Oxidation Kinetics of a Lime-Copper Concentrate Pellet

H. H. HAUNG AND R. W . B A R T L E T T C o p p e r f l o t a t i o n c o n c e n t r a t e s can be o x i d i z e d while s i m u l t a n e o u s l y f i x i n g 98 p c t of the s u l f u r a s CaSO4 and c o p p e r s u l f a t e s if a m i x e d l i m e - c o n c e n t r a t e b a l l e d p e l l e t i s r o a s t e d at low t e m p e r a t u r e s . T h e r o a s t i n g p e l l e t e x h i b i t s a r e a c t e d s h e l l s u r r o u n d i n g the u n r e a c t e d c o r e . T h e r a t e i s c o n t r o l l e d by o x y g e n d i f f u s i o n in t h e p o r e s of t h e r o a s t e d s h e l l and k i n e t i c d e t a i l s a r e given. At h i g h e r t e m p e r a t u r e s the r a t e d e c r e a s e s b e c a u s e of s i n f e t i n g and d e c r e a s e d p o r o s i t y in the s h e l l . C o m p l e t e r o a s t i n g of the p e l l e t s while cont r o l l i n g the p e l l e t t e m p e r a t u r e to p r e v e n t f o r m a t i o n of i n s o l u b l e c o p p e r f e r r i t e s i s r e quired for subsequent hydrometallurgical extraction.

for treating sulfide-copper flotation c o n c e n t r a t e s t h a t do not c a u s e a p p r e c i a b l e a i r p o l l u t i o n by SO2 e m i s s i o n a r e n e e d e d . T h e r e c e n t l y d e veloped lime-concentrate-pellet-roast (LCPR) proc e s s 1 i n v o l v e s r o a s t i n g a m i x t u r e of f i n e l y g r o u n d f l o t a t i o n c o n c e n t r a t e s and n e a r l y s t o i c h i o m e t r i c l i m e in the f o r m of a b a l l e d p e l l e t f o l l o w e d by l e a c h i n g in s u l f u r i c a c i d and e v e n t u a l r e c o v e r y of c o p p e r by e l e c t r o w i n n i n g . P e l l e t i z a t i o n i s n e c e s s a r y to r e t a i n n e a r l y a l l of the s u l f u r a s a n h y d r i t e (CaSO4) d u r i n g r o a s t i n g . When a p e l l e t i s r o a s t e d , o x i d a t i o n of the s u l f i d e m i n e r a l g r a i n s o c c u r s at the i n t e r f a c e s e p a r a t i n g t h e unreacted pellet core from a roasted shell, provided t h a t the m i n e r a l p a r t i c l e s a r e not too l a r g e . A l t h o u g h - 2 0 0 m e s h c o n c e n t r a t e s w e r e u s e d in t h e s e e x p e r i m e n t s , c o n c e n t r a t e s a s c o a r s e a s 35 m e s h have b e e n successfully treated. The reaction products are prim a r i l y CuO, Fe203 and CaSO4. If a s u b s t o i c h i o m e t r i c a m o u n t of l i m e i s u s e d at low t e m p e r a t u r e s , s o m e CuSO4 and CuO 9CuSO4 w i l l a l s o be p r o d u c e d . At high roasting temperatures some copper ferrite is formed. S u l f u r d i o x i d e g a s i s p r o d u c e d b y the r o a s t i n g r e a c t i o n and d i f f u s e s out of t h e p e l l e t t h r o u g h p o r e s in t h e r e a c t i o n p r o d u c t s h e l l . The d i f f u s i n g SO2 r e a c t s with l i m e in a d i f f u s e z o n e a d j a c e n t t o t h e c o r e / s h e l l i n t e r f a c e . Although l e s s t h a n 5 p c t of t h e SO2 e s c a p e s t h e p e l l e t u n d e r n o r m a l r o a s t i n g c o n d i t i o n s , t h e SO2 t h a t does escape originates predominantly from near the s u r f a c e of the p e l l e t e a r l y in the r o a s t i n g p e r i o d , when t h e r o a s t e d s h e l l t h r o u g h which d i f f u s i o n m u s t o c c u r i s v e r y thin. T h e p u r p o s e of t h e p r e s e n t s t u d y i s to r e p o r t on t h e single pellet roasting kinetics. The r o a s t i n g r e a c t i o n s and t h e l i m e r e a c t i o n w i t h SO2 a r e e x o t h e r m i e a n d m a y c a u s e o v e r h e a t i n g a n d f o r m a t i o n of c o p p e r f e r r i t e w h i c h i s r e l a t i v e l y i n s o l u b l e in a s u l f u r i c a c i d l e a c h . 2 F o r i n d u s t r i a l s c a l e u p , c o n s i d e r a t i o n s h o u l d be given to a c o n t i n u o u s l y f e d fluid bed r o a s t e r with w a t e r i n j e c t i o n to o b t a i n t e m p e r a t u r e c o n t r o l and t e m p e r a t u r e u n i f o r m i t y t h r o u g h out the b e d .

PROCESSES

EXPERIMENTAL

METHODS

H. H. HAUNG, formerly Graduate Student, Stanford University, has a Post Doctoral Research Appointment, University of Utah, Salt Lake City, UT. R. W. BARTLETT, formerly Associate Professor, Stanford University, is now with Kennecott Copper Corporation, Salt Lake City, UT. Manuscript submitted March 11, 1974. ME'rALLURGICAL TRANSACTIONS B

Experiments reported here were limited to flotation concentrates originating at Bingham, Utah in which c h a l c o p y r i t e w a s the p r i m a r y c o p p e r m i n e r a l . T h e a s s a y w a s 24.2 p c t c o p p e r , 21.1 p c t i r o n and 26.0 p c t s u l f u r . R e a g e n t l i m e w a s t h o r o u g h l y m i x e d with - 2 0 0 m e s h c o n c e n t r a t e with the a m o u n t of l i m e v a r i e d f r o m 85 p c t to 100 p c t of the a m o u n t r e q u i r e d to c o n v e r t a l l of the s u l f u r in t h e c h a r g e to CaSO4. W a t e r w a s a d d e d and p e l l e t s w e r e b a l l e d in a 28 cm d i a m l a b o r a tory balling drum. T h e o p t i m a l m e i s t u r e content f o r p e l l e t i z i n g w a s 14 p c t . A v e r a g e d r u m r e s i d e n c e t i m e f o r 1.1 c m p e l l e t s w a s 20 to 30 m i n , and the u n d e r s i z e p e l l e t s w e r e r e c h a r g e d a s s e e d i n g to t h e d r u m . Single pellet kinetics were determined using a q u a r t z s p r i n g b a l a n c e t h e r m o g r a v i m e t r i c a n a l y z e r shown in F i g . 1, which m e a s u r e d b o t h the w e i g h t gain a s s o c i a t e d with r o a s t i n g a n d t h e SO2 l i m e f i x a t i o n r e a c t i o n . Sulfur d i o x i d e in the effluent g a s w a s c o n t i n u o u s l y m e a s u r e d b y an i n f r a r e d a n a l y z e r d u r i n g the e n t i r e TGA oxidation experiment. A single pellet, suspended f r o m a q u a r t z h e l i x s p r i n g having a s e n s i t i v i t y of rag, w a s h e a t e d to t h e d e s i r e d t e m p e r a t u r e in a 6.5 c m ID tube f u r n a c e w h i l e the d e h y d r a t i o n of l i m e o c c u r r e d in an i n e r t a t m o s p h e r e . A f t e r d e h y d r a t i o n w a s c o m p l e t e , the d e s i r e d oxygen c o m p o s i t i o n w a s i n t r o d u c e d and the w e i g h t g a i n due to the o x i d a t i o n and s u l f a f i o n of the p e l l e t w a s f o l l o w e d a s a function of time. For each run the quartz balance was continuo u s l y o b s e r v e d a f t e r i n s e r t i n g oxygen until the i n i t i a l w e i g h t change w a s o b s e r v e d at w h i c h t i m e the t i m e r w a s s t a r t e d , t = 0. A n i n i t i a l weight change of 0.05 p c t of t h e f i n a l w e i g h t c h a n g e w a s d e t e c t a b l e . F o r e a c h r u n , the i n f r a r e d r e s u l t s w e r e c a l i b r a t e d by a b s o r b i n g a l l of t h e SOe in s o d i u m h y d r o x i d e s o l u t i o n and t i t r a t i n g with the i o d i n e m e t h o d . U p - d r a f t fixed b e d r o a s t i n g e x p e r i m e n t s w e r e c o n d u c t e d to o b s e r v e t h e r m a l e f f e c t s and d e t e r m i n e d m a x i m u m b e d d e p t h s t h a t could be u s e d without o v e r h e a t i n g . An a i r o r a i r / n i t r o g e n m i x t u r e w a s p r e h e a t e d in a v e r t i c a l tube f u r n a c e and flowed t h r o u g h a g r a t e into an i n s u l a t e d s t a i n l e s s s t e e l cup h o l d i n g the p e l l e t s . B e d d e p t h s up to 18 c m w e r e u s e d and t h e r m o c o u p l e s w e r e i n s e r t e d at v a r i o u s d e p t h s in t h e b e d . T h e r m o c o u p l e s w e r e a l s o b u r i e d in p e l l e t s within t h e b e d . T h e gas flow v e l o c i t y w a s r e g u l a t e d a t r o o m t e m p e r a t u r e t h r o u g h flow m e t e r s , b e f o r e e n t e r i n g the p r e h e a t VOLUME 7B, SEPTEMBER 1976-369

f u r n a c e . Since effluent g a s e s contained negligible SO2 they w e r e vented into the l a b o r a t o r y . A p p a r e n t d e n s i t i e s of p e l l e t s w e r e d e t e r m i n e d b e fore and a f t e r r o a s t i n g by i m m e r s i o n in m e r c u r y . P o r o s i t i e s of r o a s t e d p e l l e t s w e r e d e t e r m i n e d by benzene a b s o r p t i o n . M e a s u r e d values of volume s h r i n k a g e on r o a s t i n g and final f i r e d p o r o s i t i e s at v a r i o u s t e m p e r a t u r e s a r e shown in F i g . 2. A l l of t h e

BALANCE

s h r i n k a g e at higher t e m p e r a t u r e s o c c u r r e d on heating p r i o r to i n s e r t i o n of the oxidizing a t m o s p h e r e . Although the d a t a shown in F i g . 2 a r e a p p r o p r i a t e to this p a r t i c u l a r study and r e a s o n a b l y typical, it should be noted that p e l l e t p o r o s i t y will also depend on the amount of lime, the p a r t i c l e s i z e d i s t r i b u t i o n s of lime and concentrate, the b a l l f o r m i n g conditions and d e n s i fication. The specific s u r f a c e of roared p e l l e t s was d e t e r m i n e d by the BET nitrogen adsorption method. P e l l e t s t r e n g t h is v e r y i m p o r t a n t for i n d u s t r i a l p r o c e s s i n g . A suitable green p e l l e t should withstand 3 an a v e r a g e of 6 d r o p s f r o m 45 cm onto a s t e e l plate and have a m i n i m u m crushing s t r e n g t h of 1.5 kg. The l a b o r a t o r y b a l l e d p e l l e t s s u r p a s s these r e q u i r e m e n t s . SINGLE P E L L E T EXPERIMENTAL RESULTS AND REACTION MODEL VERIFICATION T y p i c a l weight gain c u r v e s for 1.15 cm d i a m b a l l e d p e l l e t s a r e shown in F i g . 3 for a i r r o a s t i n g at 450~ and in F i g . 4 for a i r r o a s t i n g at 800~ The m e a s u r e d weight gain i s shown with the weight a s s o c i a t e d with the SO2 gaseous effluent d e t e r m i n e d from i n f r a r e d m e a s u r e m e n t s . The total weight gain for s o l i d and gaseous products is a l s o shown and these w i l l be r e f e r r e d to as total r a t e c u r v e s . The e m i s s i o n of SO2 i n c r e a s e s with t e m p e r a t u r e .

:/ill:
~ H ~ O (OPTIONAL}

:o'r J

0.4

TOTAL

z
< N 2 02
I,'1-

0.~

Fig. 1--Combined thermogravimetric

and i n f r a r e d a p p a r a t u s

'-2_
w

for analysis of single pellet oxidation kinetics.

0.2

60

3.0

I.w d J w

a.. 0.1

O 50 V c,
E oq
W O
0.0 0
I I I ; S02 T ~ l

40
Z W rr~ LtJ

- 2.0

40 60 t (MINUTES) F i g . 3 - - S i n g l e p e l l e t o x i d a t i o n w e i g h t c h a n g e at 450~

20

80

0.4

30 n-20 ) 1.0 o3 _z 0.3

,,:::[

TOTAL

laJ

~ J

o >
_ r

.~\x~/

.~ J

,,,z
_

~I'L
13_

ILl
w J W

o,2!

O
400 500 600 ROASTING

I
700 TEMPERATURE, ~

O
800
0.0 0
I

SO2
20
I I

4-0 t (MINUTES)

60

80

Fig. 2--Physical characteristics of roasted LCPR pellets.

3 7 0 - V O L U M E 7B, SEPTEMBER 1976

Fig. 4--Single pellet oxidation weight change at 800~

METALLURGICAL TRANSACTIONS B

T h e e x p e r i m e n t a l k i n e t i c c u r v e s w e r e a n a l y z e d in t e r m s of an o x y g e n t r a n s p o r t r a t e l i m i t i n g m o d e l . I n i t i a l l y , oxygen t r a n s f e r t h r o u g h t h e b o u n d a r y l a y e r gas film surrounding the pellet is rate controlling. A c o n v e c t i v e oxygen d i f f u s i o n g r a d i e n t in r e s i d u a l n i t r o gen o c c u r s . O v e r m o s t of the r e a c t i o n p e r i o d o x y g e n diffusion t h r o u g h p o r e s in the r o a s t e d s h e l l i s r a t e c o n t r o l l i n g . T h i s r e a c t i o n m o d e l i s i l l u s t r a t e d in F i g . 5. B o u n d a r y L a y e r Gas F i l m O x y g e n T r a n s f e r I n i t i a l t a n g e n t s (t - - 0) to the t o t a l r a t e c u r v e s w e r e m e a s u r e d and u s e d to d e t e r m i n e t h e i n i t i a l o x i d a t i o n r a t e of the p e l l e t , VCp. F r o m t h e s e data, e x p e r i m e n t a l v a l u e s of the i n i t i a l m a s s t r a n s f e r c o e f f i c i e n t s w e r e d e t e r m i n e d f r o m the r e l a t i o n ,

%
and

t=o

= km4~*" (C02(g' - C02'~ ~

krn4Tvr~ C02(g)

[1]
[2]

A%
4rr~
= km

p r o p r i a t e t e m p e r a t u r e s by t h e C h a p m a n - E n s k o g f o r m u l a . T h e a i r m a s s v e l o c i t y flowing o v e r t h e p e l l e t s w a s , pgU = 0.002 g s -1 cm -2 in m o s t of t h e e x p e r i m e n t s . T h e two t h e o r e t i c a l ( c a l c u l a t e d ) m a s s t r a n s f e r c o e f f i c i e n t s and the e x p e r i m e n t a l m a s s t r a n s f e r c o e f f i c i e n t a r e shown f o r e a c h t e m p e r a t u r e in T a b l e I. T h e e x p e r i m e n t a l m a s s t r a n s f e r c o e f f i c i e n t s at e a c h temperature were obtained by taking the tangent at the o r i g i n (t = 0) and a r e s l i g h t l y l e s s than t h e c a l c u lated mass transfer coefficients. This agreement is a d e q u a t e and the d i s c r e p a n c y m a y be c a u s e d b y s u r f a c e r o u g h n e s s o f t h e p e l l e t s o r t h e r e t a r d i n g e f f e c t of t h e p e l l e t s u s p e n d i n g s a d d l e on the t r a n s f e r of o x y g e n . The experimental apparent activation energies agree with the v a l u e s f o r c a l c u l a t e d r a t e s . Single p e l l e t r o a s t i n g r a t e e x p e r i m e n t s w e r e a l s o conducted at in the b i n a r y g a s m i x t u r e s w i t h t h e o x y g e n v a r y i n g f r o m 5 to 30 p c t of the m i x t u r e with no effect on t h e m a s s t r a n s f e r c o e f f i c i e n t . T h e v a r i a t i o n s in the i n i t i a l m a s s t r a n s f e r c o e f f i c i e n t w e r e l e s s than 0.03 cm s -z. T h i s r e s u l t i s a l s o c o n s i s t e n t w i t h a boundary layer diffusion rate controlling process.

500~

CO~ t . (g)

Initial mass transfer coefficients were independe n t l y c a l c u l a t e d by two e m p i r i c a l c o r r e l a t i o n s f o r m a s s t r a n s f e r to s p h e r e s : Froessling 4

Oxygen Transfer Through the Roasted Pellet Shell T h e k i n e t i c m o d e l f o r m o s t of the r e a c t i o n p e r i o d when s h e l l d i f f u s i o n i s r a t e c o n t r o l l i n g i s b a s e d on b i n a r y g a s d i f f u s i o n in a m i x t u r e of o x y g e n and n i t r o gen w i t h i n a p o r o u s s o l i d a t c o n s t a n t t o t a l p r e s s u r e . Although SO2 i s f o r m e d at the r e a c t i o n i n t e r f a c e and d i f f u s e s o u t w a r d i t i s c o n s u m e d in a d i f f u s e z o n e n e a r t h e i n t e r f a c e and o v e r m o s t of the s h e l l - t h i c k n e s s SO2 can be n e g l e c t e d . T h e p r e s e n t s i m p l e m o d e l i m p l i c i t l y a s s u m e s t h a t a l l of the c h e m i c a l r e a c t i o n i n c l u d i n g SO2 f i x a t i o n o c c u r s at the c o r e / s h e l l i n t e r f a c e . I t i s a s s u m e d t h a t t h e p h y s i c a l c h a r a c t e r i s t i c s of t h e r o a s t e d s h e l l do not change with r o a s t i n g t i m e . N i t r o g e n in t h e p o r e s i s s t a g n a n t and t h e n i t r o g e n flu.x, N B , w i t h r e s p e c t to t h e p e l l e t i s N B = 0. T h e oxygen flux with r e s p e c t to t h e p e l l e t , NA, t a k e s the general form, 6
-C dXA [5]

2rP km= 2.0

+ 0.60

[3]

S t e i n b e r g e r and T r e y b a l ~

2rP km= 2.0 + 0 . 3 4 3 1 ~ / DAB \ U

12r p U \~

tpgDABI

~ ~

\o.31 | .

[4]

V i s c o s i t i e s and b i n a r y bulk d i f f u s i v i t i e s f o r the o x y g e n - n i t r o g e n g a s m i x t u r e s w e r e c a l c u l a t e d a t t h e up-

GAS FILM7 UNREACTED PELLET

CORE

,,..,,.~

ROASTED ......

/
l

,REACT{ON iNTERFACE

NAt

1-

1+
D A B , eft

XAr

1
+ - D K A , eft

i z g
Z tlA o

w h e r e D A B , eff i s t h e e f f e c t i v e bulk d i f f u s i v i t y and DKA, elf i s the e f f e c t i v e K n u d s e n d i f f u s i v i t y . B e c a u s e a binary system is involved, X A = 1 - X B . A s o l u t i o n to t h e o v e r a l l r e a c t i o n k i n e t i c s f o r a s p h e r i c a l p e l l e t u n d e r c o n d i t i o n s when t r a n s p o r t

:f5 Z-__-:U_--Z 7
r Z LIJ C~)p 1 0 X
0 f I
. . . . . . . . . . . 1. . . . . . . . .

Table I. Experimental and Theoretical Results of Boundary Layer Oxygen Transfer Rate Controlling Step in Pellet Oxidation

k~ (cm s-b
Experimental Froessling4 Steinberger and Treybals

450~ 1.79 2.60 2.23

500~ 1.92 2.90 2.50

600~ 2.29 3.52 3.02

700~ 2.99 4.23 3.67

800~ 3.35 5.19 4.49

Apparent Activation Energy 2,81 kcal mole"1 3.05 kcal mole"1 2.87 kcal mole"1

C(O2)~ ?

i - - - r ----. . . . . . . -q
F i g . 5--Model of a r o a s t i n g L C P R p e l l e t in c r o s s - s e c t i o n . METALLURGICAL TRANSACTIONS B

VOLUME 7B, SEPTEMBER 1976-371

t h r o u g h the r o a s t e d s h e l l i s r a t e c o n t r o l l i n g i s a v a i l a b l e f o r the c a s e of e q u i m o l a r c o u n t e r - c u r r e n t diffusion, NB = - N A , and the flux equation,

The f r a c t i o n a l c o n v e r s i o n of t h e s p h e r i c a l p e l l e t d u r i n g r o a s t i n g , F , m a y b e defined by noting that V o l u m e of u n r o a s t e d p e l l e t = ( r l ~ a Total pellet volume \ rp ] [16]

N A t = -- C D e tf dXA
dr

"

[6]

1- F =

F o r c o u n t e r - c u r r e n t e q u i m o l a r d i f f u s i o n the m o l a r flow t h r o u g h t h e s h e l l f r o m t h e s u r f a c e of the c o r e , rl, to the o u t e r l i m i t of the s h e l l , rp, i s :

I n t e g r a t i o n of the flux e q u a t i o n (Eq. [6]) l e a d s to the following e x p r e s s i o n ~ in t e r m s of f r a c t i o n a l c o n v e r sions, 6 C D etf (SAp -- XA l) t 1 + 2(1-- F ) 3 ( 1 - F ) ='s = [17]

$p = 4 rpNA .

4~r C D e t (XA l f

--

XAp )

r =r l

--

[7]

rt

rp

When t h e m o l a r flow of o x y g e n ~Vp, f o r bulk d i f f u s i o n in s t a g n a n t n i t r o g e n i s c o n s i d e r e d , NB = O, with the c o n d i t i o n DKA ' eff >> DAB, eff then t h e s o l u t i o n to Eq. [5] b e c o m e s

VVp ~- 4frCDAB, eff ln {XBp~

[8]

1
rt

1
rp

\xB

Hence, it can be shown that an o v e r a l l e f f e c t i v e diffus i v i t y f o r u s e with Eq. [7] i s

1 = 1 1 + (XB)In [9]

w h e r e ApA i s the i n c r e a s e in m o l a r d e n s i t y of oxygen r e s u l t i n g f r o m c o m p l e t e r o a s t i n g of the p e l l e t including SO2 f i x a t i o n . T h e m e a s u r e d r a d i u s of the roasted pellet was used for r#. E x p e r i m e n t a l r o a s t i n g d a t a including both weight gain and SO~ e m i s s i o n w e r e u s e d to c o m p u t e F(t) and ApA. T h e s e d a t a w e r e p l o t t e d in the f o r m of Eq. [17], (1 + 2(1 - F ) - 3(1 - F) 2/3 vs t) f o r a i r r o a s t i n g at s e v e r a l t e m p e r a t u r e s , F i g . 6. The s t r a i g h t line fit of t h e s e d a t a out to n e a r l y c o m p l e t e e x t r a c t i o n s u p p o r t the s h e l l d i f f u s i o n m o d e l . E x p e r i m e n t a l v a l u e s of D etf w e r e d e t e r m i n e d f r o m the s l o p e s of F i g . 6, taking

Deft where

DKA, eft

DAB, eff

XA1 = O.
E x p e r i m e n t a l (points) and t h e o r e t i c a l v a l u e s ( c u r v e s ) of the e f f e c t i v e d i f f u s i v i t i e s f o r r o a s t i n g in a i r , XAL = 0.21, a r e shown in F i g . 7. The d a t a a r e p r e s e n t e d p in the f o r m of an A r r h e n i u s plot: log Deft vs 1/T. B e c a u s e of d e c r e a s i n g p o r o s i t y in the r o a s t e d p e l l e t s h e l l with i n c r e a s i n g r o a s t i n g t e m p e r a t u r e at the high t e m p e r a t u r e end of the t e m p e r a t u r e r a n g e i n v e s t i g a t e d , a slight negative apparent activation energy is theor e t i c a l l y p r e d i c a t e d and e x p e r i m e n t a l l y o b s e r v e d . Good a g r e e m e n t with e x p e r i m e n t a l and t h e o r e t i c a l v a l u e s of t h e e f f e c t i v e d i f f u s i v i t y w e r e o b t a i n e d but a t o r t u o s i t y f a c t o r s l i g h t l y g r e a t e r than the u s u a l value, r = 2, i s r e q u i r e d . The e f f e c t i v e d i f f u s i v i t y should be i n v a r i a n t with c h a n g e s in the oxygen p a r t i a l p r e s s u r e and m o l e f r a c tion, XAp, p r o v i d e d the t o t a l p r e s s u r e r e m a i n s constant. Experimental effective diffusivities determined at 500~ in b i n a r y gas m i x t u r e s containing f r o m 5 p c t to 30 pct o x y g e n a r e shown in F i g . 8. A s e x p e c t e d , a

XBp -- X s l (XB) In = In (XBp/XBI)"

[10]

F o r r o a s t i n g in a i r with XBp = 0.79 and oxygen d e p l e t i o n at the r e a c t i n g i n t e r f a c e , XB l = 1.0 and the l o g a r i t h m i c m e a n v a l u e of the n i t r o g e n m o l e f r a c t i o n i s ( X s ) In = 0.89. W h e n p o r e v o l u m e f r a c t i o n , 0, and p o r e t o r t u o s i t y , r, a r e c o n s i d e r e d f o r the r o a s t e d s h e l l ,

DA B, eff - DABO T
and

[11]

DKA, elf =

DKAO
7

[12]

M e a s u r e d v a l u e s of the p o r o s i t y of f i r e d p e l l e t s w e r e u s e d in c a l c u l a t i n g e f f e c t i v e d i f f u s i v i t i e s while v a r i o u s v a l u e s of t h e t o r t u o s i t y w e r e c o n s i d e r e d . Bulk d i f f u s i v i t i e s f o r o x y g e n - n i t r o g e n m i x t u r e s , DAB , w e r e c a l c u l a t e d using,

0 00=10

84
78 .66

I ~ I/
~,40~or~ (~ ~/~ <d

.1,OOfi

DAB =

P gAff ~D, AB

~.
u_ ~

.54
.42

and the a p p r o p r i a t e C h a p m a n - E n s k o g p a r a m e t e r s . K n u d s e n d i f f u s i v i t i e s f o r oxygen, DKA w e r e c a l c u l a t e d s u s i n g t h e a v e r a g e p o r e r a d i u s , r e:

2 .48
I

--* .24

,/~//.,/~

/6/~'

DKA = 9700 r e ~ TMA

[141

S u r f a c e a r e a , p o r o s i t y , and bulk d e n s i t y m e a s u r e m e n t s of r o a s t e d p e l l e t s w e r e u s e d to d e t e r m i n e the average pore radius, 20 ,Fe = Sgpp 372-VOLUME 7B, SEPTEMBER 1976 [15]

.1s .12 D6 IO
I

20

30

40

50 MINUTES

60

70

80

90

I00

Fig. 6--Pellet roasting rate data plotted to fit a shell-diffusion model. METALLURGICAL TRANSACTIONS B

s y s t e m a t i c v a r i a t i o n in D e tf with o x y g e n c o n c e n t r a t i o n w a s not o b s e r v e d . A t e m p e r a t u r e r i s e o c c u r s in the p e l l e t s d u r i n g r o a s t i n g b e c a u s e of the e x o t h e r m i c c h e m i c a l r e a c t i o n s . A t y p i c a l t e m p e r a t u r e r i s e , r e c o r d e d by a t h e r m o c o u p l e i m b e d d e d at the c e n t e r of the p e l l e t i s shown in F i g . 9. T h e g a s t e m p e r a t u r e and i n i t i a l p e l l e t t e m p e r a t u r e w e r e 500~ A similar temperature p r o f i l e has b e e n p r e d i c t e d by a c o m p u t e r p r o g r a m b a s e d on t h e r e a c t i o n r a t e and h e a t t r a n s f e r c o n s i d e r a t i o n s u s i n g a u n i f o r m p e l l e t t e m p e r a t u r e m o d e l (ins t a n t a n e o u s t h e r m a l c o n d u c t i v i t y in t h e s o l i d ) . T h i s t e m p e r a t u r e r i s e w i l l i n c r e a s e the e f f e c t i v e d i f f u s i v i t y by only 10 to 15 p c t o v e r the v a l u e c a l c u l a t e d f o r the nominal roasting temperature. DISCUSSION O F HEAT T R A N S F E R IN A ROASTING BED T h e r o a s t i n g p r o c e s s i s e x t r e m e l y e x o t h e r m i c and h e a t t r a n s f e r d o m i n a t e s t h e r o a s t e r d e s i g n . F o r the overall reaction, CuFeS2 + - ~ O ~ + 2 C a O ~ 2 CaSO4 + CuO + 1/2 Fe~O3
o~

,07 .06
Pu

500~ O, 0

.o5

N
~

.04 .05
.02 I 5 I I0 I 15 I 20 I 25 I

121

50

OXYGEN PERCENT

Fig. 8--Oxygen p r e s s u r e independence of the experimental effective diffusivities.

I I i

60C \\ \ 550

[18]
at 527~ the h e a t of r e a c t i o n i s ~-/ = - 4 7 4 , 2 0 0 c a l p e r m o l e of CuFeS2. H o w e v e r , h e a t r e l e a s e w i l l v a r y w i d e l y b e t w e e n d i f f e r e n t c o n c e n t r a t e s d e p e n d i n g on the a m o u n t of o t h e r s u l f i d e s and gangue p r e s e n t . T h e f o l l o w i n g c o n s t r a i n t s , s o m e b a s e d on c a l c u l a t i o n s not p r e s e n t e d h e r e , m u s t be s u m m a r i z e d . T h e r a t e of h e a t r e l e a s e d c h e m i c a l l y i s d i r e c t l y p r o p o r t i o n a l to the e x t e n s i v e r a t e of c h e m i c a l r e a c t i o n , which b e c a u s e of the s p h e r i c a l p e l l e t g e o m e t r y and d i f f u s i o n c o n t r o l l e d r e a c t i o n k i n e t i c s i s g r e a t e s t d u r i n g the initial roasting period. The peUet temperature must be l i m i t e d to p r e v e n t f o r m a t i o n of f e r r i t e s t h a t a r e r e l a t i v e l y i n s o l u b l e in l e a c h i n g . T h e s e n s i b l e h e a t of t h e p e l l e t s i s only about 7 p c t of t h e c h e m i c a l h e a t r e l e a s e d , o r 20 p c t if Ca(OH)2 d e h y d r a t i o n i s i n c l u d e d .

\ xx~,\ EXPERIMENTAL x.~

UNWORM

500
0 I IO I 20 I 30 I 40 50 60

TIME (MINUTES)

Fig. 9--Experimental and numerical results of particle temperature during the course of roasting. H e n c e , the p e l l e t s a r e not a s i g n i f i c a n t h e a t s i n k and r e c y c l e of c o o l e d , r o a s t e d p e l l e t s w i l l n o t b e a p r a c t i c a l m e t h o d of e l i m i n a t i n g the h e a t r e l e a s e d . W a t e r i n j e c t i o n can be u s e d to c o o l a f l u i d i z e d b e d ( w e l l m i x e d s o l i d s ) r o a s t e r but h e a t m u s t be e l i m i n a t e d by t r a n s f e r to the r o a s t e r g a s e s p a s s i n g t h r o u g h a f i x e d p e l l e t b e d . L a r g e v o l u m e s of c o o l i n g g a s m u s t be used because gas heat capacities are small. For f i x e d b e d r o a s t e r s , p e l l e t f l u i d i z a t i o n in u p d r a f t m a c h i n e s o r a high p r e s s u r e d r o p a c r o s s t h e b e d i m p o s e a p r a c t i c a l u p p e r l i m i t on the g a s v e l o c i t i e s t h a t can b e u s e d and t h i s in t u r n l i m i t s t h e r a t e a t w h i c h h e a t can b e r e m o v e d f r o m the p e l l e t b e d and a l s o l i m i t s t h e p e l l e t b e d h e i g h t o r t h i c k n e s s t h r o u g h w h i c h the g a s i s flowing. T h i s c o n s t r a i n t e l i m i n a t e s a shaft furnace process. I n c r e a s i n g the p e l l e t s i z e r a d i c a l l y i n c r e a s e s t h e t i m e to c o m p l e t e r o a s t i n g , ~-p cc r ~ , b u t only s l i g h t l y d e c r e a s e s the i n i t i a l ( m a x i m u m ) h e a t r e l e a s e r a t e , bed I t = o cc rp, h e n c e , i n c r e a s i n g the p e l l e t r a d i u s , r p , i s an u n s u i t a b l e d i r e c t i o n t o w a r d e f f e c t i n g a d e q u a t e bed temperature control. The pellet size should be the s m a l l e s t c o n s i s t e n t with a good s u l f u r r e t e n t i o n and l e a c h i n g , and a p r a c t i c a l r a n g e of s i z e s f o r i n d u s t r i a l operating practice. W i t h t h e r e q u i r e m e n t s of a s h o r t b e d h e i g h t and v a r i a b l e h e a t r e m o v a l r a t e s and g a s v e l o c i t i e s , a c r o s s - c u r r e n t continuous p r o c e s s with r e s p e c t to bed m o v e m e n t and g a s flow w a s c o n s i d e r e d u s i n g a t r a v e l VOLUME 7B, SEPTEMBER 1976-373

T .2 800
I

(~ 500
I

700
1

600
I

450
I

T
I/} O4

1:3

.01 ,09

.10

.11 103/T

.12 (~ - I )

.15

:14

Fig. 7--Effective diffusivities for the shell-diffusion controlled roasting rate: experimentally determined points and theoretical curves. METALLURGICAL TRANSACTIONS B

i n g g r a t e m a c h i n e s i m i l a r to t h a t u s e d in i r o n o r e p e l letization. High blowing rates would be required early in t h e r o a s t i n g c y c l e w h e n t h e m a x i m u m r a t e of h e a t release is encountered. A l t e r n a t e u p - d r a f t and d o w n - d r a f t g a s f l o w c y c l i n g i s not v e r y u s e f u l . T h e c y c l e p e r i o d m u s t b e v e r y s h o r t , b e c a u s e of t h e l i m i t e d s e n s i b l e h e a t of t h e solids resulting from allowable temperature changes c a u s e d by a l t e r n a t i v e u p - d r a f t a n d d o w n - d r a f t f l o w . E x p e r i m e n t s , w i t h an u p - d r a f t f i x e d b e d p e l l e t r o a s t e r s h o w e d t h a t to p r e v e n t a n e x c e s s i v e t e m p e r a ture excursion during the initial reaction period, the b e d h e i g h t m u s t b e l i m i t e d to 7 to 15 c m f o r two c o n centrates studied. These results limit the practical a p p l i c a t i o n of a f i x e d b e d r o a s t e r a n d i n d i c a t e t h a t i n d u s t r i a l s c a l e - u p s h o u l d c o n c e n t r a t e on a c o n t i n u o u s l y operated fluid bed roaster with water injection into the b e d to o f f s e t t h e r e l e a s e d h e a t and c o n t r o l t h e r o a s t i n g temperature, NOMENCLATURE C C 02(~ C O2(g) DAB t o t a l g a s s p e c i e s c o n c e n t r a t i o n , m o l e s c c -~ o x y g e n c o n c e n t r a t i o n at t h e r e a c t i o n s i t e , m o l e s c a -~ o x y g e n c o n c e n t r a t i o n in t h e b u l k g a s , m o l e s
c a -1

re Sg t At T U ~Vp AWp XA XB (XB)ln 0 /~ pp pg ApA GAB T ~D, A B

average pore radius, cm s p e c i f i c s u r f a c e a r e a of t h e p e l l e t , c m 2 g-1 time, s time increment, s temperature, K superficial gas velocity through the bed or a r o u n d t h e p e l l e t , c m s -I m o l a r r a t e of o x i d a t i o n p e r p e l l e t , m o l e s o x y g e n p e l l e t -I s -I f i n i t e i n c r e m e n t of o x i d a t i o n of a p e l l e t , m o l e s o x y g e n p e l l e t -I m o l e f r a c t i o n of o x y g e n m o l e f r a c t i o n of n i t r o g e n l o g a r i t h m i c m e a n m o l e f r a c t i o n of n i t r o g e n , s e e E q . [10] pellet porosity (volume fraction) g a s v i s c o s i t y , g c m -~ s -~ p e l l e t a p p a r e n t d e n s i t y , g c m -s g a s d e n s i t y , g c m -s i n c r e a s e in m o l a r d e n s i t y of o x y g e n r e s u l t i n g f r o m c o m p l e t e r o a s t i n g , m o l e s c c -~ c o l l i s i o n d i a m e t e r , E q . [13], A tortuosity factor for a porous solid c o l l i s i o n i n t e g r a l , E q . [13]. SUBSCRIPTS

o r d i n a r y d i f f u s i o n c o e f f i c i e n t f o r an o x y g e n / n i t r o g e n m i x t u r e , a m 2 s -1 D A B, eff e f f e c t i v e b u l k d i f f u s i o n c o e f f i c i e n t f o r an o x y g e n / n i t r o g e n m i x t u r e in p o r e s , c m 2 s -1 Knudsen diffusion coefficient for oxygen, cm 2 DKA s-1 DK A, eff e f f e c t i v e k n u d s e n d i f f u s i o n c o e f f i c i e n t f o r o x y g e n , a m 2 s -1 overall effective oxygen diffusion coefficient, Deff a m 2 s -1 F v o l u m e f r a c t i o n of t h e p e l l e t t h a t h a s b e e n roasted m a s s t r a n s f e r c o e f f i c i e n t f o r o x y g e n , c m s -1 km m o l e c u l a r w e i g h t of o x y g e n , M / / m o l e MA m o l e c u l a r w e i g h t of n i t r o g e n , M / / m o l e MB m o l a r f l u x of o x y g e n , m o l e s c m -2 s -1 NA m o l a r f l u x of n i t r o g e n , m o l e s c m -2 s -~ NB p r e s s u r e , E q . [13], a r m P r r a d i a l p o s i t i o n in t h e p e l l e t , c m Ar rp - rl, c m

g P l r

c h a r a c t e r i s t i c of t h e b u l k g a s e v a l u a t e d at t h e p e l l e t s u r f a c e , rp e v a l u a t e d at t h e p e l l e t r e a c t i o n i n t e r f a c e , r l e v a l u a t e d at r a d i u s r . ACKNOWLEDGMENT

P a r t i a l s u p p o r t of t h i s r e s e a r c h w a s c o n t r i b u t e d by t h e U . S . B u r e a u of M i n e s u n d e r G r a n t G 133085. RE FERENCES 1. R. W. Bartlett and H. H. Haung: J. Metals, 1973, vol. 25, no. 12, pp. 28-34. 2. F. P. Hayer and M. M. Wong:MiningEng., 1972, vol. 24, no. 6, p. 52. 3. J. H. Strassberger,et al: Blast Furnace Theory and Practice, vol. 1, p. 286, Gordon and Breach SciencePublishers, New York, 1969. 4. N. Froessling:GerlandsBeitr. Geophys., 1938, vol. 52, p. 1183. 5. R. L. Steinberger and R. E. Treybah AIChEJ., 1960, vol. 6, p. 227. 6. C. N. Satterfield: Mass Transfer in Heterogeneous Catalysis, pp. 41,42, M.I.T. Press, Cambridge, Mass., 1970. 7. O. Levenspieh ChemicalReaction Engineering, chapt. 12, J. Wileyand Sons, New York, 1962.

374-VOLUME 7B, SEPTEMBER 1976

METALLURGICAL TRANSACTIONS B