidity
in. a current of air. There is need for more research to de- at which the reaction proceeds.
termine the effect of the concentration of carbon dioxide upon The accompanying graphs represent the results of deter-
the rates of calcination. minations made on over four hundred and fifty samples and
It was observed that the coarser particles of limestone were obtained from the average results plotted on a number
would begin t<> decrepitate when heated to about 570° C. of other graphs.
and that some of the material would thus be thrown out of the
Acknowled~troent
crucibles and lost. The crucibles could not be covered during
the calcination because the reaction would be greatly retarded The research was carried out at the suggestion of Prof.
<>wing to the increased concentration of carbon dioxide. S. \V. Young, of Stanford University.

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 Mvc . Co.. BAsaoa. !\.is.

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,
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
in which the quantitative consideration of the heat transfer of the temperatures of these Yarious surfaces, the thermo-
coefficients necessitates the determination of the surfa.c e couple offered the most promise because of its ruggedness,
temperatures not only of the rotating drier shells, but of accuracy, and ease of applicat ion. The use of the bare
the mo'ving sheet as well. thermocouple, however, results in such large heat losses
Probably the most important methods in use at the present from the couple that it never reaches the temperature of
time are the imbedded thermocouple, thermocouple and the surface to which it is applied. The use of an insulating
thermometer pads, and the radiation method. The im- pad diminishes the error somewha t, but even with this,
bedded thermocouple is the most accurate, but is limited except in the case noted above, the heat losses are usually
in its application. The thermocouple pad usually consists sufficient to prevent the couple from attaining the true
of one or more couples backed by an insulating pad. The temperature of the surface. It seemed possible, however,
errors connected with this method are more or less evident. that these losses could be prevented by applying to the ex-
In the first place, when applied to the surface of a. wall posed side of the thermocouple sufficient heat to prevent
through which there is a small temperature drop, the poor any heat flow through the thermocouple. Under these
heat transfer t<> the pad along with the thermal losses from conditions there should be no temperature drop from the
the pad may result in low values. On tb.e other hand, when surface to the thermocouple and the couple should indicate
applied to a wall through which there is a large temperature the true temperature of the surface. This is the principle
drop, there may be a building up of the surface temperature of the so-called compensated thermocouple for surface
beneath the pad. Although these errors tend to compensate temperature measurement.
each other, their relative magnitude is unknown and there In order to apply this idea to a practical device, it was
is no assurance of obtaining the true surface temperature. necessary to develop a means of determining the absence
The radiation method is based upon the Stefan-Boltzmann of heat flow between the surface and the couple. It was
radiation law and depends upon the black body coefficients believed that this could best be accomplished by the use of
of the radiating surface. The lack of accurate information an additional thermocouple, both couples being made in
concerning these black body coefficients, or the alternative the form of disks, placed with their surfaces adjacent. Thus,
necessity of calibrating the instrument for each surface, if the disk in contact with the surface should show a higher
renders this method of little practical value. temperature than the inner, or regulating, disk, it would
Since none of these methods were considered suitable indicate a heat flow from the surface to the disks, in which
for obtaining true surface temperatures under various case heat would be supplied by a heating element until the
conditions, it was decided to develop if possible a device two couples attained the same temperature. With this
for this purpose. condition there would be no heat flow and the tempera-
Although the development of such a device was prompted ture of either couple should be the true temperature of the
' Reooved March 12. 1926. surface.