United States Patent [191 [11] Patent Number: 4,748,010

Walker [45] Date of Patent: May 31, 1988

[54] ENERGY CONSERVING LIMESTONE ing a process and apparatus in which in a ?rst step or
CALCINING SYSTEM kiln zone limestone is heated, e.g., at l700°—2100° F.,
[75] Inventor: Daniel D. Walker, Henderson, Nev. sufficiently to achieve more than only about 50 or 60%,
e.g., 75%, partial conversion thereof to calcium oxide
[73] Assignee: Chemstar, Inc., Fort Worth, Tex. and carbon dioxide and to form a partially calcined hot
[21] Appl. No.: 710,157 mass containing sufficient retained heat for substantially
completing the conversion of the remaining uncon
[22] Filed: Mar.,11, 1985 verted limestone therein, and thereafter in a second step
[51] 1111. cu ............................................ .. C01F 11/06 or separate vacuum chamber zone substantially com
[52] US. Cl. .................................. .. 423/176; 423/175; pleting the conversion of the limestone in the hot mass
423/177; 423/438; 423/637; 423/415 R to calcium oxide and carbon dioxide by such retained
[58] Field of Search ............. .. 423/175, 176, 177, 438, heat while subjecting the partially calcined hot mass to
423/637, 415 R a vacuum sufficiently to remove substantially com
[56] References Cited pletely the resultant carbon dioxide and for a duration
suf?cient to achieve such substantially complete con
U.S. PATENT DOCUMENTS version of the limestone and thereby provide a substan
1,798,802 3/1931 Niles .................................. .. 423/ 176 tially completely calcined hot mass, the apparatus in
2,080,981 5/1937 Haas . . . . . . . . . . .. 423/ 176
cluding a closable calcining vacuum chamber separate
2,113,522 4/1938 Walker ..... .. 423/176
from and adjacent the discharge outlet of a lime kiln and
2,212,446 8/ 1940 McIntire ........ .. 423/176
3,527,447 9/1970 Kinkade et al. .... .. 423/ 176
arranged for receiving therefrom the partially calcined
3,716,095 2/1973 Ritzmann et al. 423/ 175 hot mass for completing the conversion of the limestone
3,743,697 7/1973 Jones, Jr. 423/ 175 to calcium oxide and carbon dioxide and for applying a
3,991,172 11/1976 Wicke et al. . ..... .. 423/ 177 vacuum thereto for removing the carbon dioxide, and a
4,076,796 2/ 1978 Reh et al. . . . . . . . . . . .. 423/ 177 heat retaining hood operatively enclosing the kiln dis
4,389,381 6/1983 Dinovo ............................. .. 423/ 175
charge outlet and the vacuum chamber for minimizing
Primary Examiner-Helen M. S.‘ Sneed heat loss from the hot mass in the vicinity of such dis
Assistant Examiner-Anthony McFarlane charge outlet and in the vacuum chamber.
[57] ABSTRACT
Energy conserving limestone calcining system, includ 22 Claims, 5 Drawing Sheets
US. Patent May 31, 1988 Sheet 1 of 5 4,748,010

FIG. |
30,000 -

28»°°°_. mssocmnou PRESSURE

_ OF CALCIUM CARBONATE
26,000 —

24,000 —

22,000 —

20,000 ——

|8,000 ——

PRESSURE ‘0°00 “

OVER 14,000 —

I0,000 -—

8000——

6000 ~

4000 —-—

2000 —

“IIIIN |||l|||
500 600 700 800' 900 I000 “00 I200

TEMPERATURE (°C)
US. Patent May 31, 1988 Sheet 2 of 5 4,748,010
FIG. 2 FIG. 3
LIMESTONE
m
In.
4 \5
FUEL-L
L.
n n

N1mI/l!.IN N G _\nul -L»

_
/ wm?oM8
Arln.
nU.Us
HS
AWL.l ‘I
2

AIR Y ""
..20A~ fnl/l.EHnum
-

14
CALCINING
VACUUM
I TO
CHAMBER SOURCE

COOLER

LIMESTONE
LUMP

FIG. 4 FIG.9
US. Patent May 31, 1988 Sheet 4 of 5 4,748,010
14,500 —

13,500“
—— 01550011111011
PRESSURE 0F
'2'5°°—" 01001011
_ CARBONATE

11,500

10,500

0500
002
PRESSURE
(mm Hg) 8500
OVER
011603 7500

6500

5500

4500

3500

TEMPERATURE (“0 )
us. Patent May '31, 1988 Sheet 5 of5 4,748,010
FIG. 8
800 ——

_ / YGOmmHg
750 ——~ _ _ _ — _ _

mo“ DISSOCIAHON PRESSURE

OF CALCIUM CARBONATE
650 —

600 —

550 —

500 —

450 ——
C02
PRESSURE
(mmHg) 400 '_"
OVER _

(M603 350 _

300 ——

250

200 —

I50 —

I00 ——~

550 600 650‘ ‘700 \750 800 850 900

TEMPERATURE ('0)
 4,748,010
1 2
This is due to the fact that limestone decomposes at
ENERGY CONSERVING LIMESTONE comparatively moderate temperature according to the
CALCINING SYSTEM equilbrium equation I in what may be considered as a
typical three component, two phase, and hence
BACKGROUND OF THE PRESENT INVENTION monovariant system, in which the dissociation pressure
The present invention relates to an energy conserving or vapor pressure of CO2 depends on the temperature.
limestone calcining system, especially as regards high In this regard, as is clear from the equilibrium equa
calcium and/or dolomite limestone, and more particu tion I, calcium carbonate, as a ?rst solid, decomposes or
larly to a process and an apparatus for successive stage dissociates into calcium oxide, as a second solid, and
treatment of limestone to calcine the calcium carbonate, carbon dioxide, as a gas. Since CaCO; and CaO are both
and/or magnesium carbonate, content substantially solids, their active masses or concentrations may be
completely to calcium oxide, and/or magnesium oxide, regarded as constant, such that the concentration of
and carbon dioxide with the use of comparatively less gaseous CO2 in equilibrium with solid CaO and CaCO;
energy than otherwise, i.e., by incorporating certain must be constant at a given temperature. In turn, be
thermodynamic principles of calcining limestone such cause the concentration of a gas is proportional to its
that considerable energy is saved in the overall calcin pressure, it follows that at a given temperature the pres
ing process. sure of gaseous C02 in contact with solid CaO and
Lime (calcium oxide) manufacture involves ther CaCO; is also constant.
mally heating limestone (calcium carbonate) in a lime This temperature dependent constant pressure-due to
kiln so that carbon dioxide is liberated as a gas and solid the gas formed, may be termed the dissociaton pressure
particles of calcium oxide are left as the product, i.e. or vapor pressure or partial pressure of the solid from
quicklime. which the gas is formed. The dissociation pressure of
This can be illustrated by the following chemical calcium carbonate in terms of carbon dioxide is well
equilibrium equation or reversible reaction: known as illustrated by Table l, per the Handbook of
25 Chemistry and Physics, 59th edition, 1978-1979, page
(I) F-90, as source, the list indicating the dissociation pres
sures and their related temperatures over a wide range,
with the equivalent ?gures within parentheses having
been calculated from the remaining corresponding val
30 ues given in said source, in order to provide a conve
where, according to LeChatelier’s principle, the degree nient full comparison in both °C. and ‘F. temperatures,
of dissociation is dependent on the partial pressure of and in both mmHg and atmospheres absolute pressures:
CO2.
Thus,if the partial pressure of CO2 on the'right side
of the equation is reduced, the chemical ratio of CaCO3 35 TABLE 1
on the left side of the equation to CaO on the right side ‘ Dissociation Pressure Of Calcium Carbonate (Vapor
is also reduced and calcination occurs and proceeds to Pressure Or Partial Pressure of CO2 Over CaCO3)
shift the reaction to the right side. Taperature Pressure
In a typical lime kiln, the reduction of the CO2 partial ‘0C. ‘F. mmHg atm. abs.
pressure is accomplished by supplying excess heat en 550 (1022) 0.41 (0.0005394)
ergy (A) to the mass, to shift the reaction to the right 587 (1088.6) 1.0 (0.0013157)
side, therefore making the calcination of limestone an 605 (1 121) 2.3 (0.0030263)
energy intensive process. 671 (1239.8) 13.5 (0.017763)
680 (1256) 15.8 (0.020789)
The heat energy source used may be a fossil fuel such 691 (1275.8) 19.0 (0.025)
as fuel oil, producer gas, natural gas, coal, coke, etc., but 45 701 (1293.8) 23.0 (0.030263)
due to the comparatively high cost of any such fuel, the 703 (1297.4) 25.5 (0.033553)
calcination of limestone is necessarily expensive to 711 (1311.8) 32.7 (0.043026)
727 (1340.6) 44. (0.057895)
carry out. 736 (1356.8) 54. (0.071053)
Parenthetically, in this regard, quicklime prices in 743 (1369.4) 60. (0.078947)
1984 have been stated to be about $45 to $55 per ton 50 748 (1378.4) 70. (0.092105)
(Chemical and Engineering News, Vol. 62, No. 31, July 749 (1380.2) 72. (0.094737)
777 (1430.6) 105. (0.13816)
30, 1984, page 16). » 786 (1446.8) 134. (0.17632)
In practice, limestone is calcined in lime kilns that 795 (1463) 150. (0.19737)
heat the limestone rock or stone lumps as they pass 800 (1472) 183. (0.24079)
through the kiln. There are two primary types of kilns: 55 819 (1506.2) 235. ‘ (0.30921)
8330 (1526) ~ 255. (0.33553)
(l) upright cylinders or stationary vertical shaft kilns 840 (1544) 311. (0.40921)
in which the stone is introduced at the top and allowed 852 (1565.6) 381. (0.50132)
to pass slowly down through a heated zone and out the 857 (1574.6) 420. (0.55263)
bottom; and 871 (1599.8) 537. (0.70658)
(2) rotary cylinders or horizontal rotary kilns in 881 (1617.8) 603. (0.79342)
891 (1635.8) 684. (0.9)
which the stone slowly passes through a rotating gener 894 (1641.2) 716. (0.94211)
ally horizontal tubular apparatus; 898 (1648.4) 760. atm. (1.0)
in each case in countercurrent to hot heat imparting 906.5 (1663.7) (874.76) 1.151
gases. 937 (1718.6) (1345.2) 1.170
1082.5 (1980.5) (6757.92) 8.892
In both types of kilns, however, considerable excess 65 1157.7 (2115.86) (14,202.12) 18.687
heat is required to overcome the partial pressure of the 1226.3 (2239.34) (26,093.08) 34.333
attendant carbon dioxide and cause the calcination to go 1241 (2265.8) (29,771.44) 39.094
to completion.
 4,748,010
3 4
Although it is seen from Table 1 that the carbon Similar adverse effects occur from the absorption on
dioxide equilibrium pressure (100% C02 atmosphere) the surface of the lumps of impurities, e.g. from ash
reaches atmospheric pressure (i.e. 760 mmHg or 1 atmo and/or sulfur, in the fuel, i.e., in the case where the fuel
sphere absolute) at 898‘ C. (1648' F.), nevertheless as a or its combustion products come into direct contact
practical matter, due to a tendency for the carbonate with the lumps in the kiln.
mass to superheat, it does not decompose rapidly at The use of comparatively higher calcining tempera
about 898‘—900' C. (1648'14 1652° F.), but instead re tures, even in the case of relatively pure carbonate start
quires a temperature of at least about 910° C. (1670' F.) ing material, often adversely results in undue overburn
before reasonably rapid rate decomposition is reached. ing of the surface layer of the lump, which leads to a
Moreover, the decomposing mass of carbonate stone reduction in the porosity, surface area and reactivity of
lumps must be retained at such temperature for a time the product.
suf?cient to achieve substantial completion of the disso Such undesired non-reactive forms are variously re
ciation at atmospheric pressure, and of course, the liber ferred to as “hardburned” lime, “overburned” lime or
ated or generated carbon dioxide must be removed from “dead burned” lime, as the case may be, and these sur
the vicinity of the lumps to favor the shift to the right face defective forms may contain various complex com
side per the equilbrium equation I. pounds on the surface of the lumps such as monocal
Generally, the dissociation is accelerated at a temper cium and dicalcium silicates, calcium aluminates, cal
ature of at least about l000°-l 100' C. (l832°—2012° F.), cium and dicalcium ferrite, calcium sulfate, and the like,
and especially of at least about 1038' C. (1900. F.), or in which occlude the pores of the lumps and detract from
more practical commercial scale terms is accelerated at 20 the surface area and reactivity of the product, or may
a temperature of at least about 1093°—l3l6° C. simply be overburned to the extent that the porosity and
surface area of the lumps are so reduced that the prod
(2000'-2400' F.), and especially of at least about 1204° uct is sintered and essentially chemically inert.
C. (2200‘ F.). Indeed, the higher the temperature, the Inasmuch as the burning or calcining of limestone is a
higher the rate of expulsion of the forming carbon diox 25 simple thermal decomposition, in which it is generally
ide gas from the stone lumps. necessary only to provide, as aforesaid, for a supply of
This is because the dissociation necessarily progresses heat and for the removal of the carbon dioxide which is
from the outer zone of each lump toward its center in a
formed, it would theoretically appear advntageous from
' more or less uniform circumferentially inward manner.
the inherent temperature-vapor pressure relationship
Although the degree of natural porosity aids both the involved, simply to provide for sweeping away the
1: access of heat to the inner zones of the lump and the carbon dioxide gas as rapidly as it is formed.
out?ow of liberated carbon dioxide gas therefrom, However, this advantage has not been realized in
- »- higher temperatures than the theoretical are required in practice because in industrial scale operations, the
practice to enable the dissociation to penetrate such lumps of limestone are comparatively appreciable in
inner zones effectively. 35 size, but more importantly because the crust or coating
In this regard, as the size of the lump increases, so of calcium oxide as ?rst formed on the outer zones of
also must its practical dissociation temperature and the lumps seems to act as a sponge to hold the vicinal
calcining residence time, in order for the dissociation to carbon dioxide in contact with the reacting face of a
. reach the center or core portion of the lump and for the given lump, by way of surface absorption thereat and
~ . temperature to cause the generating carbon dioxide to /or super?cial recarbonation, and thus to retard release
develop a sufficiently increased internal pressure in the of the carbon dioxide and full exchange via the pores
interior of the lump for outward escape of the gas from with the inner zones of the lump for achieving more
the con?nes of such inner zones through the existing complete conversion of the latter to calcium oxide.
pores. Consequently, the operation as a practical matter
To the extent that water and organic impurities are 45 requires the full decomposition temperature demanded
present in the lump, they are volatilized and the organic by the pressure equilibrium with the atmosphere to
impurities in turn are burned as the lump becomes achieve substantially complete calcination as desired.
heated, thereby preliminarily increasing the porosity of Where, on the other hand, the limestone is undesir
> the lump for more effective dissociation of the carbon ably calcined insu?iciently, e.g. at too low a tempera
ate within the crystal lattice of the lump once the car 50 ture and/or for too short a residence time in the kiln, a
bonate dissociation is thereafter initiated. ' comparatively large center or core of unconverted
The calcium oxide product is essentially infusible at calcium carbonate is left in the lime lumps, and such
the calcining temperatures used, and while it retains the core containing defective form is referred to as “under
general form of the original lump of starting calcium burned” lime.
carbonate, it crumbles easily. As a result of the calcin Thus, other things being equal, limestone calcination
ing, the crystalline mass has a tendancy to contract or is beset with the independent problems of minimizing
shrink in volume, thereby narrowing its pores. This adverse surface defects by the use of comparatively low
e?'ect is more prounounced as the calcination tempera calcining tempreatures, and at the same time of maxi
ture is increased. - mizing dissociation of the carbonate core by the use of
In particular, if the carbonate starting material con 60 comparatively high calcining temperatures, for a given
tains mineral impurities, especially silica, it should not residence time of the carbonate lumps in the kiln, so as
be heated much above 1000‘ C. (1832° F.) because at to avoid the doubly undesirable result of a lump product
this temperature, lime reacts with the silica and some of having both an overburned surface and an underburned
its other impurities, such as alumina and iron oxide, to core.
form a fusible slag which seems to glaze over the oxide 65 As a general rule, higher burning temperatures and
particles and adversely prevents subsequent reaction of longer calcination times lead to a harder burned lime
the product with water, as in the forming of hydrated product of comparatively high shrinkage and density,
lime or calcium hydroxide. and low porosity, surface area and chemical reactivity,
 4,748,010
5 6
whereas lower burning temperatures and/or shorter oxide, etc., and on the lump size, but also on the extent
calcination times lead to a generally more desirable soft to which associated magnesium carbonate (MgCO3) is
burned lime product of relatively low shrinkage and present with the calcium carbonate, e.g. in dolomitic
density, and high porosity, surface area and chemical limestone or in‘ magnesian limestone as compared to
reactivity, with a relatively small unreacted core and high calcium limestone. Magnesium carbonate, of
thus considered substantially completely calcined. course, decomposes at a lower temperature than cal
The degree of substantially complete dissociation of cium carbonate.
the calcium carbonate content to calcium oxide and In this regard, as to commercially available forms of
carbon dioxide, and of any other carbonate also present, carbonate rock or stone of such types usable for lime
can be conventionally measured for example by the 10 production, in addition to an impurities content, mostly
percentage by weight of loss on ignition (LOI), i.e. of silica, of, for instance, about l-3%, magnesian limestone
CO2. or magnesite has a magnesium carbonate content (e.g.
Inasmuch as lime is a poor heat conductor, and high 5-20% MgCO3) generally intermediate that of high
local overheating should be avoided, a comparatively calcium limestone or calcite (e.g. of 97-99% CaCOg)
low temperature ?ame of large volume is usually em and dolomitic limestone or dolomite (e.g. 40-43%
ployed for the calcining when conducted by direct heat MgCOg). Nevertheless, the magnesium carbonate com
exchange contact with the fuel and/or its combustion pontent of dolomite seems to decompose at higher tem
gases. peratures (e.g. 725° C. or ll33.7° E; 760 mmHg) than in
In the case of a vertical shaft kiln, the ?neness of the the case of natural magnesite.
limestone lumps used is limited by the necessity of keep 20 Ordinarily, any carbonate rock having at least about
ing the comparatively static charge open enough by 20% magnesium carbonate content is often roughly
way of void spaces throughout its extent to induce a considered to be “dolomite” and that having at most
free passage of the ?ame and the products of combus about 2—5% magnesium carbonate is in turn roughly
tion through the mass so as to avoid uneven burning or considered to be high calcium limestone. Because the
calcining of the stone. For this reason, small size stone 25 proportion of magnesium carbonate varies among rock
lumps are normally avoided in a vertical shaft kiln since species, the dissociation temperature thereof corre
they do not provide large enough void spaces for ade spondingly varies.
quate circulation of the ?ame and gases through the Consequently, upon calcination, due to the earlier
calcining mass. I dissociation of the MgCO3 content, the resulting MgO
On the other hand, since the charge is continuously content is ordinarily hardbumed to at least some extent
tumbled on itself as it passes dynamically through the prior to the ensuing dissociation of the CaCO3 content
interior of a rotary kiln, smaller size limestone lumps are to CaO, inasmuch as the mass must be retained at a
readily used therein, and the calcining residence time is relatively high temperature throughout in order to
therefore shorter than in the case of vertical shaft kilns. achieve substantial completion of the CaCOg dissocia
For the shaft kiln calcination, the fuel consumption 35 tion for forming soft burned CaO.
on an industrial sacle can, for instance, amount to about This hard burned MgO content may be minimized to
4 to 6 million Btu/ton (1112 to 1668 kcal/kg) of lime some extent by calcining the stone at minimum and
stone, e.g. in a modern central burner type vertical shaft constant temperature but for a longer residence time in
kiln, and for rotary kiln calcination it can, for instance, the kiln.
amount to about 4.7 to slightly above 7 million Btu/ton As a rule, for less pure limestone (higher MgCO3
(1307 to slightly above 1946 kcal/kg) of limestone, e.g. content), a calcining temperature of at least about 910°
in a current type rotary kiln. . C. (1670° F.) and up to about 1000' C. (1832° F.) is
Larger size lump stone such as 4 to 8 inch lump stone typically used, and for limestone of higher calcium
is normally calcined in vertical shaft kilns, and smaller carbonate content or purity (lower MgCO3 content), a
size lump stone such as that below about 4 inch lump 45 calcining temperature of between about l000°—l 100" C.
stone, and particularly 0.25 to 2.5 inch lump stone or (l832°-2012° F.) is typically used.
pebble lump stone, is normally calcined in horizontal However, the operation may be carried out at still
rotary kilns. higher temperatures, e.g. up to about 1149" C. (2100° F.)
Different size stones, of course, burn or are calcined or even up to about 1241' C. (2266’ F.), as indicated in
at different rates since as earlier noted, the dissociation 50 Table l, or in more practical commercial scale terms up
progresses from the outer to the inner zones of the to about 1204’ C. (2200° F.) or even up to 1316° C.
limestone lumps. For uniformity of results, therefore, a (2400' F.), and in some cases up to 1482. C. (2700° F.),
uniform size or narrow graduation range of stone is depending on the circumstances and the product results ‘
best. While it would seem expedient to use the minimum sought.
possible size stone in a narrow graduation range to 55 Aside from the foregoing, it will be further appreci
shorten the residence time in the kiln and conserve fuel ated that as the calcining temperature increases, so does
energy and also obtain a uniform product, this must be the tendency of the limestone impurities and those in
balanced against the cost of crushing the raw stone from any direct contact heating fuel used, such as ash constit
the quarry to achieve such narrow graduation range uents and sulfur in coal or coke, and sulfur in fuel oil, to
reduced size at acceptable levels of wastage in terms of 60 react not only with the forming lime content itself in the
?nes, dust, etc. lumps, but also with the refractory lining of the kiln.
It will be appreciated that the operation, including Where higher calcining temperatures are contemplated,
the calcining temperature and the kiln residence time e.g. above about 1100° C. (2012° F.) and especially
selected, and in turn the quality and condition of the above about 1149° C. (2100‘ F.), more expensive refrac
resultant oxide product, will necessarily depend not 65 tory linings are required for the kiln to minimize the
only on the content of impurities in the starting lime e?‘ects of this tendency.
stone and/or in any fuel or its combustion products In fact, local overheating or hot spots not only lead to
coming into contact therewith, e.g. silica, alumina, iron nonuniformity in the calcining product, but also often
 4,748,010
8
cause accretions and premature failure of the refractory bon dioxide partial pressure and the desired shift to the
?ning, especially in rotary kilns using coal as fuel, re right side per the equilibrium equation I.
quiring premature shut down for repairs. Due to the Furthermore, aside from recycling CO2 containing
nature and thickness of such linings, start up and shut exhaust gases directly or indirectly to the lime kiln, and
down of the kiln operation, which is normally a twenty aside from the relative cost of solid fuel such as coal and
four hour a day continuous operation, must be carried coke (e.g. of calori?c value of about l0,000—16,000
out by slow incremental heating and cooling, respec Btu/1b.), and liquid fuel such as fuel oil (e. g. of calori?c
tively, in order to minimize the adverse effects of ther value of about l6,000-l8,000 Btu/1b.), as compared to
mal expansion and contraction in damaging the integ gaseous fuel such as natural gas (e. g. of calori?c value of
rity of the refractory material itself, since any sudden about 900-1200 Btu/ft3), producer gas (e.g. of calori?c
change in temperature can cause the lining to disinte~ value of about 150-300 Btu/ft3 from coal), etc., it will be
te. appreciated that, other things being equal, while the
gmAs is known, these refractory linings must be reason combustion conditions may be adjusted for substantially
ably thick in order to provide structural protection of complete burning, on the one hand, of solid or liquid
metal parts and at the same time heat loss from 15 fuel theoretically to CO2 and H20 in the combustion
the kiln. Their repair and replacement further burdens gases, nevertheless, on the other hand in the case of
the cost of lime production, since apart from the cost of gaseous fuel, even where substantially completely
such repair and replacement the kiln must be kept out of burned as well, the combustion gases will inherently
service during the interim, and for each instance of contain a higher CO2 content in all cases but natural gas,
down time the kiln must be slowly cooled and in turn 20 due to the signi?cant presence of extraneous CO2 in the
slowly reheated, thereby consuming extra time and synthesized starting gas.
extra fuel without any bene?t in terms of limestone This extraneous source of CO2 will also indepen
calcining throughput. dently adversely in?uence the CO2 partial pressure in
The usual vertical shaft kiln generally consists of an the lime kiln and lead to relatively less ef?cient results
upright steel cylinder for strength and prevention of gas 25 in the same sense as occurs in recycling spent gases to
leakage, which is lined with ?re brick as refractory the kiln.
material. It may be ?red for instance with producer gas, Moreover, in the case of all such fuels, including
e.g. laterally or centrally supplied to a throat portion those synthesized gaseous fuels containing extraneous
~= near the bottom of the shaft, such that a major portion CO2, although in the primary reaction the carbon con
of the air for combustion is upwardly supplied through tent of the fuel is oxidized to CO2, and any hydrogen
v the bottom. The relatively large lump limestone is con content of the fuel is oxidized to H20, an undesired
‘:i tinuously fed to the top of the shaft, and is preheated by secondary reaction often occurs as well, in which part
the upwardly rising hot gases and then calcined at the of the CO2 present in the combustion gases reacts with
I combustion zone in the vicinity of the throat portion additional carbon, e. g. where there is relatively an insuf
supplied with the producer gas and where the gas meets 35 ?ciency of oxygen and/or an excess of hydrogen in the
the' incoming air, already itself preheated by the de combustion system, and is thereby reduced to CO.
scending mass of hot lime which exits from the bottom As earlier noted, the reduction of carbon dioxide to
; » of the shaft. The products of combustion and liberated carbon monoxide involves an endothermic reaction,
. carbon dioxide are discharged as spent gases for in and this decreases the kiln temperature, directly or
.astance laterally at a point near the top of the shaft. 40 indirectly, as well as causes potentially usable heat val
»0n the other hand, if coal is employed as the shaft ues to be lost with the spent combustion gases exiting
kiln fuel, e.g. in a ?re box of an indirect ?red kiln, this from the kiln. As a result, there is a corresponding re
same air supply principle may be used, such that sec duction in the thermal ef?ciency of the calcining opera
ondary combustion may be induced in the body of the tion.
kiln by introducing some of the air through the bottom 45 In contrast to the vertical shaft kiln which is normally
of the kiln. This prevents an excessive temperature in used for burning or calcining relatively large lump
the region adjoining the ?re box, and makes possible a stone, a horizontal rotary kiln is used normally for bum
kiln of much larger cross section than otherwise. ing relatively small lump stone, and generally consists
In particular, the use of producer gas, which is highly of a slightly inclined steel tube, which is also lined with
diluted with nitrogen and added steam, generally in 50 refractory material. It may be fired for instance by gas
sures a voluminous ?ame which penetrates throughout as above discussed or by powdered coal or by atomized
the entire central body of the kiln. The gas ?ame may be and vaporized fuel ‘oil. Because the stone is of relatively
made of even larger volume without dropping the tem smaller size, it is generally calcined in a much shorter
perature in the kiln, by the expedient of recycling to the time than in the case of the vertical shaft kiln, as earlier
intake of the producer for the producer gas some of the 55 noted.
spent‘ gases exiting from the top of the kiln since the It will be appreciated that modern day rotary kilns
carbon dioxide in this gas is partially reduced by the can readily burn coal, gas or atomized and vaporized
well known endothermic reaction to carbon monoxide fuel oil with equally good calcining results, whereas
in the hot body of the producer, and thus enriches the most existing vertical shaft kilns are normally more
fuel gas thereafter fed to the kiln. restricted in terms of their design features to burning
However, at the same time, this expedient undesir= gas or fuel oil, few being able to accommodate solid fuel
ably not only consumes heat energy in the upstream with any degree of efficiency except as producer gas
producer to compensate for such endothermic reaction, source.
even though it may not drop the temperature in the Theoretically, based on the equilibrium equation I,
downstream kiln, but also and more importantly en 65 the complete conversion of calcium carbonate (mol. wt.
riches the kiln with that part of the carbon dioxide in 100) to calcium oxide (mol. wt. 56) and carbon dioxide
such recycled spent gases which is not so reduced to (mol. wt. 44) causes a 44% reduction in weight of the
carbon monoxide, to the relative detriment of the car starting limestone solids content (theoretically 44%
 4,748,010
9 10
LOI), and provides a corresponding 56% reduced energy costs since they inef?ciently consume prohibi
weight quicklime product. Although the infusible tive quantities of thermal energy in attempting to
quieklime product obtained generally retains the form achieve such vacuum calcining operation, as is clear
of the original lumps of starting limestone, as earlier from the following.
noted, its bulk is 44% lighter in weight and, other things 5 McTighe (US. Pat. No. 736,869, issued 1903), per a
being equal, is correspondingly more porous internally. ?rst embodiment, calcines a batch of limestone, under
' or less dense due to the loss of the carbon dioxide con vacuum and by indirect heat exchange, in a closed verti
tent from the crystal lattice of the starting solids mate cal furnace to make carbon monoxide. The furnace
rial. contains a vertical central tube ?lled with coke or coal
In the case of the proportionate content of magne and ?ow connected at its top end with a series of sur
sium carbonate (mol. wt. 84.3) also present in the start rounding like tubes ?lled with limestone, all the tubes
ing carbonate rock or stone, theoretically its complete being inserted in a bed of solid fuel disposed in the
dissociation to magnesium oxide or magnesia, e.g. peri furnace. The fumace has a combustion products ?ue at
clase (mol. wt. 40.3), and carbon dioxide (mol. wt. 44) its upper end above the level of the bed fuel and an ash
causes a 52.2% reduction in its weight content (theoreti pit at its lower end separated from the bed fuel by grates
cally 52.2% LOI), and provides a proportionate 47.8% and presumably freely supplied with combustion air for
reduced weight ?nal solids content. Hence, the greater upward ?ow through the grates. A vacuum pipe is
the magnesium carbonate content in the starting car connected to the bottom end of the central coke and
bonate rock or stone, the greater will be the weight loss coal tube for applying a vacuum to all of the tubes.
after calcination. 20 Upon burning the bed fuel in the McTighe ?rst em
However, in all cases, the calcining will only proceed bodiment, the limestone and coke or coal in the respec
to substantially complete decomposition of the lime tive tubes are heated by indirect heat exchange to incan
stone when the partial pressure of the produced carbon descence at about half the temperature normally used,
dioxide is maintained constantly below the equilibrium such that the entire limestone charge is calcined under
pressure at the corresponding temperature, and this 25 vacuum and the liberated carbon dioxide is drawn from
usually requires a calcining temperature over 898°-900° the limestone tubes through the central tube for endo
C. (l648'-1652' F.)'to drive the action forward, i.e. at thermic reaction therein with the coke or coal to form
normal atmospheric pressure, such as a temperature of carbon monoxide (which thereby consumes heat and
from about l000°-1100° C. (l832°-20l2° F.), as afore produces a cooling effect), the carbon monoxide being
said. 30 recovered via the vacuum pipe as a valuable product, as
In actuality, because of the various practical factors opposed to carbon dioxide as a waste product.
involved, complete calcination of any commercially McTighe, per a second embodiment, omits the cen
available carbonate rock will never provide a product tral tube, ?ow connects the limestone tubes via ports
which-is 100% free of carbon dioxide, such being essen near their top ends directly with the fuel bed in the
tial unattainable even under strict laboratory conditions. 35 furnace, and inserts an air blast pipe and a ?rst vacuum
Instead, some super?cial recarbonation about the pipe in the ash pit. A crude petroleum oil supply pipe is
lump exterior will normally occur, due to the carbon also inserted in the ash pit and a second vacuum pipe is
dioxide rich atmosphere in the kiln traceable to the inserted directly into the ?iel bed for use in making
carbon dioxide liberated from the lump itself and that in illuminating gas. In this two phase cycle operation, ?rst
any attendant combustion gases in direct contact with air is supplied from the air blast pipe to the bed to burn
the lumps in the kiln, so that at least about 0.1—0.2% the fuel to heat to incandescence both the limestone
CD; will always be present in the calcined lump. How batch, by indirect heat exchange, and the bed fuel, by
ever, this recarbonated surface coating in fact limits direct combustion, with the combustion products exit
further recarbonation since it occludes the surface pores ing from the ?ue as in the first embodiment, and then
of the lump sufficiently to inhibit recarbonation of at 45 the air supply is terminated and the ?ue is shut, after
tendant carbon dioxide gas to a further extent within the which a vacuum is applied via the ?rst vacuum pipe to
inner zones of the lump under the normal calcining draw the liberated carbon dioxide from the limestone
temperatures involved. tubes via the tube ports through thebed of incandescent
Also, even in the case of soft burned lime, a small fuel for endothermic reaction therewith to form carbon
calcium carbonate core, e.g. about 0.25-2%, normally 50 monoxide which is recovered from the ash pit via the
remains in the center of the lump product, as attempts to ?rst vacuum pipe. When the bed is reduced by such
achieve dissociation completely of such core would reaction to a temperature below the working point, the
otherwise cause the lime to be overburned or sintered to ?rst vacuum pipe is reclosed, the ?ue is reopened and
dead burned or nonreactive condition. the air resupplied from the air blast pipe to repeat the
Hence, as contemplated herein, substantially com 55 cycle.
plete calcining embraces the concept of carbonate rock To obtain illuminating gas in the McTighe second
dissociation to such an extent that the oxide particle embodiment, during the carbon monoxide forming
product possesses at most about 0.l-0.2%, or less pref phase the ?rst vacuum pipe is closed and the second
erably at most up to about 2%, CD; as particle or lump vacuum pipe is opened while crude petroleum is sup
surface recarbonated coating, and at most about 60 plied to the ash pit, whereupon the oil is vaporized and
0.25-2%, and less preferably at most up to about 5%, drawn through the bed along with the carbon dioxide
unconverted carbonate as core material. from the tubes to produce a mixture of carbon monox
Various speci?c proposals are known for vacuum ide and hydrocarbon gas which is recovered via the
calcining of carbonate rock and the like, which employ second vacuum pipe.
direct or indirect heat exchange systems using solid, 65 Since only indirect heat exchange is used to calcine
liquid or gaseous fuels or electrical energy, generally in the limestone batch in the tubes, very low thermal ef?
arrangements of the vertical shaft kiln type. However, ciency and very high fuel consumption per unit lime
these may be deemed obsolete in terms of present day stone throughput necessarily burden the McTighe sys
 4,748,010
11 12
ten, and such negative aspects are aggravated by the dioxide will build up in the closed system which will
extra fuel consumption demands for supplying heat for o?‘set any bene?ts in reducing the carbon dioxide partial
the separate suction induced carbon monoxide forming pressure by the injection of steam, except to the extent
endothermic reaction, whether the latter consumes the that a high vacuum load is utilized and a high propor
coke or coal in the central tube per the ?rst embodiment tion of the withdrawn gases from the top of the charge
or the solid fuel of the bed itself in the furnace per the is correspondingly vented to the atmosphere, all of
second embodiment. Essentially continuous consump which will accelerate the fuel consumption rate and
tion of fuel for heating the entire charge must be carried steam consumption rate, and unnecessarily add to the
out until complete calcination is achieved, and at an cost per unit limestone throughput. Continuous con
accelerated fuel consumption rate under the suction sumption of both fuel and steam for heating the entire
induced ?ow in the system. charge must be carried out until complete calcination is
Niles (US. Pat. No. 1,798,802, issued 1931) calcines a achieved.
batch of limestone, under vacuum in the presence of Hyde (US. Pat. No. 1,810,313, issued 1931) partially
injected steam and by direct heat exchange, in a closed ealcines a continuous supply of individual batches of
vertical shaft kiln at lower temperatures than otherwise, limestone or other roastable material of mixed size
to avoid underdecomposing or overheating, recarbona lumps, preferably mixed with coal or other fuel, under
tion and semifusion, and instead produce a more uni vacuum and by direct heat exchange, on a continuously
form product. A bed of solid fuel in a ?re box, surround moving endless conveyor in a horizontal kiln. The
ing and communicating with the calcining zone of the batches are conveyed on pervious supports through a
kiln, is supplied via an air fan with primary air, pre 20 closed heating zone where fresh combustion gases from
heated by indirect heat exchange in ?ues surrounding the burning of oil, gas or powdered coal in an adjacent
the bottom discharge end of the kiln, and burned in the ?re box are drawn through the material via a suction
presence of steam injected both above and below the box below the pervious supports and optionally recy
fuel bed, for direct heat exchange calcining of the cled to a separate upstream preheater zone before dis
charge, such that the spent combustion gases and liber 25 charge as spent gases. The partially calcined material
ated carbon dioxide are withdrawn from the top of the batches are then conveyed to a separate closed, static
charge by a suction fan for recycling one portion to mix soaking zone, not provided with heat or suction re
with the fresh combustion gases above the fuel bed in moval of gases, where calcining continues of the larger
tr;v the ?re box and for venting the remaining portion to the size lumps which have not yet completely reacted, until
1: atmosphere to maintain the vacuum balance. The use of the material cools to below the reacting temperature, at
' steam injection above the fuel bed to induce the recy which point the batches are conveyed out of the kiln.
sr cled flow of the spent combustion gases and liberated In Hyde, the suction induced ?ow of the combustion
carbon dioxide can replace the suction fan, and the use gases through the heating zone necessarily accelerates
of steam injection below the fuel bed to induce the the combustion rate of the fuel, and results in incom
primary air ?ow can replace or be used in conjunction 35 plete mixing and combustion of the air and fuel, nonuni
,. with the air fan. form temperatures and especially inefficiently high fuel
._ : . In Niles, the steam injected below the fuel bed under consumption per unit material throughput, whereas the
j' goes an endothermic water gas reaction with the solid static nature of the closed soaking zone undoubtedly
fuel to form carbon monoxide and hydrogen (which causes the carbon dioxide pressure in the limestone
1 thereby consumes heat and produces a cooling effect) 40 material being calcined to build up and sti?e the system,
' and the latter in the presence of the primary air by way and in turn prematurely terminate the dissociation reac
~ of a secondary reaction form carbon dioxide and reac tion and instead regress to extensive recarbonation,
tion steam. This steam and the injected steam are said to such that the material will be nonuniformly and incom
decrease the partial pressure of the carbon dioxide and pletely calcined.
assist the release of carbon dioxide from the charge, 45 Walker I (US. Pat. No. 2,0l5,642, issued 1935) cal
whereas the recycled portion of the spent combustion cines a batch of limestone, under vacuum and by electri
gases and liberated carbon dioxide is said to cool and cal heat, in a closed chamber, after exhausting the air
dilute the fresh combustion gases above the fuel bed for therefrom, to obtain pure form carbon dioxide. The
lower temperature operation in the kiln. The vacuum is material is passed by gravity from a top preheater zone
stated to be minus four inches of water at the top of the through an intermediate constricted passage furnace
kiln and two to three inches of water above the fuel bed zone, having an upper electrical resistance preheater
in the ?re box. operating at l500°-1600° F. (8l6°-87l° C.) and a lower
Obviously, in Niles the recycled carbon dioxide bur arc electrode heater operating at 2600°—2650° F.
dens the closed system as does that formed from the (l427°-1454° C.), to a bottom discharge zone, while a
steam and solid fuel water gas reaction and the primary 55 10-15 lb. vacuum is applied to the top zone for recover
air supported secondary reaction, and the cooling e?'ect ing in pure form the carbon dioxide liberated in the
of such recycled gases and that resulting from the water furnace zone after it has preheated the material in the
gas carbon monoxide reaction not only represent a re top zone and been itself cooled thereby. The use of such
duction in thermal efficiency but, together with the high temperatures for calcining completely the entirety
need to supply heat for extraneous production of in 60 of the limestone batch, and the continuous supplying of
jected steam, also a concordantly higher fuel consump the necessary energy therefor from an electrical source,
tion per unit limestone throughput. Due to the inten involve costs that are prohibitive under current world
tional recycling of liberated carbon dioxide from the wide energy crisis conditions, regardless of economic
charge plus that in the spent combustion gases traceable conditions and electrical energy availability as of 1935,
to the combustion of the solid fuel in the tire box, which 65 or the fact that the recovered pure form carbon dioxide
enrich the normal carbon dioxide content in the fresh constitutes a salable secondary product.
combustion gases entering the calcining zone from the Walker II (US. Pat. No. 2,068,882, issued 1937) cal
?re box, an undesirably high total content of carbon cines a batch of limestone, in the presence of injected
 4,748,010
13 14
dry steam as carbon dioxide diluent and by electrical costs of operating any fans or using the extra steam to
heat, in a closed vertical shaft kiln to obtain pure form achieve proper ?ow of the gases within the system.
carbon dioxide, the steam taking the place of vacuum. Walker III (U.S. Pat. No. 2,113,522, issued 1938)
The kiln includes a top steam condensation and carbon concerns a related kiln system to Walker II, but instead
dioxide gas recovery zone, in indirect heat exchange 5 of supplying pressure injected high temperature steam,
enclosing relation to a separate closed preheater the carbon dioxide recovery suction fan is used to in
hopper, and partitioned by a water collection tray hav duce a vacuum in the batch operated closed kiln, after
ing upright entrance nipples from an intermediate reac removing the air therefrom, such that the liberated
tion zone containing an upper preheater section, a mid carbon dioxide alone serves as the inert heating medium
dle multiple distribution thin ?ow path calcining section recycled through the separate heating zone containing
and a lower soaking section. The latter zone is separated the electrical heater. This operation suffers from the
by a ?ow controlling valve from a bottom discharge same prohibitive cost drawback as Walker I and Walker
zone from which the lime product is periodically recov II in requiring a continuous supply of electrical energy
ered via a discharge valve. Dry steam at 900° F. (482° for calcining the entire charge of limestone until all of it
C.), i.e., well above the critical or condensation temper has been converted to lime.
ature of water (which is believed to be 705.20 C. or 374° Haas (U.S. Pat. No. 2,080,981, issued 1937) calcines a
C., at 217.5 atm or about 3200 psi), is injected under periodic supply of limestone, under vacuum and by
pressure separately into the soaking section and the indirect heat exchange, in a closed continuous vertical
discharge zone, part of the liberated carbon dioxide and tube whose intermediate and partially inclined portion
steam as a mixed gas is drawn off by a recycling fan 20 is enclosed in a separate furnace, to obtain pure form
from the top of the calcining section, passed through a carbon dioxide. The tube is equipped with synchro
separate heating zone containing an electrical heater nously operating gas tight rotary metering valves sepa
and then returned as hot mixed gas, e.g. 50% each, at rating it in turn into an introductory chamber, a pre
2000. F. (1093' C.) to the bottom of the calcining sec heater chamber, an inclined calcining chamber, a re
tion for recycled ?ow upwardly therethrough, and 25 serve pocket and a cooling chamber. The preheater and
condensed steam and pure carbon dioxide are recov calcining chambers are enclosed in indirect heat ex
ered from the top zone by a water pipe and suction fan change relation within a gas or oil ?red furnace having
- ' operated gas pipe, respectively. An auxiliary electrical its own combustion gas venting stack, and the cooling
' “ heater is located in the discharge zone to keep the tem
chamber is supplied with cooling air via a rotary check
perature therein above the 900° F. (482‘ C.) injected
30 valve containing inlet pipe. Also, each chamber (except
steam temperature.
the pocket) has a rotary check valve containing suction
pipe with a suction fan downstream of the check valve,
In operating the Walker II kiln, a limestone batch, the preheater and calcining chamber suction pipes lead
upon being preheated in the hopper by the condensing ing to a pure carbon dioxide collection system, and the
steam and separating carbon dioxide, which enter the 35 introductory and cooling chamber suction pipes leading
top zone through the tray nipples at about 300° F. (149° to the furnace to supply it with preheated combustion
C.) and are recovered therefrom in cooled condition, is air, including the cooling air normally fed via the inlet
charged to the reaction zone for passage as a thin stream pipe to the cooling chamber plus that entering the sys
in turn through preheater, calcining and soaking sec tem from the atmosphere when a batch of limestone is
tions in countercurrent to the injected steam and recy 40 periodically charged through the ?rst valve into the
cled electrically heated mixed gas, and the soaked cal introductory chamber and when a batch of calcined
cined product at 1600‘ F. (871° C.) is periodically fed to lime is periodically discharged through the last valve
' the discharge zone upon operating its valve. The steam from the cooling chamber, in the latter case during
injected into the soaking section cools the calcined those intervals in which the cooling air inlet pipe is
product to about 1600' F. (871° C.) and is superheated 45 closed off by its valve and prior to receiving the next
thereby before mixing with the hot mixed gas at about increment from the reserve pocket so as to prevent air
2000° F. (1093° C.) returned from the electrical heater, seepage upwardly through the pockets or sectors of ‘the
yet it is said that the cool lime even if it decreases below rotary metering valve between the cooling chamber
1600. F. (871° C.) will not recarbonate or form hy and reserve pocket.
drated lime due to the high temperature and thus dry 50 In Haas, as limestone is periodically charged to the
condition of the steam, and that the steam injected into introductory chamber any entering air is removed via
the discharge zone and the auxiliary heater therein simi its suction pipe, whereupon the charge is metered into
larly prevent such recarbonation or hydration. the preheater and calcining chambers in turn, both
In the Walker II system, the pressure of the injected within the furnace, such that the liberated carbon diox
steam is said to reduce the carbon dioxide partial pres 55 ide is recovered via their respective suction pipes while
sure and force it upwardly through the kiln, and if the the furnace combustion gases are merely vented to the
steam is in high proportion, e.g. 80% steam and 20% stack. The calcined lime is then metered into the pocket
carbon dioxide, it can be used for recycling the mixed for ?nal metering into the cooling chamber from which
gas and recovering the carbon dioxide without the recy it is periodically discharged via the last valve after being
cling fan or suction fan, the steam also serving to take air cooled. This operation is costly because it uses less
up any hydrogen sul?de stemming from impurities in efficient indirect heat exchange for calcining the lime
the limestone and dust formed during the calcining. stone with the sensible heat of the combustion gases in
However, the entire charge must be calcined to comple the separate furnace which are immediately vented to
tion by continuously supplying electrical energy and the stack, and because the entire charge must be contin
pressurized steam throughout the residence time. Thus, 65 uously heated until complete calcination is effected,
like Walker I, the operation involves prohibitive electri wholly apart from expenses in providing synchronously
cal energy costs plus additional costs for also providing operating rotary metering and check valves, and suc
very high temperature steam, wholly apart from the tion fans, to recover pure form carbon dioxide.
 4,748,010
15 16
Vogel (US. Pat. No. 2,784,956, issued 1957) covers a calcium sulfate, as regards water of crystallization, is
more recent vacuum calcining suggestion, as compared completely different from the carbon dioxide partial
to the relatively antiquated above discussed proposals, pressure in?uencing temperature controlled dissocia
which avoids the prohibitive cost of electrical heating tion and recarbonation system of calcium carbonate
as in Walker I, II and III, and the ine?iciency of indirect 5 according to the equilibrium equation 1. Indeed, cal
heat exchange with combustion gas as in McTighe and cium sulfate is often present as a lime impurity, trace
Haas, in favor of direct contact heating with such com able to precursor sulfur impurities in the starting car
bustion gases as in Niles and Hyde. bonate rock and/or in the combustion fuel which are
While similar to Niles, Vogel instead uses a producer oxidized during the calcination operation, and no doubt
gas fed central burner in the closed vertical shaft kiln, a exists as a dead burned inactive anhydrite slagging con
suction fan to vent the spend combustion gases and
liberated carbon dioxide from the top of the kiln, and a stituent as a result of calcining the rock at the usual
waste gas recycling system between the preheating and limestone calcining temperatures.
calcining zones to draw off some of the combustion SUMlMARY OF THE INVENTION
gases and liberated carbon dioxide thereat at 900° F. 15
(482' C.) under 90 psi steam injected induced ?ow for It is among the objects and advantages of the present
?rst removing the dust content in a dust trap and then invention to overcome the drawbacks and de?ciencies
recycling the same, relatively dust free, at 700° F. (371° of the prior art,_ and to provide an energy conserving
C.) admixed with the injected steam to the central limestone calcining system, especially as regards high
burner for extracting otherwise lost heat values, but 20 calcium and/or dolomitic limestone, i.e. metallic car
thereby adversely enriching the system with recycled bonate, including a process and conjoint apparatus for
liberated carbon dioxide. Temperature control is ef successive stage treatment of limestone to calcine the
fected via dampers at the suction fan and recycling calcium carbonate, and/or magnesium carbonate, i.e.
system under the surveillance of thermocouple temper metallic carbonate, content substantially completely to
ature indicators in conjunction with the steam and pro 25 calcium oxide, and/or magnesium oxide, i.e. metallic
ducer gas ?ows, such that the limestone is calcined in oxide, and carbon dioxide with the consumption of
the calcining zone at about l800°-2000° F. (982°-1093° considerably less heating energy than otherwise, re
C.) in the presence of steam and under partial vacuum. gardless of the type fuel or heating method used, and
vHere also, fuel and steam must be consumed for the particularly in part under a locally reduced partial pres
entire time that the limestone is calcined and until all of 30 sure of carbon dioxide whereby to reduce the overall
» I it is substantially converted to lime, and under acceler
ated induced ?ow through the kiln due to the presence
heat energy requirements of the calcination.
‘ " of the spent gas venting suction fan, in a manner analo
It is among the additional objects and advantages of
gous to Niles and Hyde. the present invention to provide a system of the forego
In each of the foregoing proposals, the entire charge 35 ing type, in which the calcining may be carried out such
of the carbonate material is calcined to completion wile that at least about 25% heat energy may be saved, and
~ under the continuous application of electrical or com in which lower kiln temperatures may be used as com
bustion heating energy thereto throughout the opera pared with existing systems, and such that less expen
tion. While stationary vertical shaft kilns, despite the sive refractory linings can be used in the kiln than in
above drawbacks, can be readily provided as sealed 40 existing systems.
- systems with vacuum suction, it will be appreciated that It is among the further objects and advantages of the
'- _due to the continuous movement of horizontal rotary present invention to provide such a system in which, in
kilns it would be dif?cult, if not impossible, to provide consequence of the permitted calcining at lower tem
them as vacuum suction operated sealed systems at the peratures than in existing systems, other things being
high order of magnitude calcining temperatures con 45 equal, a softer lime product can be produced which has
templated. greater porosity and higher surface area than that pro
Lastly, Kinkade (U.S. Pat. No. 3,527,447, issued duced in existing systems.
1970) teaches that a still hot (e.g. l25°-150° F. or It is among the still further objects and advantages of
52'-66° C.) batch of already low temperature kettle the present invention to provide a system of the stated
calcined (e.g. at 250'-500° F. or l2l°-260° C.) gypsum, 50 type which is such that it can be retro?t to most existing
i.e. calcium sulfate, which has meanwhile been kilns.
quenched with liquid water to form the dihydrate, can It is among the still further objects and advantages of
be subjected to indirect heating at 190°-200° F. (88°-93° the present invention to provide such a system, in which
C.) under a reduced pressure of about 0.3 in.Hg absolute
the calcining may be carried out in a two step sequence,
(29 in.Hg vacuum) in a vacuum chamber to remove
suf?cient water therefrom to form the hemihydrate (i.e. such that the limestone is partially calcined by heating
plaster of paris, a man made product which never oc the limestone at ordinary atmospheric pressure in a ?rst
curs in nature) in a condition which is said to be more step, and thereafter the calcining is substantially com
resistant to change on aging than previously manufac pleted in a second step under a vacuum, to reduce the
tured man made hemihydrate. The heating of the vac 60 partial pressure of the attendant carbon dioxide locally,
uum chamber is necessary to keep the attendant water while using for the completion of the calcining the
above its dew point so it will not condense on the walls sensible heat contained in the only partially calcined
of the chamber and recontact the hemihydrate and limestone from the ?rst step, without the need for addi
thereby reform the dihydrate, but at the same time it tionally heating the limestone in the second step,
must be such that the formation of the undesired anhy 65 whereby to reduce the overall calcination time and in
drite by overcalcination is avoided. turn the heat energy to the extent of preferably at least
Of course, the chemical system of low temperature about 25%, and consequently provide a corresponding
partial or complete dehydration and rehydration of saving in the production costs.
 4,748,010
17 18
ent to calcium oxide and carbon dioxide and to form a
BRIEF DESCRIPTION OF THE DRAWINGS partially calcined hot mass containing suf?cient re
Other and further objects and advantages of the pres tained heat for subsequently, e.g. independently, sub
ent invention will become apparent from the within stantially completing the conversion of the remaining
speci?cation and accompanying drawings, in which: unconverted limestone therein.
FIG. 1 is a schematic view of a graph showing the Thereafter, in the second step, the conversion of the
classic ?xed relation between the temperature and par limestone in the hot mass to calcium oxide and carbon
tial pressure of carbon dioxide over a wide range for the dioxide is, e.g. independently, separately substantially
calcination of calcium carbonate in accordance with the completed'by such retained heat while, e.g. locally,
dissociation parameters of the equilibrium equation subjecting the partially calcined hot mass to a vacuum
between limestone on the one hand and lime and carbon suf?ciently to remove substantially completely the re
dioxide gas on the other hand, pursuant to LeChatelier’s sultant carbon dioxide and for a duration suf?cient to
principle, achieve such substantially complete conversion of the
FIG. 2 is a schematic view illustrating an energy limestone and thereby provide a substantially com
conserving limestone calcining system according to the pletely calcined hot mass.
present invention, and including a calcining kiln for Only generally at least about 50-60%, and more par
carrying out the partial calcining of limestone in a ?rst ticularly between about 50-85% or 60-85%, e.g. be
step or zone, and a calcining vacuum chamber arrange tween about 65-85%, preferably between about
ment for completing the calcining of the limestone 70-80%, more preferably between about 72-78%, and
under a vacuum in a second step or zone, plus a cooler 20 especially about 75%, partial conversion of the lime
for cooling the completely calcined resultant product, stone is achieved in the ?rst step, and concordantly the
FIG. 3 is a schematic view similar to FIG. 2, and remainder of the conversion is achieved in the second
illustrating a calcining system which includes a vertical step.
shaft lime kiln for carrying out the ?rst step partial The limestone may be calcite, dolomite and/or mag
calcination of the limestone, 25 nesite, or the like type metallic carbonate rock.
FIG. 4 is a schematic view similar to FIG. 2, and In conjunction therewith, generally the limestone is
' illustrating a calcining system which includes a horizon heated to or maintained at a temperature of only for
tal rotary lime kiln for carrying out the ?rst step partial instance at least about 1700' F. (927° C.), generally
. calcination of the limestone, between about l700°-2700° F. (927"-l482° C.), prefera
FIGS. 5 and 6 are schematic side and interior end 30 bly between about l700°-2100° F. (927°-1149" C.),
views of a portion of an energy conserving limestone more preferably between l800°-2000° F. (982°-1093°
calcination apparatus according to the present inven C.), and especially between about 1800°-l850° F.
tion, showing the discharge end of a horizontal rotary (982‘-l0l0° C.), in the ?rst step for high throughput
kiln of the type shown in FIG. 4 in speci?c relation to efficiency, in dependence on the purity of the limestone
a calcining vacuum chamber arrangement including 35 used, and concordantly the remainder of the conversion
two alternately used separate vacuum chambers, is carried out in the second step with the retained heat
FIG. 7 is a schematic view of a graph showing a in the hot mass from the ?rst step corresponding to such
portion of the range of, yet having the same values as, temperature. I
the graph of FIG. 1, In particular, the ?rst step may be e?'ected at ordi
FIG. 8 is a schematic view of a graph showing a nary ambient or normal atmospheric pressure in a ro
I different portion of the range of, yet also having the tary kiln zone or ?rst zone and the second step may be .
same values as, the graph of FIG. 1, and per the shaded effected in a separate vacuum zone or second zone, and
area thereof speci?cally showing the corresponding the partially calcined hot mass may be recovered from
negative equilibrium pressures at corresponding tem the rotary kiln zone and fed to the vacuum zone for
peratures, below which the second step or stage vac 45 completing the conversion of the limestone in the vac
uum operation may be conducted at such temperatures cum zone.
or at higher temperatures according to the present in In this regard, the second step may be alternately
vention, and effected in a given one of at least two separate vacuum
FIG. 9 is a schematic cross sectional exaggerated subzones, such that the recovered partially calcined hot
representation of a limestone lump showing in the un 50 mass is fed in a corresponding batch amount alternately
shaded area the outer zone, e.g. of about 75% of the to a corresponding subzone.
lump volume, which is converted to the oxide in the More ‘speci?cally, an energy conserving limestone
?rst stage partial calcining in the lime kiln, and in the process of the foregoing type may be provided which
shaded area the inner zone, e.g. of about 25% of the comprises, in a ?rst step, supplying sensible heat to
lump volume, which is substantially completely con 55 limestone to heat to and/or maintain the limestone at a
verted to the oxide in the second stage vacuum chamber temperature suf?cient to dissociate the calcium carbon
arrangement, according to the present invention. ate present to calcium oxide and carbon dioxide, e.g. at
about normal atmospheric pressure, and thereby form a
DETAILED DESCRIPTION OF THE hot mass and liberated carbon dioxide, in accordance
INVENTION with an equilibrium dissociation reaction which is de
According to a ?rst main aspect of the present inven pendent on the partial pressure of carbon dioxide, and
tion, a limestone calcining process is advantageously for a duration suf?cient to achieve at least about 60%
provided for the successive stage calcination of lime partial conversion of the limestone by the sensible heat
stone comprising two steps. in the hot mass and thereby provide a retained sensible
In the ?rst step, the limestone is heated suf?ciently to 65 heat containing partially calcined hot mass in which the
achieve partial conversion, such as at least about 50% retained heat is suf?cient for subsequently indepen
or 60%, and generally more than, ‘for instance, about dently substantially completing the conversion of the
60%, partial conversion of the calcium carbonate pres remaining unconverted limestone in the hot mass, while
 4,748,010
19 20
removing the liberated carbon dioxide from the vicinity mass therefrom, as well as vacuum applying means
of the hot mass at a rate suf?cient to maintain the carbon adapted to be connected to a vacuum source for apply
dioxide partial pressure in the ?rst step below the corre ing a vacuum, e.g. locally, to the vacuum chamber
sponding equilibrium pressure at said temperature. means when the hot mass is received therein and the
In turn, the process further comprises thereafter, in a 5 entrance means and exit means are closed.
second step, continuing the dissociation reaction for Favorably, cooling means are provided outside of the
separately substantially completing the calcining of the hood means and ?ow connected thereto adjacent the
limestone, substantially in the absence of supplying exit means of the vacuum chamber means for receiving
further sensible heat to the partially calcined hot mass, and cooling the hot mass upon removal thereof via the
by subjecting the sensible heat containing partially cal IO exit means. For instance, the cooling means may include
cined hot mass, e.g. locally, to a vacuum suf?ciently to a rotary contact cooler device for rotating the hot mass
remove substantially completely the further liberated and adapted to receive a flow of cooling gas, such as air,
carbon dioxide and for a duration su?icient to achieve for contact cooling of the hot mass during such rotation.
substantially complete conversion of the limestone inde Preferably, the vacuum chamber means may include
pendently by the retained sensible heat contained in the 15 at least two separate upright vacuum chambers, each
partially calcined hot mass, and thereby provide a sub having an appropriately located vacuum applying pipe,
stantially completely calcined hot mass. a closable upper entrance and a closable lower exit.
Generally, therefore, the present invention contem Also, diverter means may be provided in the hood
plates an overall carbonate rock calcining process means at the kiln discharge outlet for alternately direct
which comprises, in a ?rst step, heating metallic carbon-= 20
ing the hot mass to the corresponding entrances of the
ate, e.g. calcite, dolomite and/or magnesite, sufficiently vacuum chambers, and chute means may be provided in
to achieve suf?cient partial conversion thereof to metal the hood means for conveying the hot mass from the
lic oxide, e.g. calcium oxide or magnesium oxide, and corresponding exits of the vacuum chambers to the
carbon dioxide to form a partially calcined hot mass cooling means.
containing sufficient retained heat for subsequently 25 Conveniently, by pass ?ow directing means may be
substantially completing the conversion of the remain provided in the hood means adjacent the kiln discharge
ing unconverted metallic carbonate therein. outlet and operatively arranged relative to the diverter
Thereafter, in a second step, the overall process fur means for by pass ?ow of the hot mass directly from the
v'j'j‘ther comprises separately substantially completing the kiln discharge outlet thereto, and the hood means may
‘ conversion of the metallic carbonate in the hot mass to 30 include a hood outlet for receiving such by pass ?ow of
" metallic oxide and carbon dioxide by such retained heat the hot mass for discharge from the hood means.
" while subjecting the partially calcined hot mass to a In particular, the kiln may be in the form of a rotary
' vacuum suf?ciently to remove substantially completely kiln having a ldln discharge end, such that the hood
the resultant carbon dioxide and for a duration sufficient means operatively encloses the kiln discharge end in
to achieve such substantially complete conversion of 35 relative rotational sealing relation therewith.
the metallic carbonate and thereby provide a substan Referring to the drawings, and initially to the graph
tially completely calcined hot mass. of FIG. 1, in connection with the equilibrium equation
Hence, preferably in this overall process, at least I and the vapor pressure Table 1 above, it is seen by
" about 50% or 60% partial conversion of the metallic extrapolation that roughly the vapor pressure or partial
“carbonate is achieved in the ?rst step, and the metallic 40 pressure of carbon dioxide almost doubles from about 1
carbonate rock is heated to a temperature of at least atmosphere absolute (760 mmHg) to almost 2 atmo
- about 1700' F. (927' C.) in the ?rst step. spheres absolute (1520 mmHg) as the temperature in
According to a conjoint second main aspect of the creases an increment of only about 50° C. (90° F.) from
present invention, a limestone calcining apparatus is about 900° C. (1652' F.) to about 950° C. (1742‘ F.), and
advantageously provided for the successive step or 45 again almost doubles from about 2 atmospheres absolute
stage calcination of limestone. to almost about 4 atmospheres absolute (3040 mmHg) as
Such apparatus comprises a limestone calcining kiln the temperature increases thatsame 50° C. (90° F.) incre
for heating limestone, e.g. at about normal atmospheric ment from about 950° C. (1652‘ F.) to about 1000° C.
pressure, for partially converting the limestone to the (1832‘ F.).
corresponding metallic oxide, e.g. calcium oxide, and 50 In a known lime kiln arrangement, as partially shown
carbon dioxide, and having a kiln discharge outlet for in FIG. 2, be it of the vertical shaft kiln or horizontal
recovering the partially calcined limestone in the form rotary kiln type, as more speci?cally partially shown in
of a hot mass from the kiln, plus closable calcining vac FIGS. 3 and 4 respectively, it is clear from the forego
uum chamber means separate from and adjacent the kiln ing that considerable excess heat is needed to overcome
discharge outlet and arranged for receiving therefrom 55 the partial pressure of carbon dioxide and drive the
the recovered hot mass for completing the converting calcination to completion per the equilibrium equation
of the limestone to the corresponding metallic oxide, I, i.e. by reducing the carbon dioxide partial pressure at
e.g. calcium oxide, and carbon dioxide and for applying the expense of excess heat energy input.
a vacuum, e.g. locally, thereto for removing such car By way of the present invention, on the other hand,
bon dioxide, as well as heat retaining hood means opera» the limestone calcination is carried out with locally
tively enclosing the kiln discharge outlet and the vac reduced partial pressure of carbon dioxide to reduce in
uum chamber means for minimizing heat loss from the turn the heat energy requirements of the calcination,
hot mass in the vicinity of the kiln discharge outlet and instead of by increased heat energy and/or temperature
in the vacuum chamber means. and/or calcining duration as in the past. This is
For instance, the vacuum chamber means may in 65 achieved speci?cally by dividing the operation into a
clude closable entrance means for receiving the hot two successive step or stage system, and using vacuum
mass from the kiln discharge outlet, and closable exit locally in the second step or stage to complete the calci~
means for removing the calcined vacuum applied hot nation of the partially calcined limestone from the ?rst
 4,748,010
21 22
step or stage solely by way of the retained sensible heat Since the pertinent equilibrium carbon dioxide partial
content already contained in the partially calcined lime pressure is a constant at a given calcining temperature,
stone. the temperature of the hot mass in the second step or
Consequently, this will decrease the overall cost of zone at any given time self de?nes such pressure below
the otherwise energy intensive process by concordantly 5 which the vacuum degree or level must be maintained
decreasing the total time or duration during which heat in the second step or zone at that temperature, in order
energy from an extraneous source, e. g. fuel for direct or to assure that the calcining of the remaining content of
indirect ?ring of the limestone, must be supplied in a the calcium carbonate therein is continued until that
positive manner in the stone or mass of starting calcium content is substantially completely calcined to calcium
carbonate. oxide and carbon dioxide, and that the carbon dioxide in
In turn, this will concomitantly decrease the quantity turn is substantially completely removed from the site
of such heat energy, e. g. fuel, and/or the temperature of or vicinity of the hot mass of calcium oxide so as to
the calcining operation. prevent reformation of calcium carbonate under the
Brie?y, according to the system comprising the con
joint process and apparatus aspects of the present inven existing temperature and pressure conditions in the
tion, limestone is heated to a point in time such that for second step or zone.
instance only more than about 60%, e.g. 75%, of the On the other hand, since the percentage of partial
limestone is calcined at about normal atmospheric pres calcining or of incompletion of the calcining is a func
sure in the ?rst step or stage in a normal calcining heat tion of the residence time of the limestone in the ?rst
supplying kiln zone, and the remaining, e.g. 25%, calci step or zone, it self de?nes the heat energy consumed to
nation is accomplished by conserving the energy, i.e. reach that point and to provide the temperature at
retained sensible heat energy, already in the stone or hot which the hot mass is fed to the second step or zone, and
mass and reducing the partial pressure of the carbon in turn self de?nes by difference the percentage saving
dioxide being generated or liberated by means of a vac in heat energy, as earlier discussed, in terms of a corre
uum locally applied in the second step or stage in a 25 sponding percentage saving in calcining time of the
calcining vacuum chamber assembly. limestone in the ?rst step or zone.
This can be conveniently accomplished by attaching For example, laboratory tests using equal portions of
or arranging one or more separate or discrete vacuum the same limestone sample were heated to the same
holding chambers constituting the calcining vacuum 30 calcination point (as measured by the residual carbonate
chamber assembly, at the discharge end or outlet of the content), with and without the application of a vacuum,
lime kiln constituting the normal calcining heat supply per the present invention feature, and the following
ing kiln zone, allowing the only partially calcined lime, results were obtained:
e.g. at generally about l800°—2000° F. (982°-1093° C.),
or at such other lower or higher temperature at which 35 TABLE 2
the ?rst step or kiln zone partial calcining is carried out, Limestone Calcination Comparison Experimental Results
to ?ll the corresponding vacuum holding chamber, and Condition Time, Temp. ‘F. (’C.) Residual Ca CO3
then placing the chamber locally under vacuum suffi Without Vacuum 20 minutes, 1850' F. .69%
ciently to achieve constant or continuous removal of ' (Comparison) (1010' C.)
I the attendant carbon dioxide, e.g. as it is generated or 40 With Vacuum 15 minutes, 1850' F. .80%
liberated, and for a selective or designated time or dura (Invention) (1010‘ C.)
, tion sufficient to complete substantially the calcination
of the attendant remaining calcium carbonate to cal As Table 2 demonstrates, the use of a vacuum per the
cium oxide at the attendant temperature. present invention results in a reduction of 25% calcina
The determining factor is that the hot mass from the 45 tion time, compared to the usual condition which omits
?rststep or zone which is intentionally only partially the use of a vacuum, and this directly relates to a corre
calcined must possess, suf?cient retained sensible heat sponding 25% saving in heat energy or fuel otherwise
energy, regardless of its temperature or degree of par needed to drive the reaction to the right side per the
tial calcining, for subsequently generally independently, equilibrium equation I.
substantially completing the calcining of the remaining 50 It will be noted from the graph of FIG. 1 that at such
uncalcined limestone in the hot mass quantity fed to the temperature of 1850. F. (1010° C.), the partial pressure
second step or zone, under the applied vacuum in the of carbon dioxide is extremely high since, by compari
second step or zone, so that the latter achieves substan
tial completion of the calcining of the starting quantity son extrapolation, at 1832‘ F. (1000° C.) the carbon
of the limestone, e.g. on a unit rate or weight basis, 55
dioxide partial pressure is around 2700 mmHg, whereas
without the need for independently supplying thereto in speci?cally at 1719' F. (937' C.) it is 1345 mmHg (1.77
a positive manner further heat energy from an extrane atm. abs.) and at 1980.5° F. (1082.5“ C.) it is 6758 mmHg
ous source, as required in the former or ?rst step or (8.89 atm. abs.), as indicated numerically in Table 1.
zone. Hence, the experimental results set forth in Table 2
It will be appreciated that partial calcining in the 60 are believed to show an unexpected or surprising differ
context of the present invention means incomplete cal ence in terms of the above discussed considerations.
cining whose percentage of incompletion is equal to the In actuality, the results of Table 2 are taken from a
percentage saving in heat energy, or stated another series of experiments carried out with cut limestone
way, whose percentage of partial completion directly cubes in order to provide specimens the mass and
de?nes by difference such percentage saving in heat 65 weight of each of which was as nearly identical to the
energy, e.g. one third incompletion equals one third others, so as to get acceptable reproducible test results,
energy saving, or two thirds partial completion by dif in accordance with the procedure of the following Ex
ference de?nes a one third energy saving. ample l:
 4,748,010
23 24
vacuum chamber or zone. In this case, when the declin
EXAMPLE 1 ing furnace temperature under the applied vacuum
A laboratory tube furnace (Lindberg, Model 55035, reached 1500' F. (816° C.), the two cubes were re
115 volts, 800 watts) was used which was provided with moved and analyzed per the above procedure. AH vac
suitable heat controls for maintaining the temperature at uum tests were carried out at the same level of vacuum,
a selectively preset temperature level. The main part of i.e. at 450 mmHg, with the plugged ceramic tube con
the furnace was 13} “long and 7" deep and of suitable nected to the Vacu/trol electric pump via the hose at its
height for accommodating the muffle part of the fur open end.
nace which consisted of a ceramic tube of ‘3"’ diameter It should be noted that the calcining temperature of
and 18" length such that when movably inserted into 1850° F. (1010’ C.) was chosen to enable the calcining
the main part of the furnace, the tube was longer than tests to be carried out at a reasonably fast burning or
the main part by a couple of inches at each end (i.e. calcining time for the small size limestone cube speci
about 2}" of the tube being exposed at each end). Nor mens so as to yield a lime product that was generally
mally, the movable tube is open at both ends and thus between 0.5% and 1.0% in residual carbonate (i.e. a
subject to normal ambient pressure or air pressure. lime cube having a 0.5 to 1.0% carbonate core). Hence,
A vacuum was obtained by closing one end of the the temperature-time relationship used in these experi
ceramic tube with a suitable high temperature plug or mental comparision tests does not necessarily simulate,
stopper and attaching a hose to the other end connected nor is it intended even to suggest, preferred or actual
in turn to a small Vacu/trol electric pump capable of commercial practice. For example, in rotary kilns, ac
pulling about 635 mmHg vacuum or suction. 20 tual commercial practice normally contemplates calcin
Preliminary experiments (not shown) were con ing at higher temperatures such as in the broad range of
ducted using limestone of good quality (i.e. calcite), 2100‘ F. (1149' C.) to 2700‘ F. (1482" C.) for high cal
crushed and screened to small lumps, -§">< +1" in cium lime, i.e. limestone of good quality (calcite) as used
size, with each test made with a charge of 6 lumps in these tests.
picked so that the total weight of each charge was 5.0 25 The results of 12 experimental tests, in which the air
grams. However, after many calcining attempts to ob calcining under furnace energy heating was carried out
tain replicate results of the degree or percent of carbon at 1850. F. (1010' C.) in each test, and the vacuum
ate remaining after the calcining, it became apparent calcining was carried out at 450 mmHg in each vacuum
that merely using lumps of different individual sizes was test, are shown in the following comprehensive Table
1'1“ not precise enough for obtaining acceptably accurate 2A:
‘data on such a small or laboratory scale testing proce
dure. TABLE 2A
Consequently, small cubes of the same type limestone Limestone Calcination Comparison Expgrimental Tests
(i.e. calcite) were instead carefully cut using a diamond Heat
saw so that each cube was very close to being precisely Condi- ing Cool/Vac. Residual
Test tion Time Condition CaC03 Avge.
the same size, i.e. 6-7 mm per side, and each weighing
4.8 grams. In this actual experimental procedure, two (Compar
.1 such cubes were used for each burn or calcining test, .12;
1 Without 20 Sealed 0.65%
and each pair was matched exactly as to weight with a Vacuum min. Cooling
~ companion pair of cubes for making duplicate tests. In 40 2 Without 20 Sealed 0.69% } ‘167%
way, good comparison results were in fact actually Vacuum min. Cooling
obtained. 3 Without 19 Sealed 0.52%
All calcining tests were made after the furnace was Vacuum min. Cooling 0 53,7
4 Without 19 Sealed 0.54% ' "
brought to the selected starting temperature of 1850’ F. Vacuum min. Cooling
(1010' C.) and allowed to remain at equilibrium for 15 5 Without 17 Sealed 17.01%
to 30 minutes.
6
Vacuum
Without
min.
11
Cooling
Sealed 14.56%
} 15 ' 8,7‘’
To start the calcine test, two limestone cubes were Vacuum min. Cooling
pushed to the center of the so heated open ended ce 7 Without 14 Open Tube 0.59%
ramic tube just over the point of the thermocouple in Vacuum min. Cooling
the main part of the furnace, and the timing of the cal 50 ‘6 min‘ 0 639'
cining was started. At the end of the predetermined a Without 14 Open Tube 0.67% ' ‘’
Vacuum min. Cooling
calcining time limit selected, the two cubes were pushed 16 min.
out of the ceramic tube and allowed to cool to ambient (Inven
in a tightly closed metal container (sealed cooling). The tion)
cold lime product cubes were then pulverized to a pow 55 9 With 15 min. Vac. Tube 0.80%
der quickly and then analyzed for CO; with a Leco
10
Vacuum
With 15 min.
13 min.
Vac. Tube 0.95%
] 0' 88¢"
carbon analyzer. Vacuum 13 min.
The above procedure for the tests involving ?rst 11 With l4 Vac. Tube 0.48%
stage partial calcining followed by second stage vac~ Vacuum min. 16 min. } o' 487‘’
uum calcining, according to the present invention, was 12 With 14 Vac. Tube o.4s%
altered slightly, i.e. at the end of the ?rst stage partial Vacuum min. 16 min.
calcining predetermined time limit selected, the furnace
power was turned off, and the ceramic tube was moved Whereas the results (not shown) of using randomly
one inch to place the two partially calcined cubes in a sized pieces of limestone were not very consistent, it is '
slightly lower temperature zone relative to the main 65 clear from Table 2A that the use of limestone precisely
part of the furnace and thereby simulate the loss of some cut with a diamond saw into cubes of 6-7 mm per side
heat in transferring the partially calcined lime product size and paired off in equal weights of 4.8 grams gave
from a calcining unit or zone to a separate and adjacent better or more consistent results, for instance with tests
 4,748,010
25 26
l and 2 showing that the conventional air calcining was TABLE ZB-continued
repeatable and the vacuum tests showing that the sec
Limestone Calcination Selective Data
ond sta‘ge continued vacuum calcining according to the
Residual _ Furnace Power On
present invention was also repeatable. CaCO3 Heating Time Condition
It should be noted that tests 9 and 10 (invention) were 5
carried out such that after 15 minutes ?rst stage heating, (Av. 4 tests, Tests 1 to 4)
0.68% 14.5 min. With Vacuum
the furnace was turned off and a vacuum was applied to (Av. 4 tests, Tests 9 to 12)
the then plugged ceramic tube in the second stage for an 15.8% 17 min. No Vacuum
additional 13 minutes (28 minutes total calcining) with (Av. 2 tests, Tests 5 to 6)
the ceramic tube being moved 1 inch from its earlier 10
mid position to simulate loss of heat in transferring the Even as between the open tube prolonged 16 minute
partially calcined lime product from the ?rst stage air tests 7 and 8 and the 16 minute vacuum tests 11 and 12
calcining zone to the second stage vacuum calcining (invention), after the same 14 minute heat applied air
zone.
calcining, based on the 0.63% average core residue per
Similarly, tests 11 and 12 (invention) were carried out 15 tests 7 and 8 and the 0.48% average core residue per
such that after 14 minutes ?rst stage heating, the furnace tests 11 and 12, for a residue difference of 0.15%, use of
was turned off and a vacuum was applied to the then
the vacuum per the present invention concept results in
plugged ceramic tube in the second stage for an addi
tional 16 minutes (30 minutes total calcining) at a ?nal a 24% reduction in the core size (i.e. 0.15/0.63). Upon
extrapolation to commercial scale limestone lump sizes,
temperature of 1500‘ F. (816° C.) with the ceramic tube 20 such
being moved 1 inch as in the case of tests 9 and 10 for 24% core size order of magnitude reduction takes
the same reason.
on particular signi?cance.
By way of a further comparison, unlike the sealed Understandably, the above distinctions as to the con
cooling of the air calcined produce per tests 1 to 6, the cept of the present invention which apply to high cal
comparison tests 7 and 8 were carried out such that 25 cium limestone or calcite in Example 1 and Tables 2, 2A
after 14 minutes heating, the furnace was turned off and and 2B, also apply analogously to dolomite, magnesite
the air calcined product merely air cooled in the un or other type metallic carbonate rock calcination.
plugged ceramic tube for an additional 16 minutes (30 The system for carrying out the features of the pres
minutes total air calcining and ?nal air cooling) with the ent invention may be appreciated from the schematic
ceramic tube being moved 1 inch as in the case of the so installation shown in FIG. 2. This includes the usual
vacuum tests 9 to 12 (invention). calcining heat supplying kiln zone or refractory lined
a It is clearly apparent from the results of Table 2A that ~ lime kiln 1 having a feed end or inlet 2 and a discharge
the vacuum calcining concept of the present invention end or outlet 3, which in thetypical known operation is
results in a signi?cant saving in energy. By reducing the direct ?ame ?red by fuel such as natural gas, producer
partial pressure of the attendant and generating carbon 35 gas, fuel oil, powdered coal or the like, or is indirectly
0
dioxide at the calcining temperature, the limestone con heated by supplying hot gases such as combustion gases
tinues to calcine at an accelerated rate. thereto from an upstream ?re box or the like, fed
Apart from the fact that the precisely cut cubes of through heat energy supply line 4.
limestone de?nitely provide more consistent results In the known operation, the limestone lump material
which are fundamentally better than in the case of ran 40 such as in the form of stone or rock granules or particles
' » dom size pieces, tests '1 and 2 as compared to tests 5 and
of desired size is fed to the kiln 1 through the feed inlet
6 show that in the case of conventional aircalcining, 2, air for combustion is typically fed through the dis
while it took 20 minutes of heating to calcine the lime charge outlet 3, and fuel is fed through supply line 4 and
stone at 1850' F. (1010' C.) to an acceptably low cal burns with the air to supply heat energy to the lime
cium carbonate residue of 0.65% or 0.69% average 45 stone, which after being calcined is recovered from the
0.67% residue, by cutting down the heating time by 3 discharge outlet 3, while the gaseous combustion prod
minutes to 17 minutes for a 15% reduction in heating ucts or exhaust gases leave the kiln 1 through the feed
time or heating energy (i.e. 3/20), an unacceptable large inlet 2.
residual core of about 17.01% or 14.56%, average Alternatively, the air may be separately supplied via
15.8% residue or core, was left in the limestone. 50
an air supply line 5 at some appropriate point and/or the
On the other hand, using a vacuum per tests 9 to 12 exhaust gases may be separately withdrawn via an ex
(invention), the heat applied calcining took place in haust gases line 6 at some other appropriate point (both
only 14 or 15 minutes, rather than 20 minutes as in the shown in phantom).
case of tests 1 and 2, to achieve an acceptably low cal
cium carbonate residue for a 25% saving in heating time 55 The limestone thus passes more or less incrementally
or heating energy at such 5 minute saving in time (i.e. or continuously through the kiln 1 in the direction of
the arrows from the feed inlet 2 to the discharge outlet
5/20). 3 generally in countercurrent to the supplied air and
Selective data from Table 2A show the following per
Table 2B: fuel combustion gases, and remains in the kiln 1 at about
mormal atmospheric pressure suf?ciently to complete
TABLE 213 substantially the calcining of the calcium carbonate
Limestone Calcination Selective Data content in the stone or rock feed to produce calcium
Residual Furnace Power On oxide and carbon dioxide.
CaCO3 Heating Time Condition The liberated carbon dioxide is taken up in the gase
0.65% 20 min. No Vacuum (Test 1) 65 ous combustion products which ?ow in countercurrent
0.69% 20 min. No Vacuum (Test 2) relation to the passage of the limestone and which are
0.48% 14 min. With Vacuum (Teat 11)
0.48% 14 min. With Vacuum (Test 12) exhausted via the feed inlet 2 or the separate exhaust
0.60% 19.5 min. No Vacuum gases line 6.
 4,748,010
27 28
The incoming air which is fed via the discharge outlet slow, overburning or at least dead time or an overex
3 or the separate air supply line 5 is in any case conve tended residence time of the limestone in the kiln 1 will
niently preheated by the calcined limestone hot mass result.
leaving the discharge outlet 3 in view of the countercur Overburned limestone represents an analogous defec
rent ?ow relationship provided. tive commercial product, while an overextended time
In the known operation, the degree or rate of removal represents a direct cost inef?ciency item since it means
of the liberated carbon dioxide from the vicinity of the that extra fuel is being burned without providing any
hot mass of the limestone being calcined is dependent bene?t regarding the further heating of the already
upon the corresponding degree or sufficiency of the (relatively prematurely) substantially completely cal
mixing of the air and fuel, plus the rate of flow of the air cined limestone still in the kiln 1.
and fuel and the gaseous combustion products through On the other hand, if the corresponding ?ow rates of
the limestone granule or particle lump mass, and con the air and fuel and gaseous combustion products are
jointly on the degree or rate of ?ow (throughput) of the too slow relative to that of the limestone, the limestone
limestone itself since these gaseous and solid ?ows are will not be supplied with suf?cient heat energy, and
in countercurrent relation. 15 thus the required residence time of the limestone in kiln
Obviously, too little air will cause incomplete com 1 must be extended to avoid underburing, which expedi
bustion of the fuel, uneven heat distribution and exces ent may not itselfbe suf?cient unless the actual temper
sive temperature, and too much air will cause cooling in ature maintained by such too slow flow rates of the air
the kiln and heat loss in the exhaust gases still containing and fuel and gaseous combustion products is suf?cient
hot but unused oxygen values. 20 for accommodating an industrial scale throughput of
For heat energy ef?ciency, the individual air and fuel limestone on a practical per unit time basis.
and conjoint gaseous combustion products ?ow rates Of course, the slower the ?ow of the gases through
must be suf?ciently slow enough for the generated or the limestone the greater the tendency for the partial
supplied heat energy (depending on the heat value of pressure of the generated or liberated carbon dioxide to
the particular fuel) to be imparted to the limestone. 25 increase disadvantageously as the concentration thereof
Otherwise, the exhaust gases leaving the kiln 1 via the builds up in the gaseous phase in the kiln 1.
feed inlet 2 or the exhaust gases line 6 will either be Each of the foregoing ?ow rate factors is indepen
incompletely burned or their contact with the limestone dently in?uential on the cost ef?ciency of the overall
be insuf?cient to transfer the mazimum of their heat operation, in terms of fuel consumption per unit time
‘1 content thereto, whereupon such exhaust gases will be 30 and per unit limestone calcined, as well as in terms of
“_ incompletely used exhaust gases. the degree of calcining, e.g., underbumed or over
In either case, the result would be a waste of heat burned, and the associated quality of the commercial
* energy. product obtained.
This could only be partly offset by the added burden More important, as regards the role of the partial
of recovering such incompletely used gases for some 35 pressure of carbon dioxide on the ef?ciency of the dis
extraneous purpose, such as for physically extracting sociation reaction according to the equilibrium equation
their remaining heat values, e.g., by indirect heat ex~ I, resort to positive suction discharge of the exhaust
aéchange. However, such expedient would be of only gases, e. g., via the separate exhaust gases line 6, to facili
iminor bene?t considering the high cost of fuel and the tate removal of generated or liberated carbon dioxide
5; limited ef?ciency of operations and equipment capable 40 taken up by such gases, would not result in greater
r'lrof physically extracting heat values residually from ef?ciency since, aside from the earlier discussed sponge
" exhaust gases. effect of the coating of the calcium oxide as ?rst formed
On the other hand, any attempt at recovering such on the limestone lumps, this would merely introduce a
incompletely used exhaust gases for the indigenous further complicating factor in the system constituting a
purpose of chemically extracting there remaining heat 45 separate source of disturbing imbalance.
values, e.g., by direct return for use as recycled combus This is because such positive suction discharge of the
tion air or as preheated ballast or diluent for carrying off exhaust gases would increase the rate of ?ow of such
carbon dioxide from the site or vicinity of the calcining gases through the kiln 1, such that the air and fuel
limestone, would enrich the gaseous phase in the kiln 1 would be incompletely burned and/or their gaseous
with further accumulating carbon dioxide, causing an combustion products would not remain in contact with
increase in the carbon dioxide concentration and thus an the limestone sufficiently to transfer the maximum of
increase in its partial pressure in a manner speci?cally thier heat content to the limestone, leading to extrane
detrimental to the desired shift to the right side of the ous heat energy inef?ciency and extraneous higher fuel
equilibrium equation I, as earlier pointed out. costs, regardless of the corresponding ?ow rate of the
Likewise, even where the corresponding flow rates limestone through the kiln 1.
of such gases are ef?ciently slow enough and uniformly In this regard, correspondingly increasing the flow
proportioned and mixed to achieve maximum combus rate of the limestone would produce an incompletely
tion as well as maximum transfer of generated heat calcined objectionable commercial product, whereas
energy to the limestone in the kiln 1 prior to withdrawal decreasing the limestone ?ow rate might lead to over
of such gases as exhaust gases via the feed inlet 2 or the burning but in any case would aggravate the extraneous
exhaust gases line 6, the ?ow rate of the limestone heat energy inef?ciency and extraneous higher fuel
through the kiln 1 in countercurrent relation to such costs since the thereby prolonged residence time of the
gases must be coordinated or matched therewith. limestone in the kiln 1 would further prolong the high
Otherwise, if the flow rate of the limestone is not relative fuel consumption per unit time and per unit
sufficiently slow, incomplete calcining of the calcium 65 limestone calcined, traceable to the use of such positive
carbonate will occur and the hot mass exiting via the suction discharge of the exhaust gases from the kiln 1.
discharge outlet 3 will constitute a defective commer Such disadvantageous fuel consumption inef?ciency
cial product, whereas if such limestone ?ow rate is too results, traceable to use of positive suction discharge of