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United States Patent (19) (11) Patent Number: 5,254,320

Malmstrom (45) Date of Patent: Oct. 19, 1993
54 METHOD FOR ROASTING SULPHIDE 5,013,355 5/1991 Eivander et al. ....................... 75/23
ORES 5,074,909 12/1991 Agar ...................................... 75/422
75) Inventor: Rolf E. Malmström, Helsinki, FOREIGN PATENT DOCUMENTS
Finland 208.205 12/1955 Australia .
73) Assignee: A. Ahlstrom Corporation, 539882 4A1957 Canada .
Noormarkku, Finland 435479
12/1990 European Pat. Off. .
33030979/1983 Fed. Rep. of Germany .
21 Appl. No.: 808,720 3814127
li/1989 Fed. Rep. of Germany .
6770508/1952 United Kingdom .
22 Filed: Dec. 17, 1991
(30) Foreign Application Priority Data Primary Examiner-David Brunsman
Attorney, Agent, or Firm-Nixon & Vanderhye
Dec. 17, 1990 FI) Finland .................................. 90620 57 ABSTRACT
51) Int, Cl. ......................... C01G 7/00; COG 5/00; A method for roasting sulphide ores or ore concentrates
CO1G 3/12; CO1G 1/12 containing precious metals is practiced in a furnace,
52 U.S. Cl. ........................................ 423/28; 423/23; typically in a fluidized bed. The ore and a sulphur-bind
423/29; 423/47; 42.3/561.1 ing lime-containing material are supplied to a roasting
58 Field of Search ....................... 423/23, 27, 28, 29, furnace in which the ore is roasted with the emission of
423/34, 47, 561.1, 75/643,733, 736, 737, 718, heat and sulphur dioxide. The lime-containing
729
material-such as calcium hydroxide-is mixed into the
56) References Cited cooling water for the roasting furnace and sprayed into
U.S. PATENT DOCUMENTS the furnace as a line-containing aqueous slurry. Roast
ing occurs at about 600-850° C. (e.g. 650–750° C.).
1,377.012 5/1921 Howard ................................ 423/47
2,650,159 8/1953 Tarr, Jr. et al. ....... ... 423/47 Roasted material is discharged from the furnace and
4,615,729 10/1986 Victorovich et al. . ... 75/643 acted upon to recover gold, silver and copper metal.
4,670,228 6/1987 Braaten .............................. 423/2.
4,872.423 10/1989 Pillai ...................................... 22/40 20 Claims, No Drawings
 5,254,320
1. 2
METHOD FOR ROASTING SULPHIDE ORES CaCO3- SO2 + --O = CaSO4- CO

BACKGROUND AND SUMMARY OF THE The sulphur is bound as calcium sulphate in the first
INVENTION 5 roasting furnace. However, the furnace temperature
should be maintained below 1000 C. because the cal
The present invention relates to a method for roasting cium sulphate formed is decomposed at higher tempera
sulphide ores or concentrated ore products containing tures. The roasting material is passed from the first stage
precious metals, such as gold, which are to be recov on to a second smelting stage where it is mixed with
ered from the ore in a subsequent process stage, and O fresh copper concentrate. Pure oxygen is supplied to the
possibly some impurity, such as arsenic furnace, resulting in the formation of lime-containing
In prior art methods, sulphide ore or the ore concen ferrite slag, pure copper, and gas rich in sulphur diox
trate and a sulphur-binding lime-containing material are
charged into a roasting furnace, the sulphide ore or the ide. This gas should then be treated or used, e.g. in a
ore concentrate is roasted, with the emission of sulphur sulphuric acid plant, before it can be emitted into the
dioxide and heat, the roasting furnace is cooled by the 15 atmosphere. The two-stage method described in U.S.
injection of cooling water into it, the sulphur dioxide Pat. No. 4,615,729 thus requires a separate plant for the
formed is reacted with the sulphur-binding lime-con recovery of sulphur dioxide.
taining material to form calcium sulphate, and the In the roasting of sulphide ores for subsequent recov
formed calcium sulphate or calcium sulphite and the ery of precious metals or other valuable metals, as in
20 plants which are remote from other industries and in
roasting material from the roasting process are dis
charged from the furnace. which the use of the sulphur dioxide of the off gases
The term "sulphide ore materials' as used in the from roasting, for instance as sulphuric acid, is not de
present specification and claims includes sulphide ores, sirable, the sulphur dioxide formed should be taken care
and sulphide ore concentrates. The term "precious 25
of, for instance as gypsum, in connection with roasting.
metal' as used in the present specification and claims The reaction between SO2 and CaCO3 during gas
includes gold, copper, silver, and like metals found in cleaning, as in conventional flue gas cleaning, involves
sulphide ore materials. a velocity-inhibiting factor because of the diffusion of
The sulphide ore materials are typically fine-grained gases both into and out of the reaction zone in a lime
ore or sulphide ore concentrate dressed in some man particle. This applies especially to roasting furnaces
30 where the ore is roasted in a fluidized bed and where the
ner. The method according to the invention is well
Suited e.g. for processing auriferous pyritic ores, and in lime is charged as relatively large particles. In such
some cases also for copper ores, such as copper pyrite relatively large particles, the lime in the surface layer of
or other metal-sulphide-containing ores having rela the particles first reacts with the sulphur dioxide. On the
tively high sulphur contents and a recoverable amount 35 particle surface a layer of calcium sulphate is then
of precious metals. Roasting is suitably effected in a formed, preventing additional sulphur dioxide from
roasting furnace with a fluidized bed. During roasting, penetrating into the particle to react with the unspent
the ores normally have a particle size of about 30-300 portion of lime in the particle. This results in long reac
microns tion times and a high consumption of absorbent when
The sulphide ore materials often also contain as impu using limestone, for a reasonable degree of utilization of
rities arsenic, antimony or bismuth minerals. Consider the lime. Although the use of burnt lime (CaO) ought to
able amounts of arsenides, for instance, may be present involve far more favorable conditions, the gypsum
in the material to be treated, contents of up to 10-15% (CaSO4) formed also has a reaction-inhibiting effect, so
being not unusual The arsenic in the arsenides is oxi that an adequate degree of utilization of the burnt lime
dized in the same way as the sulphur in the sulphides. In 45 is not achieved. A sulphur absorption method where the
roasting with an almost equivalent oxygen amount, flue gases are treated with calcium oxide or calcium
volatile arsenic compounds, such as As2O3, are formed, carbonate which is charged as particles directly into the
which are generally expelled from the roasting furnace combustion or roasting furnace has thus been found to
with the flue gases. The volatile arsenic compounds require a substantial excess of the lime-containing mate
desublimate only at relatively low temperatures of 50 rial for removing sulphur from the flue gases. Such
about 100 C. excess line is harmful in the following process stage.
It is known that the sulphur content offlue gases from Thus, when using lime, CaCO3 or CaO, in connection
roasting furnaces as well as from combustion furnaces with the roasting of sulphide materials, a fairly good
can be reduced by what is known as a dry process, by elimination of SO2 can be achieved only with a consid
supplying solid calcium oxide to the furnace, or calcium 55 erable excess of lime. Although, in most cases, this can
carbonate or some other alkaline compound, such as be done without having a negative heat balance, both
dolomite, which reacts with the produced sulphur diox costs and consumption of material will increase.
ide so as to form calcium sulphate, i.e. gypsum, or cal If the material to be roasted should thereafter be
cium sulphite. subjected to leaching, which is often the case, for recov
U.S. Pat. No. 4,615,729 (the disclosure of which is ering valuable metals from the roasting material, a large
hereby incorporated by reference herein) describes a excess of lime will have a cost-increasing effect on this
two-stage method for sulphide copper concentrate. The process stage. When leaching gold or silver from the
copper concentrate is supplied to a roasting furnace roasting material by cyanidation, a slight lime excess is
together with dry limestone CaCO3 or line CaO as of no major consequence, since leaching takes place in
absorbent, and is roasted at temperatures above 850 C, 65 an alkaline environment, whereas when leaching e.g.
i.e. above the temperature at which CaCO3 is thermally copper, Cu, taking place in an acid environment, any
decomposed to CaO. At this temperature the following excess of free lime means an equivalent consumption of
reaction occurs: acid.
 5,254,320
3 4.
To increase the reactivity of the limestone and the and/or pyrrhotite) which cannot be leached with cya
lime in sulphur absorption, different supplementary nide or other complexing agents, without oxidation.
methods have been suggested. These deposits are usually quite small, and a plant for
Swedish Patent SE 451,158 suggests a method where producing H2SO4 is too expensive and often there is no
the absorbent particles in a fluid bed furnace are disinte- 5 market for the acid. If such a deposit is located in the
grated in the furnace by blowing gas at a high velocity vicinity of residential or agricultural areas, it often re
into the fluidized bed through a special feeding nozzle. mains unexploited because of the difficulty of making
In this manner, particles in the bed are caused to collide the ore suitable for gold leaching.
with each other at a high velocity and are to some The roasting according to the present invention
extent disintegrated, such that unspent absorbent pres- 10 makes the roasting material leachable and offers a possi
ent in the particle interior is exposed and can be used for bility of recovering valuable metals from the ore. The
absorbing sulphur dioxide from the flue gases. roasting material can then be subjected to cyanidation
Swedish Patent SE 457,014 describes another method to recover the valuable metals. As a result of the inven
for making the interior of absorbent particles available tion, it is possible to avoid large excessive amounts of
for absorption by withdrawing the particles from the 15 unreacted lime in the roasting material, which would
furnace and treating them with water vapor. Calcium adversely affect the process.
oxide and calcium carbonate in the material withdrawn The required amounts of lime are minimized, since
then react with the water vapor, with the formation of the lime in aqueous slurry forms a highly reactive cal
calcium hydroxide. These reactions are sufficiently cium hydroxide, and as an aqueous slurry it can easily
vigorous for splitting the particles. Unused absorption 20 be evenly distributed with the cooling water in the
material in the particle interior is exposed and becomes roasting furnace The amounts of cooling water are
available for absorption. The calcium hydroxide formed normally sufficient for the required amount of lime so
has, as a fine powder, high reactivity because of a large that the lime slurry does not become too thick, which
available reaction surface. would give rise to clogging problems in the injection
According to the present invention, a method is pro- 25 nozzles. The water evaporates in the roasting furnace
vided for roasting sulphide ores, in which sulphur diox and does not cause any waste water problems. The
ide formed during roasting can be easily and efficiently cooling water is preferably sprayed into the roasting
removed from the gases formed during roasting. The furnace, e.g. through nozzles provided in the roof of the
sulphur dioxide can be bound as a material which is roasting furnace.
solid and readily removed. The method of the invention 30 The present invention is applicable to roasting in
is especially well suited for roasting precious-metal different types of roasting furnaces, such as rotary fur
bearing sulphide ores, and also can allow the recovery naces, multi-stage ovens, fluid bed furnaces and also in
of arsenic, possibly released during roasting, as a com fluid bed furnaces of the circulating-bed type.
pound which can be stably dumped. The method according to the invention thus is well
By the present invention it has become possible, in a 35 suited, e.g. for-roasting of auriferous pyritic ore with
surprisingly simple manner, to solve the problems of subsequent leaching with cyanide, and-roasting of
sulphur dioxide absorption in the roasting methods de copper ore with a first stage including cyanidation of
scribed above, by mixing lime-containing material into precious metals, and subsequent stages including acid
the cooling water of the roasting furnace so as to supply leaching of copper with subsequent recovery of metal
a reactive lime slurry into the furnace. The line slurry 40 lic copper. Since the amounts of lime are minimized,
is e.g. a slurry of slaked lime or limestone, or e.g. a both alkaline and acid leaching can be performed to
slurry of dolomite line. Roasting is carried out under recover precious metals, including copper.
conditions promoting the formation of calcium sul In roasting and subsequent gold leaching, the roasting
phate, the sulphur being efficiently bound to the lime as temperature should be selected so that no sintering of
calcium sulphate, or calcium sulphite (which already is 45 the particles occurs, but rather the roasting material
present in the roasting furnace), and no additional sul becomes porous and easy to leach.
phur-removing plant is required. The calcium sulphate The roasting temperature for roasting sulphides for
or calcium sulphite can be withdrawn from the roasting subsequent leaching should be below the lowest sinter
furnace with the rest of the roasting material. ing temperature that may occur in the particle, but
Thus, the roasting according to the present invention 50 above the sulphating temperature of iron. To obtain as
results, in the case of ordinary roasting, in binding SO2 porous a material as possible, this means a suitable
to CaSO4 directly in the reactor. The reactor may be a working range between about 600 C. and 850 C.
regular roasting furnace, a reactor with a "bubbling'- Within this range, it would be almost impossible to use
type fluidized bed, or a circulating fluidized bed, or of a CaCO3 also CaO would give an unsatisfactory yield.
type therebetween. The process is usable when gypsum 55 Ca(OH)2, on the other hand, reacts much more com
or calcium sulphite is formed and any existing free lime pletely than do both limestone and burnt lime. Since the
does not interfere with the following treatment. The roasting furnaces, under generally prevailing condi
process is of course especially useful when the SO2 tions, are normally cooled and controlled by direct
formed during roasting cannot be used in a sensible way water injection, the injection of lime slurry consisting of
for other purposes, or cannot be emitted into the atmo- 60 water and slaked lime can easily be brought about. This
sphere. Also in roasting plants close to ore deposits and gives an active absorption material well distributed in
remote from other industries, the sulphur should be the reaction chamber The water injection technique is
removed from the flue gases even if it is not economical generally known within the roasting technology, but no
to reuse it as pure sulphur or sulphuric acid. The sul one has earlier demonstrated that it can be used for
phur should then be stored in stable form. Calcium 65 desulphurising gases formed during roasting.
sulphate is such a stable form, suitable for dumping. In addition to being supplied with the cooling water,
The roasting method according to the invention is a supplementary amount of solid Ca(OH)2 can be sepa
conveniently used, e.g. on auriferous sulphides (pyrite rately supplied to the furnace should the process so
 5,254,320
5 6
require. In the roasting of ores requiring such large CaSO4, a considerably larger amount of air is required,
amounts of lime that the cooling water slurry might since all the SO2 should be oxidized to sulfur trioxide
have an excessively high content of lime if all the lime and then form CaSO4. This sulphating reaction releases
were supplied with the cooling water, part of the Ca a substantial amount of heat. This means that although
(OH)2 therefore be supplied as solid material. 5 the amount of air increases to 2400 Nm air per ton
The difference in the results obtained with prior-art concentrate (13% excess) and CaO is supplied in an
roasting methods and the present invention can be ex amount of 610 kg per ton concentrate in the form of
pressed such that with CaO supplied to the bed there is Ca(OH)2, about 900 kg water perton concentrate is still
achieved, under favorable conditions, a desulphurising required to cool the reaction.
efficiency of about 50% is achieved, whereas with Ca- 10 A process with 610 kg CaO added per ton concen
(OH)2 a 90% desulphurising efficiency is achieved. This trate thus required 900 kg water per ton concentrate.
means that the use of CaO requires twice the theoretical 610 kg CaO corresponds to 810 kg Ca(OH)2, and the
amount of lime, while the use of Ca(OH)2 requires only required amount of water is 700 kg. This gives a density
a 10% excess above the theoretical amount. The conse value of 54%. Should considerably larger amounts of
quence of this, in terms of material and additional neu- 15 Ca(OH)2 be required, e.g. for concentrates with unfa
tralization costs in the subsequent leaching, is easily vorable sulfur content/heat value ratios, additional
appreciated.
Many of the auriferous sulphide ores that can be solid Ca(OH)2 can be supplied directly to the bed.
While the invention has been herein shown and de
pretreated by roasting in many cases also contain signifi scribed in what is presently conceived to be the most
cant amounts of arsenic. Roasting with excess air/oxy- 20 practical embodiment, it will be seen by those of ordi
gen, which is required for the formation of sulphate, nary skill in the art that many modifications may be
also involves the formation or arsenate, preventing the made thereof within the scope of the invention, which
arsenic from subliming as As2O3 and leaving the process scope is to be accorded the broadest interpretation of
with the flue gases. To obtain fast and readily reacting the appended claims so as to encompass all equivalent
arsenates, the supply of CaO to the system is compul- 25 processes and methods.
sory. By carrying out the roasting according to the What is claimed is:
invention, in the presence of reactive line and with 1. A method of roasting sulphide ore materials con
excess air, the arsenic will be bound in the form of cal
cium arsenates. At temperatures where iron sulphates taining precious metals and impurities using a furnace,
are decomposed, the arsenic is also bound as iron arse- 30 the
ide
roasting resulting in the production of sulphur diox
gas, comprising the steps of:
nates. However, to obtain a more complete and faster (a) feeding sulphide ore material containing precious
reaction, the calcium salts are preferred.
The temperature in connection with roasting in a metals and impurities into a furnace;
fluidized bed should advantageously be maintained in (b) roasting the sulphide ore material in the furnace at
the range of about 600 C.-850 C., preferably within 35 a roasting temperature of about 600-850 C. to pro
the range of about 650 C.-750° C. Complete oxidation duce a roasted material;
of arsenic compounds into arsenates requires a tempera (c) mixing lime-containing material with water to
ture of about 600° C. to be efficient. Temperatures produce an aqueous slurry;
above 850 C. are however hazardous, since such high (d) supplying the aqueous slurry to the furnace to
temperatures may give rise to sintering of the bed. 40 cool the furnace and to effect reaction of sulphur
The calcium arsenates or iron arsenates formed are dioxide gas with linie to form calcium sulphate;
barely soluble. Since, in the roasting, all the CaO has (e) discharging calcium sulphate and/or sulphite
not been converted to CaSO4, a certain excess of Ca from the furnace; and
ions will be present, which further reduces the solubility (f) discharging roasting material from the furnace,
of the arsenates. Moreover, since Fe-ions are always 45 and acting on the roasted material to recover pre
available and since the Fe-arsenates have a lower solu cious metal therefrom.
bility product than the Ca-arsenates, this will further 2. A method as recited in claim 1 wherein steps (c)
reduce the soluble As-amount. A release of arsenate and (d) are practiced by utilizing calcium hydroxide as
ions upon decomposition of the calcium arsenate by the the lime-containing material.
formation of CaCO3 owing to CO2 present in the atmo- 50 3. A method as recited in claim 2 wherein step (d) is
sphere is prevented, since there is always a sufficient practiced by spraying the aqueous slurry into the fur
amount of Fe-ions to form poorly soluble iron arsenate. C.
The vapor emanating from the cooling water during 4. A method as recited in claim 3 wherein the sul
roasting is discharged directly with the flue gases. The phide ore material contains arsenic as an impurity, and
heat in the flue gases may, if desired, be taken care of, 55 wherein steps (d) and (e) are practiced so as to cause the
e.g. in a common flue gas boiler. formation of stable calcium arsenates, which are dis
EXAMPLE
charged with the calcium sulphate and/or sulphite.
5. A method as recited in claim 4 wherein step (f) is
The roasting of iron pyrite concentrate (38.6% Fe, practiced by acting on the roasted material with a cya
31.4% S, 30% gangue) requires, in normal roasting with 60 nide containing material to recover gold, copper, or
10% excess air, 1760 at standard cubic meter air per ton silver metal.
concentrate. When roasting with a bed temperature of 6. A method as recited in claim 3 wherein a first
800 C., heat is released which, considering a 10% mois impurity in the sulphide ore material reacts with lime
ture content in the concentrate and the heat losses of the during the practice of step (d) to form stable calcium
furnace, requires direct water injection of 400-450 kg 65 compounds containing the first impurity.
H2O/ton concentrate. 7. A method as recited in claim 6 wherein the first
If the same roasting is performed at the same temper impurity is arsenic, and wherein the practice of step (d)
ature, but with Ca(OH)2 and with the formation of results in the formation of calcium arsenate.
 5,254,320
7 8
8. A method as recited in claim 3 wherein step (b) is
practiced at a temperature of about 650-750° C.
9. A method as recited in claim 2 comprising the
further step of supplying calcium hydroxide, in addition
to that in the aqueous slurry, in solid form to the fur
nace, to react with sulphur dioxide gas.
10. A method as recited in claim 1 wherein step (b) is
practiced at a temperature of about 650-750° C.
11. A method as recited in claim 1 wherein step (d) is
practiced by spraying the aqueous slurry into the fur
3C.
12. A method as recited in claim 11 wherein the fur
nace has spray nozzles in the roof thereof, and wherein
step (d) is practiced by introducing the aqueous slurry
into the furnace through the nozzles.
13. A method as recited in claim 1 wherein the sul
phide ore material contains arsenic as an impurity, and
wherein steps (d) and (e) are practiced so as to cause the
formation of stable calcium arsenates, which are dis
charged from the calcium sulphate and/or sulphite.
14. A method as recited in claim 1 wherein a first
impurity in the sulphide ore material reacts with lime
during the practice of step (d) to form stable calcium
compounds containing the first impurity.
15. A method as recited in claim 1 comprising the
further step of supplying line containing material, in
addition to that in the aqueous slurry, in solid form to
the furnace, to react with sulphur dioxide gas.
16. A method as recited in claim 1 wherein the sul
phide ore material comprises iron pyrite concentrate.
17. A method as recited in claim 1 wherein the fur
O nace contains a fluidized bed, and wherein steps (a)-(d)
are practiced continuously.
18. A method as recited in claim 17 wherein the sul
phide ore material is in the form of particles having a
particle size of about 30-300 microns.
15 19. A method as recited in claim 1 wherein step (f) is
practiced by acting on the roasted material with a cya
nide containing material to recover gold, copper, or
silver metal.
20. A method as recited in claim 1 wherein step (c) is
20 practiced by mixing with water a material selected from
the group consisting essentially of slaked lime, lime
stone, and dolomite lime.
k k
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40
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50
55
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