United States Patent 19 11 4,061,492

Fey et al. 45) Dec. 6, 1977

54) METHOD OF ORE REDUCTION WITH AN (56) References Cited
ARCHEATER
U.S. PATENT DOCUMENTS
75 Inventors: Maurice G. Fey, Pittsburgh, Pa.; 3,140,168 7/1964 Halley et al. ............................ 75/40
Edna A. Dancy, Beaconsfield, . 3,862,834 1/1975 Von Waclawiczek et al......... 75/11
Canada
Primary Examiner-M. J. Andrews
73 Assignee: Westinghouse Electric Corporation, Attorney, Agent, or Firm-L. P. Johns
Pittsburgh, Pa. 57 ABSTRACT
21) Appl. No.: 699,297 A two-stage process for converting metal-bearing ore
to a metal or an alloy characterized by the steps of, first,
22) Filed: June 23, 1976 partially reducing an ore having a relatively higher
valence state to an intermediate product of a lower
valence and, second, treating the intermediate product
Related U.S. Application Data in an arc heater having a carbon-bearing reductant at
(63) Continuation of Ser. No. 553,401, Feb. 26, 1975, mosphere in an amount in excess of that required to
abandoned. reduce the intermediate product to the metal form,
whereby to produce a substantially pure metal or an
51 Int. Cl’................................................ C21C 5/52 alloy, such as ferrochromium, and an unused excess
52) U.S.C. ....................................... 75/10 Rs 75/11; reducing gas or derivative thereof which are recircu
75/38; 75/130.5; 75/133.5 lated to the first step to assist in the partial reduction.
(58 Field of Search ................... 7.5/11, 26, 12, 13, 38,
75/130.5, 133, 133.5, 10 R 5 Claims, 5 Drawing Figures
U.S. Patent Dec. 6, 1977 Sheet 1 of 4 4,061,492

SNA SN
U.S. Patent Dec. 6, 1977 Sheet 2 of 4 4,061,492

42
Zaa
A.
2 [22Z
NSNSSS
NNar

a
NNNS YSSY

N
NSNSNr.
U.S. Patent Dec. 6, 1977 Sheet 3 of 4 4,061,492

CH4 AT 8OOO F Fe A 34O°F

ARC HEATER
2 H2 AT 3140°F
FeO AT 34O° F CO AT 34O9 F

HEAT LOSSES

8 H2O AT 1340°F CO AT 224O F

FLUIDZED
O.82 H2 AT 134OF BED 2 H2 AT 224 OF
O66 CO2 ISAT O.66 CO2 AT 34OF PRE
REDUCER
O.34, COCHANGER O.34 CO AT 34O°F
2.68 N2 AT 34O°F

CH4AT 77 F HEAT LOSSES

FIG. 3
 4,061,492
1.
METHOD OF ORE REDUCTION WITH AN ARC
HEATER
This is a continuation of application Ser. No. 553,401,
filed Feb. 26, 1975, now abandoned.
CROSS REFERENCE TO RELATED
APPLICATION
This invention is related to the copending application
of Maurice G. Fey entitled "Process for Reduction of
Complex Metallic Ores,” Ser. No. 553,404, filed Feb.
26, 1975, now U.S. Pat. No. 3,997,333.
BACKGROUND OF THE INVENTION
2
of that required to reduce the metallic oxides and com
pounds to the metal, whereby to produce a substantially
pure metal and the unused excess reducing gas or deriv
atives thereof being recirculated to step (a) to assist in
5 the preheating and partial reduction of the incoming
metal oxide.
The advantage of the process of this invention is that
the exhaust gases for an arc heater are used to prereduce
and preheat ore, thus reducing the electrical require
O ments for an arc heater reduction process. The fluidized
bed reactor used in series with an arc heater is the pre
ferred device for prereduction and preheating of the
Oe,

1. Field of the Invention 15 BRIEF DESCRIPTION OF THE DRAWINGS

This invention relates to a process for refining metal FIG. 1 is a diagrammatic view showing a two-step
ore containing at least one metal oxide. More particu benefication process for the direct reduction of a metal
larly, it pertains to the direct conversion of an ore to a lic ore to the state of a pure metal, or ferroalloy;
metal or an alloy by a continuous procedure involving FIG. 2 is an elevational view, partially in section, of
two reducing steps in series. 20
an arc heater; and
2. Description of the Prior Art FIGS. 3 to 5 are diagrammatic views showing three
The application of plasma technology to high tem examples for practicing this invention.
perature processes in the organic, inorganic, and extrac
tive metallurgy areas has been widely researched. Pre DESCRIPTION OF THE PREFERRED
vious investigations have included the plasma produc 25 EMBODIMENT
tion of the acetylene and other hydrocarbons, nitrogen The method of this invention involves a process for
fixation, the production of oxides, carbides, and nitrides, the direct reduction of an ore to a pure metal or ferroal
the reduction of metal oxides and halides, benefication loy. Basically, the process comprises a two-step proce
of complex minerals, and plasma remelting and refining. dure including the steps of
An example of a method and archeater is shown in U.S. 30
a partially reducing an ore containing at least one
Pat. No. 3,765,870, entitled "Method of Direct Ore metallic oxide and other metallic compounds in a gas
Reduction Using a Short Gap Arc Heater,' by Maurice solid reactor, and
G. Fey and George A. Kemeny, issued Oct. 16, 1973. b. treating the partially reduced metallic oxides in an
Other examples of similar processes are disclosed in that arc heater in an atmosphere of a reducing gas in an
patent. 35
Despite extensive research, there are relatively few amount in excess of that required to reduce the metallic
large scale commercial processes based on plasma tech oxides and compounds to the metal, whereby to pro
nology. In general, those commercial processes have duce a substantially pure metal and the unused excess
been confined to processes requiring temperatures not reducing gas or derivatives thereof being recirculated
attainable by a conventional technique, to applications to step (a) to effect the partial reduction
in which reduced capital requirements were of impor The process of this invention may be used for the
tance, or to processes where the plasma method re reduction of ore of a metal comprising at least one oxide
sulted in a product with unique characteristics. In most of a metal, and is preferably used for the reduction of
cases, the plasma route has not been economically com metals in Group Numbers for the 5b, 6b, 7b, and 8 of the
petitive because of higher energy costs. However, the 45 Periodic Table. More particularly, those metals include
situation is changing due to the shrinking supplies of vanadium, chromium, manganese, iron, cobalt, nickel,
light hydrocarbon fuels and to the development of a niobium, tantalum, molybdenum, and tungsten which
stable electric energy economy. usually exist in the combination with oxides of other
More specifically, heretofore the electrical require elements.
ments for an arc heater operated to reduce ores or ox 50 The apparatus, by which the process of this invention
ides of most metals including iron, chromium, manga is preferably performed, includes a prereducer 1 (FIG.
nese and vanadium have not been economically feasible. 1) and an arc heater 3. The apparatus of this invention
Inasmuch as the power requirement of an archeater for also includes other apparatus such as a metal holding
an ore reduction process are the primary operating furnace 9, conduits 11, 13, 15, 17 and 19, a cyclone
costs, it is necessary that such costs be minimized wher 55 separator 23, and a heat exchanger 25.
ever possible. The prereducer 1 is a gas-solid rector which is usually
SUMMARY OF THE INVENTION
operated at an elevated temperature, such as a packed
bed, spouted bed, rotary kiln, multiple hearth furnace,
In accordance with this invention it has been found or a fluidized bed. The prereducer 1 is preferably a
that the conditions for the use of an arc heater for the fluidized bed having a hopper 21 by which ground or
reduction of metal ores and oxides may be greatly im pulverized ore 27 is introduced into the fluidized bed or
proved by a process comprising the steps of (a) partially prereducer 1 through a screw conveyor 28. Expended
reducing at least one metallic oxide in a gas-solid reac gas leaves the prereducer 1 through the cyclone separa
tor, such as a fluidized bed, by taking a metal ore from tor 23 and the heat exchanger 25 to heat the incoming
a relatively higher valence state to a lower valence 65 methane (CH) and then through an off gas vent 26.
state, and (b) treating the partially reduced metallic Fine particles of ore 27 and of partially reduced oxides
oxide ore and compounds in an arc heater in a reducing are carried with exhaust gases (CO, CO, H., H2O, N,)
gas atmosphere, such as methane, in an amount in excess to the separator from where the fine particles are car
 3 4,061,492 4.
ried through a conduit 16 for the preheated methane on ides in the previous steps form a slag 57 which accumu
its way to the arc heater 3. lates on the surface of a metal body 59. Both slag 57 and
Within the fluidized bed 1 the ore 27 is preheated and metal 59 are drained periodically from the furnace 9
prereduced from an oxide form having a relatively into appropriate receptacles.
higher valence state to a lower valence state, such as, 5 In the metal holding furnace 9 excess reducing gases
for example, as shown in the following formulae (1-3) comprising carbon monoxide, and hydrogen from the
in which it is recognized that thermodynamic equilib conduit 17 pass through the upper portion of the fur
rium dictates the stoichiometric gas ratios: nace 9 and through the conduit 19 into the prereducer
or fluidized bed 1.
Fe:O + CO + H-FeO + CO + HO (1) 10 The ores or oxides of several metals such as iron,
FeO + CO + H-FeO + Fe + CO + HO (2)
chromium, manganese, nickel, vanadium, and the like,
either alone or in combination, for example, as spinels,
Fe0 - CO - H->Fe + CO -- HO (3) may be reduced to pure metals or alloys, such as ferroal
15
loys, by the process of this invention, and the following
examples are illustrative of the process of this invention:
The solid products of reduction, such as the oxides of EXAMPLE I
lower valence of iron as well as some metallic iron,
leave the fluidized bed 1 through the conduit 17 having Elemental iron is produced in accordance with the
a rotary lock hopper 18 to the arc heater 3. Simulta formula (4):
neously the hot metallic oxides move through the con 20
duit 15 with the preheated methane. Fe0 - CH-) Fe + CO + 2H (4)
The arc heater 3, being the second step of the overall
process of this invention, is the stage where the final by the two-step process, i.e., prereduction and reduc
reduction of ore or oxide occurs. The arc heater 3 is tion as shown more particularly in FIG. 3. Iron oxide
similar in construction and operation to that disclosed in (Fe2O3) together with oxygen and nitrogen are intro
the U.S. Pat. No. 3,765,870. Because of the full disclo duced into the fluidized bed 1 at temperatures of about
sure in that patent the description of the arc heater 3 is 77 F. In addition, carbon monoxide and hydrogen,
limited herein to the basic structure and operation. The both from the arc heater 3, are introduced into the
are heater 3 (F.G. 2) is a single-phase, self-stabilizing fluidized bed at temperatures of about 2240 F. The
A.C. device capable of power levels up to about 3500 30 resulting compounds leaving the fluidized bed at about
kilowatts or up to 10,000 kilowatts for a three-phase 1340 F are iron oxide (Fe0), water, hydrogen, carbon
plant installation. For the practice of this invention it is dioxide, carbon monoxide, nitrogen. All of those mate
preferred that three arc heaters 3 be provided, one for rials except iron oxide are delivered to the heat ex
each of the three phases of the A.C. power supply. Two changer 25 for the purpose of preheating methane from
arc heaters 3 are shown in FIG. 1. 35
a temperature 77° F to 800 F. In the arc heater 3 the
As shown in FIG. 2 the arc heaters 3 have two annu iron oxide (Fe0) and methane are combined to produce
lar copper electrodes 29, 31 which are spaced at 33 elemental iron as well as hydrogen and carbon monox
about 1 millimeter apart to accommodate the line fre ide, all at a temperature of approximately 3140 F.
quency power source of about 4 kV. An arc 35 occurs A heat balance for the fluidized bed 1 is as follows:
in the space 33 and incoming feed stock gas 37 immedi 40 TABLE I
ately blows the arc 35 from the space into the interior of HEAT BALANCE
the arc chamber 39. The arc 35 rotates at a speed of Kcals
about 1000 revolutions per second by interaction of the Required Available
arc current (several thousand amps AC) with a DC 45 Reaction at 1340 F -82
magnetic field set up by internally mounted solenoid 2H, from 2240 F to 1340 F -7
coils 41, 43. The velocities yield a very high operating CO from 2240 to 1340 F -4
efficiency for equipment of this type. In addition to the 0.5 Feo from 77°F to 1340 F
0.67 O, from 77°F to 1340 F
-- 12
--4
feed stock gas 37, a secondary feed stock can be intro 2.68 N, from 77 F to 1340 F --14
duced at 45 (axially into the chamber 39 as well as at --30 --93
47). Exit enthalpies ranging, for example, up to about 50
15,000 BTU per pound when operated on methane are Thus, there is more than enough heat available at step
easily obtained at good thermal efficiencies at the exit one of the process to take care of the process itself and
end 49 of the arc chamber 39. The feed stock gas 37, 45, any heat losses that could reasonably be expected. It is
47 is a carbon-bearing reductant, such as mathane, natu
ral gas, or other hydrocarbons. 55 noted that the action in the fluidized bed 1 has been
Additional gas is preferably injected at 53 (FIG. 1) to taken as far as the CO/CO and H/HO ratios that
carry the preheated and prereduced ore 27 from the would be in equilibrium with Fe0 at 1340 F.
injector through the conduit 15 and into a manifold 55 A heat balance for the heat exchanger 25 is shown in
where the ore 27 enters the second stage of the process, the following Table II:
and in which the ore is reduced from an oxide form to 60 TABLE II
the pure metal such as iron. The temperature range for HEAT BALANCE -
the second step of the reduction in the reactor 3 is from
about 3000 F to 5000' F. The gaseous atmosphere in Required
which the second step of the reduction occurs com 1.18 HO from 1340 F to 800 F
prises hot reducing gases including hydrocarbons and 0.82 H from 1340 F to 800' F
0.66 CO, from 1340 F to 800 F
their dissociation products which exist in sufficient 0.34 CO from 1340 F to 800 F
quantities to reduce the desired metal oxides to the 2.68 N. from 1340 F to 800' F
elemental metal which in turn moves through the con CH, from 77° F to 800 F --S
duit 17 to the metal holding furnace 9. Unreduced ox --5
 4,061,492
5 6
Thus, there is more than enough heat available in the is very damp or very impure), the required heat could
effluent gases from the fluidized bed for preheating the be reduced by preheating the incoming CH, air, and
methane. After the gases leave the heat exchanger, ore using the effluent gases from the fluidized bed.
credit could be taken for their calorific value. These gases have a vastly greater heat content than is
A heat balance for the arc heater 3 is shown in Table 5 needed for preheating the methane being fed to the arc
III as follows: heater. It should be noted that the reaction in the fluid
ized bed prereducer 1 has been taken as far as the CO/-
TABLE II CO, and H/HO ratios that would be in equilibrium
HEAT BALANCE with Fe/FeO at 1340 F. The heat balance for the heat
kcals 10 exchanger 25 is indicated in Table V as follows:
Required
Reaction at 3140 F - 49 TABLE V
FeO from 1340 F to 3140 F --23 HEAT BALANCE
CH, from 800 F to 3140 F --25 kcals
--97 Required Available
15
3.85 HO from 1340 F to 800 F - 11
6.15 H from 1340 F to 800 F - 13
2.27 CO, from 1340' F to 800 F -9
2.73 CO from 340 F to 800 F -6
The heat required for the reaction in the arc heater 3 is 16.24 N from 1340 F to 800 F -37
manifestly obtained electrically. 20
CH, from 77°F to 800 F -4
The heat balance for the overall process indicates that -4 -76
the only energy input is at the arc heater stage. For the
other stages there is more than enough heat available As indicated in Table V there is a vast excess of heat
and the net energy requirement is 97 kcals/55.8g Fe, available for preheating the methane. Some of the ex
which is 3110 Btu/lb Fe, or 0.92 kWh/lb Fe. cess heat could be easily used to preheat the feed to the
The material balance for the overall process includes 25 fluidized bed 1 if this should prove to be necessary.
an FeO requirement of 1.43 lb/lb of Fe, and a CH The heat balance for the arc heater 3 is indicated in
requirement of 0.29 lb/1b Fe. Table VI as follows:
In summary, it is possible to effect a savings of 41% in
electric power and 33% in methane as compared with a 30 TABLE VI
process in which the entire reduction process is carried HEAT BALANCE
out in an arc heater without the fluidized bed prere kcals
required
ducer.
Reaction at 340 F --49
CH, from 800 F to 3140 F --25
EXAMPLE II 35
FeO from 1340 F to 3140 F --23
Fe from 1340 F to 340 F -- 4
Iron is also produced by a slight variation of the - 111
process shown in Example 1. As shown in FIG. 4, car
bon monoxide and hydrogen gas are introduced into the Here again heat losses were not taken into account
fluidized bed 1 at a temperature of 2240 F after leaving
the archeater 3. Iron oxide, methane, oxygen, and nitro for this part of the process. The heat balance for the
gen are simultaneously introduced at about 77 F. The overall process of Example II involves energy input at
resulting gases include steam, hydrogen, carbon diox the archeater stage where the net energy requirement is
ide, carbon monoxide, and nitrogen which at 1340 F 111 kcals/111.6g of iron, which is 1785 Btu/lb, or 0.52
pass through the heat exchanger 25 for the purpose of kWh/lb of iron. The material balance involves an Fe
preheating methane before it enters the arc heater 3. AtO requirement of 1.43 lb/lb of iron and a methane
45
the same time iron oxide (Fe0) and iron leave the prere (CH) requirement of 0.69 lb/lb of iron. Thus, there is a
ducer 1 and enter the arc heater at 1340 from which considerable savings in electric power (66%) compared
elemental iron, hydrogen, and carbon monoxide are with Example I. However, this is at the expense of an
delivered at a temperature of 3140 F. increased consumption of methane (61%). The process
A heat balance for the fluidized bed 1 is shown in 50 of this example might, therefore, be desirable in a part of
Table IV as follows: the country where natural gas is relatively cheap but
power is relatively expensive.
TABLE IV EXAMPLE III
HEAT BALANCE 55 The process of this Example involves the production
Required
kcals
Available
- of ferrochrome from chromite which is a commercially
available ore. The reactions occur according to the
Reaction at 1340 F -273 formula:
2H from 2240° F to 1340 F -7
CO from 2240 F to 1340 F -4
4CH, from 77 F to 1340 F --37 3Fe+ 2.58CrO. 2.3MgO. 1.33AlO3.0.14SiO,->
Fe0 from 77° F to 1340 F --24 3Fe + 5.16Cr + 0.14Si + 2.3MgO + 1.33 AlO
4.06O from 77°F to 1340 F --22
16.24N, from 77°F to 1340 C --83
-- 166 -284 Here again it is shown that if prereducing and preheat
ing stages are introduced, considerable savings in both
power and methane can be achieved compared with the
process where all the desired reduction is effected in the
If the excess of heat evolved over the heat required arc heater. As shown in FIG. 5 carbon monoxide and
should prove to be too small, (for example, if the Fe03 hydrogen gas having been preheated to 2240 F, are
 4,061,492
7 8
introduced into the fluidized bed 1 to prereduce and TABLE IX-continued
preheat a mixture of oxides or iron, chromium, magne HEAT BALANCE
sium, aluminum and silicon entering at a temperature of kcals
77 F. Oxygen and nitrogen are also introduced at the Required Available
same temperature. The resulting gases including steam, - 1057
hydrogen, carbon dioxide, carbon monoxide, and nitro
gen leaving the fluidized bed 1 at 1340 F are intro As in the previous example the heat losses have not
duced into the heat exchanger 25 in order to preheat the been taken into account for this part of the process.
methane which subsequently enters the arc heater at a The heat balance for the overall process of Example
temperature of 800 F. From the fluidized bed 1 re O III involves a heat input only at the arc heater stage. At
duced iron as well as the oxides of the indicated materi all the other stages there is enough energy available.
als enter the arc heater at a temperature of approxi The net energy requirement is 1057 kcals/435.5 lbs
alloy, which is 4360 Btu/lb of alloy, or 1.28 kWh/1b of
mately 1340 F from which they emerged as elemental alloy. The materials balance for the overall process
iron, chromium, and silicon at a temperature of 3140 F. 15
indicates an ore requirement of 1.64 lb/lb of alloy and a
In addition oxides of magnesium and aluminum, are also methane requirement of 0.30 lb/lb of alloy.
eliminated as slag 57 at an excess of carbon monoxide As was shown in the iron ore reduction, considerable
and hydrogen at 3140 F are available for reintroduc savings can be effected in the cost of electric power and
tion into the fluidized bed prereducer 1. natural gas by prereduction. These amount to 29% in
electricity and 25% in natural gas.
The heat balance for the fluidized bed prereducer is 20 In conclusion, the precise manner in which the whole
indicated in Table VII as follows: process is conducted is dependent upon the local eco
TABLE VI nomics, particularly on the relative costs of reductant,
methane, and electric power. In Examples I and II iron
HEAT BALANCE - ore is reduced to iron to achieve considerable savings of
kcals both electric power and methane requirements. De
Required Available 25 pending upon circumstances, the Example II indicates a
Reaction at 1340 F -36 greater savings in electric power at the expense of
16.04H from 2240 F to 1340' F
8.02CO from 2240 F to 1340 F
-60
-33
greater methane consumption. It is emphasized that the
3FeO from 77 F to 1340 F --26 processes described here are not optimized processes.
2.58CrO from 77° F to 1340 F --52 They are given only as Examples of the sort of savings
2.3MgO from 77° F to 1340 F - 17 30 that could be achieved if the heat content and reducing
1.33AlO from 77° F to 1340 F
0.14SiO, from 77°F to 1340 F
--25
--2
power of the waste gases from the arc heater reduction
2.050, from 77° F to 1340 F --11 are taken advantage of. In particular, it should be em
8.2ON, from 77° F to 1340 F -- 42 phasized that the reduction of chromites (Example III)
-175 -409 was chosen for illustrative purposes only. It is recog
nized that many other metallic ores can be reduced by
35 the process disclosed herein.
As shown there is a sufficiently large excess of heat What is claimed is:
available over the heat required. The H2/HO and 1. In a process for producing a metal or an alloy
CO/CO, ratios in the effluent gas are those that would comprising the steps of
be in equilibrium with iron. Gases with those ratios a partially reducing in an initially fresh supply of
would not be significantly reducing to any of the other 40 reducing gas in a gas-solid reactor at least one
oxides. metallic oxide and other metallic compounds from
a relatively higher valence state to an intermediate
The heat balance for the heat exchanger 25 is shown product of a lower valence state that is mixed with
in Table VIII as follows: a quantity of exhaust gases,
TABLE VIII b. conducting the exhaust gases through a heat ex
HEAT BALANCE 45 changer to preheat a second supply of reducing
gas,
Kcals c. striking an electric arc in an axial gap between
Required Available generally tubular electrodes spaced along a com
5.02HO from 1340 F to 800' F
11.02H from 1340 F to 800 F
-14
-24
mon axis to provide an arc heated stream,
3.08CO, from 1340 F to 800 F - 12
d. introducing a feed stock carbon-bearing reductant
4.94CO from 340 F to 800 F - 11 50 through the axial gap to provide a reducing atmo
8.2ON, from 1340 F to 800 F - 19 sphere in the arc heated stream,
8.02CH from 77°F to 800 F --36 e. feeding the intermediate product of partially re
--36 -80 duced metallic oxide and compounds and pre
heated second supply of reducing gas into the arc
heated stream in an amount in excess of that re
As shown in Table VIII there is more than enough 55
quired to reduce the metallic oxide and compounds
heat available. from the lower valence state to substantially pure
The heat balance for the arc heater 3 is shown in elemental metal, and
Table IX as follows: f recirculating to step (a) the unused excess reducing
TABLE X gas or derivative thereof to assist with the fresh
60 supply of reducing gas in the partial reduction.
HEAT BALANCE 2. The process of claim 1 in which step (a) occurs in
kcals a fluidized bed.
Required Available 3. The process of claim 1 in which the reducing gas is
Reaction at 340 F --677 a hydrocarbon.
8.02CH, from 800 F --201 4. The process of claim 1 in which the reducing gas is
3Fe from 1340 F to 340 F --42 65 methane.
2.58CrO from 1340' F to 3140 F -64
2.3MgO from 1340 F --29 5. The process of claim 1 in which the derivatives of
1.33AlO from 1340 F to 3140 F
0.14SiO, from 1340 F to 3140 F
--41
--3
the reducing gas include CO and H.