Saturation of Copper-Iron Mattes with Solid Magnetite

D. L. KAISER and J. E ELLIOTT Conditions which lead to the saturation of simple copper-iron mattes with solid magnetite have been evaluated in this study. Diagrams have been developed which illustrate quantitatively the surface of saturation of matte with magnetite in the phase and stability diagrams for the Cu-Fe-S-O system at 1468 K and 1 atm total pressure. Conditions fo. simultaneous saturation of matte with magnetite and gas (Pso2 + Ps2 = 1 atm) have also been estimated by extrapolation of the data on magnetitesaturated mattes. Comparison of the results with compositions of mattes from oxygen-enriched smelters indicates that these smelters operate at magnetite saturation under conditions close to equilibrium. Conditions during oxygen-enriched smelting can be predicted from the diagrams given in this paper and correlation equations for the oxygen and sulfur concentrations in magnetitesaturated matte which were previously developed from the experimental data.

I.

INTRODUCTION

Cu

C O P P E R matte smelting furnaces may be operated with conditions that lead to saturation of the matte phase with magnetite. Modern matte smelting processes can operate at relatively high states of oxidation leading to the possible formation of magnetite, tl'21 In the traditional reverberatoryconverter system, the recirculation to the reverberatory furnace of converter slags that usually contain magnetite can result in magnetite saturation of the matte phase. This paper develops information regarding conditions for which simple copper-iron mattes are saturated with magnetite, and discusses briefly the application of the results to industrial matte smelting operations. Copper-iron mattes belong to the quaternary Cu-Fe-S-O system. A schematic phase diagram of this system at 1468 K and 1 atm total pressure shown in Figure 1 illustrates the liquid matte phase field. The boundaries of the phase field are surfaces of saturation of matte individually with various phases, these being Cu(1), Fe(~/), "FeO"(s), Fe3Oa(s ) (spinel solid solution), and gas (Pso2 + Ps2 = 1 atm). Of particular interest is the surface of saturation with Fe3Oa(s), surface ABCDA in Figure 1. There have been several reported studies of mattes simultaneously saturated with F e 3 0 4 ( s ) + C u ( l ) , [4] F e 3 0 4 ( s ) + Cu(1) + "FeO"(s), pl and F e 3 0 4 ( s ) + gas(Pso2 + Ps2 = 1 atm). [6'7] In a recent publication, [81 we have presented experimental results from a study on unsaturated mattes near magnetite saturation and magnetite-saturated mattes containing from 35 to 72 wt pct Cu. These results are used to describe quantitatively the magnetite surface of saturation of moderate to high grade mattes in the phase and stability diagrams for the Cu-Fe-S-O system at 1468 K. The resulting diagrams are presented here.

~/
II.

GQs (Pso2+Psz 1olm) =

Fe

Fig. 1 - The matte phase field in the 1468 K isothermal tetrahedron of the Cu-Fe-S-O system, 1 atm pressure. I31

THE EXPERIMENTAL METHOD

D. L. KAISER, formerly Research Fellow at Massachusetts Institute of Technology, is Materials Research Engineer, National Institute of Standards and Technology, Gaithersburg, MD 20899. J.F. ELLIOTT is AISI Distinguished Professor and Professor of Metallurgy, Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139. Manuscript submitted September 27, 1985.

The experimental method was described in detail in the previous paper. Isl In principle, the method was very simple. A matte of known copper to iron ratio was equilibrated at 1468 K with a flowing stream of gas at a total pressure of one atmosphere. The gas was a mixture of prepurified CO(g), CO2(g), and SO2(g) and its composition was controlled to give a fixed sulfur potential (log Ps2) throughout a run. During a run, the oxygen partial pressure was increased in carefully controlled increments from approximately 3 x 10-~~ atm to a value above the point at which solid magnetite precipitated from the matte. At each value of oxygen potential (log Po2) the liquid matte was brought into equilibrium with the gas phase over a period of 24 hours. At the end of each equilibration period, the matte was sampled. The oxygen and sulfur concentrations of each sample were determined by the hydrogen extraction method, tg'l~ The values of the oxygen and sulfur potentials and the matte composition (wt pct O, wt pct S, and WFe = wt pct Fe/ (wt pct Fe + wt pct Cu)) at magnetite saturation as reported in the earlier paper are shown in Table I.

METALLURGICALTRANSACTIONS B

VOLUME 19B, DECEMBER 1988--935

Table I. Experimental Data ml for Magnetite-Saturated Mattes*

Matte Composition

log Ps2
-2.97 -2.97 -2.97 -2.97 -2.97 -2.97 -2.49 -2.48 -2.04 -2.02 -2.02 -2.01 -2.01 -1.83 -1.82 -1.82 -1.74 -1.74 -1.64 - 1.64

log Poz -8.76 -8.86 -8.86 -8.96 -8.96 -9.16 -8.65 -8.95 -8.22 -8.43 -8.53 -8.74 -8.74 -8.33 -8.63 -8.63 -8.32 -8.32 -8.32 -8.32

WFe
0.091 0.183 0.285 0.278 0.372 0.481 O. 174 0.476 0.092 O. 175 0.283 0.380 0.494 0.290 0.476 0.483 0.384 0.384 0.488 0.488

Wt Pct 0 0.50 0.93 1.76 1.76 2.87 4.21 0.95 3.90 0.47 0.85 1.80 2.67 4.19 1.63 3.86 3.84 2.37 2.34 3.47 3.54

Wt Pct S 21.75 22.86 23.55 23.33 23.55 23.06 22.89 23.63 21.62 23.15 23.45 24.24 24.21 24.47 24.13 24.18 24.9 25.17 25.01 24.94

A vertical section of the stability diagram at and near the magnetite surface of saturation at WEe ----0.5 is shown in Figure 3. The matte/magnetite phase boundary was determined from the data in Table I. For gas compositions which lie above this boundary, matte is in equilibrium with FeaOg(s). Conversely, matte in equilibrium with atmospheres in which the oxygen and sulfur partial pressures both lie below the boundary is unsaturated. The isoconcentration curves for oxygen in unsaturated matte, given by the broken curves, were calculated using the following correlation for oxygen in unsaturated matte: I81 wt pct O = 2.50P62200 s-0142(1 + 9.0WEe)219 0 P 2 [1]

"1468 K, 1 atm total pressure.

III.

THE Cu-Fe-S-O SYSTEM

A. Stability Diagram
At constant temperature and total pressure, the stability diagram of the Cu-Fe-S-O system is a three-dimensional diagram. The axes of the schematic stability diagram shown in Figure 2 are oxygen potential (log Po2), sulfur potential (log Ps2), and iron metal weight fraction of the matte (WEe = wt Fe/(wt Fe + wt Cu)). The stability field of liquid matte is bounded by surfaces of saturation with Cu(1), F e ( 7 ) , " F e O " ( s ) , F e 3 0 4 ( s ) , and gas ( P s o 2 4- P s 2 = 1 atm). Although F e 3 0 4 forms a spinel solid solution with CuO, magnetite in equilibrium with matte (WFe = 0.1 to 0.5) was found to contain less than 0.5 wt pct Cu. m

A projection of isO-WFe curves on the magnetite surface of saturation of the matte stability field onto the log Po2 vs. log P $ 2 plane is shown in Figure 4. Data points on the curves are from Table I. The isO-WFe curves are similar in form, having positive slopes and upward concavity. It is apparent that the matte grade at saturation increases (WEe decreases) with increasing Po2 and decreasing Ps2. For matte of constant WEe, the oxygen pressure required for saturation increases with increasing sulfur pressure. The surface of saturation of matte with magnetite is bounded at low oxygen partial pressures by the line of twofold saturation with "FeO"(s) (line A-D in Figure 2) for which POE = 6.86 10 -1~ atm at 1468 K . Ill] As seen in Figure 4, the matte sample from one of our experiments at WEe = 0.485 may have been doubly-saturated with wustite and magnetite. At high oxygen partial pressures the surface

-8.0

MATTE * Fe304(s) -8.5 LINE OF Fe304 SATURATION oo

t'NJ

%0=3.50~. ~.~'& ,/ I 4I[9/T //I

/II

-9.0 .... "',/" I " -9.5

s s

J--G

(.9 0 _J

-4

GAS(Pso2*Ps2:1 atm) Fe.~04 (s) i-8" ~ . - c/\ (SPINELk s.s.) ~ / ~ D / \

"
I
f

MATTE (UNSATURATED)

-8"
o~ ,

...... 4t "---Ireu II

-? \ / . L ~ _ ~ : . . ~ _ , , . _ -4 _.+_+:_._.~

~"

-I0.0
I

----..... 9
i

W! %0: 3.0 3.5 4.0 Fe304 sotn. expt. pt.

t

-3.o

-2.5

-2.0

-u

LOG Ps2
- -8 -6 -4 -2 O

cu

LOG Psz (otm)

Fig. 2 - - T h e field of stability of the liquid matte phase, 1473 K, 1 atm total pressure, m 936-- VOLUME 19B, DECEMBER 1988

Fig. 3--Vertical section near magnetite saturation of the stability diagram for the Cu-Fe-S-O system at 1468 K, 1 atm pressure, and WF0 = 0.5. Isoconcentration curves for oxygen in unsaturated mattes (dashed lines) were obtained from Eq. [1], and the matte/Fe304 phase boundary was determined using data from Table I. METALLURGICAL TRANSACTIONS B

of magnetite saturation is bounded by line B'-C' in Figure 4, which represents simultaneous saturation with gas (Pso2 + Ps2 = 1 atm). Line B'-C' is a segment of line B-C in Figures 1 and 2. The location of the projected line of two-fold saturation with magnetite and gas (Pso2 + Ps2 = 1 atm) at 1468 K was estimated as follows. Since $2 and SO2 are the major species in the gas phase and the total pressure is one atmosphere, Pso2 = 1 - Ps2 I2]

so that a projection of this surface onto the log Po2 v s log Ps2 plane is a single curve. By extrapolating the projected isO-WF~ curves on the magnetite surface out to intersect the line for saturation with gas, it is possible to construct line B'-C' in Figure 4. Table II gives the oxygen and sulfur concentrations in doubly-saturated mattes which were calculated using the correlations for oxygen and sulfur* in
*The square term in the fifteenth term of the sulfur correlation equation was omitted in Reference 8. The equation as written here is correct.

magnetite-saturated mattes wt pct O = - 3 . 0 6 + 2.39WFe + 12.0W2e - 1.60 log Ps2

Combination of this equation with the equilibrium constant u21 for the reaction 89
K m

+ 02(8) = SO2(g);

[6]
wt pct S = 1045.7 + 111.9 log Po2 + 1238.6 log Ps2
[3]

Pso2
S2 9 0 2

p l/2 19

1.174 x 109

-- 312.5WFe -- 217.0wZe + 515.4(log - 80.31(log

es2)2

yields the relation K = (1 - Psz)

p 1~2 la
S 2 'tO 2

eo2)WFe

+ 131.5(log Po2) log Ps2 + 68.59(log Ps2)3 [4] - 0.4273(log Po2)2 log Ps2 + 56.42(log Ps2)2 log Po2 - 25.32(log Po2)W2e - 4.948WFe(1og POz)2 + 17.66(log

The equation of the surface of saturation of matte with gas (Pso2 + Ps2 = 1 atm) is log Po2 = log(1 - Ps2) - ~ log Ps2 - log K
1

[51

Ps2)W2e
[7]

- 0.0728(log Poz)Z(log Ps2)WFe + 7.508(log Ps2)3 log Po2

-7.0
I i I I

THIS STUDY WFe 9 0.485

m 0.378 *- 0.006 0.284 -+ 0.006

x ROSENQVISTAND HARTVIG WFe

0 0.57

-7.5

-8.0

PRESENT ~ F%O4(s)+GAS* STUDY Q'~x SATURATION

~',>~'.. J
cl

I
,,

~ (D
._J

-8.5

w,.:

that were reported in the previous paper, ml and the values of WF~, Po2, and Ps2 for several points on the line of two-fold saturation. The calculated line of two-fold saturation with Fe30 4 and gas from this study is compared in Figure 4 with the equivalent line obtained from the data of Rosenqvist and Hartvig. I61 As expected, their line is displaced downwardly from the line of the present investigation because of the lower temperature (1458 K) of their experiments. Their results for the two mattes with WEe values of 0.27 and 0.36 are in reasonably good agreement with our results. However, relative to our results, their reported sulfur pressures in the gas phase for the mattes with WFe = 0.48 and 0.57 are somewhat higher.

B. Phase Diagram
-9.C The liquid matte phase field in the Cu-Fe-S-O system is shown in Figure 1. The data points on the surface of magnetite saturation (Table I), surface ABCDA, are projected
"FeO" (s) + F%0 4 (s) SATURATION
I I I I

-9.5 -3.0

Table II. Locations of Points on the Calculated Line of Fe304 q" Gas (Pso2 + Ps2 = 1 atm) Saturation, Line B'-C' in Figure 4. T = 1468 K

-2.5

-2.0

-I.5

LOG Ps2
Fig. 4--Projection of isO-WFe curves on the surface of magnetite saturation (Fig. 2) onto the log Po2 vs log Ps2 plane. Lines of two-fold saturation (Fe304 + gas, 1 atm) from the present study (calculated, 1468 K) and from Rosenqvist and Hartvig 161 (measured, 1458 K) are indicated. (*Pso2 + Ps2 = 1 atm) METALLURGICAL TRANSACTIONS B

WEe 0.091 0.180 0.284 0.378 0.485

log Po2
-8.09 -8.16 -8.19 -8.23 -8.27

log Ps2 - 1.96 -1.84 -1.76 - 1.69 -1.63

Wt Pct O* 0.39 0.70 1.40 2.26 3.53

Wt Pct S# 22.23 23.94 24.98 25.44 25.23

*calculated from Eq. [6]. %alculated from Eq. [7].

VOLUME 19B, DECEMBER 1988--937

onto the oxygen concentration vs sulfur concentration plane in Figures 5 and 6. The sulfur isobars in Figure 5 show maxima in sulfur concentration at an oxygen concentration of 2.5 to 3.5 wt pct, and are displaced in the direction of higher sulfur concentration with increased sulfur pressure. The solid curves in Figure 6 are projections of isO-WFe curves on the surface of magnetite saturation. Mattes at higher values of W F e for a fixed sulfur level have higher oxygen concentrations at magnetite saturation. At constant WF~, as the sulfur concentration in the saturated matte increases, the oxygen concentration remains constant initially and then decreases. The calculated line of two-fold saturation of matte with F e 3 0 4 and gas (Pso2 + Ps2 = 1 atm) shown in Figure 6 was constructed from the data in Table II. For comparison, the experimental data for doubly-saturated mattes from Rosenqvist and Hartvig [6] and Johannsen and Knah1171 are also shown with the values of Wve as indicated.
I i I i I ' I

WFe

CURVE Log Ps2

a b c d e f - 2.97 -2.48 -2,02 - 1.82 -1.74 -1.64

o I--

z"

Q 0

0.485 + 0.009 0,378-+0,006 0284-+ 0006 0,180-+ 0.005 0.091 -+ 0.001

Rosenqvist and Hartvig reported similar oxygen levels in mattes with WFe values of 0.27 and 0.36, whereas the resuits of both the present study and Johannsen and Knahl's investigation show that the oxygen concentration increases with WFe. In addition, the sulfur concentrations in their mattes re considerably lower than those found in our work. A line of two-fold saturation was constructed from Johannsen and Knahl's data. In accordance with the results of this study, these investigators found that the oxygen concentration in doubly-saturated mattes is strongly dependent on WF~. Their reported matte compositions at low values of WF~ (0.10 to 0.32) are in good agreement with our calculated compositions. At higher values of WF~ (>0.32), however, their mattes were lower in oxygen and higher in sulfur than the mattes from this investigation. Since Johannsen and Knahl used pure sulfide charges and short (2-hour) equilibration times, it is probable that their experiments with high-WFe mattes were not run long enough to make the large adjustments in oxygen and sulfur concentrations necessary to reach equilibrium. A matte of low WFe and correspondingly low oxygen concentration could possibly reach equilibrium in their experimental system in two hours. In this work, matte was reacted with a gas phase for 24 hours to ensure equilibrium. IV. APPLICATIONS TO INDUSTRIAL S M E L T I N G

l-z z 0 z >x o

a\ 4

cd

A. Comparison of Matte Compositions

2

20

22

24

26

28

SULFUR CONCENTRATION, WL %
Fig. 5 - Effect of WF~ and sulfur pressure on the equilibrium oxygen and sulfur concentrations in magnetite-saturated mattes. Sulfur isobars are indicated. T = 1468 K. (*log Ps2 + 0.02)

T'HISST'UDY,1468K

'

WFe
6 9 a o 9 o 0.485 --- 0.009 0.378+_9,006 0.284 +- 0.006 3.180+-9.005 0.091 + 0.001

WFe x ROSENQVIST co 0.57 AND HARTVIG, ~ h s 1458 K < ~ 0.48 + JOHANNSEN ( e 0.57 AND KNAHL, Ifg 0.44 t 1473 K 0.32

WFe c 0.36 d 027 h 0.21 i '.3.10

z o c12 z w
o o z uJ (_9 >x o

Fe304 + GAS ,, SATURATION 0.485 . q~h~(PRESEN Z . . / ~" , STUDY .~" 0.378 -a..... ', / f / d ~ '"I"
x Cx ,~c~.~

0284-6Z3~o 0180., WIF = 0 0 9 1 - o ~ e

'l I 0~" L

, ,,+" ' ,,g. S ~.

h
I

, ~ , ~'%
i

JOHANNSEN AND KNAHL 7

I a I

"-2 -''A'~''-''+'~"

20

22

24

26

28

SULFUR CONCENTRATION, Wl%

Fig. 6--Compositions of magnetite-saturated mattes. Points with a flag symbol (L) at the 5 o'clock position are mattes doubly-saturated with magnetite and gas (Pso2 + Ps2 = 1 aim), Table II. 938--VOLUME 19B, DECEMBER 1988

The reported compositions of mattes from several types of industrial copper smelters are given in Table III. These mattes contain less than 2.0 wt pct (Zn + Pb + Ni), but there are no related data on the partial pressures of oxygen and sulfur in the gas phase. The data in Table III are plotted in Figures 7 and 8 where the hatched areas denote the range of equilibrium compositions of magnetite-saturated mattes as determined from the data in Tables I and II. The solid boundaries of the magnetite saturation regions show the compositions of mattes for sulfur pressures in the gas phase of 0.001 to 0.01 atm. As the sulfur pressure is increased beyond 0.01 atm (holding WFe constant), the oxygen concentration in saturated mattes decreases until two-fold saturation with Fe304(s) + gas (Ps2 + Pso2 = 1 atm) is reached (bold dashed line in Figure 7). For comparison, the light dashed line in the figure shows the compositions of unsaturated mattes in equilibrium with gas having a sulfur pressure of 0.01 atm and an oxygen pressure one order of magnitude lower than the pressure required for magnetite saturation at the same value of WFe. (The oxygen concentrations in the unsaturated mattes were calculated from Eq. [113 The activity of Fe304 in the unsaturated mattes lying on the light dashed line was estimated to be 0.1. The majority of the mattes from reverberatory smelters are lower in oxygen than magnetite-saturated mattes and have values of aFe304 from 0.1 to 0.9, as estimated from Figure 7. Nagamori and Mackey Hm have taken the activity of Fe304 in reverberatory mattes to be 0.1 to 0.2. These values of aFc3o4 appear somewhat low since reverberatory furnaces often contain solid magnetite from recycled converier slag. However, mixing of the matte may be limited so that magnetite introduced into the furnace will remain unreduced. Under these circumstances, the matte will have a lower oxygen concentration than expected for equilibrium with solid magnetite.
METALLURGICAL TRANSACTIONS B

REVERBERATORY

a OUTOKUMPU (FLASH) 9 OXY6EN SPRINKLE

5
-t---

u NORANDA :~ .... PRESENT STUDY, "~:-~ MA6NETITE SATURATION, 1468K (1195~

1
o ~--

:50

28

z"

o REVERBERATORY a OLITOKUiVlPU (FLASH) 9 OXY6EN SPRINKLE D NORANDA . . . . . PRESENT STUDY, ........... MAGNETITE SATURATION 1468 K (1195~ @o Fe3 04+ 6AS*

26
SATURATION ,, '~

o o oo

Z"

c# ~Ooo
0

Fe 3 04 (s)
z LO Z 0 Z LtJ (_9 >.-

SATURATION

//o
0 0,"" 0 0"" 0

Ooo

[~r IC) 0 S o %o
; o o ,,o

c'r" F-Z I,I z 0

24
/ ;

/'"

'

22
D_ ._J O'3

/
o

TION

/i,o,S / / "o~
_
/ /

2C

~(Fe304 ( s ) + 6AS* SATURATION

0~

18

0 0.6

0.2

0.4

0.6

0.2 WFe

0.4

WFe
Fig. 8 - - C o m p o s i t i o n s (wt pct S and WF~) of mattes from industrial smelters (Table III) and the equilibrium compositions of magnetitesaturated mattes from this study at 1468 K. (*Pso~ + Ps2 = 1 atm)

Fig. 7 - - Compositions (wt pct O and WFe) of industrial mattes (Table III) and the equilibrium compositions of magnetite-saturated mattes from this study at 1468 K. The light dashed line gives the estimated compositions of unsaturated mattes with aFe304 ~ 0.1. (*Pso2 + Ps2 = 1 atm)

The oxygen sprinkle, Noranda, and Outokumpu flash smelting processes all utilize oxygen-enriched injection gas, and mattes from these processes have been reported to be saturated with solid magnetite, u'2']9] The magnetite settles to the bottom of the reactor vessel or forms a mushy zone between the matte and slag layers. Since there is an appreciable pressure of nitrogen in the furnace atmosphere and in bubbles formed in the matte phase, (Psoz + Ps2) is less than one atmosphere. In contrast, the INCO flash smelter operates with 95 pct Oz(g), and it is probable that the matte is saturated with both Fe304(s) and gas (Pso2 + Ps2 = 1 atm). The mattes from the Outokumpu flash smelter have compositions which lie near or at magnetite saturation. The Noranda matte has slightly higher oxygen and lower sulfur concentrations as compared to magnetite-saturated matte with an identical value of WFe, possibly as a result of overoxidation in the fumace or the inclusion of solid magnetite in the sample. The oxygen concentration in the matte from the oxygen sprinkle smelter is somewhat lower than magnetite-saturated matte of the same WFc value. Even so, mattes from the three oxygen-enriched processes have oxygen and sulfur levels close to those of matte in equilibrium with F e 3 0 4 ( s ).
METALLURGICAL TRANSACTIONS B

Industrial smelters typically operate at 1423 to 1523 K. The operating temperature for the oxygen sprinkle furnace {18] was 1422 to 1461 K. Johannsen and Knahl F} found that the oxygen concentration in magnetite-saturated matte increases with temperature at a constant value of WFe. Thus, the lower oxygen concentration in the oxygen sprinkle matte as compared to our magnetite-saturated matte could have resulted from the lower temperature in the smelting furnace. Operating temperatures for the other smelters referenced in Table III were not available. However, the slight differences in composition between the industrial mattes and our saturated mattes could result from the operating temperatures differing from 1468 K.

B. Prediction of Smelting Conditions

From the previous discussion, it appears that oxygenenriched smelting processes operate reasonably close to equilibrium. Since the mattes in these smelters are in contact with solid magnetite, the correlation equations and diagrams which were developed for magnetite-saturated mattes may be used to predict conditions during oxygenenriched smelting. Given the oxygen and sulfur concentrations in an industrial matte, the equilibrium values of Ps2 and WFe can be determined from Figures 5 and 6, respectively. The oxygen partial pressure in the smelter gas can then be determined indirectly by use of the correlation for sulfur (Eq. [7]).
VOLUME 19B, DECEMBER 1988-- 939

Table III.
Type of Smelter Reverberatory

Compositions of Industrial Mattes

Matte Composition (Wt Pct)

Pct Cu 66.1 47.1 44.8 44.5 43.6 45.0 42.2 41.0 39.5 38.9 38.2 38.2 36.6 36.2 35.9 35.0 34.9 34.9 34.2 33.0 32.7 32.1 30.6 31.0 30.0 29.2 29.4 28.8 28.0 77.6 69.6 58.6 57.9 40.6 46.1 70.7 wt pct Fe

Pct Fe 10.3 24.8 26.1 27.2 26.8 30.6 28.8 30.9 30.5 31.7 31.7 31.9 33.1 33.8 33.8 33.8 35.3 34.3 35.8 35.2 36.2 38.2 39.4 39.5 37.6 39.0 39.1 39.4 40.5 1.2 7.2 15.4 15.8 29.8 25.5 3.3

Pct Zn -1.1 1.1 0.7 1.3 1.5 1.1 -1.2 -1.2 0.6 1.0 !.0 0.6 1.5 1.2 1.3 -1.7 1.4 ---1.4 1.1 0.7 1.2 1.1 0.2 0.7 1.2 1.2 ----

Pct Pb ----0.4 ---0.3 -0.7 ----0.4 0.6 0.2 -0.3 0.1 ---0.5 --0.1 ----0.3 ----

Pct Ni -------------------------------0.2 -1.2 ---

Pct S 21.6 24.8 21.6 25.1 24.8 25.0 25.1 24.9 25.1 26.2 24.2 26.3 25.2 24.9 26.5 25.6 25.7 25.5 26.1 25.2 25.5 25.7 27.4 26.3 25.2 25.5 27.0 26.5 24.8 20.4 21.7 23.6 23.3 25.2 25.2

Pct O 0.3 1.6 2.5 1.8 1.9 1.4 2.0 1.6 2.4 2.7 3.1 2.0 2.5 2.8 2.3 2.7 1.9 2.4 2.7 3.4 2.8 2.8 2.6 2.9 3.5 3.3 2.8 2.8 3.4 0.1 0.3 0.8 0.8 3.0 1.7

W*e 0.13 0.34 0.37 0.38 0.38 0.40 0.41 0.43 0.44 0.45 0.45 0.46 0.47 0.48 0.48 0.49 0.50 0.50 0.51 0.52 0.53 0.54 0.56 0.56 0.56 0.57 0.57 0.58 0.59 0.02 0.09 0.21 0.21 0.42 0.36

Ref. 13 14 14 14 14 15 14 16 14 7 14 14 14 14 14 14 17 14 7 7 14 7 7 7 14 7 7 7 7 7 7 7 7 7 18

Flash smelter (Outokumpu)

Oxygen sprinkle Noranda

*W~e =

19.7

0.4

0.04

(wt pct Cu + wt pct Fe)

T o p r e v e n t t h e f o r m a t i o n o f m a g n e t i t e o r to d i s s o l v e m a g n e t i t e in a m a t t e s m e l t i n g f u r n a c e o r c o n v e r t e r , t h e o x y g e n a n d s u l f u r partial p r e s s u r e s in the gas p h a s e m u s t lie b e l o w the a p p r o p r i a t e isO-WFe c u r v e in F i g u r e 4 c o r r e s p o n d ing to the v a l u e o f WF~ in the m a t t e . T h u s , s m e l t i n g c o n d i t i o n s m i g h t p o s s i b l y b e c o n t r o l l e d to e l i m i n a t e m a g n e t i t e , w h i c h is an u n d e s i r a b l e c o m p o n e n t in s m e l t e r s .

a n d gas (Pso2 + Ps2 = 1 a t m ) h a v e also b e e n d e t e r m i n e d . The calculated compositions of high grade doubly-saturated m a t t e s (WFe = 0 . 1 0 to 0 . 3 2 ) a r e in e x c e l l e n t a g r e e m e n t with the measured compositions from Johannsen and K n a h l . 17j A c o m p a r i s o n o f the c o m p o s i t i o n s o f m a g n e t i t e - s a t u r a t e d mattes from several oxygen-enriched smelting processes w i t h t h o s e o f o u r s a t u r a t e d m a t t e s i n d i c a t e s that the s m e l ters p r o b a b l y o p e r a t e at c o n d i t i o n s c l o s e to e q u i l i b r i u m . T h u s , the d i a g r a m s p r e s e n t e d in this p a p e r a l o n g w i t h o u r c o r r e l a t i o n e q u a t i o n s for t h e o x y g e n a n d s u l f u r c o n t e n t s o f m a g n e t i t e - s a t u r a t e d m a t t e s tSj m a y b e u s e d to p r e d i c t c o n d i tions d u r i n g o x y g e n - e n r i c h e d s m e l t i n g .

V.

S U M M A R Y AND CONCLUSIONS

T h e surface o f s a t u r a t i o n o f m a t t e w i t h m a g n e t i t e in the p h a s e a n d s t a b i l i t y d i a g r a m s f o r the C u - F e - S - O s y s t e m at 1468 K h a s b e e n d e s c r i b e d q u a n t i t a t i v e l y u s i n g e x p e r i m e n t a l data o n m a g n e t i t e - s a t u r a t e d mattes. T h e m o s t inform a t i v e t w o - d i m e n s i o n a l r e p r e s e n t a t i o n s o f the s u r f a c e are p r o j e c t i o n s o f iso-WFe c u r v e s o n the surface o n t o the o x y g e n p o t e n t i a l v s s u l f u r p o t e n t i a l p l a n e a n d the o x y g e n c o n c e n tration vs sulfur concentration plane. The matte and gas c o m p o s i t i o n s at t w o - f o l d s a t u r a t i o n o f m a t t e w i t h m a g n e t i t e
940--VOLUME 19B, DECEMBER 1988

ACKNOWLEDGMENTS
T h e a u t h o r s g r a t e f u l l y a c k n o w l e d g e s u p p o r t o f t h e res e a r c h p r o g r a m b y the N a t i o n a l S c i e n c e F o u n d a t i o n ( C o n tract N o . C P E - 8 2 0 4 0 2 9 ) a n d a t w o - y e a r f e l l o w s h i p to D. Kaiser provided by ASARCO Corporation.
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REFERENCES
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