Metallurgical and Other Processes

Metallurgical and Other Processes
In 1944, Dorr-Oliver Company acquired rights to Exxon's fluidization know-how

for use in fields outside the petroleum industry. Concentrating on noncatalytic
gas-solid reactions, they soon developed the FluoSolids system for roasting
sulfide ores. The first unit was constructed in 1947 in Ontario, Canada, to roast
arsenopyrite and to obtain a cinder suitable for gold production by cyanidation.
In 1952 at Berlin, New Hampshire, Dorr-Oliver used the FluoSolids roaster to
produce S 0 2 from sulfide ores.
Independently, and as early as 1945, the German company Badische
Anilin und Soda-Fabrik (BASF) had begun to develop fluidized bed roasters
based on experience acquired with the Winkler gas producer. In 1950, their first
commercial roaster went on stream at Ludwigshafen with a capacity of 30 tons
of ore per day. Scale-up was rapid, and a unit with capacity of 120 tons/day was
constructed in 1952.
From the time of their introduction, these remarkable roasters progressively
replaced existing technology centering about multihearth roasters and
rotary kilns, both in the sulfuric acid industry and for the preparation of a wide
variety of solid materials needed in metallurgical industries.
Dorr-Oliver engineers pioneered two additional important uses of fluidized
beds: one for drying powdery materials, the other for calcining limestone. Thus,
in 1948 the first FluoSolids unit (1.7 m ID) for the drying and sizing of dolomite
particles < 4 mesh, and having a capacity of 50 tons/day, was put in operation in
the Canaan plant of the New England Lime Company. The following year they
constructed a large multistage unit for calcining powdery limestone (multistaging
was used primarily to reduce the otherwise high fuel consumption for this
process).
These initial successes spawned much interest in fluidization, and a variety
of new processes have been reported in the literature and in patents. Although
we consider examples of these later, we single out three of them now because of
their potential influence on three different major industries: polymers, semiconductors,
and biotechnology.
First, we have the production of granular polyethylene, todays largest
volume plastic, by polymerization of its gaseous monomer in fluidized beds. This
process is rapidly replacing liquid-phase technology. Second, the fluidized bed is
finding its niche in the expanding semiconductor industry to produce ultrapure
silicon and its precursors. Third, it is used in the food and pharmaceutical
industries, particularly for efficient cultivation of microorganisms.
On looking back, it seems that the path to commercial success with
fluidized processes has been unusually painful and complex, with many stages of
scale-up and more than its expected share of embarrassing failures. These
difficulties stem largely from the lack of satisfactory answers to the many
questions on which design decisions should be based, and this in turn stems
from a lack of reliable predictive knowledge about what goes on in these beds.
Such design uncertainties, coupled with the large investment involved, have led
to a general conservatism and caution in many of these developments. However,
the large payoffs that have accompanied successful processes continue to spur
research and development efforts on fluidization in numerous applications.
We now look more closely at the use of fluidization in industry.
Solidification of a Melt to Make Granules

To spread urea on fields from the air requires coarse granules in a narrow size
range. For this purpose, Mitsui-Toatsu engineers developed the solidification
process sketched in Fig. 3(a). Sprayed molten urea falls as droplets through a tall
tower while cold air passes upward through the tower, cooling and solidifying
the droplets. The few big droplets still needing to be frozen fall into a fluidized
bed of urea particles at the base of the tower; they are quickly covered by a layer
of smaller solids, move around the bed, and then solidify.
Requirements for better control of particle size then led to the process
shown in Fig. 3(b), which combines a shallow fluidized bed with several spouted
beds. Molten urea is fed to the nozzle at the bottom of each spout, and air is
used for spouting and as the fluidizing gas. Product solid is removed from one
end of the unit, and the undersized fines are returned to the other side. This
type of operation gives a much narrower size distribution of solids than does the
conventional granulation unit.
Coating Metal Objects with Plastic

Looking at Fig. 2(a) again, consider a bed of fine plastic particles fluidized by
ambient air. Then metalware, heated to a temperature somewhat higher than
the melting point of the plastic, is dipped for a short time (2-12 s) into the bed.
Particles impinging on the surface of the metal fuse and adhere to it to form a
thin layer. To smooth the coating, the metalware may have to be reheated in hot
air. According to Gaynor [4], the thickness of the coating film varies exponentially
with time because its deposition rate is proportional to the heat transfer rate,
which depends on the film thickness.
Drying of Solids
The fluidized bed dryer is used extensively in a wide variety of industries
because of its large capacity, low construction cost, easy operability, and high
thermal efficiency. It is suited to any kind of wet solid as long as the solid can be
fluidized by hot gas. Iron and steel companies are using huge driers to dry coal
before feeding it to their coke ovens, whereas tiny but efficient driers serve the
pharmaceutical and other fine chemical industries. Figure 4 shows several
designs of conventional fluidized bed driers.
Inorganic materials, such as dolomite or blast furnace slag, are usually
dried in single-bed driers illustrated in Fig. 4(a), because the residence time
characteristics of the particles to be dried are not important. Since the water in
the particles vaporizes in the bed, the bed temperature need not be high, and
60°-90°C is usually sufficient. Thus, the energy content of hot air or flue gas,
often wasted, can be efficiently used in this type of operation.
When the particles require nearly equal drying times, the residence time
characteristics of solids in the fluidized beds must be considered. Single-stage
operations, as in Fig. 4(a), approximate mixed flow, wherein a large fraction of
the solids stay only a short time in the vessel, in effect bypassing it. Multistaging
for the flowing solid greatly narrows its residence time distribution and eliminates
bypassing. Figures 4(b) and (c) show multistage driers that are formed
from vertical partition plates placed in the bed.
Figure 4(d) illustrates a simple design wherein counterflow contacting of
gas and solid is achieved. Perforated plates or large screens act as gas redistributors
and stage separators, thus eliminating overflow pipes and downcomers.
Very delicate materials, such as some pharmaceuticals, may require identical
drying times for all particles. Figure 4(e) is a design for such operations. The
distributors rotate on schedule to drop a batch of particles from bed to bed, and
this ensures an ideal batch-continuous treatment of the particles.
For certain temperature-sensitive materials, the inlet gas temperature
must be kept low. To counter the resulting reduction in thermal efficiency, heat
can be recovered from the exiting dry solids. An example of such an operation is
shown in the two-stage salt drier of Fig. 4(f).
When the feedstock is very wet, particles are likely to agglomerate and not
fluidize at the feed location in the designs of Figs. 4(b), (c), or (d). A possible
solution is to first use a backmix dryer, like Fig. 4(a), followed by a plug flow
dryer such as 4(b), (c), or (d).
In the designs of Figs. 4(a)-(f), the heat content of the fluidizing gas is the
energy source for the drying particles. However, heat can be supplied by heat
exchange tubes or plates within the fluidized bed, as shown in Fig. 4(g). With
this design, the volume of fluidizing gas needed can be greatly reduced,
resulting in smaller pumping cost, less particle attrition, and lower construction
cost of the exhaust gas cleaning system.
The design of Fig. 4(g) is suitable for drying very wet feedstock. By
operating at high pressure and fluidizing with superheated steam, one can obtain
thermal efficiencies far higher than from ordinary dryers. In addition, medium
Fluidized Combustion of Coal

In the hope of finding an alternative combustion system suitable for low-grade
coal and oil shale fines, fuels that cannot be burned efficiently in conventional
boiler furnaces, researchers in Britain and in China turned to fluidized bed
FI
Incineration of Solid Waste

Incineration of municipal solid waste is inevitable in crowded areas, and chain
grate or inclined grate incinerators are being used for this purpose. Countercurrent
or crosscurrent modes of contacting, though thermally efficient, are
sometimes troublesome because of the noxious odors of the flue gas from these
operations. This problem can be avoided with fluidized bed incineration.
Figure 18 illustrates some of today's operating commercial units, from
[32]. Garbage is coarsely shredded, iron and steel are removed by magnetic
separators, and the garbage is sent to the fluidized bed incinerator. Since the
operating temperature is 800°-900°C, organics are decomposed and burned in
the bed and freeboard.
To remove surplus heat from the bed, water is poured into the bed in
simpler designs, whereas deficient air in the bed followed by secondary
combustion in the freeboard is used in more advanced designs. Solids are
completely burned, and ash is discharged from the bottom of the bed. Also, a
waste heat boiler, carefully designed to handle the dirty corrosive gas stream, is
installed to recover heat from the flue gas.
Municipal solid waste often contains large lumps of inorganic materials.
Hence, it is important to design the solid feed and discharge systems to
is used, and Fig. 22(a) shows the first commercial unit of this type; see White
and Kinsalla [44]. The original unit, designed and built in 1949 for the New
England Lime Company, had a diameter of 4 m and a height of 14 m. Raw
material 6-65 mesh is fed to the top stage of the unit and flows downward from
stage to stage. In the calcination stage, fuel oil is sprayed into the bed through
12 nozzles arranged around the perimeter of the bed, mixed with fluidizing air,
and burned.
Mitsubishi later developed the New Suspension Preheating System for
cement clinkering, which incorporated a fluidized bed calciner for limestone
powder. This was followed by an alternative limestone calcination process that
combined a fluidized calciner with suspension preheaters (in effect, cyclone heat
exchangers), as shown in Fig. 22(b).
Dorr-Oliver's two-bed process for calcining paper mill lime sludge
(<50 ìð\) operates as follows. Dried and powdered lime mud is fed to the
upper bed, which is fluidized by air and is fed fuel that burns in the bed. At a
high enough temperature, about 770°C, calcium carbonate calcines to calcium
oxide, and trace constituents in the feed, such as sodium carbonate, fuse, act as a
binder, and cause agglomeration, eventually resulting in the formation of
spherical pellets of lime. Proper control of particle growth is important. The
particles then flow to the lower bed, which acts as an air preheater [45].
Fine powdery lime obtained from the calcination of lime sludge is in
demand by the steel industry, and Fig. 22(c) shows a reactor designed to
produce this material. The fluidized bed contains a carrier of coarse agglomerated
lime particles. Fines from the slurry are injected into the bed, stay there for
a short time, and are then elutriated, collected, and rapidly cooled to prevent
the reverse reaction from proceeding significantly at lower temperature. This
rapid cooling is crucial for satisfactory operation.
To upgrade the poor-quality phosphate rock that is plentiful in the western
United States, Dorr-Oliver developed a three-stage fluidized calcination system
FI G

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Metallurgical and Other Processes

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Metallurgical and Other Processes

In 1944, Dorr-Oliver Company acquired rights to Exxon's fluidization know-how

Solidification of a Melt to Make Granules

Coating Metal Objects with Plastic

Fluidized Combustion of Coal

Incineration of Solid Waste

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