U.S. patent number 3,901,489 [Application Number 05/429,295] was granted by the patent office on 1975-08-26 for continuous process for refining sulfide ores.
This patent grant is currently assigned to Mitsubishi Kizoku Kabushiki Kaisha. Invention is credited to Takashi Suzuki, Kazuo Tachimoto.
United States Patent |
3,901,489 |
Suzuki , et al. |
August 26, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
Continuous process for refining sulfide ores
Abstract
A continuous process for refining metal sulfide ores which is
carried out by arranging a smelting furnace and a blister furnace,
each maintaining discreteness in the reaction zones, wherein a
separator is provided subsequent to the smelting furnace so as to
limit the function of the smelting furnace to the melting of the
raw material and absorption of the copper content in a slag formed
in and returned from the subsequent process furnace into a matte
layer thus achieving the smelting process at a higher furnace rate.
The reaction products in the smelting furnace are all tapped out
simultaneously without being separated each other, and transferred
to this separator where they are separated and tapped out therefrom
individually.
Inventors: |
Suzuki; Takashi (Urawa,
JA), Tachimoto; Kazuo (Tokyo, JA) |
Assignee: |
Mitsubishi Kizoku Kabushiki
Kaisha (Tokyo, JA)
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Family
ID: |
27291852 |
Appl.
No.: |
05/429,295 |
Filed: |
December 28, 1973 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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356172 |
May 1, 1973 |
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Foreign Application Priority Data
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May 4, 1972 [JA] |
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47-44302 |
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Current U.S.
Class: |
266/162; 266/171;
266/214; 266/186; 266/227 |
Current CPC
Class: |
C22B
5/02 (20130101); C22B 23/025 (20130101); C22B
15/005 (20130101) |
Current International
Class: |
C22B
15/00 (20060101); C22B 23/02 (20060101); C22B
23/00 (20060101); C22B 5/00 (20060101); C22B
5/02 (20060101); C22b 009/10 () |
Field of
Search: |
;266/9,11,24,34R,35
;75/72-74,75 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Post; Gerald A.
Attorney, Agent or Firm: Wenderoth, Lind & Ponack
Parent Case Text
This is a division of application Ser. No. 356,172, filed May 1,
1973.
Claims
What we claim is:
1. A system for continuous processing of metal sulfide ores to
produce crude metal therefrom, which consists of:
a. a smelting furnace 1 for smelting the raw material metal sulfide
ores, which is provided with a lance 6, a burner 7, a melt
discharging port 8, a sealing damper 9 fitted on the outside of the
melt discharging port 8 in a manner to be sufficiently wide to
close the discharging port and movable up and down to control a
slag layer in the furnace at a required constant thickness, a melt
overflow weir 10, and a revert slag charging port 22a;
b. a separator 2 for separating matte and slag in the melts
transferred from the smelting furnace, which is provided with
heating means 13 to maintain the same at a required temperature, a
melt charging port 14 being communicated with the melt overflow
weir 10 of the smelting furnace, a slag discharging port 15, a
matte tapping port 16, a matte siphon 17, and a matte overflow weir
17a; and
c. a blister furnace 3 for making white metal, crude metal and
blister furnace slag from the matte transferred from the separator,
which is provided with a lance 26, a matte charging port 18, a
blister furnace slag discharging port 22, a crude metal tapping
port 23, a crude metal siphon 24, and a crude metal overflow weir
25,
said smelting furnace, separator, and blister furnace being
arranged in such a manner that the reaction conditions such as
temperature, composition, surface level, and interfacial level of a
melt residing in each furnace may be controlled independently of
the other; the feeding quantity of the melt into the separator
being equilibrated with the rate of feeding of the raw material
into the smelting furnace by maintaining the melt overflow weir 10
and the bottom end of the sealing damper at their respective
required constant levels to set the residence quantities of the
matte and slag in the smelting furnace; and the feeding quantity of
the matte into the blister furnace being equilibriated with the
feeding rate of the melt into the separator by maintaining the slag
charging port 15 and the matte overflow weir 17a at their
respective constant levels to set the residence quantities of the
matte and slag in the separator.
2. The system according to claim 1, wherein the separator is
elongated in the direction of the flow of the melt and wherein the
separator contains at one end thereof, a matte sump, a matte siphon
and a charging port for the melt and at the other end thereof, a
slag discharging port.
3. The system according to claim 1, in which the bottom end of the
sealing damper is adjusted to be at a position lower than the level
of the melt overflow weir to maintain constant thickness of the
slag layer within the smelting furnace.
4. The system according to claim 1, wherein the matte overflow weir
and the slag discharging port 15 are positioned at constant levels
having a definite difference in height therebetween to maintain a
constant thickness of the slag in the separator as well as the
residence quantities of the slag and matte.
5. The system according to claim 1, wherein the crude metal
overflow weir and the slag discharging port 22 are positioned at
constant levels having a definite difference in height therebetween
to maintain a constant thickness of the slag in the blister furnace
as well as the residence quantities of the slag and crude
metal.
6. The system according to claim 1, wherein the crude metal
overflow weir and the slag discharging port 22 are positioned at
constant levels having a definite difference of height therebetween
to maintain a constant thickness of the slag in the blister furnace
as well as the residence quantities of the slag and white
metal.
7. The system according to claim 1, in which levels of the melt
overflow weirs of the smelting furnace, separtor, and blister
furnace are sequentially lowered to permit transfer of the melt
under its own gravity, while the blister furnace slag is recycled
to the smelting furnace by a forced transfer means.
8. The system according to claim 1, wherein the blister furnace
slag discharging port is positioned at a level higher than the melt
surface of the smelting furnace to permit the blister furnace slag
to be transferred under its own gravity, while the matte from the
separator is transferred to the blister furnace by a forced
transfer means.
9. The system according to claim 1, wherein the liquid surface in
both smelting furnace and separator is made common by maintaining
the level of the melt discharging port 8 of the smelting furnace
lower than the level of the slag discharging port 15 of the
separator, thereby maintaining constant the residence quantities of
the matter and the slag in the smelting furnace.
Description
The present invention relates to a continuous process for refining
sulfide ores and an apparatus therefor. More particularly, the
present invention is directed to a continuous method for refining a
sulfide ore of metal such as copper, nickel, and cobalt and an
apparatus therefor, wherein the sulfide ore is treated in a
continuous and consistent manner by means of a series of furnaces
to obtain the intended metal in a large quantity and in a most
economical manner.
This invention is an improvement in the invention disclosed in U.S.
patent application Ser. No. 881,226, now U.S. Pat. No.
3,725,044.
It is a primary object of the present invention to provide an
improved method and an apparatus therefor, wherein each of the
process steps essential for the metal refining is connected each
other so as not to cause any difficulty in operations as well as in
sequence of the operations as a whole, while the structure of the
furnaces in charge of the respective refining process steps and the
devices to connect these furnaces with each other are made simple
and durable, thereby to facilitate the construction, operations,
and maintenance thereof, and to carry out the furnace operations in
a consistent and continuous manner over a long period of time,
thereby to obtain a high thermal efficiency within the furnaces and
a high yield of the objective metal.
The foregoing object as well as the operations of the method and
apparatus according to the present invention will become more
apparent from the following detailed description of the invention
when read in conjunction with the accompanying drawing.
In the drawing:
FIG. 1 is a longitudinal cross-section showing the basic
arrangement and connection of the furnaces according to the present
invention;
FIG. 2 is an enlarged view showing an overflowing part of the melt
in the smelting furnace to be used in the first process step;
FIG. 3 is an enlarged view of a longitudinal cross-section showing
an example wherein the smelting furnace and the separator are
integrally constructed;
FIG. 4 is a longitudinal cross-section showing another example of
the separator; and
FIG. 5 is a longitudinal cross-section showing an example wherein a
white matte is produced in the blister furnace 3 shown in FIG.
1.
The method according to the present invention may be applied for
treating copper ore as well as other metal ores such as nickel and
cobalt that may be refined by the same or similar reaction as
copper. Hereinbelow, however, the present invention will be
described with reference to copper as an example.
The process disclosed in the prior U.S. patent application Ser. No.
881,226 now U.S. Pat. No. 3,725,044, which is essential in the
ordinary refining method of copper, comprises three process steps:
the first process step for smelting copper ore (formation of matte
and slag) and simultaneous recovery of copper content in a slag
produced in the second process step; the second process step
wherein the iron content in the matte produced in the first process
step is oxidized and removed (formation of white metal and slag);
and the third process step wherein the sulfur content in white
metal produced in the second process step is oxidized and removed.
These three process steps are carried out by use of three furnaces
corresponding to the abovementioned, respective process steps,
i.e., a smelting furnace, slagging furnace, and a blister furnace,
all these furnace being connected with each other to enable
continuous transfer of a melt to be realized therebetween, and each
of the furnaces being so arranged that the compositions,
temperatures, and residence quantities of matte, slag, white metal,
and blister copper residing in the furnace may be controlled
independently of the other two furnaces, whereby a blister copper
can be produced in a continuous manner as a whole. In this process
wherein each process step for copper refining is carried out in a
furnace corresponding thereto, it is possible to control the
reaction conditions, mainly the slag composition, independently of
the other two steps. Consequently, in each individual furnace, the
furnace efficiency in each process step can be increased without
disturbing the discreteness in the furnace operation in each step,
which might arise in a furnace having a plurality of reaction
zones, by convection and agitation of the melt formed therein due
to supply of the raw material and air, so that the operational
efficiency of the entire system can also be improved.
In this method, however, for the reaction products to be tapped out
of the furnace in the state of their being separated each other,
the matte and the slag should exist separately in at least a part
of each furnace with the result that when the furnace efficiency is
to be increased to a considerable extent, there would appear
restriction from this point. Particularly, as the slag produced in
the first process step is an ultimate tailing, reduction in the
copper content in this slag to the minimum possible degree
constitutes an important factor affecting the economy of the copper
refining process per se.
Therefore, it is the ordinary practice to provide a settling
furnace to recover a part of the copper content residing in the
slag as a matte, the copper content existing mainly in the form of
matte dispersed in the slag. In this case, as the matte to be
recovered is small in quantity, it is practically troublesome and
not desirable in the actual operation to recycle the matte into the
refining process in a continuous manner.
According to the present invention, on the other hand, a separation
step is provided subsequent to the first process step, whereby the
function of the smelting furnace for the first process step is
limited to the smelting of the raw material and absorption of the
copper content in a slag formed in the second process step into a
matte layer therein, and the reaction products are all tapped out
simultaneously without being separated each other, and transferred
to the subsequent separation step, where these reaction products
are separated and tapped out therefrom individually, thereby
further improving the furnace efficiency of the smelting furnace,
and ensuring the separation of the matte and the slag more
satisfactorily. By thus providing the separation process, the
present invention has successfully achieved reduction in the copper
loss as well as orderly arrangement of the flow path of a melt to
facilitate the maintenance and control of the entire system.
More particularly, the present invention may be carried out by
properly arranging a furnace for smelting sulfide ore in the main
(smelting furnace), a furnace for chiefly separating products
formed in the smelting furnace into matte and slag (separator), and
another furnace for principally oxidizing iron and sulfur contained
in the matte to produce white metal or blister copper (blister
furnace), each of which is so designed that the composition,
temperature, surface level, and interfacial level of a melt
therewithin may be controlled and maintained constant independently
of the remaining furnaces, and is further connected each other by
means of mutual transfer of the melt therebetween, whereby the
entire refining system may be operated in a continuous manner as a
whole. The essentials of the operations in each furnace and between
them will be set forth hereinbelow.
FIRST PROCESS STEP (SMELTING PROCESS)
In this process step, a raw material to be smelted which consists
principally of a sulfide ore and a flux (hereinafter referred to
simply as "raw material") is mixed with fuel and air at an
appropriate mixing ratio in accordance with predetermined reaction
conditions such as grade of matte to be produced, composition of
slag, a furnace temperature, and so forth, and the raw material is
then fed directly and continuously into a melt bath which is the
reaction products formed in the first process step at a prescribed
feed rate per unit time (hereinafter referred to as "a raw material
feeding rate") and is caused to melt without delay, thereby forming
matte and slag. On the other hand, a slag formed in the
aforementioned blister furnace (blister furnace slag) is
transferred back to the smelting furnace in a substantially
continuous manner, and the major portion of the objective metal
contained in the blister furnace slag is caused to be absorbed into
the smelting furnace matte, while the products formed in the
smelting furnace are being discharged simultaneously out of the
furnace in a substantially continuous manner, and then transferred
to the separator for the second process step. The term
"substantially continuous manner" referred to hereinavove
designates a transfer system, in which, even if the transfer of the
melt is batchwise from the micro-analytical standpoint, the
transfer quantity thereof at every one time is so small in
comparison with the residence quantity of the melt within the
smelting furnace that variations in the reaction conditions
therewithin for such batch system becomes negligible from the
metallurgical standpoint. Furthermore, transfer of the melt from
the smelting furnace to the separator is carried out by the gravity
of its own utilizing difference in the surface level between the
two furnaces.
SECOND PROCESS STEP (SEPARATING PROCESS)
In this process step, all kinds of the reaction products formed in
the first process step is continuously charged into the separator
and caused to stand therewithin for a certain period of time,
thereby separating matte from slag and tapping each of these melts
continuously out of the separating furnace.
THIRD PROCESS STEP (BLISTERING PROCESS)
In this process step, the matte separated in and tapped out of the
separator (second process step) is charged into the blister furnace
in a substantially continuous manner, while air, flux, and coolant
are mixed at an appropriate ratio to be determined in accordance
with the raw material feeding rate in the foregoing first process
step, the admixture of which is charged directly and continuously
into a melt within the blister furnace consisting of reaction
products formed in the third process step so as to produce and
separate crude metal and slag (blister furnace slag) without delay,
and tap each of these melts out of the blister furnace. The crude
metal is then forwarded to a refining process of known type, and
the blister furnace slag is recycled to the smelting furnace in a
substantially continuous manner so as to be subjected to the
treatment as stated in the foregoing. In this case, transfer of one
of the crude metal and the blister furnace slag between the blister
furnace and the smelting furnace or refining process is carried out
by the gravity of the melt utilizing difference in the surface
level between the furnaces concerned (automatic transfer), and the
other by physical force being applied from outside (forced
transfer).
Furthermore, by maintaining constant the residence quantity of each
melt of matte, slag, and crude metal in the respective process
steps, the rate of production of each melt and the rate of transfer
thereof between the respective furnaces are so regulated as to be
equilibriated to the rate of feeding of the raw material in the
first process step as well as to the rate of feeding of the coolant
in the third process step, and, at the same time, the composition,
temperature, surface level, and interfacial level of the melts in
each furnace are controlled independently and maintained constant,
thereby producing the intended metal from the corresponding ore in
a continuous and highly economical manner.
More detailed explanation of the operations of the furnaces
according to the present invention will be made hereinbelow with
reference to the accompanying drawings.
In FIG. 1, a smelting furnace 1 accommodating therein slag 4 and
matte 5 is provided with a lance 6, a burner 7, a melt discharging
port 8, a melt overflow weir 10, and a revert slag charging port
22a; a separating vessel (or a separator) 2 accommodating therein
matte 11 and slag 12 is provided with a device 13 for keeping the
separator at a required temperature, a charging port 14 for the
melts formed in the smelting furnace, a discharging port 15 for a
separated slag 12, a matte tapping port 16, and a matte siphon 17;
and a blister furnace 3, in which layers of white metal 19, blister
copper 20, and slag 21 are held, is provided with a matte charging
port 18, a blister furnace slag discharging port 22, a blister
copper tapping port 23, a blister copper siphon 24, a blister
copper overflow weir 25, and a lance 26.
In the smelting furnace 1, a raw material which is principally
composed of sulfide ore and a flux such as a silicic ore is mixed
with fuel and air at an appropriate ratio being suitable for the
predetermined reaction conditions, the mixture of which is charged
directly and continuously, at a predetermined feed rate, into a
melt consisting of the matte 5 and the slag 4 which are the
reaction products in the smelting furnace. While any practical
method may be employed for feeding the mixture material, the raw
material may better be crushed into a powder or granular form and
then blown into the melt carried on a gas current through the lance
provided in the furnace, whereby a large quantity of the raw
material can be smelted quickly and, also, generation of dust can
be prevented. In this case, the pressure of the gas supplied is
determined automatically by the inner diameter of the lance as well
as the position of the tip end thereof at a value which is
sufficiently high to feed the gas current and the raw material
directly into the melt. As the result of this, the melt is agitated
satisfactorily, and the reaction within the furnace proceeds
rapidly, whereby the furnace efficiency can be improved. The matte
grade may be controlled at any desired level by adjusting the air
ratio to the raw material. Here the air ratio signifies the ratio
between the net quantity of air for reaction which is the balance
after substraction of the quantity of air necessary for combustion
of the fuel from the total air quantity injected into the furnace.
More particularly, when the grade of the matte to be produced is
raised, there is resulted such an advantage that the heat generated
from oxidation-reaction of the iron and sulfur contents in the raw
material ore can be utilized effectively for smelting the raw
material, etc., whereas the copper loss in the slag inevitably
increases. In this case, addition of a reducing agent such as
pyrite into the saparator, in a manner as will be stated later on,
will prevent the copper loss from increasing to a certain
extent.
Any kind of fuel having fluidity, including solid fuel in a powder
form, may be used for the present invention, and, furthermore, the
consumption of the fuel to be used for the smelting may be reduced
by substituting the whole or a part of air for equivalent amount of
oxygen. Fuel may not be necessarily fed to the same place in the
furnace as that of the raw material, but it had better be blown
directly into the melt bath in the same manner as the raw material
for the significantly increased heat transfer efficiency. In this
consequence, the temperature of the furnace atmosphere and the
exhaust gas therefrom can be lowered to a level almost equal to
that of the melt with the result that capture and treatment of the
exhaust gas is facilitated and the life of the furnace walls can be
extended remarkably.
Fuel may be burnt by a burner 7. In this case, the fuel consumption
may be reduced by preheating and/or oxygen-enriching the air for
the combustion.
All kinds of the products formed in the smelting furnace are tapped
out of the furnace through the melt discharging port 8. Explaining
this with reference to FIG. 2 which shows an enlarged partial view
of the melt discharging port, the melt formed in the smelting
furnace is tapped out of the furnace through the melt discharging
port 8, wherein a sealing damper 9 fitted on the outside of the
melt discharging port 8 prevents the furnace gas from puffing out,
or the atmospheric air from infiltrating into the furnace, and the
slag layer 4 retained within the furnace can be controlled and kept
at a required constant thickness by fixing the bottom end 9a of the
sealing damper 9 at a certain constant difference in the level
which is lower than the melt overflow weir. The sealing damper 9
should be wide enough for closing the melt discharging port 8 and
be made movable up and down. The durability of the sealing damper 9
may be further increased by means of a water cooling jacket
provided thereon. In the case that the matte and the slag are
tapped out separately through a siphon and a slag discharging port
22 directly provided on the furnace as in the case of the blister
furnace 3 shown in FIG. 1, it may be dificult to reduce the
thickness of the slag layer to one thinner than a certain critical
value (about 100 mm) for the purpose of effecting the separation of
the matte and the slag to a satisfactory degree, and preventing the
matte from mixing into the slag. It is, however, possible to form a
slag layer having a desired thickness of even thinner than 50 mm by
means of the aforementioned sealing damper 9, whereby the rate of
reaction between the melt and the air supplied thereinto through
the lance is improved significantly.
By maintaining the melt overflow weir 10 and the bottom end 9a of
the sealing damper 9 at required constant levels so as to cause the
residence quantities of the matte and the slag to be maintained
constant within the furnace, the feeding quantity of the melt into
the separator can be equilibrated with the rate of feeding of the
raw material into the smelting furnace, whereby a constant feed
rate thereof may be maintained. As the result, the melt is
continuously charged into the separator 2 by way of a launder and
through the melt charging port 14, where it is caused to stand for
a certain period of time until it is separated into the matte 11
and the slag 12. The slag 12 is then tapped out of the separator
through the slag discharging port 15, and dumped as indicated by
the arrow (h) either as it is or after it has been caused to stand
within a settling furnace to settle the matte particles contained
therein. On the other hand, the matte 11 is taken out of the
separator through the matte tapping port 16, and then the matte
siphon 17, after which it is allowed to overflow from the matte
overflow weir 17a and fed into the blister furnace 3 in a
continuous manner.
The separator 2 may be kept at a required temperature by means of a
burner (not shown) or an electric heating device 13. Also, as shown
in FIG. 3, the separator 2 may be integrated with the smelting
furnace 1, thereby simplifying the installation. In this case, by
maintaining the level 10a of the melt discharging port 8 of the
smelting furnace lower than the level of the slag discharging 15 of
the separator, the liquid surface in both smelting furnace and
separator is made common, and the residence quantities of the matte
and the slag within the smelting furnace are maintained constant.
As shown in FIG. 4, the separator 2 may be formed in a shape
longitudinally extended in the flow direction of the melt (e.g.
oval, rectangular, etc.) with a matte sump 27, a matte siphon 17,
and a melt charging port 14 being provided at one end thereof, and
a slag discharging port 15 provided at the other end thereof,
whereby the matte particles in the slag can be sedimented more
perfectly. In this case, the rate of recovery of the copper content
in the slag may be increased further by addition of a reducing
agent such as pyrite, coke, and so on. The matte separated in the
separator and a matte newly produced as the result of extraction of
the copper content from the slag by addition of pyrite are tapped
out of the furnace in combination through the matte tapping port 16
and then the matte siphon 17, the entire matte as combined being
then fed into the blister furnace 3. In either case, thickness of
each of the matte layer and the slag layer retained in the
separator can be kept at a fixed value by maintaining constant the
slag discharging port and the matte overflow weir at fixed heights,
respectively. In this consequence, the flow rates of the slag and
the matte are brought to an equilibrium with the feed rate of the
melt transferred from the smelting furnace.
The matte from the separator 2 is continuously charged into a melt
bath in the blister furnace 3 consisting of blister furnace slag
21, white metal 19, and blister copper 20, all of which are the
reaction products in the third process step, while air and a flux
are simultaneously fed directly and continuously thereinto. A
coolant (or cold dope) containing the objective metal such as the
raw material or scrap to be charged into the melt bath can be fused
by the excessive heat generated in this third process step, thereby
preventing the furnace temperature from exceeding the ordinary
operating temperature, and simultaneously allowing the entire
treating capacity of the ore to increase further. The way, in which
these materials are fed into the blister furnace, is carried out
through the lance 26 provided therein in the same manner as in the
smelting furnace. The total quantity of the air to be introduced
into the blister furnace should be in such quantity that is
sufficient to convert the total quantities of the matte and the
coolant to be charged into the blister furnace slag and a blister
copper, and thickness of a white metal layer residing in the
furnace is maintained constant. The blister copper is tapped out of
the furnace through the blister copper tapping port 23 and then the
blister copper siphon 24, after which it is caused to continuously
overflow from the blister copper overflow weir 25, and is forwarded
to the refining process of known type. On the other hand, the
blister furnace slag is continuously discharged out of the furnace
through the blister furnace slag discharging port 22, the melt
transfer passage (g), and then recycled to the revert slag charging
port 22a provided in the smelting furnace in a substantially
continuous manner by a forced transfer. Any practical means such as
a bubble pump (air-lift), a bucket conveyor operated in a
continuous motion, an electromagnetic transfer, and so on may be
employed for the forced transfer.
Transfer of the blister furnace slag to the smelting furnace may
preferably be achieved in the molten state taking advantage of its
own temperature. However, it is also possible to transfer the
blister furnace slag in the solidified or granulated form to
facilitate handling. In case the grade of matte is high and the
formation of blister furnace slag is small, increase in the fuel
consumption required for remelting the blister furnace slag is not
so large in comparison with what will be required in the event that
the matte grade is low and the quantity of the blister furnace slag
is large.
In the above-described example, the level of the melt bath in the
separator is made to be lower than that in the smelting furnace,
while the melt bath level in the blister furnace is made to be far
lower than that in the separator, whereby the transfer of the matte
is carried out by the gravity of the melt in taking advantage of
the difference in head among these three furnaces. On the other
hand, when the surface level of the melt in the blister furnace is
made higher than that in the smelting furnace, the transfer of the
blister furnace slag is carried out by the gravity thereof, whereas
the transfer of the matte from the separator to the blister furnace
may be accomplished by a forced transfer.
White metal 19 is an intermediate product of the blister making
step, which is not tapped out but is maintained in a constant
residence quantity by adjusting the reaction conditions.
The thickness and residence quantity of each of the melt layers in
the blister furnace can be maintained constant by setting the slag
discharging port and the blister copper overflow weir 25 at
constant levels in the same manner as in the separator. In this
consequence, the rates of production of the slag and the blister
copper in the blister furnace are controlled by the rate of feeding
of the matte thereinto (which is governed by the reaction
conditions and the rate of feeding of the raw material in the
smelting furnace) and the rate of feeding of the coolant into the
blister furnace (which is governed by the grade of the matte to be
fed into the blister furnace and the reaction conditions
therewithin), whereby the entire reaction system can be controlled
under certain constant reaction conditions.
The reaction in the blister furnace may also be carried out under
co-existence of the two phases of slag and blister copper only,
without presence of a white metal in the furnace, by charging
thereinto more quantity of air than required to oxidize principally
the entire quantities of iron and sulfur contained in the matte and
the coolant. In this case, the sulfur content in the blister copper
can be reduced below the saturated concentration thereof by
increasing the ratio of air to be supplied to a desired extent.
That is, as the ratio of air increases, the copper content in the
slag is also increased, whereas the sulfur content in the blister
copper is decreased. Here, the air ratio signifies the ratio of air
to the total quantities of the matte and coolant. When a white
metal layer exists in the blister furnace, the copper content in
the slag ranges from 2 to 6%, whereas the copper content may be
increased to a range of from 40 to 50% when no white matte is
present in the furnace. However, the matte grade and the reaction
conditions in the blister furnace should be set within such a range
where the copper content in the slag formed in the blister furnace
does not exceed the copper content in the materials fed thereinto,
and, further, the flux (particularly lime) fed into the blister
furnace does not exceed the amount which is needed in the entire
system. In the ordinary converter process, silica sand is used as a
flux, whereas, in the blister furnace according to the present
invention, the fluidity of the slag formed therewithin can be
increased by use of lime or a mixture of lime and silica sand.
Exhaust gas discharged from each furnace in the above-stated
process steps is collected and let out through a flue duct (c), and
the total quantity thereof is cooled and utilized as a raw material
for production of sulfuric acid.
According to another embodiment of the present invention, the third
process step may be further divided into two stages to conduct the
entire furnace operations in four process steps. In this case, the
third process step carries out production of white metal and
blister furnace slag in the blister furnace 3. More particularly,
as shown in FIG. 5, while the matte is being continuously fed into
the blister furnace through the matte charging port 18, air and a
flux are charged through the lance 26 into the melt which is
composed of the blister furnace slag 21 and the white metal 19
formed by the reaction within the furnace. The excess heat
generated at this time is utilized for melting the coolant in the
same manner as in the previous example. Air should be charged at
such a feed rate as required to oxidize principally the entire part
of iron and a part of sulfur contained in the matte and the coolant
fed into the furnace, respectively, and to produce a white metal
and a slag. The flux used in this case may be silica sand as in the
case of the ordinary slag-forming process by a converter.
The slag 21 is then caused to flow continuously out of the furnace
through the slag discharging port 22, and, as in the previous
example, is transferred and recycled into the smelting furnace. It
has been confirmed that the copper content in the slag exists
principally in the form of white metal particles and metallic
copper particles. Instead of returning the slag into the smelting
furnace in a molten state, it may be crushed and treated by
floatation, thereby to concentrate the copper content therein,
after which the concentrate may be recycled to the smelting
furnace.
On the other hand, the white metal 19 is tapped out of the furnace
through the tapping port 23 and then the siphon 24, thereafter
caused to flow over the overflow weir 25. The white metal which is
principally composed of a single or a plurality of the objective
metal sulfides may in some cases be regarded as the final product
in this treating process. When the objective metal is nickel, for
instance, the white metal is forwarded as it is to an electrolytic
process, or transferred to a reducing process after it has been
crushed and roasted. Furthermore, when white metal produced from a
raw material contains therein two or more kinds of metals such as
copper, nickel, and cobalt in such quantities that none of these
metals can be neglected from the economical or technical
standpoint, the white metal is sent to a process to separate the
objective metals from each other by such means as, for example, a
floatation treatment after it has been cooled slowly. When a white
metal is principally composed of sulfides of copper, the white
metal is transferred in its molten state to another blister
furnace, wherein the fourth process step is carried out. The
blister furnace used in this fourth process step may be an ordinary
converter, but should preferably be another unit of blister furnace
according to the present invention, whereby the white metal can be
treated in a continuous manner. The operational process of the
fourth process step is exactly same as that of the third process
step in the foregoing first embodiment, except that the material
charged thereinto is the white metal and the quantity of a slag
produced therein is extremely small. The quantity of the slag to be
produced from the white metal is less than 10 percent by weight of
the white metal, normally in a range of from 2 to 6%, with the
result that transfer of the slag in its molten state back to the
smelting furnace becomes somewhat difficult. In this consequence,
the slag tapped out of the furnace is once solidified and then
charged together with the other raw materials into the smelting
furnace.
In order to restrain the slag formation in the fourth process step,
a coolant which is not contributive to the slag formation such as a
scrap of the objective metal may be fed into the blister furnace
for the fourth process step.
The treatment of exhaust gas discharged from this blister furnace
can be done in the same manner as in the afore-mentioned first
example.
The above-described process according to the present invention has
not only the generally known advantages associated with a
continuous process such as a lower cost for construction and
operations thereof than the batch system, and facilitating
introduction of an automatic control system thereinto, but also the
following additional features owing to the unique process steps and
reaction system thereof.
In the process according to the present invention, the smelting
furnace is caused to function only for reaction (i.e., smelting) of
the raw material charged thereinto, while the separation of slag
and matte produced in this smelting furnace is carried out in the
separator, whereby the agitation of the melt in the smelting
furnace can be performed without any restriction and the charges
such as the raw material can be fed into the furnace covering the
largest possible area of the furnace bed with the result that the
furnace efficiency (i.e., smelting rate) is remarkably improved.
Furthermore, the thickness of the slag layer formed in the smelting
furnace can be decreased and, at the same time, the agitation of
the melt can be strengthened, whereby the contact between the matte
and the slag becomes satisfactory, and the copper content in the
revert slag (blister furnace slag) is absorbed quickly and
completely into the matte phase until the equilibrium therebetween
is reached.
It has been confirmed by a microscopic observation on a quenched
sample that, under the reaction conditions according to the present
invention, most part of the copper content in the slag exists in
the form of matte granules, each having a diameter of from about
0.5 to about 3 mm. The copper granules was found to have settled
rapidly as to be readily calculated from the Stoke's equation and
to have been able to be separated from the slag easily in the
separation furnace, whereby a satisfactory result could be obtained
without installing a settling furnace along with the separator.
As to the slag layer, the thickness thereof in the smelting furnace
according to the present invention could be reduced to as thin as
from one tenth to one twentieth of that formed in an ordinary
reverberatory furnace. As the result of this, a sufficiently high
rate of reaction in the furnace could be achieved, even if the
pressure of air to be blown into the melt was considerably low,
without immersing the tip end of the lance into the melt, whereby
economical effects such as a saving of the power consumption and an
extended life of the lance can be resulted. In other words, as the
air reacts with the matte in the main, and as there is only an
extremely thin layer of the slag in the melt bath, which prevents
the air from contacting the matte, the contact between the air and
the matte is improved and the reaction rate therebetween in the
furnace increases significantly.
Also, a reducing agent such as pyrite may be added into the
separator to further improve the rate of recovery of copper. In
this case, the recovered matte is merged into the smelting furnace
matte separated within the separator and continuously transferred
in its entirety into the blister furnace through the one and same
flow path, so that the melt flow path can be simplified and the
furnace control is facilitated. (It is a well known fact that, when
a flowing quantity of the melt in the launder is small, there is
accompanied great difficulty in the transfer operation
thereof.)
Furthermore, in the process according to the present invention,
corrosion of the bricks constituting the furnace can be suppressed.
Slag is the principal cause of corrosion of the bricks. In the
present process, the slag layer is maintained extremely thin, hence
the area of contact between the slag and the furnace walls is
small, whereby economical burden to be derived from use of a
refractory material or a jacket having particularly excellent
durability (these being most expensive, of course) to cover such
contact area can be reduced significantly.
In order to reduce the present invention into practice, the
following preferred examples are presented. It should, however, be
noted that these examples are just illustrative, and do not intend
to limit the scope of the present invention as set forth in the
appended claims.
EXAMPLE 1
6,000 kg per hour of a copper concentrate consisting of 24.0% of
copper, 34.2% of iron, 34.2% of sulfur, and 3.7% of SiO.sub.2,
1,500 kg per hour of silica sand containing 90.0% of SiO.sub.2, and
500 kg per hour of lime stone containing 53.4% of CaO were directly
charged into a melt bath which was the reaction product in the
smelting furnace together with 1,500 Nm.sup.3 per hour of air
having a gauge pressure of 2 kg per square centimeter through a
lance provided in the furnace. By use of another lance, 3,500
Nm.sup.3 per hour of air having a gauge pressure of 0.8 kg per
square centimeter and 500 Nm.sup.3 per hour of oxgygen for
industrial use were mixed, and the mixed gas was directly charged
into the melt bath in the same manner as was done with the above
raw material. The raw material had all been previously classified
into granules, each having a diameter of less than 10 mm, and dried
until the water content thereof ranged from 1 to 2%.
On the other hand, 250 liters per hour of fuel oil was burnt with
aid of 2,500 Nm.sup.3 per hour of air having a gauge pressure of
0.2 kg per square centimeter and preheated to 300.degree.C by use
of a burner provided on top of the furnace. A blister furnace slag
was fed into the furnace through a blister furnace slag charging
port provided therein. Thickness of the slag layer within the
furnace was maintained at about 20 mm. The products consisting
principally of matte and slag were caused to continuously flow out
of the furnace through a melt discharging port provided in the
furnace and further caused to flow into a separator by the dead
weight thereof. The SO.sub.2 content in the exhaust gas discharged
from the smelting furnace was from 8 to 10%. The temperature within
the furnace was kept in a range of from 1,220.degree. to
1,260.degree.C by adjusting the fuel supply thereinto.
The separator employed herein was of the type shown in FIG. 4, and
its capacity to hold the melt was about 10 tons. 150 kg per hour of
pyrite containing 45% of sulfur and 50 kg per hour of coke breeze
were charged into the separator. The thickness of the slag layer
and the residence quantities of slag and matte within the separator
were kept constant by maintaining a matte overflow weir at a level
120 mm lower than a slag overflow weir also provided in the
separator. The slag was caused to flow out of the separator through
a slag discharging port provided in the separator and then
granulated with water jet. The slag quantity thus produced was
5,600 kg per hour and the composition thereof was controlled to be
from 0.4 to 0.6% of copper, from 33 to 35% of SiO.sub.2, and from 5
to 6% of CaO. The matte was continuously tapped out of the furnace
through a siphon provided therein and fed into a blister furnace.
The grade of the matte thus produced was controlled to have from 59
to 62% of copper.
Into the blister furnace, there were charged 200 kg per hour of the
above-mentioned silica sand, 100 kg per hour of lime stone, and 100
kg per hour of precipitate containing 60% copper, together with
2,400 Nm.sup.3 per hour of air at a gauge pressure of 2 kg per
square centimeter. The charges were supplied directly into the melt
bath formed by reaction therewithin through a lance provided in the
furnace. The copper content in the slag formed in the furnace was
controlled to be from 20 to 25% with the result that no white metal
was formed in the furnace and the melt bath formed therewithin was
found to have been composed of two layers of slag and blister
copper respectively. The slag thus formed was composed of from 8 to
13% of SiO.sub.2, from 4 to 6% of CaO, and from 38 to 45% of iron.
Most part of iron was found to have been composed of Fe.sub.3
O.sub.4. The slag was then caused to continuously flow out of the
furnace through a slag discharging port provided in the furnace,
and transferred to the aforementioned smelting furnace by a bucket
conveyor being operated in continuous motion. The blister copper,
on the other hand, was caused to flow out of the furnace through a
siphon provided contiguous to the blister copper tapping port. The
rate of production of the blister copper was 1,550 kg per hour, and
its composition was from 98 to 99% of copper and from 0.2 to 0.3 of
sulfur.
When adjustment was so made as to cause a white matte layer to
exist in the blister furnace by changing the rate of feeding of the
afore-mentioned silica sand and lime stone into the smelting
furnace to 1,700 kg and 350 kg per hour, respectively, and by
changing the kind of the flux to be fed into the blister furnace to
lime stone at a rate of feeding of 250 kg, and by reducing the rate
of feeding of air into the blister furnace by approximately 2% less
than the afore-described example, the slag produced therein was
found to have been composed of from 6 to 8% of copper, from 12 to
16% of CaO, and from 55 to 65% Fe.sub.3 O.sub.4, and the quantity
of copper recycled to the smelting furnace was reduced, whereas the
sulfur content in the blister copper increased to 1% and above.
Furthermore, it was observed that the fluidity of the slag tended
to lower, when the content of calcium oxide (CaO) in the slag was
reduced to 5 to 7%.
The rate of production of the blister furnace slag was
approximately 1,000 to 1,500 kg per hour. In such case of low rate
of production of the slag, a portion of the slag solidified in the
course of its transfer to the smelting furnace, but this did in no
way adversely affect the operation of the smelting furnace. Sulfur
dioxide (SO.sub.2) contained in the exhaust gas discharged from the
blister furnace was from 14 to 16%, and the temperature within the
furnace was from 1,200.degree. to 1,270.degree.C.
The exhaust gas from each furnace was all collected and cooled,
after which it was delivered to a sulfuric acid production plant.
The flue dust contained in the exhaust gas collected in the dust
chamber was found from 1 to 2% with respect to the total quantity
of the raw material used.
EXAMPLE 2
Into the smelting furnace, there were charged 5,000 kg per hour of
copper concentrate consisting of 18.9% of copper, 33.8% of iron,
36.5% of sulfur, and 1.5% of silicic acid, 1,400 kg per hour of
silica sand containing therein 89% of SiO.sub.2, 570 kg per hour of
lime stone containing therein 53.4% of CaO together with 200
Nm.sup.3 per hour of air at a gauge pressure of 2 kg per square
centimeter. The charges were supplied directly into the melt bath
composed of reaction products within the furnace through a lance
provided therein together with 3,000 Nm.sup.3 per hour of air at a
gauge pressure of 0.8 kg per square centimeter and 510 Nm.sup.3 per
hour of oxygen gas for industrial use. At the same time, 160 liters
per hour of fuel oil was blown into the furnace together with 1,700
Nm.sup.3 per hour of air at a gauge pressure of 0.8 kg per square
centimeter through a separate lance, and was burnt therewithin. In
the meantime, blister furnace slag was continuously charged into
the melting furnace through the blister furnace slag charging port
provided therein. The matte and slag thus produced were introduced
into a separator which had been integrally formed with the smelting
furnace as shown in FIG. 3 thereby to separate matte and slag each
other. The slag layer within the smelting furnace was maintained in
a thickness of 20 mm. Also, the rate of feeding of fuel was so
adjusted as to maintaining the temperature within the furnace in a
range of from 1,220.degree. to 1,270.degree.C. The exhaust gas
discharge from the smelting furnace was found to have contained
from 13 to 16% of SO.sub.2.
In the separator, the matte overflow weir provided therein was set
at a certain level which was lower by 70 mm than the level of the
slag outlet port also provided therein, whereby the slag layer
within the furnace was maintained in a thickness of about 300 mm.
The slag thus formed was caused to continuously flow out of the
furnace through the slag discharging port, and then
water-granulated. The composition of the slag was controlled to
have from 32 to 34% of SiO.sub.2 and from 5 to 6% of CaO. The slag
contained from 0.30 to 0.45% of copper and the rate of production
thereof was 5,900 kg per hour. The matte thus produced, on the
other hand, was caused to flow continuously out of the furnace
through a siphon provided contiguous to the matte tapping port, and
then charged into the blister furnace. The matte was controlled to
contain from 39 to 42% of copper.
Into the blister furnace, there were charged 1,000 kg per hour of
the aforementioned raw material ore and 500 kg per hour of silica
sand together with 3,040 Nm.sup.3 per hour of air at a gauge
pressure of 2 kg per square centimeter. The charges were fed
directly into a melt bath consisting of the reaction products
formed by reaction within the furnace. The reaction products were
composed of white matte and slag, and the slag layer within the
furnace was kept in about 100 mm thick. The slag thus produced was
caused to continuously flow out of the furnace through a slag
discharging port provided therein, and then recycled to the
smelting furnace by means of a bubble pump. The slag contained from
22 to 24% of SiO.sub.2 and from 2 to 6% of copper, and the rate of
production thereof was about 2,300 kg per hour according to
calculation. The white matte thus produced, on the other hand, was
caused to continuously flow out of the furnace through a siphon
provided contiguous to the white matte tapping port and then
forwarded to a copper refining process of known type. The matte was
controlled to contain from 77to 79% of copper. The sulfur content
therein was from 19 to 20%, and the temperature within the furnace
was from 1,250.degree. to 1,300.degree.C. The exhaust gas
discharged from the furnace contained from 13.5% to 15.0% of
SO.sub.2. The exhaust gas from each furnace was treated in the same
manner as stated in Example 1.
It is of course possible that various modification in the refining
process may be made by employing the existing copper refining
facilities without changing the basic principles of the present
invention. For example, in the first process step, a
heretofore-known reverberatory furnace or an electric furnace may
be employed in place of the above-mentioned smelting furnace
according to the present invention. In this case, a revert slag
charging port is provided therein, as the case may be, through
which the blister furnace slag is charged into the furnace.
Further, in order to control the grade of the matte produced, a
lance may be provided in these substitute furnaces in the same
manner as in the foregoing smelting furnace according to the
present invention to supply air therethrough into a melt bath
within the furnace, or whole or a part of the ore charged thereinto
may be rotated beforehand.
In the first process step, a heretofore-known flush-smelting
furnace or blast furnace may be employed singly or in combination
with the smelting furnace according to the present invention. In
the latter case, the products formed in these two furnaces are all
charged into a separator provided subsequent to the first furnace,
whereas the blister furnace slag is charged into the smelting
furnace only according to the present invention, whereby treatment
of the slag can be done efficiently.
* * * * *