July 31, 1962 W. W.

JUKKOLA 3,047,365
TEMPERATURE CONTROL IN THE FLUIDIZED ROASTING PROCESS OF
SULFIDIC ORES WITH THE BY-PRODUCT RECOVERY OF STEAM
Filed April 13, 1959

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 United States Patent Office
uper-rearmoravarteresserraries - s:
3,047,365
Patiented July 31, 1962
2
and then removing the remainder of the heat, and con
3,047,365 Sequently attaining final temperature control, by direct
TEMPERATURE CONTROL EN THE FLUEBIZEED heat removal means, such as water injection or excess
ROAST-NS PERC) CESS OF SUSEFEDC GERES WETH air or both, or perhaps by the addition of substances
THE BY-PE233UCT REGOVERY OF STEAM which absorb heat in undergoing endothermic reactions
Wa:$red W. Jakoia, Westport, Conn., assigror to Dorr in the bed-advantageously such materials should yield
Cliver Air corporated, Stalia ford, Co., a corporation SOa gas upon decomposition, for which purpose one can
of Delaware
Fied Apr. 13, 1959, Ser. No. 365,825 enploy a sulphate material not incompatible with the
5 Claims. (C. 23-79) ore being roasted, sulfuric pickling liquor and like sub
IO stances. The cooling by the addition of such materials
This invention relates to the contacting of solids with may provide the sole means of absorbing any balance of
gases in accordance with the so-called solids fluidization heat of excess reaction not absorbed by the heat exchange
technique. The invention is of primary importance in elements or it may supplement the heat absorbing activity
connection with the roasting of sulfide ores, such as achieved by water injection or excess air.
pyrites, for the production of sulfur dioxide gas and iron for example, a fluidized solids furnace designed to
oxide calcines, however, it is equally applicable to tem roast 100 metric tons per day of 46% 9% sulfur pyrites
perature control in the fluidized roasting of any finely should be operated at a temperature of 1650 F. The
divided materials which react exothermically at roasting desirad stean temperature from the coils is 460 F.
temperatures. i&casting with a slight excess of air (10%) the excess
Fluidization may be described as that technique in 20 heat of reaction generated in the chamber is 8,620,000
which a mass of finely-divided solids (say up to 1/2' or 3.t..'s per hour. The coils absorb 6,900,000 B.t.u.'s
So) is Suspended in an uprising gas stream under such per hour, water injected directly into the bed absorbs
conditions that the mass expands and is agitated so that 1,720,000 B.E.L.'s per hour as latent and sensible heat.
it behaves very much like turbulently boiling water. This quantity of heat absorbed by the injected water, is
Under these conditions the solids are in turbulent zig-zag carried froin the reactor in the exit gases and the sensible
motion throughout. Such a suspended mass is referred heat content is recovered in a waste heat boiler. Under
to as a fluidized bed. the foregoing conditions the steam recovery is 1.40 tons
Gas solids contact in a fluidized bed is amazingly of steam per ton of pyrite. In the same reactor operating
efficient and the mixing is so thorough that, for all prac inder the same conditions but at a feed rate of only 80
tical purposes, uniformity of temperature and chemical metric to:ns per day, the excess heat of reaction is
composition exists throughout the bed. By its very 6,900,000 B.t.u.'s per hour. This is entirely removed by
ilature, a fluidized bed must consist predominantly of the cois and no water injection is required. Under these
completely treated material. Incoming feed material is conditions steam recovery is 1.51 tons of steam per ton
immediately distributed throughout the bed which serves of pyrites. in the same reactor under conditions where
as a heat reservoir and a feed distributing means thus the the feed raie is 120 metric tons per day the excess heat
feed material almost instantly assumes the tempertaire of reaction is i0,350,000 of which 6,900,000 B.t.u.'s per
of the fluidized mass as does the uprising gas so that hoir are removed by coils and 3,450,00 by water injec
wine; the feed and the treatinent gas contact each other tion. Under these conditions 1.34 tons of steam are
they are already at reaction temperatures. 4.0
recovered for each ton of pyrite roasted.
The firidized roasting of sulfides is an exothermic re When roasting pyrite, it is generally desirable to operate
acticín which releases a considerable quantity of heat. the reactor at nearly the maximum possible temperature
If the fied rate and sulfur quantity in the feed are suffi and minimum amount of excess air in order to obtain
ciently great then the excess heat released must be re Inaximum SO2 production while having a low SO3 con
noved from the bed otherwise the temperatures will tent in the gases, also, the high temperature favors max
2xceed the fusion point of the roasted particles in the imum by-product steam recovery. For most pyrites,
bed thereby causing these particles to fuse with a conse optimum roasting results are obtained when the reactor is
quent defluidization of the entire bed. operated at a temperature of about 900 C. and 10% ex
it is therefore necessary to control the temperature of cess air. A slight increase in temperature, say 25 C., is
the bed in order to prevent fusion of the bed particles. usually sufficient to cause the bed to defluidize due to
Temperature control is also necessary in order to main fusion or softening of the particles. On the other hand,
tain optimulin operating conditions. Generally speaking a drop in temperature below the optimum tends to pro
the bed tempgrature for sulfide roasting should be in the mote the formation of SO since the equilibrium between
range from 1650° F. to 1750 F. if the temperature is SO2, SO3 and O2 is a function of temperature.
decreased nuch below this point, a considerable loss of A study of the SO2, SO3 and C equilibrium also indi
Suifur as SO3 will occur due to change in the 55 cates the desirability of using a minimum amount of ex
SC-C-SOs equilibrium. cess air when low SO is desired. However, in practice
it is known to extract heat from a fluidized bed by it has been found that usually 5 to 10% excess air is re
ineaths of coils or other heat exchange elements immersed quired to obtain the desired removal of sulfur from the
in the bed. The coolant flowing through the coils may calcines.
be water and the heat absorbed used for the production 60 The following reaction shows the heats of reactions for
of stealin. However, these coils are inflexible in that pyrite and pyrrhotite when roasting with less than 5%
they are norfinally designed for optimum heat extraction excess air and more than 5% excess air.
at fixed teiperature differentials between the bed and LESS THAN 5% EXCESS AIR
coolant medium. Any variation in the bed temperature
psets these optinhum conditions and results in improper FeS2 +%O, 4 Fe:O+2SO, 2860 B.t.u./# FeS
fu actioning. Moreover, cooling coils are not sensitive FeS118-1.85O2->/3 Fe3O4-1.18SO
control ineans because they cannot be adapted readily to 2850 B.t.I./ik FeS1.18
wide variations in heat production to maintain a constant MORE THAN 5%, EXCESS AIR
bed temperature such as is required for most efficient
desulfurization of the ore. 2995 B.t.u./# FeS
This invention proposes to overcome this disadvantage FeS118-- 1. .93O-> /2Fe2O3-- 1.18SO
by rer:}oving only the major portion of the heat by coils 3020 B.t.u./#FeS1.4
 3,047,865
3 4.
In roasting a pyrite or pyrrhotite only a small portion steam coils. The level controller 3 automatically con
of this heat of reaction is needed for bringing the re trols the input of feed water to a steam drum 4 in the
actants and products up to the operating temperature. system by regulation of the diaphragm valve 5. The
Thus to maintain the unit at the desired operating ten by-product steam is automatically discharged through the
perature, all of the excess heat of reaction must be re pressure regulator 6. This discharge rate will be essen
moved by some means. In all units, some heat losses will tially constant for a given system. The saturated Steam.
occur. However, according to this invention, the bulk will be discharged at a pressure of about 450 p.S.i.g. and
of excess heat is removed by use of steam coils and, to 456 F. If super heated steam is desired, the saturated
obtain operating flexibility, the remainder of the excess steam can be passed through superheater coils installed
heat is removed by direct injection of water into the bed. O in a waste heat boiler or in the reactor. Except for the
The objects and advantages of this invention over the water make-up control rate, and steam pressure regula
prior art, illustrated by German Patents 15,681 published tion, no other controls are involved in the system. The
April 28, 1955, and 18,198 published March 30, 1954, in water circulation rate through the coils is maintained
which the heat exchange coils are moved relative to the constant by the circulation pump 7 or the system can be
fluidized bed and vice-versa are manifest. Other objects designed for natural circulation.
and advantages are as follows: The actual temperature control in the reactor is car
A constant amount of steam at constant pressure and ried out by the direct water injection system. The thermo
temperature is produced regardless of operating (roast couple 8 senses the temperature in the fluid bed and sends
ing) rate between the ranges of say 80% to 120% of an electrical impulse to the temperature controller 9.
design capacity. 20 The temperature controller compares the magnitude of
With the system, the by-product steam production from the impulse with a set point and if higher or lower,
the combination of coils and waste heat boiler will be changes the pneumatic pressure to the diaphragm valve
90%-- of the maximum possible when using only steam 10 which regulates the flow rate of water to the water
coils and waste heat boiler. Thus considerable operating injection nozzle is. This latter item may be merely a
flexibility is obtained with sacrifice of less than 10% in small diameter pipe projecting inside of the reactor. The
by-product steam production. nozzle may be inclined slightly downward and installied
Temperature is automatically and easily maintained at above the level of the fluid bed. Although the cooling
a fixed point. water can be sprayed or spread out over a wider area
Operating temperature can be readily changed. This of the bed by means of air or special nozzles, this is not
merely requires changing the set-point on the temperature 30 an important feature of the system.
controller from one number to another (just turning a A number of alternate methods are available for con
dial). trolling the rate of water injection to the bed based on
Variations in the moisture content of the feed due to the temperature variations. However, the preferred sys
rains, seasonal changes, etc. has little effect on the opera tem is similar to that shown in which electrical impulses
tion of the roaster. The temperature controller would 35 are compared and then converted to pneumatic pres
automatically compensate for the Water introduced with sures for actual control. These systems are capable of
the feed. easily and automatically maintaining the bed temperature
Using the combined temperature control system, it is within -10° F. of the set point.
not necessary to know accurately all physical and chem It will be evident from the foregoing that the method
ical properties of the ore in order to design an operable 40 and apparatus according to this invention provides a
system because the coils do not have to be designed and simple reliable and inexpensive system for obtaining tem
sized to remove the exact amount of excess heat produced perature control of a fluidized reactor with the neecssary
in the roasting operation. This also makes it possible flexibility required for a wide range of operating condi
for the operator to have selection of raw material based tions while providing a source of steam at constant tem
on economic consideration rather than strictly chemical 45 perature, pressure and quantity.
properties of the ore. This application is a continuation-in-part of applica
A roasting system can be designed to operate at Say tion Serial No. 586,651, filed May 23, 1956, now aban
80% to 120% of design capacity without making any doned.
equipment alternations. Thus the production can be I claim:
readily adjusted to demand. 50 1. In the roasting of sulfidic ores in a fluidized bed re
The drawing diagrammatically illustrates a control sys action chamber with the fluidized material in the bed un
tem for fluidized roasting using a combined steam coil dergoing exothermic reaction with the fluidizing air to
heat exchanger and direct water injection for the tempera produce SO2 containing gases, the method of maintain
ture control of the fluidized bed with production of steam ang a required reaction temperature at fluctuating load
at constant temperature and pressure and in maximum 55 rates in the bed by the controlled withdrawal of excess
quantity consistent with optimum flexibility of tempera heat from the bed with byproduct steam generation by
ture control of the reactor. said heat, characterized thereby that a predetermined
The steam coils 2 are sized so that they would remove major portion of the excess exothermic heat is removed
about 80% of the excess heat of reaction when the reactor from the bed at a constant rate by means of heat ex
1 is operated at its design rate and at optimum operating 60 change elements having predetermined heat transfer area
conditions. The operation of these coils merely requires located in the bed whereby sufficient water is circulated
passing water through the coils at a given rate which is at a constant rate through said elements to produce satu
determined by the heat exchanger requirement of a given rated steam with a portion of the water passing through
reactor. Since the coils are installed in an atmosphere said elements being continuously converted into satu
conducive to the formation of H2SO4, the operating con rated steam with the result that heat removal from the
ditions of the steam system must be such that HSO will bed is effected at a constant rate by said elements, while
not condense on the coil surfaces, causing corrosion and the remainder of said excess heat is removed directly
subsequent failure of the tubes. As a result, the steam and instantaneously by feeding into the bed injection
system is designed to operate at a pressure of about 450 water while controlling the rate of feed thereof into said
p.s.i.g. and temperature 456 F. so that the temperature bed in accordance with temperature changes in the bed,
of the coils is maintained above the HSO, dew point at thus maintaining the reaction temperature constant ir
all times. respective of load changes in the bed, and while main
A preferred steam circuit consists of a steam drum taining a constant differential between the temperature
with separators, pressure regulators, etc., a water level of the reacting fluidized material and the surface tem
controller, water make-up system, circulating pump, and 75 perature of the exchange elements by holding the pres
 3,047,865
5 6
sure of the saturated steam constant at a point at which rated steam is subjected to superheating by the roaster
the corresponding temperature of the saturated steam gases.
will keep the temperature of the elements themselves suffi 5. The method according to claim 1, wherein the satu
ciently high to prevent corrosion of said elements by rated steam is subjected to superheating by the roaster
H2SO4 incident to the roasting reaction in the bed, and gases, and that the roaster gases are then further utilized
thus maintaining the byproduct steam generation at a in a waste heat boiler.
uniform rate, with uniform temperature and uniform
pressure of the saturated steam, while maintaining pre 3References Cised in the file of this patent
determined reaction temperature in the bed. UNITED STATES PATENTS
2. The method according to claim 1, wherein the steam 10
pressure and temperature are maintained substantially at 2,242,763 Smith ----------------- May 20, 1941
450 p.s.i.g. and at 456 F. respectively. 2,493,498 Peery ------------------ Jan. 3, 1950
3. The method according to claim 1, wherein said in 2,506,317 ReX ------------------- May 2, 1950
jection water is introduced in a direction from above into 2,761,764 Johannsen et al. --------- Sept. 4, 1956
the surface of the bed. 2,853,455 Campbell et al. ---------- Sept 23, 1958
4. The method according to claim 1, wherein the satu 2,889,202 Johannsen et al. --------- June 2, 1959