United States Patent (19) 11) 4,070,180

Waslo 45 Jan. 24, 1978

(54) PROCESS FOR THE PASSWATON OF 3,617,394 11/1971 Mayer ...................................... 75/34
SPONGE IRON UTILIZNG REDUCNG 3,844,764 10/1974 Beggs .........
GASES CONTAINING FREE OXYGEN 3,850,616 1 1/1974 Cruse, Jr. ................................. 7.5/9
(75) Inventor: Stephen Waslo, Penn Hills Primary Examiner-M. J. Andrews
Township, Allegheny County, Pa. Attorney, Agent, or Firm-Arthur J. Greif
(73) Assignee: United States Steel Corporation, 57 ABSTRACT
Pittsburgh, Pa. Passivation of sponge iron by a mild reoxidation thereof
21 Appl. No.: 716,398 is effected by contact, at a temperature of 200 to 600
F, with a gaseous atmosphere consisting essentially of
22 Filed: Aug. 23, 1976 25 to 80% H, 15 to 70% CO and 0.5% to 4.0% O for
51) Int. Cl............................. C23F 7/04; C23F 9/02 a time in excess of about 1 hour. The passivation atmo
52 U.S. C. ..................................... 75/05 BA; 75/34 sphere may be produced by dilution of a free-oxygen
58 Field of Search ................ 75/34, 35, 91, 26, .5 R, containing gas with conventional reducing gases,
75/.5 B, .5 BA Therefore, the process is particularly amenable to the
(56) References Cited in-line passivation of hot reduced pellets i.e. wherein
U.S. PATENT DOCUMENTS
passivation may be effected directly within the lower
portion of a shaft furnace.
2,578,800 12/1951 Hamister .................................. 75/34
3,160,498 12/1964 Olt et al. .............................. 75/35 X 10 Claims, 3 Drawing Figures
U.S. Patent Jan. 24, 1978 Sheet 1 of 2 4,070,180

360 1.
550 -- A
AAOU CA/OM A7AS/AEAVCA
340 SYMMAOL rad/ar 2 time, M/w.
A - 5.3 s
330 O m 6.2 59

32O

O ... 2 .4 9 W. O.
% of w COOL/AvG Gas-aaZaAvoce AAPUC//wG GAs
A/6. /.

// OO
A/6. 2.
9 OO

7OO

5OO

3OO

WOO
O 2O 40 60 O WOO f2O
7/MA, M/MW.
U.S. Patent Jan. 24, 1978 Sheet 2 of 2 4,070,180
 1
4,070,180
2
These and other objects of the invention will be more
PROCESS FOR THE PASSIVATION OF SPONGE readily apparent from a reading of the following de
IRON UTILIZNG REDUCING GASES scription when taken in conjunction with the appended
CONTAINING FREE OXYGEN claims and the drawings in which:
This invention relates to passivation of sponge iron FIG. 1 is a graph showing the effectiveness of simul
(i.e. reduced oxides having a metallization of about 80 to taneous cooling and passivation in the lower portion of
about 97%, either in the form of particles or pellets shaft furnace as a function of the oxygen concentration
from a shaft furnace or in the form of briquettes from a of the cooling gas,
fluidized bed process) and is more particularly related FIG. 2 is a graph comparing normal cooling of pellets
to the passivation of such sponge iron, utilizing conven 10 in a shaft furnace (curve A) with that of an adjusted
tional reducing gases, which are made oxidizing by the cooling curve (B), to achieve passivation by heat hard
addition of a small amount of free-oxygen-containing ening, and
gas such as air or oxygen. FIG. 3 is a flow sheet, illustrative of how passivation
Sponge iron produced by the reduction of iron oxide by both heat-hardening and mild reoxidation may be
in the solid state, whether in the form of particles, pel 15 accomplished in-line.
lets or briquettes, exhibits a tendency to revert back to The art has employed a large number of different test
the oxide state when exposed to natural environments. procedures to evaluate the effectiveness of various pas
In many cases, the deterioration of the sponge iron sivation techniques. U.S. Pat, No. 3,617,394 shows one
product, through the exothermic formation of more or such technique in which piles of both passivated and
less hydrated oxides may even progress to complete unpassivated ore are exposed to an oxidizing environ
destruction of stockpile material through a spontaneous ment, the piles being equipped with thermocouples to
ignition process. In those instances where the reduced determine and record the progress of temperature in
material acquires moisture, conditions can exist, within crease due to oxidation of iron. For unpassivated or
an enclosed stock pile; where, in the absence of oxygen, only slightly passivated sponge iron, there exists a tem
the dominant corrosion reaction evolves hydrogen gas 25 perature and/or an oxygen concentration at which the
and may result in an accumulation of dangerous com temperature rise exhibits a tendency to increase expo
bustible air/hydrogen mixtures. nentially with respect to time. The studies reported
In an attempt to prevent the deterioration of sponge herein utilized a somewhat analogous test procedure, in
iron, the art has in some cases employed existing tech which a small insulated pile is initially heated to a pre
niques for the protection of structural metals from cor 30 scribed temperature with nitrogen, and thereafter
rosion, i.e. impervious coatings such as paints, tars, oils treated with air at the same temperature for a 1 hour
and various other organic materials have been applied period. Reoxidation with air is performed at variable
to the surface of the iron bearing particles. While imper temperatures (generally at 25 F intervals) until expo
vious-type coatings have been effective agents for pre nential reoxidation is seen to occur. This test has been
venting reoxidation, such coatings cannot always be 35 found particularly useful in evaluationg the relative
applied economically because of the high surface areas effectiveness of various treatments to prevent reoxida
involved. Equally important, these substances often act tion even though these treatments, in themselves, may
as contaminants in the steelmaking process. The art has not achieve what may be termed "effective" passiv
therefore resorted to a number of passivation tech ation, i.e. passivation sufficient for the desired end use.
niques, wherein the reduced materials are rendered Passivation studies were conducted on a pilot plant
passive by controlled treatments in oxidizing atmo size (5 ton per day) counter current shaft furnace utiliz
spheres to form a thin, continuous oxide film on the ing commercially available oxide pellets. The hydrogen
surface of the sponge iron. Exemplary of such proce to carbon ratio of the gases employed to reduce these
dures are those shown in U.S. Pat, Nos. 2,578,800, pellets varied from 1:1 to 3:1, and contained from about
3,617,394 and 3,844,764. The common factor in all these 45 88 to 92 percent CO plus H, thus simulating various
prior art procedures is that they utilize an essentially partially oxidized or reformed commercially available
inert carrier gas which is made mildly oxidizing by fuel gases. Reduction was conducted so that iron was
dilution with air, oxygen, or small amounts of water initially formed at about 1300 F, with the final reduc
vapor. As a result thereof, such prior art passivation tion temperature being about 1600 F. In a modification
techniques have, of necessity, been relegated to passiv 50 of the procedure wherein cool reducing gas is injected
ation of sponge iron in a chamber or zone separate from near the lower portion of the furnace, described more
that used for effecting reduction of the iron oxides. The fully in U.S. Patent application Ser. No. 644,249, filed
increased capital costs incurred by the need for such a Dec. 24, 1975, air was added to the cool reducing gas in
separate chamber and the increased operating cost re quantities of from 0.2 to 1.0 percent oxygen. Ore pellets
sulting from the need to use a carrier gas different from 55 were introduced at feed rates of 5.3 and 6.2 tons/-
that which is normally available in the direct reduction day/[Link]. of furnace, so as to provide residence times of
process, have therefore added substantially to the cost 68 and 58 minutes, respectively, in the cooling let (pas
of production of direct-reduced sponge iron. sivation zone) of the furnace. The data obtained thereby
It is therefore a principle object of this invention to is summarized in FIG. 1, where it is seen that for such
provide a passivation process utilizing carrier gases residence times, i.e. about 1 hour in length, effective
readily available in conventional direct reduction pro passivation is achieved by utilizing a reducing gas con
cedures. taining in excess of about 0.8 percent oxygen. Addi
It is a further object of this invention to provide a tional studies showed that if residence times in excess of
procedure in which passivation may be effected directly about 1.5 hours are employed, the oxygen concentra
within a zone of the direct reduction furnace. tion of the gas may be reduced to as low as about 0.5
It is a further object of this invention to provide a percent. Oxygen concentrations of up to 4.0 percent
passivation process whereby passivation may be ef may be employed without suffering significant loss of
fected in the lower portion of a shaft furnace. metallization. However, to assure against loss of metalli
 4,070,180 4.
3
zation while achieving effective passivation, it is prefer descend through reducing zone 8, where heating and
able that the air or other free-oxygen containing gas be reduction occurs. The pellets then descend from the
intermixed so as to provide an oxygen concentration of reducing zone, past the hot gas inlet stream 3 and into
between 1 and 2 percent. the uppermost portion of cooling zone 7 of the shaft. In
It should be borne in mind that the tendency of vari- 5 this Zone, the time-temperature profile is adjusted to
ous sponge irons to reoxidize and their ability to be provide a residence time of elevated temperature suffi
passivated varies widely with the nature of the ore feed cient to induce the hardening described above (see FIG.
and the conditions at which such ore has been reduced. 2). Sponge iron at a temperature of 300 to 500 F then
The above noted application Ser. No. 644,249, describes proceeds from the shaft, in a condition already more
an alternative method for effecting passivation which 10 resistant to reoxidation and degregation then would
consists of exposing the reduced iron particles to ele have been the case, had not the proper conditions for
vated temperature, to achieve a hardening or sintering hardening been provided in the cooling leg.
treatment. The hardening method disclosed therein The reduced iron 17 is then charged into passivation
basically involves an adjustment of the conventional unit 18. The passivation gas 15, obtained by the con
cooling curve A as shown in FIG. 2 so as to achieve a 15 trolled oxidation of fuel gas with air in burner-quencher
cooling curve similar to that of curve B. This adjust 13, preferably contains from about 1 to 2 percent oxy
ment in cooling curve may be achieved either: (i) by gen. Alternatively, a similar passivation gas could be
running the shaft with insufficient gas to cool the prod produced by the admixture of oxygen or air with flue
uct so as to maintain the solids at elevated temperature 20 gas from reformer 1. The reduced iron 17 and passiv
for a longer time or (ii) by increasing the total residence ation gas 15 then flow co-current through the passiv
time, i.e. by decreasing the solids and gas rate approxi ation zone at very near isothermal conditions. The
mately proportionately or more preferably by increas sponge iron which has now been further passivated by
ing a volume of the cooling portion of the shaft. By use the mild reoxidation treatment, passes into the cooling
of such expedients, or a combination thereof, the cool 25 zone at the lower portion of the passivation unit 18, for
ing curve is adjusted so that the reduced material is held countercurrent cooling with recycled cooling gas 19
at temperature in excess of about 1500' F, for a period obtained by passing the uncombined passivation and
generally in excess of about 45 minutes. cooling gases in stream 20, through a scrubber-cooler
It is therefore a further embodiment of the instant 21, and then through compressor 20. A bleed 23 is pro
invention to utilize a combination of both techniques; (i) vided to balance the addition of passivation gas 15. The
the mild reoxidation treatment described herein and (ii) 30 cooled sponge iron 24 which has now been passivated
the heat hardening treatment of Ser. No. 644,249; to both by heat hardening and by the mild reoxidation
acheive further insurance against catastrophic reoxida treatment of this invention then proceeds to product
tion and/or in those instances where a pellet feed is storage.
utilized which cannot be "effectively' passivated by In a further preferred embodiment, additional cost
either reoxidation or heat hardening alone. A flow 35 benefits are realized by the elimination of passivation
sheet, illustrative of how these various embodiments unit 18 and its ancillary equipment. Here, air or other
may be utilized in combination, is shown in FIG. 3. Gas free-oxygen containing gas is added to cooling gas
stream 2 from reformer 1, at a temperature of, for exam stream 5. In both instances, the process is designed so as
ple, 1700' to 1800' F and a pressure of 15 to 30 psig, is to provide contact of the solids with the oxygen-con
divided into two fractions. Stream 3 is introduced hot taining passivation gas for a period in excess of about 1
into the shaft at hot zone 4, Stream 5 flows through hour, preferably 1.5 to 2.5 hours, at a temperature
waste heat boiler 6 where it is cooled prior to introduc within the range 200' to 600' F, preferably 350' to 450
tion into the shaft furnace, at the lower portion thereof F. Contact for passivation should always be effected at
7. The flow rate of stream 5 is determined by the
amount required to cool the reduced iron particles to 45 temperatures
tures the
below 600' F, since at higher tempera
gaseous mixture again becomes reducing and
the desired extent, e.g. to a temperature between 300 cannot therefore produce the desired reoxidation,
and 500' F. The distance between the entry points, into which provides a magnetite
the shaft, of gas streams 3 and 5 is sufficient to provide iron surfaces and throughoutoxide the
layer on the exposed
pore structure of the
the residence time required for passivation by heat pellet.
hardening. Stream 5 rises through the shaft, recuperat I claim:
ing a portion of the sensible energy of the solids. It then 1. A process for the passivation of sponge iron which
mixes with stream 3 in hot zone 4 and the combined
streams proceed upwardly through the shaft, perform comprises, contacting the sponge iron at a temperature
ing the tasks both of heating and reducing iron oxide 55 atmosphererange
within the of 200' to 600 F with a passivation
consisting essentially of 25 to 80% H, 15 to
feed 16. After completion of these tasks in preheat and 70% CO and 0.5 to 4%. O, for a time of about 1 to 3
reducing zone 8, the combined gas exit stream 9 now hours, and wherein the time
contains considerable amounts of H2O and CO2, created about 1.5 hours when said [Link] is greater than
concentration is below
by the reaction of a portion of the H, and CO contained about 0.8%.
therein with the iron oxide feed. After scrubbing and 2. The process of claim 1, wherein said gaseous atmo
conditioning in unit 10, stream 9 still contains enough sphere is produced by the admixture of a free-oxygen
energy producing, combustible H, and CO to fire the containing gas and the gaseous effluent resulting from
reformer unit. A portion thereof 11 is therefore referred the reforming of natural gas or carbonaceous fuels,
to reformer unit 1, while a second stream 12 may be
exported for other uses, say an oxide pellet plant. Addi wherein said effluent is composed of (i) H, and CO in
tionally, some fuel from stream 12 may be sent to burn 65 the sum of 85 to 95% and (ii) residual constituents corn
prising CO2, CH, N, and H0.
er-quencher unit 13 for combustion with air stream 14 3. The process of claim 2, in which said contact is
to produce passivation gas stream 15. Iron oxide feed 16 effected for a time of 1.5 to 2.5 hours at a temperature of
is charged to the top of the shaft. The ore or pellets
 4,070,180
5 6
350 to 450 F, and said passivation atmosphere contains 5. The process of claim 4, in which said second zone
O, within the range 1 to 2%. is within the shaft furnace, at the lower portion thereof,
4. In the direct reduction of iron ore pellets in a shaft wherein prior to initial contact said sponge iron is at a
furnace wherein said pellets are permitted to substan temperature within the range 300 to 500 F and said
tially continuously descend in said shaft furnace, and passivation atmosphere is at a temperature of 200 to
are contacted in a first zone with a reducing gas which 500 F, said contact being effected for a time up to about
2.5 hours.
is substantially composed of the effluent resulting from 6. The process of claim 5, in which said sponge iron
the reforming of natural gas or carbonaceous fuels, said and said passivation atmosphere are at sufficiently low
reducing gas containing (i) Hand CO in the sum of 85 10 temperatures whereby said contact of up to about 2.5
to 95% and (ii) residual constituents comprising CO, hours is effected at a temperature of 350 to 450 F.
CH, N, and H2O, said contact being effected at a tem 7. The process of claim 5, in which the Oconcentra
perature 1400 to 1750 F for a time sufficient to pro tion of said passivation atmosphere is within the range 1
duce a sponge iron product, to 2%.
the improvement for passivating said sponge iron in 15 8. The process of claim 6, in which the O concentra
an in-line process which comprises, in a second tion of said passivation atmosphere is within the range 1
to 2%.
zone, at a temperature of 200 - 600 F, contacting 9. The process of claim 4, wherein said second zone
said sponge iron with a passivation atmosphere comprises a separate passivation unit, which is outside
consisting essentially of 25 to 80% H, 15 to 70% of the shaft furnace.
CO and 0.5 to 4% O, said contact being for a 10. The process of claim 9, wherein said contact is
period of about 1 hour to 3 hours and wherein the effected for a period of about 1 to 2.5 hours at a temper
time employed is greater than about 1.5 hours ature of 350 to 450 F.
when said O. concentration is below about 0.8%,
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