Eport On Best Available

Th e Fi n n i sh En vi r o n m e n t 316
M arja Riekkola-Vanhanen
Fin n ish exp ert rep ort on

best available tech n iqu es
in cop p er p rod u ction an d
by-p rod u ction of p reciou s
metals
H ELSIN KI 1999
FI N N I SH EN V I RO N M EN T I N ST I T U T E
ISBN 952- 11- 0 50 6- 2
ISSN 1238 - 7312
Phot o: Out okum pu Oyj

La yout : Dia idea Oy
Oy Edit a Ab
Helsinki 1999 Helsingfor s
2 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ The Finnish Environment 316

For ew or d
○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
Th e Eu rop ean Cou n cil Directive on In tegrated Pollu tion Preven tion an d Con trol
(IPPC-Directive, 96/61/EC of Sep tem ber 24, 1996) is aim ed at an in tegrated ap p ro-
ach of p reven tion an d con trol of p ollu tion arisin g from categories of in d u strial
activity listed in its An n ex I. Accord in g to article 16.2 of th e Directive th e Com m is-
sion sh all organ ise an exch an ge of in form ation betw een Mem ber States an d th e
in d u stries con cern ed on best available tech n iqu es, associated m on itorin g, an d d e-
velop m en ts in th em . Th is in form ation sh ou ld lead to a Eu rop ean Best Available
Tech n iqu es referen ce d ocu m en t (BREF) on each in d u strial sector.
O ne of the activities includ ed in the Directive concerns the prod uction of non-
ferrou s m etals, accord in g to th e d efin ition of category 2.5 (a) in An n ex I: ”In stalla-
tion s for th e p rod u ction of n on -ferrou s cru d e m etals from ore, con cen trates or
second ary raw materials by metallurgical, chemical or electrolytic processes”. These
in stallation s are p art of th e in d u strial sectors to be stu d ied in 1998.
With in th e above m en tion ed fram ew ork, th e Fin n ish En viron m en t In stitu te
an d O u toku m p u Tech n ology O y h ave d ecid ed to con tribu te to th e exch an ge of
in form ation in th e Eu rop ean Un ion by m akin g a stu d y on Best Available Tech n i-
qu es for th e p rim ary p rod u ction of n on -ferrou s m etals. O u toku m p u Research O y
h as been requ ested to p erform th is stu d y. Raim o Ran tan en is resp on sible for th e
w ork an d th e rep ort h as been w ritten by Marja Riekkola-Van h an en . Maija-Leen a
Metsärin ta h as p rep ared a literatu re su rvey on th e su bject.
Primary n on -ferrou s metal p rod u ction in Fin lan d con cern s on ly cop p er, n ick-
el, zin c an d ferroch rom iu m . Gold an d oth er p reciou s m etals are p rod u ced as by-
p rod u cts of cop p er p rod u ction . Th is rep ort d escribes th e p rim ary p rod u ction of
cop p er an d th e p rod u ction of gold an d oth er p reciou s m etals as by-p rod u cts. Th e
p rim ary p rod u ction of n ickel, zin c an d ferroch rom iu m are d escribed in sep arate
rep orts.
Th e m ain objective of th is BAT rep ort is to id en tify available tech n iqu es for
th e red u ction of em ission s an d en ergy u se in th e p rim ary cop p er p rod u ction in
Fin lan d . O n ly th e p yrom etallu rgical flash sm eltin g p rocess is in u se in Fin lan d to
recover cop p er from su lp h id e con cen trates an d is th e m ain p rocess d escribed in
th is rep ort. Th e in form ation p resen ted is largely based on en viron m en tal p erm it
applications, the corporate environmental programme and permit regulations con-
cern in g O u toku m p u . Ad d ition al in form ation con cern in g gen eral issu es of cop p er
p rod u ction an d com p arison s is obtain ed from th e available literatu re.
Th e p roject h as been gu id ed by a steerin g grou p th at p rovid ed com m en ts on
th e d raft rep orts an d offered a p latform for d iscu ssion on th e scop e, th em es an d
resu lts of th e stu d y. Th e steerin g grou p members rep resen ted th e follow in g organ -
isation s: Fin n ish En viron men t In stitu te, Sou th w est Fin lan d Region al En viron men t
Cen tre, O u toku m p u O yj, O u toku m p u Tech n ology O y, O u toku m p u H arjavalta
Metals O y, O u toku m p u Zin c O y an d O u toku m p u Ch rom e O y.
The Finnish Environment 316 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

3
Con t en t s
1 General Information................................................................. 7
2 Applied Processes and Techniques.......................................... 10

2.1 Pyrometallurgical Copper Production ...................................................11
2.1.1 Smelting of concentrate to matte .................................................11
2.1.2 Flash furnace smelting ...................................................................12
2.1.3 Converting ........................................................................................13
2.1.4 Slag cleaning ....................................................................................13
2.1.5 Copper refining, anode casting and electrorefining................ 14
2.2 Single Furnace Coppermaking ................................................................14
2.3 Continuous Converting .............................................................................14
2.4 Outokumpu Flash Smelting Process at H arjavalta Plant ................... 15
2.4.1 Raw material reception and storage ............................................15
2.4.2 Blending and drying of the concentrate .....................................15
2.4.3 Flash smelting ..................................................................................16
2.4.4 Gas cleaning .....................................................................................16
2.4.5 Copper converting...........................................................................17
2.4.6 Slag flotation ....................................................................................18
2.4.7 Copper refining and anode casting ............................................. 18
2.4.8 Sulphuric acid plant .......................................................................19
2.4.9 Copper electrolysis .........................................................................19
2.4.10 Utilities and Off-Sites at the H arjavalta plant .......................... 23
2.4.11 Utilities and Off-Sites in the copper electrolysis at Pori ........ 24
2.5 Outokumpu Flash Converting .................................................................24
2.6 Outokumpu D irect Blister Smelting ......................................................25
2.7 H ydrometallurgical Copper Production ................................................ 25
2.7.1 Copper heap leaching.....................................................................26
3 Present Consumption and Emission Levels............................. 30

3.1 Present Consumpion Levels.....................................................................30
3.1.1 Energy consumption .......................................................................30
3.2 Environmental Emissions .........................................................................30
3.2.1 General ..............................................................................................30
3.2.2 Emissions to air ................................................................................31
3.2.3 Legislation and regulation in Finland ........................................ 33
3.2.4 Emissions to air at Outokumpu H arjavalta M etals.................. 34
3.2.5 Off-gas monitoring..........................................................................35
3.2.6 Releases into air ...............................................................................35
3.2.7 Emissions to water ..........................................................................36
3.2.8 Solid waste management ...............................................................38
3.2.9 N oise abatement ..............................................................................40
3.2.10 Environmental management system ........................................... 40
3.2.11 D ata management and training....................................................40

5
4 Candidate Best Available Techniques..................................... 41
4.1 General ..........................................................................................................41
4.2 Feed Preparation .........................................................................................42
4.3 D rying ...........................................................................................................42
4.3.1 Rotary dryer (rotary kiln) ..............................................................42
4.3.2 Steam dryer .......................................................................................42
4.3.3 Pneumatic drying/Flash dryer ......................................................43
4.4 D ry Concentrate Conveying System ......................................................44
4.5 Concentrate Feeding System ....................................................................44
4.5.1 Volumetric concentrate feed system............................................ 44
4.5.2 Loss-in-weight feeding system .....................................................44
4.6 Smelting Techniques..................................................................................45
4.7 Slag Cleaning...............................................................................................47
4.7.1 Electric furnace ................................................................................47
4.7.2 Slag concentrator .............................................................................47
4.8 Converting....................................................................................................48
4.9 Anode Furnace.............................................................................................49
4.10 Gas Cooling..................................................................................................49
4.11 D ust Separating...........................................................................................50
4.12 Sulphur Fixation .........................................................................................51
4.13 Acid Plant .....................................................................................................53
4.14 Tail and Secondary Gas Cleaning and Scrubbing ............................... 54
4.15 Waste Acid and Water Treatment .............................................................55
4.16 Comparison of Copper Smelting Processes ..........................................56
4.17 Electrolytic Refining ..................................................................................60
5 Best Available Technique ........................................................ 61
6 Emerging Techniques.............................................................. 63
6.1 Pyrometallurgical Processes.....................................................................63
6.2 H ydrometallurgical Processes..................................................................63
7 Conclusions and Recommendations ....................................... 65
Literature ...................................................................................... 66

Gen er a l I n f or m a t i on
○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
Metallic cop p er h as been fou n d at several location s in th e w orld . It w as kn ow n to

early m an in abou t 7000 BC. Its early u ses w ere in jew ellery, u ten sils, tools an d
1
w eap on s. Its u se in creased grad u ally over th e years an d th en saw a d ram atic
grow th in th e 19th an d 20th cen tu ry w ith th e m ass ad op tion of electricity. Cop p er
is an excellen t con d u ctor of electricity an d h eat an d is easily w orked in to w ire, rod
an d cable. Electrical con d u ctivity, corrosion resistan ce an d th erm al con d u ctivity
are still th e p rop erties m ost exp loited in th e u se of cop p er /1/.
Copper is most commonly present in the Earth’s crust as copper-iron-sulphid e
an d cop p er su lp h id e m in erals su ch as for exam p le ch alcop yrite (Cu FeS2) an d ch al-
cocite (Cu 2S). Th e con cen tration of th ese m in erals in an orebod y is low. Typ ical
cop p er ores con tain from 0.5 to 2 % cop p er. Pu re cop p er m etal is m ostly p rod u ced
from th ese ores by con cen tration , sm eltin g an d refin in g.
Cop p er also occu rs in oxid ised materials, carbon ates, oxid es, h yd roxy-silicates
an d su lp h ates, bu t to a lesser exten t. Cop p er m etal is u su ally p rod u ced from th ese
minerals by hyd rometallurgical method s. Hyd rometallurgy is also used to prod uce
cop p er m etal from secon d ary su lp h id e m in erals, e.g. ch alcocite (Cu 2S) an d m in e
w aste d u m p s.
A th ird m ajor sou rce of cop p er is recycled cop p er. Secon d ary raw m aterials
accou n t for abou t 40 % of th e u se of cop p er an d its alloys in Eu rop e an d w orld -
w id e.
Th e core of th e EU cop p er in d u stry is in sm eltin g, refin in g an d sem i-m an u -
factu rin g, as th e m in in g cap acities are n egligible. Th ere is sizeable cop p er m in e
p rod u ction on ly in Portu gal (N eves Corvo, 106,500 ton s of cop p er in 1997) an d
Sw ed en (Bolid en , 86,600 ton s of cop p er in 1997). Accord in g to th ese figu res, th e
EU accou n ts for arou n d 2 % of th e w orld cop p er m in e ou tp u t (Table 1).
Ta ble 1. Copper pr oduct ion 1997 in 10 0 0 t ons of copper / 2/ .
Ar ea Mine Sm elt er Refiner y
EU 239 1 168 1 8 54
NonEU Eur ope 1 135 1 310 1 271

Afr ica 64 2 562 531
Asia 1 884 3 330 3 630
Am er ica 6 952 4 58 6 6 000

Ocea nia 672 20 8 271
An n u al refin ed cop p er p rod u ction in th e EU reach ed 1,854,000 ton n es in 1997

w h ich is 13.7 % of w orld w id e p rod u ction . Refin ery ou tp u t is in th e form of cath -
od es th at are often m elted an d cast on th e p rem ises in to billets, cakes etc. Abou t
60 % of th e feed su p p lies to th e EU cop p er sm elters an d refin eries are p u rch ased
on th e in tern ation al m arket in th e form of cop p er con cen trates, blister cop p er or
scrap . Th e rem ain in g 40 % com e from d om estic cop p er con cen trates as w ell as
d om estic cop p er scrap . EU cop p er p rod u ction is p resen ted in Table 2.
EU cop p er d em an d follow s th e slow grow th p attern of a m atu re m arket.
Recyclin g is at a h igh level as cop p er can be rep rocessed w ith ou t th e loss of its

7
in trin sic p rop erties an d m an y secon d ary m aterials are available. Refin in g cap aci-
ty in th e EU cou n tries h as been able to grow p rim arily by secu rin g raw m aterials
on th e in tern ation al m arket an d m akin g u se of cop p er or brass scrap an d resid u es
gen erated by con su m ers an d p rocessors. Com p u ter scrap an d p rin ted circu it
board s are becom in g m ore com m on secon d ary sou rces.
Ta ble 2. Eur opea n copper pr oduct ion 1997 in 10 0 0 t ons of copper / 61/ .
Mining Refining
Benelux 20 3
Finla nd 9 116
Fr a nce 6
Ger m a ny 296
It a ly 6
Por t uga l 10 8
Spa in 37 229
Sweden 87 95
UK 9
Tot a l EU 239 959

Nor wa y 7 33
Pola nd 4 17 4 21
Ma cedonia 87 10 4
Th ere are five m ajor refin eries in th e EU w h ich u se m ain ly p rim ary raw m ateri-
als. Th ese p rod u cers are p resen ted in Table 3. It is estim ated th at th e cop p er refin -
in g in d u stry em p loyed m ore th an 5000 p eop le in 1994.
Ta ble 3. Pr im a r y r efined copper pr oducer s in EU.
Count r y Com pa ny Loca t ion Ca pa cit y t / y
Spa in At la nt ic Copper S.A. Huelva 250 0 0 0

Sweden Boliden Miner a l AB Rönnskä r 128 50 0
Ger m a ny Nor ddeut sche Affiner ie AG Ha m bur g 38 0 0 0 0
Finla nd Out okum pu Ha r ja va lt a Met a ls Oy Ha r ja va lt a , Por i 125 0 0 0

Belgium Union Minier e Hoboken, Olen 28 5 50 0
Th e p oten tial for exp an sion of cop p er sm eltin g cap acities in th e EU is lim ited d u e
to th e access to feed su p p lies an d th e h eavy in vestm en t costs. H ow ever, n early all
of the primary smelters have increased prod uction output. This significant increase
in p rod u ction cap acity h as been m ad e sim u ltan eou sly w ith en viron m en tal im -
p rovem en ts.
Th e d em an d for cop p er com es m ain ly from th e electrical an d electron ics in -
d u stries, abou t 50 % of total EU con su m p tion . Th e con stru ction sector, p lu m bin g,
roofin g, d ecoration etc. accou n ts for 25 % of con su m p tion . Th e rest is u sed in in -
d ustrial machinery and equipment, transportation equipment and consumer prod -
u cts. Cop p er ap p lication s are w ell d evelop ed an d th e grow th p attern of cop p er
con su m p tion closely follow s th e cycle of in d u strial activity in gen eral.
Th e p rice of m etallic cop p er is gen erally govern ed by th e Lon d on Metal Ex-
ch an ge (LME) qu otation s for Grad e A cop p er. Price tren d s reflect th e global bal-
an ce of su p p ly an d d em an d , bu t are of cou rse su scep tible to sp ecu lative in flu en c-
es an d im balan ces in th e global d istribu tion of th e m etal. In ad d ition to p rovid in g
the ind ustry with a price reference, the LME offers a hed ging med ium against price
flu ctu ation s.

Recyclin g is at a h igh level as cop p er can be rep rocessed w ith ou t loss of its
in trin sic p rop erties an d m an y secon d ary m aterials are available. Th e EU cop p er
refin in g in d u stry h as been able to grow p rimarily by secu rin g raw materials on th e
in tern ation al market an d makin g u se of scrap s an d resid u es gen erated by con su m-
ers an d p rocessors. At th e sam e tim e it h as been able to com p ly w ith in creasin gly
strin gen t en viron m en tal con strain ts.

9
2 A p p l i ed P r ocesses a n d Tech n i q u es
○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
Ap p roxim ately 90 % of th e w orld cop p er p rod u ction from ores is n ow m an u fac-

tured from sulphid ic ores by pyrometallurgical techniques (see Figure 1). Five steps
can be d istin gu ish ed in th e p rim ary p rod u ction of cop p er:
I. m in in g of cop p er ores
II. isolation of th e cop p er m in eral p articles in an ore by flotation
III. sm eltin g of th e resu ltin g con cen trate to m olten h igh cop p er m atte
IV. con vertin g of m olten m atte to m olten blister cop p er
V. fire- an d electrorefin in g of th e blister to p u re cop p er.
Th is stu d y focu ses on th e sm eltin g, con vertin g an d electrorefin in g step s. Th e m in -
in g an d flotation p rocesses are also exclu d ed in th e EU Referen ce Docu m en t on
Best Available Tech n iqu es in N on Ferrou s Metals In d u stries. Table 4 sh ow s w orld
cop p er sm elter cap acities an d p rod u ction in 1995 /61/.
H yd rom etallu rgical p rod u ction of cop p er from ores h as becom e m ore im p or-
tan t in th e p ast d ecad e. Th e m aterials m ost com m on ly treated th is w ay are oxid e
an d secon d ary su lp h id e cop p er min erals. Tod ay more th an 10 % of th e w orld min e
p rod u ction of cop p er is p rod u ced by h yd rometallu rgical p rocesses an d th e grow th
in th is area is still con tin u in g. It is exp ected th at in th e year 2000 m ore th an 20 %
of cop p er w ill be p rod u ced by leach in g of cop p er ores or con cen trates (see Figu re
1).
Ta ble 4 . Wor ld copper sm elt er ca pa cit ies a nd pr oduct ion in 1995.
Pr im a r y Copper Ca pa cit y Mt Pr oduct ion Mt Num ber of Num ber of

Sm elt ing Technology Sm elt er s using Sm elt er s using
t his Technology only t his Technology
Out okum pu Fla sh Sm elt ing 4 .1 3.5 26 25

Rever ba t or y Fur na ce 2.8 1.8 27 16
Modified El Tenient e Conver t er Conver t er 0 .9 0 .8 7 0

Elect r ic Fur na ce 0 .7 0 .5 5 5
Bla st Fur na ce 0 .6 0 .4 8 7
INCO Fla sh Sm elt ing 0 .5 0 .4 3 2

Mit subishi 0 .4 0 .3 2 2
Va nyukov 0 .4 0 .3 2 0
Isa sm elt 0 .3 0 .2 2 1
Nor a nda Rea ct or 0 .3 0 .2 2 1
Cont op 0 .1 0 .1 1 1
Ba iyin 0 .1 0 .1 1 1
Tot a l 11.1 8 .6 76 61

Mining
O re Leaching
Concentrating
Smelting to Matte Solvent Extraction
Converting to Blister
Anode Casting
Electrorefining to Cathode Electrowinning
Figure 1. Flowsheet of primary copper product ion.
O n ly th e p yrom etallu rgical cop p er p rocess is u sed in Fin lan d to recover cop p er
from cop p er con cen trates. Th is Flash Sm eltin g p rocess at O u toku m p u H arjavalta
Metals O y is d escribed in th is stu d y. A brief d escrip tion is also given of th e oth er
cop p er p rod u cin g p rocesses ap p lied elsew h ere. Th e p rocesses d evelop ed by O u -
toku m p u an d u sed also ou tsid e th e EU are also d escribed .
2.1 Pyrometallurgical Copper Production

2.1.1 Smelting of concentrate to matte
Matte sm eltin g en tails m eltin g con cen trate in a large fu rn ace at abou t 1,200°C in
an oxid isin g atm osp h ere. Th e objective of th e sm eltin g is to oxid ise som e of th e
su lp h u r an d iron in th e con cen trate an d to p rod u ce a molten su lp h id e p h ase (mat-
te) rich in cop p er an d to sep arate th e rest as slag.
Th e p rod u cts of th e sm eltin g are m olten su lp h id e m atte, 35 to 70 % Cu , con -
tain in g m ost of th e cop p er in th e con cen trate feed an d a m olten oxid e p h ase (slag)
as free of cop p er as p ossible. Th e m olten m atte is su bsequ en tly con verted in a con -
vertin g fu rn ace to form im p u re cop p er m etal. Th e slag is d iscard ed , u su ally after
a cop p er recovery step .
Su lp h u r d ioxid e bearin g gas is also gen erated . SO 2 is h arm fu l to th e en viron -
m en t an d m u st be rem oved before th e off gas is released . Th is is alm ost alw ays
d on e by recoverin g th e SO 2 as su lp h u ric acid or liqu id SO 2.
An im p ortan t objective of m atte sm eltin g is to p rod u ce a slag w h ich con tain s
as little cop p er as p ossible. Th is is d on e by keep in g th e slag n ear silica satu ration
an d by keep in g th e fu rn ace su fficien tly h ot th at th e slag is m olten an d flu id .
Sm eltin g is m ost often p erform ed in flash fu rn aces. It u sed to be carried ou t
to a con sid erable exten t in reverbatory fu rn aces, bu t th is old er tech n ology is be-
in g rep laced .

11
2.1.2 Flash furnace smelting
Th e oxid ation reaction s p rovid e m u ch or all of th e en ergy for h eatin g an d m elt-
in g of th e p rod u cts. Fossil fu el bu rn ers are often em p loyed to con trol fu rn ace tem -
p eratu res, bu t m ostly th e p rocess is au togen eou s. Th e oxygen en rich m en t d egree
is u sed for th e tem p eratu re con trol. Th e m olten m atte an d slag are tap p ed sep a-
rately from th e fu rn ace as th ey accu m u late.
Th ere are th ree typ es of in d u strial flash fu rn aces in u se: th e O u toku mp u typ e,
w h ich u ses oxygen en rich ed air as th e oxid an t (Figu re 2); th e In co typ e, w h ich u ses
tech n ical oxygen as th e oxid an t; an d th e Con top ap p lication , w h ich u ses cyclon e
bu rn ers to in trod u ce oxygen en rich ed air an d con cen trate in to th e sm eltin g fu r-
n ace. Th is ap p lication w ill be closed in Sp rin g 1999.
Flash fu rn aces accou n ted for abou t 47 % of th e w orld ’s cop p er con cen trate
sm eltin g in 1995.
2.1.2.1 Reverbatory Furnace Smelting

Reverbatory fu rn ace sm eltin g accou n ted for m ost of th e w orld ’s cop p er sm eltin g
as late as 1975. H ow ever, th e last reverbatory sm elter w as bu ilt in 1976 an d th e
existing furnaces are grad ually being replaced by flash and other smelting furnaces.
Th e reverbatory fu rn ace is a h earth fu rn ace in w h ich a solid ch arge of con -
cen trates an d flu x is m elted at abou t 1,200°C by h ot com bu stion gases sw eep in g
over th e h earth . Th e com bu stion gases are p rovid ed by bu rn in g fossil fu el in en d -
wall or roof burners. The prod ucts of the process are molten matte and molten slag.
Reverbatory furnace smelting is primarily a melting process in contrast to flash
sm eltin g w h ich is an oxid ation /m eltin g p rocess. Reverbatory sm eltin g m akes lit-
tle u se of th e en ergy from su lp h u r an d iron oxid ation for h eatin g an d m eltin g. It
also p rod u ces large qu an tities of fossil fu el com bu stion gas con tain in g abou t 1 %
SO 2. It is d ifficu lt to rem ove SO 2 at th is low con cen tration w h ich m ean s th at th e
off-gases are an air p ollu tion p roblem /1/.
2.1.2.2 Other smelting processes
In recen t d ecad es man y n ew p rocesses h ave been d evelop ed . Th ese p rocesses, like
flash sm eltin g, u se th e oxid ation of iron an d su lp h u r in th e con cen trate feed to
p rovid e en ergy for h eatin g an d m eltin g.
Th e Isasm elt, N oran d a, Ten ien te, Mitsu bish i, Van yu kov an d Baiyin p rocess-
es u se bath sm eltin g. O xygen en rich ed air is blow n to th e fu rn ace w ith vertical
lan ces or th rou gh su bm erged tu yeres. All th ese p rocesses are d iscu ssed later in
Ch ap ter 4.
Th e N oran d a p rocess w as com m ission ed at th e com p an y ’s H orn e sm elter in
1997. Th e p rocess can p rod u ce blister cop p er w h en u sin g con cen trates w ith low
im p u rity levels. Th e n orm al op eratin g p ractice is to p rod u ce cop p er-rich m atte to
u n d ergo fu rth er con version .
Th e Ten ien te p rocess is sim ilar to th e N oran d a p rocess. Th e m ain d ifferen ces
are th e ad d ition of “seed ” m atte, w h ich is p eriod ically ad d ed to th e fu rn ace to
m ain tain th e h eat balan ce; th e in jection of d ry con cen trate th rou gh som e of th e
tu yeres an d th e ch argin g of m oist con cen trate above th e bath ; an d th e fact th at n o
coal is in clu d ed in th e fu rn ace ch arge. Six sm elters u se Ten ien te fu rn aces in con -
ju n ction w ith reverbatory fu rn aces /36,37/.
Th e Isasm elt p rocess /39/ u ses m oist feed th at is fed to th e fu rn ace con tin u -
ou sly w ith flu xes. Fu el oil or coal an d oxygen are in jected in to th e fu rn ace th rou gh
a steel lan ce, w h ich is su bm erged in th e m olten bath . Th e lan ce stirs th e bath an d
p rod u ces a slag alon g w ith m atte. Th e sep aration of th e m olten p h ases takes p lace

on a fore-h earth an d th ey are tap p ed p eriod ically. Th e fu rn ace is n orm ally u sed
on a batch basis w h en con d ition s in th e fu rn ace, su ch as th e gas blow n th rou gh
th e lan ce, are ch an ged at th e en d of th e batch . Isasm elt is u sed in Cyp ru s an d Mt
Isa.
A few exam p les of trad ition al m atte sm eltin g p rocesses also rem ain in u se
arou n d th e w orld , p articu larly electric fu rn ace sm eltin g an d blast fu rn ace sm elt-
in g.
2.1.3 Converting
Cop p er con vertin g con sists of air oxid ation of th e m olten m atte from sm eltin g.
Con vertin g rem oves th e iron an d su lp h u r from th e m atte to p rod u ce cru d e m ol-
ten m etallic blister cop p er (99 % Cu ) w h ich is sen t forw ard to p yro- an d electrore-
fin in g.
Liqu id m atte is tran sferred from th e sm eltin g fu rn ace in large lad les an d
poured into the converter through a large central mouth. The oxid ising blast is then
tu rn ed on an d th e con verter is rotated forcin g th e blast in to th e m atte th rou gh a
lin e of tu yeres alon g th e len gth of th e vessel. Th e h eat gen erated in th e con verter
by iron an d su lp h u r oxid ation is su fficien t to m ake th e p rocess au togen eou s.
Con vertin g is d on e in tw o stages. Th e first is th e slag form in g stage, in w h ich
iron an d su lp h u r are oxid ised . Th e secon d stage is th e cop p er-m akin g stage, in
w h ich th e su lp h u r in th e Cu S2 is oxid ised to SO 2.
Peirce-Smith converters account for 90 % of copper matte smelting. This is d ue
to th eir sim p licity an d h igh ch em ical efficien cy. Th ere is, h ow ever, sign ifican t leak-
age of SO 2 in to th e atm osp h ere d u rin g ch argin g an d p ou rin g. Several altern atives
h ave th erefore been d evelop ed . Th e H oboken con verter h as an im p roved gas col-
lection system . In th e flash con verter solid ified an d grou n d m atte is sm elted w ith
oxygen en rich ed air in a closed flash sm eltin g fu rn ace.
2.1.4 Slag cleaning

Th e cop p er sm eltin g fu rn ace slag can be clean ed eith er in an electric fu rn ace or in
a slag con cen tration p lan t.
2.1.4.1 Electric furnace

Cop p er sm eltin g fu rn ace slag is tap p ed th rou gh slag tap h oles alon g lau n d ers in to
the electric furnace. Coke and reverts are added through the furnace roof. Slag from
th e electric fu rn ace is tap p ed in to gran u lation or cast in blocks an d sold or tran s-
p orted to th e slag storage area. Matte from th e electric fu rn ace is p eriod ically
tap p ed th rou gh tap p in g h oles an d lau n d ers in to lad les an d tran sferred by cran es
to con verters for fu rth er treatm en t.
Th ere are th ree or six electrod es in th e electric fu rn ace to su p p ly en ergy in to
th e fu rn ace. Electric p ow er is n eed ed for th e red u ction reaction s, h eat losses an d
sm eltin g of reverts. Th e red u ctive agen t is coke. Electric fu rn ace off-gases are first
bu rn ed in an in cin erator, th en cooled an d taken th rou gh a bag filter or a scru bber
to th e stack.
2.1.4.2 Slag concentrator

Molten slag is tap p ed th rou gh tap h oles an d alon g lau n d ers in to lad les, w h ere th e
slag is cooled con trolled by w ater sp rayin g. After coolin g th e lad les are tran sp ort-

13
ed an d u n load ed on to th e slag stockp ile, from w h ich th e slag is tran sp orted on to
a grizzly w h ere oversized lu m p s are broken . Metallic cop p er is sep arated as th e
grizzly oversize. The grizzly undersize is transported to the screening station where
lu m p s, p ebbles an d fin es are sep arated in to sep arate bin s. Grin d in g con sists of
au togen ou s lu m p m ills an d p ebble m ills. Both grin d in g stages are equ ip p ed w ith
h yd rocyclon es. Flotation is carried ou t in th ree m ain stages. Recovered cop p er
con cen trate is th icken ed an d filtered by a p ressu re filter. Th e filtered con cen trate
is con veyed in to th e d ryer. Slag m ill tailin gs are p u m p ed in to a n earby tailin g area.
Th e clarified w ater from th e tailin g p on d is u sed as p rocess w ater.
2.1.5 Copper refining, anode casting and electrorefining

Molten blister copper is refined in an anod e furnace in ord er to remove the remain-
in g su lp h u r an d oxygen . Th e refin ed cop p er is cast in op en an od e-sh ap ed mou ld s.
In electrorefin in g cop p er is first d issolved electroch em ically from th e im p u re
an od es in to th e cop p er su lp h ate-su lp h u ric acid -w ater electrolyte an d th en d ep os-
ited from th e electrolyte on to cop p er or stain less steel cath od es.
Fu lly grow n cath od es are rem oved from th e cells, w ash ed w ith w ater an d
p acked . Th ey are sold for meltin g, castin g an d fabrication of cop p er semi-p rod u cts.
2.2 Single Furnace Coppermaking

Sm eltin g an d con vertin g are con trolled oxid ation p rocesses w h ich p rod u ce SO 2,
iron oxid e an d even tu ally cop p er. It seem s n atu ral th at th e tw o p rocesses sh ou ld
be carried ou t in a sin gle step , i.e. in on e fu rn ace.
Un til n ow cop p er h as been mad e in a sin gle fu rn ace at on ly tw o p laces, w h ich
u se O u toku m p u Flash Sm eltin g. Cop p er con cen trates con tain in g over 35 % cop -
p er or sp ecial con cen trates con tain in g on ly sm all am ou n ts of iron can be treated
by the Direct Blister Flash Smelting Process. Suitable concentrates can be made from
ch alcocite or born ite-ch alcocite ores w h ich h ave h igh cop p er con ten ts or w h ose
cop p er/iron ratios are h igh com p ared to ch alcop yritic con cen trates.
2.3 Continuous Converting

O ver th e last d ecad e th ere h as been con sid erable p ressu re to m od ern ise con vert-
er p ractice. Firstly, th ere is th e n eed for even h igh er levels of su lp h u r recovery as
en viron m en tal regu lation s are tigh ten ed arou n d th e w orld . Secon d ly, th ere is a
d rive to elim in ate th e batch op eration s in h eren t in con ven tion al con verter op era-
tion s an d th u s both im p rove efficien cy an d su lp h u r cap tu re of both th e p rocess
an d th e fu gitive gases. Th e sch ed u lin g of all th e m ovem en ts an d activity w h ich
takes p lace in th e con verter aisle requ ires con sid erable skill if th e op eration is to
be carried ou t efficien tly.
Th e con tin u ou s flash con verter w as d evelop ed by O u toku m p u an d Ken n e-
cott an d th e first in stallation w as bu ilt at Ken n ecott´ s Garfield sm elter in 1995.
Th e Mitsu bish i p rocess em p loys th ree in tercon n ected fu rn aces, a bath sm elt-
in g fu rn ace, an electric slag clean in g fu rn ace an d a con vertin g fu rn ace /33/. Th e
cop p er con cen trate is sm elted in th e bath fu rn ace to a cop p er m atte an d slag, th en
m atte an d slag overflow in to th e electric fu rn ace w h ere th ey are sep arated an d a
d iscard able slag is form ed . Th e m atte is th en tran sferred by gravity flow in to th e
con vertin g fu rn ace, w h ere it is con tin u ou sly con verted in to blister cop p er. Th e

converter slag is recirculated to the smelting furnace. Mitsubishi smelters were built
in N aosh im a an d Kid d Creek in 1991 /32,34,35/.
2.4 Outokumpu Flash Smelting Process at Harjavalta

Plant
Th e Flash Sm eltin g Process in volves several stages as d escribed in Figu re 2. Th ese
stages are briefly in th is p aragrap h . Th e sm eltin g an d con vertin g p rocesses are
situ ated in H arjavalta in Western Fin lan d an d th e cop p er refin ery in Pori, abou t
30 kilom etres aw ay. O u toku m p u H arjavalta Metals O y is p art of th e Base Metals
bu sin ess area of O u toku m p u O yj. In 1997 it p rod u ced 200,000 ton s of cop p er an d
n ickel in H arjavalta an d Pori. O u toku m p u H arjavalta Metals O y p rod u ces n early
30 p rod u cts. A con sid erable am ou n t of th e p rod u ction is exp orted .
Th e first cop p er sm elter w as bu ilt in Im atra in 1936. Du rin g th e w ar it w as
rebu ilt in H arjavalta in 1944. Th e Flash Sm eltin g p rocess w as in trod u ced in 1949.
Th e cop p er electrolysis w as bu ilt in 1941 in Pori n ext to th e cop p er sem i-p rod u cts
fabrication . In 1959 an d 1960 th e n ickel Flash Sm eltin g Fu rn ace an d n ickel electrol-
ysis began op eration . Th e last exp an sion of th e w orks w as com p leted in 1996. Th e
n u m ber of p erson n el is abou t 1,000. Th e n u m ber of p erson n el w orkin g on ly in th e
cop p er p rocess is 540.
N early all p arts of th e w orks are certified to ISO 9002 requ irem en ts. Th e last
d ep artm en ts w ill be certified in th e n ear fu tu re. Th e EMAS system of th e cop p er
refin in g p art in Pori w as registered in 1998.
Safety fu n ction s are organ ised as an essen tial p art of n orm al bu sin ess u n it
op eration s.
2.4.1 Raw material reception and storage

Most of th e raw m aterials are im p orted to Män tylu oto h arbou r. Th e con cen trate
is u n load ed d irectly to th e h arbou r tran sit term in al from th e sh ip w ith grabs. Rail-
w ay w agon s are load ed in th e term in al w ith fron t-en d load ers. Th e w agon s are
covered w ith h yd rau lic lid s. Th e w agon s are w eigh ed electron ically both in load -
ed an d em p ty con d ition s. Th e load ed w agon s are d elivered by train to th e H ar-
javalta w orks, w h ich is located som e 45 km from th e h arbou r.
Th e con cen trates are stored in H arjavalta in a large w areh ou se for 50,000 ton s
of con cen trate.
2.4.2 Blending and drying of the concentrate

The concentrates are premixed during feeding to the feeding bins. Precipitates from
th e p rocess are also m ixed w ith th e con cen trates.
Prep aration of p rim ary feed m ixtu re is carried ou t au tom atically by u n load -
in g th e p rop er am ou n t of feed in g m aterial from th e feed in g bin s on to a belt con -
veyor. It is screen ed , cru sh ed an d th e iron p ieces are sep arated by a m agn et sep a-
rator before th e m ixtu re is con veyed to m u lticoil steam d ryers, w h ere it is d ried to
a m oistu re con ten t of less th an 0.2 % as requ ired for flash fu rn ace op eration . H eat
for d rying is supplied by saturated steam. The off-gases from the d ryers are cleaned
in bag filters p rior to d isch arge th rou gh th e stack to th e atm osp h ere. Th e d ry feed
m ixtu re is con veyed to th e flash sm eltin g fu rn ace feed in g bin s by a p n eu m atic
con veyor.

15
2.4.3 Flash smelting
Dried cop p er con cen trate feed m ixtu re is fed by a loss-in -w eigh t feed in g system
in to th e reaction sh aft of th e fu rn ace th rou gh on e con cen trate bu rn er. Th e m ixin g
of gas an d feed is effective an d th e con cen trate p articles react rap id ly in su sp en -
sion w ith oxygen in th e h ot reaction sh aft. In old er in stallation s p rocess air p re-
h eatin g of abou t 200–800°C w as u sed in ord er to ach ieve an au togen eou s reaction ,
but tod ay in the majority of installations autogeneous operation is reached by using
h igh er oxygen en rich m en t, 30–90 % of oxygen in p rocess air. Th e d egree of oxid a-
tion is con trolled by th e total oxygen /con cen trate ratio an d th e tem p eratu re by th e
d egree of oxygen en rich m en t. Th e sm eltin g takes p lace in th e reaction sh aft w ith -
ou t an y extern al fu el ad d ition , i.e. th e ch em ical en ergy of th e con cen trate is u ti-
lised for sm eltin g. Part of th e su lp h u r is oxid ised to form SO 2 an d p art of th e iron
is oxid ised to iron oxid es. Th e iron oxid es an d gan gu e form fayalite slag w ith th e
silica san d fed in to th e fu rn ace in th e feed m ixtu re.
Th e reaction p rod u cts from th e reaction sh aft are sep arated in th e settler p art
of th e fu rn ace. Rich cop p er m atte an d slag sep arate fu rth er in th e bath form ed in
th e settler. Th ey are tap p ed ou t of th e fu rn ace sep arately th rou gh tap p in g h oles
an d lau n d ers. Th e fu m es an d SO 2 from lau n d ers are collected in h ood s. Cop p er
m atte is fu rth er oxid ised in con verters to blister cop p er. It is th en fed in to th e an -
od e fu rn ace for fin al oxid ation an d red u ction before an od e castin g. Th e slag is
cooled in large lad les an d cru sh ed an d grou n d before flotation for cop p er recov-
ery. Th e slag con cen trate is fed in to th e Flash Sm eltin g Fu rn ace togeth er w ith th e
p rim ary con cen trate. Th e rem ain in g con cen tration san d is stable, becau se th e re-
m ain in g sm all am ou n ts of m etals are vitrified in th e silicate m atrix.
Th e fu el bu rn ers in th e fu rn ace are available to en su re fu rn ace tem p eratu re
d u rin g in terru p tion s. Th e flash sm eltin g fu rn ace is p rovid ed w ith a jacket w ater
coolin g system . Warm ed w ater from th e coolin g system is collected an d led to
coolin g tow ers an d th en retu rn ed to th e w ater tan ks.
2.4.4 Gas cleaning

Th e fu m es from slag an d m atte lau n d ers are collected in h ood s an d taken to tail
gas scru bbin g w ith alkalis. Th e gas p rod u ced in th e reaction s in th e reaction sh aft
goes th rou gh an u p take sh aft an d is cooled in a w aste h eat boiler con sistin g of a
rad iation section follow ed by a con vection section . Th e boiler is a forced circu la-
tion boiler, w h ich p rod u ces satu rated steam . Part of th e d u st settles in th e w aste
h eat boiler an d th e rest in th e electrostatic p recip itator. All of th e d u st is collected
togeth er an d con veyed by a p n eu m atic con veyor in to th e flash sm eltin g fu rn ace
flu e d u st bin for recyclin g.
Process gas fan s are located after th e electrostatic p recip itator to m ain tain a
sligh t u n d erp ressu re in th e fu rn ace, w aste h eat boiler an d p recip itator an d blow
th e p rocess gases to su lp h u r recovery. Th e h igh su lp h u r d ioxid e con ten t of th e gas
m akes it p ossible to recover su lp h u r as liqu id SO 2 an d su lp h u ric acid .
Th ere is a sep arate d u ct to carry th e h ot gases by-p assin g th e w aste h eat boil-
er and electrostatic precipitator to the stack. This can be used d uring feed stoppages
an d oth er d isru p tion s, w h en th e gases can n ot be sen t to th e acid p lan t. In stead
th ey are scru bbed before ven tin g ou t th rou gh th e stack.

Concentrate Flux
Copper sludges
Concentrate Dust
unloading
Magn separation
crushing, screening
Steam Steam O ff gas Bag O ff gas to stack

Slag concentrate dryer filter
Air Recirculated
dust O ff
Fuel oil Flash gas Waste heat
O xygen Air smelting heat boiler
plant O xygen furnace
Slag Electrostatic
precipitator
Tailings to tailings area
Slag
concentrator O ff gas to
Fugitive gases Sulfuric stack
SO 2 off H 2 SO 4
collected from acid plant
tapholes and SO 2 plant Liquid SO 2

gas
launders, Hg- Weak acid
By-pass gases removal Hg-sludge
to Kokkola zinc plant
Slag Flux Bag O ff gas to stack

Scrap filter
Coke
Waste heat
O xygen Converters heat boiler
Air
Fugitive Electrostatic
gases precipitator
Fuel oil O ff
LPG Anode gas Bag O ff gas to stack
Air furnaces filter
Anode
casting
Anode
Figure 2. Flowsheet of t he H arjavalt a copper smelt er.
2.4.5 Copper converting

Th e m ain raw m aterial for con vertin g is th e m olten Cu -Fe-S m atte from sm eltin g.
Th e oth er raw m aterials are silica flu x, coke an d oxygen en rich ed air. Cop p er scrap
can also be fed to th e con verter. Con vertin g is d on e in a Peirce-Sm ith con verter as
a batch p rocess. Th e oxygen en rich ed air is blow n in to th e m olten m atte th rou gh
su bm erged tu yeres. Th e p rocess is au togen eou s, th e en ergy u sed is th e ch em ical
en ergy con tain ed in th e m atte.

17
Con vertin g is d on e in tw o stages. Th e first on e is th e slag-form in g stage, in
w h ich iron an d su lp h u r are oxid ised . Th e con verter is ch arged w ith m atte in sev-
eral step s, each step bein g follow ed by th e oxid ation of FeS from th e ch arge. Slag
is skim m ed from th e con verter after each oxid ation step an d a n ew m atte ad d ition
is m ad e. Th e secon d stage is th e cop p er m akin g stage, in w h ich th e su lp h u r in th e
Cu S2 is oxid ised to SO 2. Th e blister cop p er con tain s abou t 99 % cop p er.
Th e con verters are d riven by electric m otors, bu t th ere are p n eu m atic-p ow-
ered m otors for th e au tom atic em ergen cy tu rn ou t. Tu rbo-typ e air blow ers su p p ly
th e p rocess air to th e con verters.
Th e gas p rod u ced in th e con verter is taken th rou gh a tigh tly fitted h ood sys-
tem in to a w aste h eat boiler, w h ere it is cooled by gen eratin g steam from w h ich
th e en ergy is recovered . After th e w aste h eat boiler th e gas is clean ed in an elec-
trostatic p recip itator an d taken to th e su lp h u ric acid p lan t. Th e d u st recovered in
th e electrostatic p recip itator is fed back in to th e Flash Sm eltin g Fu rn ace.
Fu gitive gases from th e con verter h ood s are collected by secon d ary h ood in g
an d treated by bag filter or on e stage w et scru bbin g w ith a d esu lp h u risin g agen t.
2.4.6 Slag flotation

Th e basic fu n ction of slag flotation is to sep arate cop p er from th e slag by u sin g flo-
tation technology and to send the slag concentrate obtained back to the flash smelt-
in g fu rn ace. Th is m eth od offers an extra m ean s of elim in ation of im p u rities in
com p arison to th e electric fu rn ace slag treatm en t w h ere th e m atte form ed is car-
ried straigh t to con vertin g.
Th e slag is cooled in large lad les, first slow ly in th e air an d th en by w ater jets
for 1–2 d ays. Du rin g th e coolin g p eriod th e cop p er an d m atte p articles grow an d
it becom es easier to sep arate th em from th e slag. After th e coolin g p eriod th e slag
is cru sh ed an d grou n d . Cop p er recovery in flotation in creases as th e grin d in g
d egree becom es fin er. Flotation is carried ou t in th ree step s in O u toku m p u flota-
tion cells. Th e slag con cen trate slu rry is p u m p ed from th e flotation cells to a th ick-
en er. Th e th icken ed con cen trate is filtered with a p ressu re filter. Th en th e filter cake
is con veyed to th e d ryer in ord er to be fed in to th e flash sm eltin g fu rn ace. Th e slag
m ill tailin gs are p u m p ed to th e tailin g area n earby. Th e clarified w ater from th e
tailin g p on d is recircu lated to be u sed as p rocess w ater.
2.4.7 Copper refining and anode casting

Blister cop p er is refin ed in th e an od e fu rn ace in ord er to rem ove th e rem ain in g
su lp h u r an d oxygen . Th e su lp h u r con ten t of cop p er m u st be red u ced to th e level
0.005 % so th at an od es w ith a sm ooth su rface can be cast. In th e first step su lp h u r
is rem oved by blow in g air in to th e fu rn ace. As a resu lt th e oxygen con ten t of th e
cop p er is 0.6–0.9 %. In th e secon d step th e extra oxygen is rem oved as gaseou s
carbon m on oxid e an d w ater by in jectin g liqu id p rop an e gas to th e m olten cop p er
u n til th e oxygen con ten t is 0.05–0.2 %. Th e refin ed blister cop p er is th en cast in to
an od es. Th e O u toku m p u -d esign ed au tom atic an od e castin g system p rod u ces
an od es of u n iform sh ap e, size an d w eigh t.
The spent anod es returned from electrorefining are conveyed to the converter
w h ere th ey are fed to th e secon d stage of cop p er con vertin g.
Th e an od e fu rn ace is covered by a m ovable h ood con stru ction . Th e fu rn ace
gases go th rou gh a bag filter to th e stack.

2.4.8 Sulphuric acid plant
Th e gases from th e flash sm eltin g fu rn aces an d th e con verters go th rou gh a d u st
elim in ation step an d on to th e su lp h u ric acid p lan t. Th e gases are m ixed togeth er
an d d ilu ted , if n ecessary to th e p rocessin g con cen tration 8.5–13.5 % SO 2.
Th e con version rate of th e d ou ble con tact p lan ts is h igh er th an 99.7 %. Th e
con cen trated w eak acid p rod u ced in th e first gas w ash in g stage is u sed in
O u toku m p u ´ s zin c p lan t in Kokkola an d in th e Pyh äsalm i m in e. Th e H g p recip i-
tate is also u sed in Kokkola, w h ere O u toku m p u h as a m ercu ry p lan t. Gyp su m an d
in ert p recip itates are taken to a mu n icip al lan d fill. Th e sales p rod u cts from th e acid
p lan t are su lp h u ric acid , liqu id SO 2 an d en ergy.
H2 O Anodes HCl H2 O
steam Thiourea vaporization

Bone glue
H 2 SO 4 (93% ) Electrolysis
Electrolyte bleed
H2 O
Crystallization CuSO4 *5H 2O Grade A

cathodes
Anode
Electrolyte
slime
Liberators Cathodes
Anode scrap
As-removal
H 2 SO 4 (50% ) Liberators
As 2 O3
Cu3 As
CrO 3 Crystallization H2 O
CCA-process
Filtration NiSO 4 *H 2 O
CCA H 2 SO 4 (70% )
Wood preservative
Figure 3. Flowsheet of copper elect rolysis.
2.4.9 Copper electrolysis

Th e fin al refin in g of th e an od e cop p er is carried ou t in electrolytic cells in a tan k
h ou se. Ap p lication of an electrical p oten tial betw een th e cop p er an od e an d a metal
cath od e in a Cu SO 4-H 2SO 4-H 2O electrolyte cau ses th e d issolu tion of cop p er from
th e im p u re an od e an d its d ep osition on th e cath od e. Som e im p u rities are p recip -

19
itated in th e an od e slim e on th e bottom of th e electrolysis cells d u e to th eir in sol-
u bility in th e electrolyte u sed . Th e d issolved im p u rities are taken in th e bleed to
solu tion p u rification (Figu re 3).
Th e in itial cath od es u sed are th in , p u re-cop p er startin g sh eets, w h ich are
p rod u ced in th e refin ery itself. Fu lly grow n cath od es are rem oved from th e cells,
w ash ed w ith w ater an d p acked . Th ey are sold for m eltin g, castin g an d fabrication
of cop p er sem i p rod u cts.
2.4.9.1 Solution purification in copper electrolysis

In th e solu tion p u rification p lan t th e im p u rities are rem oved from th e electrolyte.
To m ain tain th e cop p er su lp h ate balan ce som e of th e cop p er su lp h ate is also re-
m oved by crystallisation an d sold to cu stom ers.
From th e cop p er su lp h ate crystallisation th e electrolyte is con d u cted to a tw o-
step cop p er electrolysis. In th e first step th e cop p er is rem oved from th e solu tion
as cop p er cath od es by electrow in n in g w ith in solu ble lead an od es. Th ese im p u re
cop p er cath od es are retu rn ed to th e sm elter. In th e secon d step arsen ic is electrow-
on as cop p er arsen id e p recip itate on th e cop p er sh eets.
The solution obtained is taken to nickel removal. Nickel is crystallised as nickel
su lp h ate in a vacu u m evap orator. N ickel su lp h ate m on oh yd rate is tran sp orted to
H arjavalta to th e N i p rocess.
The wood preservative CCA is manufactured from the copper arsenid e which
origin ates in electrolytic refin in g. CCA is a sales p rod u ct an d as su ch an excellen t
ou tlet for th e arsen ic in th e p rocess.
Elem en ts n obler th an cop p er form an in solu ble an od e slim e w h ich settles to
th e bottom of th e electrolytic cells. Th e an od e slim e is led from th e electrolysis to
th e Preciou s m etal p lan t.
2.4.9.2 Precious metals recovery
Th e an od e slim e m ain ly con tain s elem en ts electroch em ically n obler th an cop p er

(Te, Se, Ag, Au , Pt, Pd ). Th e slim e slu rry is p u m p ed electrolysis to th e Preciou s
Metals p lan t. In th e O u toku m p u p rocess th e recovery of silver is 97 % an d th at of
gold 99.7 %.
Th e slim e is first leach ed in an au toclave at 170°C w ith 6–7.5 bar oxygen p res-
sure in order to dissolve nickel, copper and tellurium. Tellurium is precipitated from
th e solu tion as cop p er tellu rid e an d sold (Figu re 4).
2.4.9.2.1 Selenium
Selen iu m is recovered from th e filter p ress cake in an electrically h eated fu rn ace
w h ere th e tem p eratu re is arou n d 400–600° C. O xygen an d SO 2 gas are u sed as re-
agen ts. Selen iu m com p ou n d s react at th is tem p eratu re form in g gaseou s selen iu m
d ioxid e. Th e selen iu m d ioxid e gas (SeO 2 (g)), is su cked from th e fu rn ace th rou gh
th e ejector in to an aqu eou s solu tion (Figu re 5). In th is solu tion selen iu m d ioxid e
is red u ced to elem en tal selen iu m by su lp h u r d ioxid e at th e tem p eratu re of 80°C.
Th e selen iu m is com m ercial grad e selen iu m (> 99.5 %). Selen iu m recovery is h igh .
Th e selen iu m con ten t of th e roasted slim e is n orm ally arou n d 0.5% /18–23/.
Du e to th e fact th at th e roaster is fu rn ish ed w ith gas circu lation d evices, it
offers h om ogen ou s atm osp h eric con d ition s th rou gh ou t th e roaster, w h ich lead s
to n early com p lete rem oval of selen iu m d u rin g th e p rocess. Th e ou tlets from th e
fu rn ace are alm ost n il. Th e rem ain in g aqu eou s solu tion is fed back to cop p er elec-
trolysis.

Anode slime O xygen
Autoclave H 2 SO 4 (70% )
leaching
SO 2 (g) Cu scrap
Se, Ag- Tellurium Cu telluride

precipitation cementation Filtrate to electrolyte bleed
SO 2 (g)
Se- Se- Se- Raw selenium

furnace reduction distillation
O xygen Trof- Bag O ff gas to stack

Butane converter filter Fue dust
Dore slag
Dore metal HNO 3
Casting Ag- Smelting &

electrolysis granulation Ag-granules
Gold mud Cu powder
H 2 SO 4 Affination Ag
sementation
Silver bearing
Gold sand concentrate
H2 O 2
HCl Leaching AgCl
Gold Gold Smelting &

precipitation casting Gold bars
PGM Pt/Pd concentrate

precipitation
Figure 4. Flowsheet of precious met al recovery.
2.4.9.2.2 Silver
Th e d eselen ated slim e is m elted w ith flu xes to d oré m etal. After red u ction th e
p rim ary slag is rem oved from th e fu rn ace. Th e im p u rities (Te, Cu , Pb) are oxid ised
an d th e m etal is cast to an od es. Th e d oré m etal con tain s m ain ly silver an d gold ,
som e p latin u m , p allad iu m an d sm all am ou n ts of im p u rities. A secon d ary slag is
p rod u ced in th e oxid ation stage. Th is slag is sold .

21
Concentrate Concentrate Drying
June, 1997
Concentrate
Storage Flash Revision 1
mtpa
% Cu Smelting Furnace gas
Gas cleaning &
FCF slag circulation
Nm 3/h SO 2 Sulphuric acid
mtpa
FCF dust
% Cu
% CaO
production
30%
Furnace slag
mtpa
mtpa
> 2% Cu
70% Cu
FCF gas
Matte
Granulation
Nm 3/h SO 2
Matte Drying
and Grinding
mtpa Lime Flux
70% Cu
Dust circulation
Matte
70% 100 %
Homogenization
Sulphuric acid
Flash Converting
tpd
Anode furnace slag
mtpa
% Cu
Waste slag
EF matte to FCF
mtpa mtpa
% Cu
FCF slag Slag Cleaning < 1% Cu
mtpa
% Cu
% CaO Blister Copper
mtpa
0.2% S
Cathode Copper
mtpa
Anode Refining & Electrolytic Refining

Casting
Figure 5. Copper product ion by Flash Smelt ing and Flash Convert ing.
Th e d oré an od es are electrolysed to silver in aqu eou s silver n itrate solu tion .
Th e silver crystals are d ep osited on cath od es. Th e elemen ts w h ich are n ot leach ed ,
like gold and platinum group metals, fall to the bottom of the anod e-bags. The crys-
tallin e silver is m elted at 1,300°C an d gran u lated . Th e silver gran u les are d ried ,
w eigh ed an d p acked .
2.4.9.2.3 Gold
Th e slim e from th e an od e bags is leach ed w ith h yd rogen p eroxid e an d h yd roch lo-
ric acid to recover gold an d p latin u m m etals. Gold is red u ced from th e solu tion

by bisu lp h ate an d filtrated . Th e gold san d is m elted an d cast in to gold bu llion s.
Th e p latin u m grou p m etals are recovered from th e solu tion as Pt/Pd con cen trate,
w h ich is sold as su ch .
2.4.10 U tilities and Off-Sites at the Harjavalta plant
2.4.10.1 Electric Power Supply
Th e m ain p art of th e electricity u sed is p u rch ased from th e p u blic grid . Th e O u to-
kumpu power plant prod uces electrical energy from the extra steam from the waste
h eat boilers of th e flash fu rn aces an d con verters. Th is en ergy is u sed for in -p lan t
h eatin g an d sold for d istrict h eatin g. En ergy red u ction an d con servation tech -
n iqu es are p revalen t th rou gh ou t th e p lan t.
2.4.10.2 Steam and Condensate System

Th e h ot gases p rod u ced in th e flash sm eltin g fu rn aces an d cop p er con verters are
cooled in w aste h eat boilers by gen eratin g steam . Th e steam form ed is u sed in th e
d ryin g of th e con cen trates, in th e p rew armin g of th e p rocess air for th e flash smelt-
in g fu rn aces an d in th e n ickel p rocess. Th e p ow er p lan t p rod u ces electric en ergy
from th e extra steam .
2.4.10.3 Fuels Supply

All fu els u sed are su p p lied to th e p lan t. Coke is stored in a storage bu ild in g. Th e
oil storage vessels are stored at th e p ow er p lan t. Prop an e is also stored in a stor-
age vessel. Both oil an d p rop an e are d istribu ted via th eir ow n p ip elin es to th e
variou s p lan ts.
2.4.10.4 Oxygen Supply

O n th e site th ere are also oxygen an d h yd rogen p lan ts. Th e th ree oxygen p lan ts
p rod u ce oxygen for sm eltin g an d at th e sam e tim e som e argon , w h ich is sold .
Th e tw o h yd rogen p lan ts p rod u ce h yd rogen for th e n ickel p rocess. H yd ro-
gen is also u sed in th e p u rification of argon .
2.4.10.5 Process Effluent and Surface Water Treatment
All w aste an d rain w ater is collected an d p u m p ed to reactors w h ere all m etals are
p recip itated w ith sod iu m h yd roxid e. Th e slu d ge form ed is taken to clarification
basin s. Th e overflow is p u m p ed to san d filters. Th e filtered w ater is d isch arged to
th e river. Th e slu d ge from th e bottom of th e clarification basin is p u m p ed to a
slu d ge basin . Th e settled slu d ge is tran sferred to a san d bed . Th e filled san d bed
is d ried an d fed to th e flash smeltin g fu rn ace. Th e w ater overflow s from th e slu d ge
treatm en t are collected in th e rain w ater basin , from w h ich th ey are taken back to
th e begin n in g of th e p rocess.

23
2.4.11 U tilities and Off-Sites in the copper electrolysis at Pori
2.4.11.1 Electric Power Supply

Th e refin ery h as n o p ow er p lan t. Electricity is p u rch ased from th e p u blic grid .
En ergy red u ction an d con servation tech n iqu es are p revalen t th rou gh ou t th e re-
fin ery.
2.4.11.2 Steam and Condensate System

Steam is bou gh t from th e m u n icip al p ow er p lan t.
2.4.11.3 Fuel Supply

Th e refin ery is con n ected to th e m ain fu el gas p ip elin e of th e cop p er-sem is fabri-
cation p lan t located on th e sam e site.
2.4.11.4 Process Effluent and Surface Water Treatment

All p rocess w aters are in a closed circu it an d n o efflu en ts are d isch arged from th e
cop p er refin in g p lan t. Th e su rface w aters are taken to th e river w h ich bord ers th e
refin ery.
2.4.12 Commercial Quality Control and Process Control Laboratories

Th ere is a w ell-equ ip p ed m od ern an alytical laboratory in H arjavalta. It h as th ree
assay team s, th e first on e for com m ercial assays, th e secon d on e for p rod u ct assays
an d th e th ird on e for p rocess an d en viron m en tal assays. Th e sam p lin g team su p -
p lies rep resen tative sam p les to th e laboratory.
In th e cop p er refin ery in Pori th ere is a sm all laboratory for an alysin g som e
of th e local p rocess sam p les. O th er p rocess sam p les are sen t to H arjavalta.
2.5 Outokumpu Flash Converting

H igh grad e m atte is gran u lated d irectly from th e flash sm eltin g fu rn ace w ith ou t
an y lad le tran sp ort (see Figu re 5). Th u s th e revert formation rate an d th e emission s
to th e w orkin g atm osp h ere are low. Gran u lated m atte is grou n d an d sim u ltan e-
ou sly d ried in a roller m ill before feed in g in to th e flash con vertin g fu rn ace.
Cop p er m atte is sm elted w ith oxygen en rich ed air (65–75 % O 2) in th e flash
con vertin g fu rn ace in w h ich th e ch em ical en ergy of th e m atte is u sed in ord er to
p rod u ce m olten blister cop p er an d slag. Th e d u st can be recircu lated back in to th e
flash con vertin g fu rn ace or in to th e flash sm eltin g fu rn ace in ord er to recover th e
valu able m aterials in th e d u st.
Th e same ch emical en ergy con tain ed in th e matte th at is u sed in con ven tion al
Peirce-Sm ith con vertin g is also u tilised in flash con vertin g. Th e reaction s in th e
sh aft are m ain ly exoth erm ic. Most of th e tim e both flash sm eltin g an d flash con -
vertin g fu rn aces are able to op erate au togen ou sly w ith h igh oxygen en rich ed air
on ly, w ith ou t extern al fu el for sm eltin g. H igh oxygen en rich m en t in both fu rn ac-
es also m ean s th at th e gas volu m e leavin g both fu rn aces is low an d th erefore th e
in vestm en t costs of gas clean in g are also low an d h igh su lp h u r recovery is p ossi-
ble.
In th e reaction sh aft th e m atte p articles are h eated rap id ly an d th ey ign ite.
Th e oxid isin g reaction s th erefore p roceed very fast. Metallic blister cop p er an d slag

sep arate in th e settler p art of th e fu rn ace. Th e blister cop p er is tap p ed from th e
flash con vertin g fu rn ace via lau n d ers d irectly in to th e an od e fu rn ace. Th e slag is
gran u lated before feed in g back in to th e flash sm eltin g fu rn ace for th e recovery of
valu able m aterial. O n e op tion is to retu rn th e slag in m olten form to th e flash
sm eltin g fu rn ace. Both blister an d slag lau n d ers are covered by a h ood in ord er to
collect fu gitive em ission s an d SO 2.
Process gas, rich in SO 2, flow s con tin u ou sly th rou gh coolin g an d clean in g
step s to th e su lp h u r recovery p lan t. Su lp h u r recovery can be over 99.9 %.
As th e tw o sm eltin g p rocesses are n ot d irectly con n ected togeth er, it is p ossi-
ble to op erate on e fu rn ace even if th e oth er is n ot op eratin g. Th is en su res h igh on -
lin e availability for th e w h ole p rocess /3-14/.
2.6 Outokumpu Direct Blister Smelting

Cop p er con cen trates con tain in g over 35 % cop p er or sp ecial low iron con cen trates
can be econ om ically treated by th e Direct Blister Flash Sm eltin g Process. Su itable
con cen trates can be m ad e from ch alcocite or born ite-ch alcocite ores, w h ich h ave
h igh cop p er con ten ts or w h ose cop p er/iron ratios are h igh com p ared to ch alcop -
yritic con cen trates.
A d ried cop p er con cen trate feed m ixtu re is fed in to th e reaction sh aft of th e
flash smeltin g fu rn ace th rou gh on e con cen trate bu rn er. Th e mixin g of gas an d feed
m ixtu re is effective an d th e con cen trate p articles react rap id ly in su sp en sion w ith
oxygen in th e h ot reaction sh aft. Th e sm eltin g takes p lace au togen ou sly in th e
reaction sh aft w ith ou t an y extern al fu el ad d ition , i.e. th e ch em ical en ergy of th e
con cen trate is u tilised for sm eltin g. Su lp h u r is oxid ised to form SO 2 an d iron is
oxid ised to iron oxid es. Th e iron oxid es form fayalite slag w ith th e silica san d fed
in to th e fu rn ace in th e feed m ixtu re.
Th e reaction p rod u cts from th e reaction sh aft are sep arated in th e settler p art
of th e fu rn ace. Blister cop p er an d slag sep arate fu rth er in th e bath form ed in th e
settler. Th ey are tap p ed ou t of th e fu rn ace sep arately th rou gh tap p in g h oles an d
lau n d ers. Th e fu m es an d SO 2 from th e lau n d ers are collected by h ood s. Blister
cop p er is th en fed in to th e an od e fu rn ace for fin al oxid ation an d red u ction before
an od e castin g. Cop p er in th e slag is recovered in an electric slag clean in g fu rn ace.
Th e w aste slag from th e slag clean in g fu rn ace is stable becau se th e sm all am ou n ts
of m etals left are vitrified in th e silicate m atrix.
Th e gas p rod u ced in th e reaction s in th e reaction sh aft goes to a w aste h eat
boiler, w h ere it is cooled by gen eratin g steam from w h ich th e en ergy is recovered .
After th e w aste h eat boiler th e gas is clean ed in an electrostatic p recip itator an d
rou ted to su lp h u r recovery. Th e h igh su lp h u r d ioxid e con ten t of th e gas m akes it
p ossible to recover su lp h u r as liqu id SO 2 an d su lp h u ric acid . Th e d u st recovered
in th e electrostatic p recip itator is fed back to th e Flash Sm eltin g Fu rn ace /15-17/.
2.7 Hydrometallurgical Copper Production

Th e research d on e to d evelop leach in g p rocesses for su lp h id e con cen trates h as
resu lted in mu ch bein g learn t abou t th e ways in wh ich su lp h id e min erals react an d
it h as been recogn ised th at th ere are m arked d ifferen ces in th e stability an d ease
of d issolu tion of variou s su lp h id es. Am on gst th e cop p er su lp h id e m in erals, ch al-
cocite, Cu 2S, is th e easiest to d issolve an d ch alcop yrite, Cu FeS2, th e m ost abu n d an t
cop p er m in eral, is th e m ost refractory an d d ifficu lt to leach .
O f th e m an y p rocesses th at h ave been p rop osed for th e h yd rom etallu rgical
p rod u ction of cop p er, th e majority h ave been d evelop ed on ly as far as ben ch scale,

25
a few h ave reach ed p ilot scale an d on ly th ree h ave been commercialised . Th e Clear
an d Arbiter p rocesses op erated for on ly a few years an d p roved to be com m ercial
failu res, p rim arily becau se th ey w ere n ot able to p rod u ce cop p er of a h igh en ou gh
qu ality at a com p etitive p rice.
Th e Escon d id a p rocess h as been in u se for som e years. It is an am m on ia leach
to d issolve on e cop p er from Cu 2S an d leave Cu S u n d issolved . Dissolved cop p er is
tu rn ed in to m etallic cop p er by solven t extraction -electrow in n in g. Cu S is con cen -
trated an d m elted . Th e p lan t w as, h ow ever, closed in sp rin g 1998 d u e to low cop -
p er p rices.
2.7.1 Copper heap leaching

Th e m ost com m on w ay to p rocess cop p er su lp h id e ores, th e flotation -sm eltin g-
refin in g p rocess, accou n ts for over 80 % of global cop p er p rod u ction . Th e h yd ro-
m etallu rgical rou te, leach in g-solven t extraction -electrow in n in g, is exp ected to
accou n t for 20 % of w orld cop p er p rod u ction by th e year 2000. Th e figu re con sists
m ain ly of oxid e cop p er ores (azu rite, m alach ite, ten orite, ch rysocolla, broch an tite,
en argite), bu t h as recen tly been exp an d ed to in clu d e su lp h id e ores (ch alcocite,
covellite, born ite). Th e leach in g of su lp h id e ores is catalysed by com m on iron an d
su lp h u r oxid isin g bacteria /24,25/. Th e cop p er h eap leach in g flow sh eet is sh ow n
in Figu re 6.
The main minerals leached on industrial scale today are porphyry copper ores.
Most of th ese ore d ep osits can be m in ed as low cost op en -p it m in es becau se of th e
geology of th ese min eralization s. Th e ore p rep aration , ore p lacemen t, h eap d esign ,
solu tion ap p lication an d solu tion m an agem en t are u su ally d esign ed con sid erin g
th e sp ecific ore typ e, th e local geology an d clim ate.
2.7.1.1 Crushing
Th e h eap leach in g of cop p er n orm ally requ ires a com m in u tion step . Th is ach ieves
th e d esired size ran ge to op tim ise cop p er recovery an d lon g-term ore p erm eabil-
ity. Th e size of th e cru sh ed p rod u ct is n orm ally betw een 6 an d 20 m m d ep en d in g
on th e ore typ e. O n e lim it im p osed on th e fin es con ten t h as been a m axim u m of
10 to 15 %–100 m esh . A bigger fin es con ten t red u ces th e ore p erm eability in h eap
leach in g an d su bsequ en tly th e u ltim ate cop p er recovery.
Cru sh in g h as th ree stages w h ere th e last stage, tertiary cru sh in g, u ses th e
w ater flu sh tech n iqu e. O re is fed to th e p rim ary cru sh er an d th e d isch arge feed s
th e ad jacen t secon d ary con e cru sh ers. Cru sh ed ore is th en con veyed to a stock-
p ile. From th e stockp ile th e ore is fed to tertiary w ater flu sh cru sh ers. After terti-
ary cru sh in g th e ore p u lp is screen ed w ith d ou ble d eck screen s. Th e oversize is
recycled to cru sh in g an d th e in term ed iate size is fed to h eap leach in g. Th e cyclon e
slime is th icken ed an d th e u n d erflow is tran sp orted by gravity to th e d isp osal area.
Dry cru sh in g h as been fu rn ish ed w ith an effective d u st collection system ,
w h ich takes th e d u st back to th e p rocess after agglom eration w ith m oistu re.

Run of mine ore feed
PRIMARY CRUSHING
SEC.& TERT. CRUSHING
water
AGGLO MERATIO N
sulphuric acid
HEAP LEACHING
PREGNANT SO LUTIO N
PO ND
SO LVENT EXTRACTIO N RAFFINATE SO LUTIO N

PO ND
STRIPPING
ELECTRO WINNING
grade A cathodes
Figure 6. Flowsheet of t he copper heap leaching process.
2.7.1.2 Agglomeration
Th e cru sh ed ore is agglomerated w ith su lp h u ric acid an d w ater in a rotatin g d ru m.
In ord er to get good agglom erates w ith cru sh ed ore a w ettin g m ed iu m is n eed ed .
Th is can be w ater or raffin ate solu tion . If th e ore is su lp h id e ore, raffin ate or a bac-
terial in ocu lu m is u sed in ord er to get th e bacteria even ly d istribu ted th rou gh ou t
th e wh ole h eap . Agglomeration bin d s th e fin e p articles to th e su rface of th e coarser
p articles, p assivates th e silicate su rfaces an d low ers th e con cen tration of im p u ri-
ties in th e p regn an t leach in g solu tion . After agglom eration th e ore is left to rest,
“to cu re”, for at least 24 h ou rs. Du rin g th is p eriod th e solven t w ill start to attack
th e ore m akin g th e leach in g p eriod sh orter an d easier.

27
2.7.1.3 H eap building
O xid e an d su lp h id e ores are stacked an d leach ed sep arately d u e to d ifferen t re-
qu irem en ts in th eir leach in g beh aviou r. Th e base of th e leach in g area is levelled ,
com p acted an d covered w ith an H DPE lin in g. Th e in clin ation of th e base is 5 %
tow ard s th e collection d itch of th e p regn an t leach in g solu tion . Th e m ain d rain in g
p ip es are p laced at 6 m etre in tervals from each oth er d irectly on th e lin er. Th e aer-
ation of su lp h id e h eap s is p rovid ed by p ip es p u t every six m eters in th e h eap bot-
tom to p erm it oxygen flow for th e bioleach in g.
Th e tran sp ortation of th e ore to th e oxid e or su lp h id e h eap leach area is p er-
form ed by overlan d con veyors. Th e stockp ilin g of th e h eap s is d on e by grassh op -
p er con veyors an d rad ial stackers. Th e su lp h id e ore is stacked in 6 m etre h igh lifts
an d th e oxid e ore in 8–12 m lifts.
Th e leach in g solu tion is ap p lied on top of th e h eap by d rip p ers. Th ey are
p laced on a grid p attern of 0.8 by 1 m . Th e raffin ate solu tion from th e solven t ex-
traction p lan t is p u m p ed to large h ead ers ru n n in g th e len gth of th e h eap . Secon d -
ary h ead ers carry th e solu tion to th e top of th e h eap . Th e solu tion is ap p lied at th e
rate of 5–10 l/h /m 2.
2.7.1.4 H eap leaching
Th e raffin ate solu tion from solven t extraction is ap p lied to th e top of th e h eap by
d rip p ers at a rate of 5–10 l/h /m 2. Irrigation is con tin u ed u n til th e cop p er con cen -
tration in solu tion falls u n d er a p re-estim ated valu e i.e. 0.5 g/l. Th e leach in g tim e
for oxid e ore is n orm ally from 50 to 100 d ays. Su lp h id e ore n eed s a m u ch lon ger
tim e, abou t 300 d ays.
Th e d ifferen ce betw een th e leach in g m ech an ism s of oxid e an d su lp h id e cop -
p er ore is th at th e oxid e ore is on ly leach ed w ith p roton s (H + ), bu t su lp h id e ores
n eed oxygen , p roton s (H + ) an d active bacteria (Thiobacillus ferrooxidans, Thiobacil-
lus Thiooxidans, Leptospirillum ferrooxidans etc.) Th e m ain p oin t in th e leach in g of
oxid e cop p er ore is p rop er irrigation an d w ettin g of p articles in sid e th e h eap , bu t
th e leach in g of su lp h id es n eed s en ou gh d issolved air in th e leach in g liqu or an d
correct livin g con d ition s for th e bacteria, e.g. tem p eratu re, p H, n u trien ts, oxygen
an d carbon d ioxid e.
2.7.1.5 Solvent extraction

In th e solven t extraction p rocess for cop p er th e solu tion p u rification stage after
leach in g is carried ou t by a liqu id -liqu id extraction p rocess. In th e first stage cop -
p er is selectively extracted from th e p regn an t solu tion to th e organ ic p h ase. In th e
secon d stage, cop p er is selectively strip p ed from th e organ ic p h ase to th e aqu e-
ou s electrolyte, w h ich is th en rou ted to electrow in n in g.
In th e liqu id -liqu id extraction p rocess th e sep aration of th e d ifferen t p h ases
is very im p ortan t in ord er to be able to p rod u ce h igh grad e cop p er in th e elec-
trow in n in g p rocess an d to avoid organ ic p h ase reagen t losses in to th e leach in g
p rocess. Th e solu tion in th e O u toku m p u VSF (Vertical Sm ooth Flow ) p rocess to
th is is th at p u m p in g an d m ixin g are sep arated . With a sop h isticated p u m p in g
d evice (DO P, Disp ersion O verflow Pu m p ) an d a h elical, low sh earin g stirrer th e
droplet size of the dispersed phase can be maintained ideal for copper mass transfer
betw een th e p h ases. At th e sam e tim e th e form ation of sm all d rop lets an d an
em u lsion can be avoid ed . In ad d ition , th e sp ecific en ergy con su m p tion of th e
w h ole m ixer-settler is low er th an in con ven tion al p rocesses.
After th e d isp ersion stage th e p h ases are sep arated in a n ew ly d esign ed set-
tler, w h ich m akes it p ossible to red u ce th e settlin g tim e i.e. to in crease th e sp ecific

flow rate of th e p rocess u n it an d still to obtain a clear p rod u ct solu tion from th e
cop p er solven t extraction circu its.
Sm ooth m ixin g of th e p h ases also p reven ts th e con tact of oxygen in th e air
an d th e organ ic p h ase. Th is p reven ts th e loss of organ ic reagen ts by d egrad ation
an d also red u ces cru d form ation in th e p rocess. Th e ten d en cy for cru d form ation
as w ell as reagen t d egrad ation are fu rth er red u ced by coverin g th e p rocess u n its
so th at d u st can n ot settle in th e p rocess u n its. Th is also red u ces th e ch an ce of vol-
atile organ ic carbon em ission s to th e en viron m en t from th e organ ic p h ase.
Th e p rocess is able to op erate in variable con d ition s. N orm ally th e tem p era-
tu re at leach in g-solven t extraction -electrow in n in g p lan ts varies a lot d ep en d in g
on th e tim e an d d ate. H ow ever, th e variable sp eed p u m p in g an d m ixin g are able
to resp on d to th e variation s of viscosity cau sed by tem p eratu re ch an ges as w ell as
flow rate variation s /62-67/.
2.7.1.6 Electrowinning
Strip p in g th e load ed solven t p rod u ces a relatively sm all volu m e of aqu eou s solu -
tion , typ ically con tain in g 40–50 g/l cop p er w ith low levels of im p u rities. Th is solu -
tion is p u m p ed to th e tan k h ou se for electrow in n in g.
Electrow in n in g is th e fin al stage in th e p rod u ction of cop p er in th e leach in g-
solven t extraction -electrow in n in g p rocess. Th e acid ic cop p er su lp h ate solu tion is
p assed th rou gh cells in w h ich in solu ble an od es (p ositive) an d cath od es (n egative)
are su sp en d ed . Th e an od es are m ad e from a lead , tin an d calciu m alloy an d th e
p erm an en t cath od es are m ad e of stain less steel. Th e reaction occu rrin g in th e cell
is:
CuSO 4 + H 2O —> Cu + H 2SO 4 + 0.5O 2 (1)
Th e regen erated acid , con tain in g abou t 20–30 g/l cop p er, is recycled to th e solven t
extraction p lan t to be u sed as strip p in g solu tion . O xygen is released at th e an od e.
Abou t on ce a w eek th e cath od es are rem oved , w ash ed an d th e cop p er is
strip p ed u sin g au tom ated strip p in g m ach in es, w h ich sam p le, w eigh , m ark an d
strap th e cath od es in bu n d les of 2.5 ton n es read y for th e m arket.

29
3 P r esen t Con su m p t i on a n d
Em i ssi on Lev el s
○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
3.1 Present Consumpion Levels

3.1.1 Energy consumption
Th e en ergy con su m p tion u sed in cop p er p rod u ction in H arjavalta w as as follow s
in 1996:
3.1.1.1 Copper smelting from concentrate to anodes
Prod u ction cap acity 160,000 t/a, cap acity u tilisation 94 %

oil 50 – 70 kg/ t Cu
elect r icit y 50 0 – 70 0 kWh/ t Cu
3
na t ur a l ga s 30 – 60 Nm / t Cu
coke 30 – 50 kg/ t Cu
oxygen 70 0 – 8 0 0 kg/ t Cu
3.1.1.2 Copper refining
Prod u ction cap acity 130,000 t/a, cap acity u tilisation 96 %

elect r ica l ener gy 320 – 390 kWh/ t Cu
3.1.1.3 Energy recovery

Th e h ot gases p rod u ced in th e flash sm eltin g fu rn ace an d cop p er con verters are
cooled in w aste h eat boilers by gen eratin g steam from w h ich th e en ergy is recov-
ered . Th e steam form ed is u sed for exam p le in th e d ryin g of con cen trates, in th e
p re-w arm in g of th e p rocess air from th e flash sm eltin g fu rn ace an d in th e n ickel
p rocess. Electricity is mad e from th e extra steam in th e p ower p lan t. In 1996 389,640
t of steam w as regen erated from th e w aste h eat boilers. 52,230 MWh w as sold as
d istrict h eat an d 32,230 MWh w as u sed for th e h eatin g of th e p lan t an d w orkers
h ou ses.
3.2 Environmental Emissions

3.2.1 General
Th e m ain en viron m en tal issu es in th e refin ed cop p er p rod u cin g in d u stry are air
an d w ater p ollu tion an d th e gen eration of h azard ou s w astes. In gen eral, cop p er
plants have their own water treatment plants. This chapter d escribes emissions and
abatem en t tech n iqu es for air an d w ater p ollu tion as w ell as w aste p rod u ction an d
treatm en t in th e Fin n ish cop p er in d u stry.
O u toku mp u p rod u ces cop p er an d n ickel at its H arjavalta p lan t. Both p rod u c-
tion p rocesses u se th e O u toku m p u flash sm eltin g tech n iqu e an d u se su lp h id ic
con cen trates in th is in tegrated p rocess. Th e m ain en d p rod u cts are an od e cop p er,

electrolytic n ickel an d n ickel p ow d er. Th e em ission s to air an d w ater m easu red are
a resu lt of th is in tegrated p rocess. Th e on ly w ay to get d ata on th e cop p er p rocess
is to d ivid e th e em ission s by th e ratio of th e cop p er an d n ickel p rod u ced .
Th e cop p er an od es p rod u ced are refin ed to cath od es at th e Pori p lan t situ at-
ed 30 km from H arjavalta. Th e Pori p lan t con sists a cop p er refin ery, fou n d ries an d
cop p er sem i-p rod u cts fabrication . Th e em ission s to w ater m easu red are again re-
su lts from th e w h ole p lan t.
Th e p rod u ction valu es for 1997 w ere:
Cu a nodes 159,30 0 t
Ni 35,30 0 t
H2 SO4 58 0 ,20 0 t
SO2 ( liquid) 35,90 0 t
Cu ca t hodes 116,30 0 t
Au 3,90 0 kg
Ag 32,20 0 kg
Se 4 3,20 0 kg
NiSO4 90 0 t
CuSO4 3,20 0 t
Pt - , Pd- concent r a t e 4 50 kg
CCA wood pr eser va t ive 1,74 0 t
Cu t ellur ide 4 ,20 0 kg
3.2.2 Emissions to air

Th e em ission s to air con sist of p articu late m atter an d SO 2. Su lp h u r d ioxid e gas
com es from th e flash sm eltin g fu rn ace an d con verters. It is rou ted to th e su lp h u -
ric acid p lan t. Du st is form ed w h en ever th e con cen trate is h an d led , d u rin g con -
cen trate u n load in g, steam d ryin g, in th e flash sm eltin g Fu rn ace, in th e con vert-
ers, in th e an od e fu rn ace an d in th e slag con cen tration p lan t. All th ese d u st-con -
tain in g gases are rou ted th rou gh bag filters to th e stack. All collected d u st is sen t
back to th e flash sm eltin g fu rn ace.
Th e sou rces of d u st an d su lp h u r d ioxid e are sh ow n in Table 5.
Ta ble 5. Releva nce of com ponent s wit h r espect t o a ir pollut ion.
Em ission sour ce Dust a nd m et a l com pounds Sulphur dioxide
Ma t er ia l ha ndling r eleva nt not r eleva nt

St or a ge r eleva nt not r eleva nt
Dr ying r eleva nt r eleva nt

Scr a p t r ea t m ent r eleva nt not r eleva nt
Sm elt ing r eleva nt r eleva nt *
Sla g t r ea t m ent r eleva nt not r eleva nt

La dle t r a nsfer s r eleva nt not r eleva nt
Conver t ing r eleva nt r eleva nt *
Fir e r efining r eleva nt not r eleva nt

Anode ca st ing r eleva nt not r eleva nt
Elect r or efining r eleva nt not r eleva nt
Sulphur ic a cid pla nt not r eleva nt r eleva nt

* t he emissions from t he smelt ing and convert ing st ages are t reat ed in t he gas cleaning st eps and t he sulphuric acid plant ; t he
remaining emissions of sulphur dioxide from t he sulphuric acid plant are st ill relevant .

31
Beside these process emissions, components will also be emitted diffusely. This
can lead to locally en h an ced con cen tration levels. Th e abatem en t of th is fu gitive
em ission is an on goin g p rocess an d d em an d s good h ou sekeep in g. Possible m eas-
u res in clu d e better sealin g of equ ip m en t, forced ven tilation com bin ed w ith bag
filters etc.
3.2.2.1 Sulphur dioxide

Su lp h u r d ioxid e can be em itted from th e p rim ary feed p rep aration an d d ryin g
stages bu t th e amou n t is u su ally very low so th at simp le gas scru bbin g is ad equ ate.
Th e m ost sign ifican t sou rces of su lp h u r d ioxid e are th e sm eltin g an d con vertin g
stages. Th e sealed Flash Sm eltin g Fu rn ace allow s th e su lp h u r d ioxid e to be collect-
ed . Th e oxygen en rich m en t u sed p rod u ces a h igh su lp h u r d ioxid e con cen tration
w ith m in im al variation s in con cen tration . Th is th erefore allow s efficien t con ver-
sion to su lp h u ric acid in th e d ou ble con tact su lp h u ric acid p lan t.
Th e con version stage u sin g th e Peirce-Sm ith con verter also p rod u ces a sig-
n ifican t con cen tration of su lp h u r d ioxid e. It is n ot as w ell sealed as th e sm eltin g
stage. Th e feed in g an d tran sfer of m atte is a sign ifican t sou rce of fu gitive fu m es.
Th e su lp h u r d ioxid e con cen tration in th e gases varies sign ifican tly d ep en d in g on
th e stage of th e con version . Several con verters are th erefore u sed in a p h ased se-
quential operation and the off-gases are combined to red uce this effect. These gases
are m ixed w ith th e stead y, m ore con cen trated gases p rod u ced by th e Flash Sm elt-
in g Fu rn ace to m ain tain stead y con d ition s in th e su lp h u ric acid p lan t.
After h eat recovery an d clean in g in electrostatic p recip itators th e gases are
m ixed togeth er an d d ilu ted , if n ecessary, to th e p rocessin g con cen tration of 8.5–
13 % SO 2. O n e sou rce of su lp h u r d ioxid e em ission is also th e su lp h u ric acid p lan t,
w h ere th e gas is con verted w ith an efficien cy of 99.7 % to su lp h u ric acid in th e
d ou ble absorp tion p rocess.
3.2.2.2 D ust and dust-bound metals

Th ese can be em itted from m ost stages of th e p rocess. Direct an d fu gitive d u st
em ission s from th e sm eltin g, con vertin g an d refin in g stages are p oten tially h igh .
Th e sign ifican ce of th e em ission s is also h igh as th ese p rocess stages are u sed to
rem ove volatile m etals su ch as Zn , Pb, As, Cd an d H g from cop p er an d th ese m et-
als are p resen t in th e d u st. Th e Flash Sm eltin g Fu rn ace is effectively sealed to m in -
im ise fu gitive em ission s. Good m ain ten an ce of th e fu rn ace an d d u cts is p ractised
an d th e gases are treated in d u st rem oval system s an d a su lp h u r recovery p roc-
ess.
Th e con version an d fire refin in g stages are n ot as w ell sealed as th e sm eltin g
stage. Th e feed in g an d tran sfer of m atte is a sou rce of fu gitive fu m es. More im p or-
tan tly th e u se of th e lad le tran sfer system is a sign ifican t sou rce of fu m e an d also
in h ibits th e effectiven ess of th e fu m e collection h ood s w ith th e Peirce-Sm ith con -
verters.
Electrolysis aerosol em ission s take p lace in th e h all. Th ese em ission s leave th e
h all via n atu ral ven tilation . Metal aerosols from electrolysis are con sid ered to be
relevan t.
Th e m ain em ission s from th e cop p er refin ery com e from th e p reciou s m etals
p lan t. In th e selen iu m fu rn ace th e selen iu m d ioxid e gas is su cked from th e fu rn ace
th rou gh an ejector in to an aqu eou s su lp h u ric acid solu tion w h ich is recircu lated
in the process. Some SO 2, selenium and d ust is emitted through the exhaust air tube
from th e recircu lated solu tion tan k. Th e em ission s are taken to th e p reciou s m et-
als p lan t stack.

Th e d eselen ated slim e is m elted in th e Trof con verter. Th e gases from th e fu r-
n ace an d its en viron m en t are taken to bag filters. Som e SO 2, selen iu m an d d u st
p en etrate th rou gh th e filter m em bran e.
Th e th ird p ossible em ission from th e p reciou s m etal p lan t com es from th e
p rep aration of silver n itrate w h en silver gran u les are d issolved in n itric acid . Th e
N O x-fu m es are w et scru bbed from th e gas p h ase.
3.2.3 Legislation and regulation in Finland

Fin lan d h as n o sin gle en viron m en tal law at th e m om en t. En viron m en tal legisla-
tion is com p osed of a n u m ber of in d ivid u al acts /27/. A n ew En viron m en tal Pro-
tection Act is currently und er preparation and will combine the environmental acts
accord ing to the requirements of the Council Directive 96/61 /EC of September 1996
con cern in g in tegrated p ollu tion p reven tion an d con trol (IPPC).
Presen tly, th e in tegrated ap p roach is in clu d ed in th e tw o sep arate p erm it
p roced u res: th e en viron m en tal p erm it p roced u re, accord in g to th e En viron m en -
tal Perm it Proced u re Act (735/1991) an d Decree (772/1992) an d th e w ater d isch arge
p erm it p roced u re, accord in g to th e Water Act (264/1961) an d Decree (282/1962).
Th e En viron m en tal Perm it Proced u res Act com bin es th e p erm it p roced u res
of th e Air Pollu tion Con trol Act an d Decree, th e Waste Act an d Decree, th e H ealth
Protection Act an d Decree an d th e Ad join in g Prop erties Act. Th e com p eten t au -
th ority in en viron m en tal p erm it m atters is, d ep en d in g on th e lin e of activities,
eith er th e Region al En viron m en t Cen tre or th e local en viron m en tal board .
Wh en d isch argin g w aste w aters, th e Region al En viron m en t Cen tre m u st be
notified in advance regarding any plans for the discharge of wastewater in the cases
listed in th e Prior N otification Decree. Th e Cen tre assesses th e n otification an d
ju d ges w h eth er th e activity w ill cau se w ater p ollu tion . If p ollu tion is u n avoid a-
ble, th e p ollu ter m u st ap p ly for a p erm it from th e Water Cou rt or from th e local
en viron m en tal board . Su bstan tial p ollu ters sen d th eir ap p lication s d irectly to th e
Water Cou rt. Pollu tin g of grou n d w ater is totally forbid d en ; th is m ean s th at n o
p erm it can be gran ted for d isch argin g p ollu tan ts in to th e grou n d w ater.
In the metallurgical ind ustry, an environmental permit granted by the Region-
al En viron m en t Cen tre an d a w ater d isch arge p erm it gran ted by th e Water Cou rt
are n eed ed .
Alth ou gh th e en viron m en tal legislation is based on a sectoral ap p roach , th e
p erm it system in each sector follow s certain u n iform lin es in clu d in g th e follow-
in g elem en ts (both in en viron m en tal an d w ater p erm it m atters):
• An ap p lication d escribin g th e activity an d its en viron m en tal effects is to be
su bm itted to th e com p eten t au th ority. Th e d ata an d in form ation th at th e
op erator of an in d u strial p lan t (th e ap p lican t) h as to su bm it in th e form of an
ap p lication to th e au th ority is p rescribed in th e above m en tion ed Acts an d
Decrees.
• Th e d ocu m en ts are p u blic an d th e p erson s an d organ isation s affected by th e
p roject h ave a righ t to com m en t on th em .
• The competent authority makes a d ecision includ ing emission limits and other
p erm it con d ition s.
• Th ose con cern ed h ave th e righ t to ap p eal again st th e d ecision .
• A revision of th e d ecision s an d p erm it con d ition s is m ad e by a certain d ead -
lin e stip u lated in th e p erm it (3-10 years w h ere w astew ater d isch arges are
con cern ed ) or w h en th ere are sign ifican t ch an ges in op eration or em ission s
or w h en u n exp ected effects are d etected .
Righ t at th e p relim in ary stage of p lan n in g a n ew establish m en t, th e n ecessary
p erm its an d en viron m en tal asp ects are to be su rveyed . Th e en terp rise is exp ected

33
to recogn ise th at th e en viron m en tal criteria m ay affect sitin g as w ell as oth er eco-
n om ic an d tech n ical d ecision s. Even in th e case of ch an gin g th e p rod u ction , raw
materials or tech n ical d evices at an existin g p lan t, th e au th orities mu st be in formed
as soon as th ese d ecision s are m ad e, an d n egotiation s sh all be in itiated to su rvey
th e p ossible n eed for ren ew in g th e p erm its.
Th e legislation is based on th e Pollu ter Pays Prin cip le in th e sen se th at th e
polluter pays all pollution abatement costs, which also include the monitoring costs.
In ad d ition , p ollu ters of w atercou rses are obliged to p ay in d em n ities to th e ow n -
ers of w ater an d sh ore areas as w ell as to p rofession al fish erm en for an y d am age
cau sed . A typ ical featu re of th e p erm it p roced u re is th e case-by-case con sid eration
of ap p lication s an d tailor-m akin g of th e p erm it con d ition s. Th e p erm it con d ition s
are exp ressed as em ission lim its an d com p u lsory m easu res an d n ot as tech n ical
stan d ard s.
3.2.4 Emissions to air at Outokumpu Harjavalta M etals

Th e am bien t air con cen tration s allow ed by th e au th orities for th e w h ole in tegrat-
ed H arjavalta p lan t, w h ich p rod u ces both cop p er an d n ickel, (th e p erm it in force
w as gran ted 27.2.1995) are as follow s:
3.2.4.1 SO 2
1. SO 2 con cen tration (m ean valu e d u rin g an h ou r) in op en air h as to rem ain
u n d er 250 µg/m 3 after 31.12.1999 an d th e m ean valu e d u rin g 24 h ou rs m u st
rem ain u n d er 80 µg/m 3. From th e h ou rly m ean s n ot m ore th an 1 % can ex-
ceed th e valu e 250 µg/m 3 d u rin g 30 d ays an d from th e d aily m ean s 1 can
exceed th e valu e 80 µg/m 3 d u rin g 30 d ays.
2. If th e SO 2 con cen tration is excep tion ally h igh or exceed s 250 µg/m 3 th e rea-
son for th e h igh valu e m u st be fou n d ou t im m ed iately.
3. If th e SO 2 con cen tration exceed s 1000 µg/m 3 d u rin g th ree con secu tive h ou rs,
th e em ission s h ave to be fu rth er restricted .
4. After 1.1.1997 th e su lp h u r em ission s from th e su lp h u ric acid p lan t m u st n ot
be m ore th an 2.7 kg/ton of 100 % su lp h u ric acid p rod u ced calcu lated as a
m ean of six m on th s.
5. Th e oil fu els u sed m u st n ot con tain m ore th an 1 w eigh t-% of su lp h u r. Th is
d oes n ot con cern u se in p laces from w h ich th e gases are rou ted to th e su l-
p h u ric acid p lan t.
6. After 1.1.1997 the total emission of sulphur compounds calculated as SO 2 must
n ot exceed 4500 t/a.
3.2.4.2 D ust
7. Th e d u st sep aration system in th e d ryin g of cop p er an d n ickel con cen trates
m u st be su ch th at th e d u st con ten t of th e gas d oes n ot exceed 10 m g/m 3.Th e
bag filters u sed for th e gas com in g from th e sm elters, con verters an d an od e
fu rn ace m u st be d esign ed in su ch a w ay th at th e d u st con ten t after th e filters
d oes n ot exceed 1 m g/m 3.
8. Du st em ission s from th e p ow er p lan t m u st n ot exceed 40 m g/MJ.
9. Th e total d u st em ission s from th e p lan t m u st n ot exceed 90 t/a after 1.1.1997.

10. After 1.1.1997 th e h eavy m etals an d arsen ic em ission s m u st n ot exceed th e
follow in g lim its:
Cu 12 t / a
Ni 5 t/ a
Zn 10 t / a
Pb 5 t/ a
As 2 t/ a
Cd 0 .5 t / a
Hg 20 kg/ a
3.2.5 Off-gas monitoring

In H arjavalta th e em ission s to air are m easu red from all stacks w h ere em ission s
are sign ifican t. Th e d u st em ission s are m easu red on ce a m on th for 1–2 w eeks from
all th e stacks after th e filterin g d evices. Th e SO 2 em ission s an d th e gas flow s are
m easu red con tin u ou sly from th e stacks. Th e resu lts are registered in th e local n et-
w ork.
In Pori O u toku m p u Research O y p erform s th e air em ission m easu rem en ts
accord in g to th e m on itorin g p rogram d efin ed in th e licen ce for th e Pori site. O u -
toku m p u Research h as a certified qu ality system accord in g to th e SFS-ISO 9001
stan d ard . Th e SO 2, d u st an d metals con cen tration an d mass flow measu rin g meth -
od s h ave been accred ited by th e Cen tre for Metrology an d Accred itation accord -
in g to th e stan d ard s SFS-EN 45001 an d ISO /IEC Gu id e 25.
3.2.6 Releases into air

Actu al su lp h u r d ioxid e em ission s at th e H arjavalta p lan t in 1997 are p resen ted in
Table 6. Th e total volu m e of gas at th e H arjavalta p lan t is 1,700,000 N m 3/h , from
w h ich 1,000,000 N m 3/h goes th rou gh th e filters. Th e am ou n t of gas from th e su l-
p h u ric acid p lan t is 200,000 N m 3/h .
Th e SO 2 con cen tration s in th e am bien t air h ave been m easu red from th ree
p laces in th e vicin ity of th e p lan t. Th e valu es m easu red h ave been low. Th e con -
cen tration s h ave been m u ch low er th an th e lim it valu es.
Th e d esign valu es for th e bag filters h ave been 1 m g d u st/N m 3. With th e n ew
bag filters in stalled th e actu al em ission s w ere low er th an th e lim it valu es in 1995.
Du rin g th e n ext tw o years th ere w ere d ifficu lties w ith th e filters an d th e lim it val-
u es w ere n ot reach ed . Th is year, 1998, th e m atter h as been brou gh t u n d er con trol.
Th e air em ission s in th e Pori cop p er refin ery in 1997 are p resen ted in Table 8.
Th e on ly p erm it con d ition given to th e cop p er refin ery is th e am ou n t of selen iu m
in th e p reciou s m etals p lan t off-gases, w h ich m u st be u n d er 300 kg/a.

35
Ta ble 6. Sulphur dioxide em issions a t Ha r ja va lt a in 1997.
Height of st a ck Ar ea t / a 1997 specific em ission
Sm elt er vent ila t ion ga ses 14 0 m Conver t er s 1 0 66

Sm elt ing fur na ces 1 176
Sum 2 24 2 16 kg SO2 / t m et a l ( Cu+ Ni)
Off- ga ses fr om sulphur ic a cid pla nt 14 0 m R6 229 1.6 kg SO2 / t H2SO4

R7 294 0 .7 kg SO2 / t H2 SO4
Sum 523
Dr yer st a ck 70 m Ni- dr yer 57

vent ila t ion ga ses 11
Cu dr ying 40 m 0
Fugit ive ga ses 14 7

Sum 2 98 0
Ta ble 7. Dust a nd m et a ls em ission t o a ir in 1998 .
Lim it t / a t / a in 1998 Specific em ission
Dust 90 72 0 .37kg/ t m et a l ( Cu+ Ni)

Cu 12 12 0 .0 8 kg/ t Cu
Ni 5 1 0 .0 3 kg/ t Ni
Zn 10 5
As 2 2
Pb 5 2
Cd 0 .5 0 .4
Hg 0 .0 2 < 0 .0 2
Ta ble 8 . Air em issions in t he copper r efiner y in 1997.
t / a 1997 specific em issions
SO2 33 0 .28 kg/ t Cu

dust 0 .0 8 0 .0 0 0 7 kg/ t Cu
Se 0 .1 0 .0 0 8 kg/ t Cu
As 0 .7 0 .0 0 6 kg/ t Cu
NOx a s NO2 0 .4 0 .0 0 3 kg/ t Cu
CO2 316 2.7 kg/ t Cu
3.2.7 Emissions to water

Efflu en st to th e w aterw ays con tain p rocess w aters from th e acid p lan t an d a bleed
of th e w ater u sed in th e slag con cen trator, coolin g w aters, e.g. th e w ater u sed to
cool th e an od es, circu latin g via coolin g tow ers an d su rface d rain age. All th ese
w aters are collected an d treated in th e w ater treatm en t p lan t. Th e clean ed w aters
are d isch arged to th e river w h ich flow s by th e sid e of th e p lan t. Th e p recip itates
are sent back to the flash smelting furnace. Some of the sewage water from the plant
is taken to th e m u n icip al p u rification p lan t. Coolin g w ater an d p rocess w aters are
recycled w ith in th e p rocess as lon g as p ossible.
3.2.7.1 Suspended solids and metal compounds
These can be emitted from most stages of the process. Surface water can result from
eith er rain fall or from th e wettin g of stored material to p reven t d u st formation . Th e
oth er p oten tial sou rce of su sp en d ed solid s an d m etal com p ou n d s are th e coolin g

an d gran u latin g step s. In gen eral th ese system s are eith er sealed an d th e w ater is
recircu lated or th ey are n ot in con tact. System leakage can occu r. Wash w aters,
sp en t electrolyte an d p rocess efflu en ts are also p rod u ced in th e tan k h ou se an d
scru bbers. Th ese efflu en ts con tain sign ifican t qu an tities of m etal com p ou n d s in
solu tion an d are treated alon g w ith liqu ors bled from th e sealed coolin g an d gran -
u latin g system s before d isch arge to th e w aterw ays.
Slu d ges from all p ossible p rocesses are u su ally retu rn ed to th e flash sm eltin g
fu rn ace in ord er to recover th eir m etallic p ortion . In th e m ercu ry rem oval step in
th e su lp h u ric acid p lan t th e circu latin g acid in th e d ryin g tow ers is treated w ith
th iosu lp h ate to p recip itate m ercu ry. Th e p recip itate is taken to th e com p an y ’s
m ercu ry p lan t in Kokkola.
Th e m ain w ater em ission s from th e cop p er refin ery com e from th e con d en s-
ing water of the air-conditioning. It contains small amounts of copper and sulphuric
acid . Th e selen iu m gran u latin g w ater con tain s an am ou n t of selen iu m w h ich is
h ard ly m easu rable. Th e rem ain d er of th e gold p rocess con tain s som e h yd roch lo-
ric acid , bu t it is n ow ad ays ad d ed to th e electrolysis as a ch lorid e ad d ition . Som e
su rface d rain age com es from th e refin ery, too.
The permit cond itions for Harjavalta (permit of Water Rights Court 31.12.1992)
are as follow s. Th e p rocess w aters m u st be clean sed in su ch a w ay th at th e efflu -
en ts released from th e p lan t d o n ot con tain m ore th an :
Cu 3.6 t / a ( = 10 kg/ da y)
Ni 3.6 t / a
Zn 3.6 t / a
As 1.8 t / a
Pb 1.0 8 t / a
Cd 0 .10 8 t / a
Hg 0 .0 10 t / a
3.2.7.2 Waste water monitoring stations
At both Harjavalta an d Pori, th e d rain system ou tlets are equ ip p ed w ith flow meas-
u rin g an d sam p lin g station s. Tem p eratu res an d p H are also m easu red on a con -
tin u ou s basis. Flow m easu rem en ts are d on e u sin g electrom agn etic flow m eters.
Flow, p H an d tem p eratu re read in gs are registered in to th e p lan t con trol system .
Sam p lin g is d on e p rop ortion ally to th e flow. Com p osite sam p les are taken for
an alysis every d ay.
3.2.7.3 Analysis and reporting of waste waters
Th e an alytical laboratories in Harjavalta an d Pori an alyse th e n ecessary metal com-

p ou n d s from th e d aily com p osite sam p les. Resu lts are rep orted in tern ally via lo-
cal n etw orks. Both laboratories are covered by th e p lan ts’ ISO 9002 certificates.
3.2.7.4 Effluents in 1997
Th e em ission s to w ater at H arjavalta in 1997 are sh ow n in Table 9. Th e total w ater

flow w as 31,000,000 m 3/a in clu d in g coolin g w aters.

37
Ta ble 9. Act ua l em issions a t t he Ha r ja va lt a pla nt in 1997 wer e:
Lim it t / a t / a 1997 Specific em ission
Cu 3.6 3.6 0 .0 23 kg/ t Cu

Ni 3.6 4 .4 0 .124 kg/ t Ni
Zn 3.6 1.7
As 1.8 0 .4
Pb 1.0 8 0 .17
Cd 0 .11 0 .0 6
Hg 0 .0 1 0 .0 1
Th e h igh n ickel valu es w ere d u e to h eavy rain s, w h ich w ash ed d u st from th e yard s
to th e w aste w ater treatm en t p lan t. Th e rain w ater p on d w as n ot large en ou gh to
h old all rain w ater an d so more w ater came to th e w aste w ater treatmen t p lan t th an
cou ld be treated . In 1998 a n ew big rain w ater con tain er w as bu ilt in ord er to p re-
ven t overbu rd en in g of th e w aste w ater treatm en t p lan t.
Th e estim ated em ission s to w ater from th e cop p er refin ery in Pori w ere in
1997:
Cu 0 .50 t / a specific em ission 0 .0 0 4 kg/ t Cu
As 0 .14 t / a 0 .0 0 1 kg/ t Cu
Se 0 .25 t / a 0 .0 0 2 kg/ t Cu
Th e total am ou n t of w ater u sed w as 710,000 m 3/a.
3.2.8 Solid waste management
Nickel
OK OK
Harjavalta Metals Polarit
Cu-Ni recyclings Harjavalta Tornio
Cu scrap Weak acid OK
Pyhäsalmi Mine
Copper cathodes Pyhäsalmi
OK Ni metal Cu precipitates Copper concentrates
Poricopper
Pori
Zn dusts
O K Zinc Hg residue
Kokkola Zinc concentrate
Residue acid
Ag precipitates
Zinc metal
Figure 7. Int egrat ion of Out okumpu plant s in Finland.
Man y of th e m aterials gen erated d u rin g th e p rod u ction of cop p er can be d efin ed
as h azard ou s w astes. Most of th ese m aterials h ow ever con tain recoverable qu an -
tities of cop p er an d oth er n on -ferrou s m etals an d are th erefore u sed as raw m ate-
rials in th eir ow n righ t. All cop p er-bearin g m aterials are recycled back to th e cop -
p er p rocess.
O u toku m p u is an in tegrated m etal p rod u cer. Th e in tegration of th e p lan ts is
sh ow n in Figu re 7. All p ossible m aterials are recycled to a p lan t w h ere th ey can be
u sed eith er as raw m aterials or as ch em icals. H arjavalta Metals p rod u ces cop p er

an d n ickel, Poricop p er cop p er p rod u cts, Kokkola Zin c zin c an d Polarit stain less
steel. Pyh äsalm i Min e p rod u ces cop p er, zin c an d p yrite con cen trates.
In cop p er sm eltin g, a large ton n age of w aste is solid , p rin cip ally d iscard ed
slag. Dep en d in g on th e cop p er con ten t of th e con cen trate, th e am ou n t of slag can
vary betw een 0.5 to 2.5 tim es th e qu an tity of cop p er p rod u ced . Th e p u rified slag
is fayalite, w h ich con sists main ly of iron oxid e an d silicate. Table 10 sh ow s th e com-
p osition of typ ical cop p er w aste.
Ta ble 10 . Com posit ion of t ypica l copper sm elt ing wa st e.
Com ponent Wa st e sla g fr om elect r ic fur na ce % Fina l sla g fr om concent r a t or %
Copper 0 .7 0 .3– 0 .5
Ir on 37– 4 4 40– 44
Silica 27– 33 28 – 30
Th e fin al slag is con veyed as slu d ge to a p on d , w h ere th e fayalite slag settles to

th e bottom an d th e w ater u sed is p u m p ed back to th e flotation p rocess.
O th er solid s p rod u ced in a cop p er sm elter, su ch as lad le sku lls, scrap , boiler
an d p recip itator d u st, are recycled to th e sm eltin g fu rn ace an d n ot d iscard ed as
w astes. Th e on ly solid w astes are th e slag an d slu d ges p rod u ced in th e n eu tralisa-
tion of p lan t efflu en ts.
All th e flu e d u sts collected in th e electrostatic p recip itators are fed back to th e
flash sm eltin g fu rn ace. Th e d u st from th e bag filters an d th e m etals p recip itated
in th e w aste w ater treatm en t p lan t are also fed to th e flash sm eltin g fu rn ace.
Th e m ercu ry p recip itate from th e su lp h u ric acid p lan t is tran sp orted to th e
comp an y ’s mercu ry p lan t in Kokkola. Th e w eak acid from th e su lp h u ric acid p lan t
is u sed in O u toku m p u ’s zin c p lan t in Kokkola an d in Pyh äsalm i Min e.
Th e w astes p rod u ced in th e cop p er electrolysis in Pori are tran sp orted to
H arjavalta an d ad d ed to th e sm eltin g p rocess, if p ossible. Th e on ly w aste stored
on th e p lan t w as th e CCA d issolu tion w aste, abou t 30 t/a.
Fin n ish legislation d em an d s th at d an gerou s w aste m u st be d elivered to or-
gan isation s w h ich are au th orised to h an d le su ch m aterials an d take resp on sibility
for th eir treatm en t an d fin al d estin ation .O ils an d solven ts w h ich can n ot be recy-
cled an d th e filters are tran sp orted to h azard ou s w aste treatm en t p lan t. Un u sable
m etal scrap is sold to th e scrap bu sin ess an d p ap er to a card board p lan t.
3.2.8.1 Overview of the solid wastes produced

Materials to be recycled
sla g concent r a t e 4 6,0 0 0 t / a t o fla sh sm elt ing fur na ce
r ever t s 29,0 0 0 t / a t o t he conver t er
Hg- pr ecipit a t e ( a cid pla nt ) 50 t / a t o Out okum pu´ s zinc pla nt
Wastes for fin al d isp osal

Du rin g 1997 th e follow in g w astes w ere form ed in H arjavalta:
t a ilings 350 ,0 0 0 t / a t o t he t a iling pond
m et a l scr a p 750 t / a sold for scr a p
oils a nd solvent s 150 t / a t o ha za r dous wa st e t r ea t m ent pla nt
filt er m a t er ia ls 75 t / a t o ha za r dous wa st e t r ea t m ent pla nt

st or a ge ba t t er ies a nd la m ps 1 t/ a t o ha za r dous wa st e t r ea t m ent pla nt

39
3.2.9 N oise abatement
Regard in g n oise abatem en t in H arjavalta all p ossible m easu res h ave been taken
in ord er to red u ce th e n oise level from m ach in ery. Th e n oise level in th e p lan t is
m on itored by th e O ccu p ation al H ealth d ep artm en t.
A w orkin g grou p on n oise h as been establish ed by th e City of Pori. Th is w ork-
in g grou p com m ission ed a n oise su rvey of Pori in 1997. Measu rem en ts h ave been
d on e in th e vicin ity of th e O u toku m p u site as a sep arate com m ission , an d th e re-
su lts w ill be com p iled in to a n oise m od el com p risin g th e w h ole of th e City of Pori.
3.2.10 Environmental management system

Th e en viron m en tal m an agem en t system ap p lied in th e O u toku m p u com p an ies in
Pori is in accord an ce w ith th e EMAS regu lation of th e Eu rop ean Un ion .
In tern ally th e en viron m en tal m an agem en t system m ean s th at th e en viron -
m en tal view p oin t sh all be taken in to con sid eration in all field s of op eration : in
p rod u ction , m ain ten an ce, p lan n in g, research etc. Th e d evelop m en t of en viron -
m en tal m an agem en t aim s at con crete im p rovem en ts in en viron m en tal action s.
Th e en tire staff p articip ates in fu lfillin g th e en viron m en tal m an agem en t sys-
tem . Each p erson take th e resp on sibility for th e en viron m en t. In accord an ce w ith
th e en viron m en tal p olicy, w ork is p erform ed in a resp on sible m an n er, w ith ou t
w astin g en ergy or resou rces an d w ith ou t h arm in g th e en viron m en t.
3.2.11 Data management and training

Data man agemen t of en viron men tal matters is p erformed w ith th e u se of d atabas-
es. Th e system is an active real-tim e rep ortin g ch an n el an d also serves as an en vi-
ron m en tal m an u al an d arch ive. All u sers of th e local n etw orks h ave access to th e
d atabases.
Th e d atabases im p rove in form ation d istribu tion , an d th u s give better op p or-
tu n ities for follow-u p an d d evelop m en t of en viron m en tal p roced u res.
In ord er to imp lemen t th e en viron men tal man agemen t system effectively, th e
w h ole p erson n el h as been train ed to be aw are of th e effects of th eir w ork on th e
environment, and the possibilities of affecting environmental performance through
their own initiative. New workers are familiarised with practical environment work
in con n ection w ith th eir on -th e-job train in g.

Ca n d i d a t e B est A v a i l a b l e
Tech n i q u es
○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
4.1 General
4
Th e p yrom etallu rgical treatm en t of cop p er su lp h id e con cen trates com m on ly in -
clu d es tw o typ es of op eration s: sm eltin g an d con vertin g. In sm eltin g th e con cen -
trate is m elted an d oxid ised w ith a siliceou s or lim e flu x, w h ich com bin es w ith th e
oxid ised iron to form a liqu id silicate or calciu m ferrite an d to p rod u ce a solu tion
of m olten su lp h id es. In con vertin g, m ore su lp h u r is d riven off th e su lp h id e m elt,
an d th e rem ain in g iron is oxid ised an d flu xed for rem oval as a silicate or calciu m
ferrite. Th e fin al p rod u ct is blister cop p er or a m atte for fu rth er p rocessin g.
Th e p ollu tan ts of con cern h ere are th e on es associated w ith liqu id an d solid
w astes an d , above all, w ith gaseou s em ission s.
Liqu id efflu en ts from p yrom etallu rgical p rocesses are of m in or im p ortan ce
becau se th ese p rocesses are essen tially d ry. Liqu id efflu en ts com e from th e cool-
in g w ater system , from th e su lp h u ric acid p lan t attach ed to th e sm elter an d from
w et gas clean in g system s. Wet gas clean in g system s, like th ose requ ired to clean
p rocess gases for acid p rod u ction , rem ove su lp h u r trioxid e an d p rod u ce a w eak
acid . Th ey also collect arsen ic, m ercu ry, selen iu m , an d fin e d u st p articles con tain -
in g oth er im p u rities.
In cop p er sm eltin g, a large ton n age of w aste is solid , p rin cip ally d iscard ed
slag. Dep en d in g on th e cop p er con ten t of th e con cen trate, th e am ou n t of slag can
vary betw een 0.5 to 2.5 tim es th e qu an tity of cop p er p rod u ced . O th er solid s p ro-
d u ced in a cop p er sm elter, su ch as lad le sku lls, scrap , boiler an d p recip itator d u st,
are recycled to th e sm eltin g fu rn ace an d n ot d iscard ed as w astes. Th e on ly solid
w astes are th e slag an d slu d ges p rod u ced in th e n eu tralisation of p lan t efflu en ts.
Th e m ajor en viron m en tal p roblem s in th e p yrom etallu rgy of su lp h id e con -
cen trates resu lt from th e release of SO 2 an d p articu late em ission s w h ich can be
categorised as eith er p rocess or fu gitive em ission s.
Every sm eltin g p rocess m ay con tain several p rocess u n its:
• con cen trate storage an d feed p rep aration
• d ryin g
• sm eltin g
• slag clean in g
• gran u latin g, d ryin g an d grin d in g
• con vertin g
• an od e refin in g an d castin g
• gas coolin g
• gas clean in g
• acid p lan t
• tail gas clean in g
• secon d ary gas clean in g
• w aste acid an d w ater treatm en t
Every on e of th ese p rocess step s m u st be op tim ised an d m u st fu n ction in th e best
p ossible w ay in ord er to be BAT. A cop p er p rod u ction p rocess is alw ays a com p ro-
mise, sin ce th e p rocess h as to p rod u ce cop p er at a saleable an d p rofitable p rice an d

41
at th e sam e tim e m in im ise th e u se of en ergy an d raw m aterials an d th e form ation
of em ission s an d w astes.
In th is ch ap ter all u n it p rocesses are first d iscu ssed an d com p ared w ith each
oth er. Secon d ly th e total p rocesses w h ich con sist of u n it p rocesses are com p ared .
Th e com p arison s m ad e are based on th e literatu re available.
4.2 Feed Preparation

Th e con cen trates are tran sferred by con veyor belts u p to th e d osage silos. Con se-
qu en tly it is u n n ecessary to store con cen trates in op en areas an d th u s em ission s
d ecrease. Th e w areh ou ses h ave tru ck w ash in g station s so th at sp read in g of con -
cen trate from th e w h eels an d tru ck bed s can be avoid ed . Th ese facilities can n ot
be u sed in th e N orth ern cou n tries in w in ter.
Feed p rep aration is carried ou t by m ean s of variable sp eed feed ers w h ich
u n load in d ivid u al p rod u cts of kn ow n com p osition from th e d ay storage bin s on to
a com m on belt con veyer w h ich takes th em to th e d ryers.
4.3 Drying
4.3.1 Rotary dryer (rotary kiln)
Th e d ryer is fired by n atu ral gas or oil. N itrogen is som etim es u tilised in p lace of
secon d ary air to con trol th e tem p eratu re an d also to m ain tain an oxygen -d eficien t
atmosphere which red uces potential concentrate ignition and combustion. The d ry
ch arge, averagin g 0.1 % m oistu re, is d isch arged th rou gh a d ou ble trom m el screen
in to a d rag con veyor for tran sp ort to th e p n eu m atic lift system . Dryer off-gas is
d irected to an electrostatic p recip itator or bag filter for d u st rem oval. All d u st is
retu rn ed to th e d ryer d isch arge d rag con veyor. O ff-gas from th e electrostatic p re-
cip itator/bag filter p asses th rou gh an in d u ced d raft fan to th e stack.
4.3.2 Steam dryer

Th e m u lticoil steam d ryer h as been ad ap ted for con cen trate d ryin g on com m er-
cial scale in th is d ecad e. It con sists of a rotor in a station ary recep tacle. Heatin g coils
are located p arallel to on e an oth er. Each set is con stru cted from several con cen tric
tu be rin gs. Th e steam from th e w aste h eat boiler system , w h ich is con trolled by
tw o red u cin g station s, serves as a th erm al carrier w h ich flow s th rou gh th e coils
an d is th u s u sed for d ryin g p u rp oses. Th e steam u sed is fed back in to th e steam
n etw ork an d th e con d en sate is recycled back to th e feed w ater system of th e w aste
h eat boiler.
Th e con cen trate an d ad d itives m u st be screen ed before bein g fed in to th e coil
d ryer. For th is reason th ere are screen in g p lan ts in stalled in th e con cen trate con -
veyeor. Th e m aterial is screen ed to less th an 15 m m p article size. A m agn et sep a-
rator rem oves an y iron p ieces before sievin g. Th e oversize p articles are cru sh ed
after screen in g by a cru sh er an d recycled /47/.
Th e d ryer coil sp acin g h as been d esign ed for sm ooth p rod u ct flow an d less
w ear an d tear. As th e exh au st gas volu mes are low on ly a small size bag filter n eed s
to be p rovid ed in th e d ryer to clean off-gases before d isch argin g th rou gh a stack
to th e atm osp h ere. Du st leakage is very low becau se th e d ryer bod y is station ary
an d n o d ifficu lt seals are n eed ed . Ad d ition ally th e bag filter is in tegrated to th e
steam d ryer so th at th e d u st d rop s straigh t back in to th e d ryer an d n o oth er d u st

h an d lin g or tran sp ortation is n eed ed . Th is resu lts in very low d u st em ission s. Th e
m u lticoil d ryer is en viron m en tally safe. O n ly w ater is evap orated an d th e gas
volu me an d emission s are min imal. In steam d ryin g th e satu rated steam p rod u ced
in th e w aste h eat boiler con n ected to th e FSF can be u tilised . Th is m ean s th at p art
of th e ch em ical en ergy of th e con cen trate is u sed for d ryin g an d n o extra fossil fu el
is n eed ed for h eatin g /48/.
In vestm en t costs for a steam d ryin g in stallation are low. O p eratin g costs are
also low. For exam p le th e con su m p tion of electrical en ergy is on ly 60 % com p ared
to a rotary d ryer. Th e h igh efficien cy, safety an d clean lin ess ch aracteristics of th is
tech n ology h ave been w id ely p roven /49/.
For th e follow in g reason s th e steam d ryer system h as often been ch osen in -
stead of th e con ven tion al fossil fu el-fired rotary d ryer:
a) Low h eat losses an d a sm all volu m e of exh au st gas, resu ltin g in good th er-
m al efficien cy in th e d ryin g p rocess an d low cop p er losses.
b) N o su lp h u r d ioxid e em ission s an d risk of fire ou tbreak d u e to th e low an d
even op eration tem p eratu re of arou n d 120°C.
c) As th e volu m e of gases is low, on ly a bag filter n eed s to be p rovid ed for d u st
collection an d recyclin g.
d ) Du st leakage is very low as th e d ryer bod y is station ary an d a good arran ge-
m en t is p ossible.
e) Th e size of th e d ryer is on e th ird of th e con ven tion al fu el-fired d ryer. In vest-
m en t an d op eration costs are exp ected to be abou t 80 % an d 50 % of th e con -
ven tion al d ryer /44/.
f) Th e ch oice of m u lticoil-typ e d ryers is often based on en viron m en tal con sid -
eration s. Th e carrier air to absorb th e w ater steam is su cked from th e en vi-
ron m en t in th e ratio 1:1. Th e m oist off-gas is d ed u sted in a jet filter p lan t. Th e
resid u al d u st con ten t of th e off-gas is less th an 5 m g/N m 3 /47/.
Th e reason s for selectin g a mu lticoil d ryin g p lan t in p referen ce to a con ven tion al
rotary d ryer are th e relatively simp le off-gas system an d its sen sitivity to material
variation s (moistu re, comp osition an d qu an tity) an d th e small sp ace requ ired /47/.
Th e in vestmen t an d op eration costs are low.
4.3.3 Pneumatic drying/Flash dryer

In th e flash d ryer, th e con cen trate p articles d isp ersed in th e h ot gas flow are d e-
h yd rated by h eat tran sferred from th e h ot gas th rou gh flow m ovem en t. Cu rren t-
ly, th e flash d ryer p erforms th e imp ortan t role of effective u tilisation off-gases from
th e su p er h eater an d th e an od e fu rn ace.
The pneumatic d rying system consists of three parts: rotary kiln, cage mill and
p n eu m atic d u ct. Th e feed is scattered , an d th e m oistu re is red u ced to 3 % or less
in th e cage m ill. At th e ou tlet of th e m ill, th ere is a classifyin g fu n n el. Coarse m a-
terial is d isch arged from th is fu n n el. In th e p n eu m atic d u ct th e m oistu re is fu rth er
red u ced to 0.3 % or less /45,50/.
Electrical en ergy con su m p tion p er ton of d ry con cen trate is 10–12 kWh /50/.
A com p arison of d ryin g system s p rep ared by O u toku m p u En gin eerin g O y is p re-
sen ted in Table 11.

43
Ta ble 11. Com pa r ison of dr ying syst em s.
Cr it er ia Spr a y dr yer Rot a r y dr yer St ea m dr yer Fla sh dr yer Fluid bed dr yer
Invest m ent cost – – + + + + + + –

Oper a t ing cost – – – + + + + – – –
Ga s flow – – – + + + – – –
Fugit ive em ission cont r ol – – + + + – –

Oper a t iona l flexibilit y – + + + + + – – –
Ma t er ia l ha ndling + – – – –
Fut ur e expa nsion – – + + + + – –

Envir onm ent a l com plia nce – – – + + + – – –
Pr ocess sophist ica t ion + + + + + +
Pr ocess m a t ur it y + + + + + + + + + + + + +
Gener a lit y + + + + + + + + +
4.4 Dry Concentrate Conveying System

Dried con cen trate sh ou ld be stored in an in term ed iate bin an d be extracted w ith
a d rag con veyer an d ch arged to th e d en se p h ase p n eu matic con veyin g system th at
w ill con vey it to th e d ry con cen trate bin . Air from th e p n eu m atic con veyer w ill be
clean ed in a bag filter an d cyclon e before ven tin g to th e atm osp h ere th rou gh a
stack.
4.5 Concentrate Feeding System

Th e con trol requ irem en ts of a m od ern h igh -in ten sive flash sm eltin g fu rn ace w ith
h igh oxygen en rich m en t are at a very h igh level. Th e con cen trate feed in g system
m u st be able to p rovid e a con stan t an d accu rate con cen trate feed to th e bu rn er.
H igh oxygen en rich m en t m ean s au togen eou s op eration .
Th e latest gen eration of O u toku m p u con cen trate bu rn er is sp ecifically d e-
sign ed for h igh oxygen en rich m en t, w id e tu rn -d ow n ratio an d for p recise con trol
requ iremen ts as well as for h igh feed rates in both flash smeltin g fu rn aces an d flash
con vertin g fu rn aces /48/.
4.5.1 Volumetric concentrate feed system

A volu m etric con cen trate feed system h as often been d esign ed for flash fu rn aces.
Th is system h as som etim es been associated w ith in h eren t p roblem s su ch as flu id -
isation resu ltin g in u n con trolled con cen trate exp osu re to th e fu rn ace.
4.5.2 Loss-in-weight feeding system

O u toku m p u h as d evelop ed a gravim etric feed system w h ich is an ap p lication of
th e loss-in -w eigh t feed er. Th e gravim etric feed system con sists of a d osin g valve
an d a d osin g bin p rovid ed w ith a screw con veyor u n d ern eath .
Both in local and remote mode the operation of the loss-in-weight feeder starts
w ith th e fillin g of th e d osin g bin . Th e fillin g is stop p ed w h en th e bin is at h igh level
(m ax) an d th e feed in g is started . Wh en th e m aterial reach es th e low level th e bin
is refilled . During refilling the screw conveyer runs at a previously controlled speed
u n til th e fillin g stage is com p leted .

Th e m aterial is fed by screw con veyor in to a ch arge d rag con veyor w h ich
tran sfers th e m aterial fu rth er via a con cen trate ch u te in to th e con cen trate bu rn er.
Th is arran gem en t en su res good accu racy an d a con stan t con cen trate feed rate to
th e fu rn ace.
Th e loss-in -w eigh t meth od may even imp rove th e th rou gh p u t of con cen trate
com p ared to a trad ition al volu m etric feed in g system w ith u n even feed . Above all,
h ow ever, th e m ain ben efit of th e loss-in w eigh t feed in g system is better con trol of
th e fu rn ace an d also a low er Cu con ten t in th e slag /48/.
O n e im p ortan t p rogress step in th e d evelop m en t of th e p rocess h as been th e
ad op tion of th e loss-in -w eigh t feed system by w h ich th e real am ou n t of m aterial
en terin g th e fu rn ace can be con trolled . Th is h as low ered th e tim e d u rin g w h ich
th e feed mixtu re an d oxygen are n ot in balan ce. Th u s th e clear ad van tage h as been
th at th e am ou n t of m agn etite an d over-oxid ised cop p er en terin g th e bath h as
d ecreased an d th e average cop p er con ten t of th e slag h as d ecreased /14,31/.
4.6 Smelting Techniques

In the selection of a copper smelting process, the following factors are relevant with
regard to th eir effect on th e en viron m en t /41/:
• m in im u m en ergy requ irem en t by u sin g
– laten t h eat of th e con cen trate
– oxygen en rich m en t of com bu stion air
– w aste h eat recovery
• m in im u m gas volu m e, cau sin g th e low est em ission s, by p rovid in g:
– oxygen en rich m en t of com bu stion air
– as little n eed as p ossible for th e in p u t of fossil fu els
• low gaseou s SO 2 em ission s by m axim isin g
– th e SO 2 con cen tration in sm elter gases
– th e p rop ortion of total SO 2 gen erated in SO 2-rich gas
– SO 2-con version efficien cy (d ou ble catalysis in H 2SO 4 p rod u ction )
• m in im isation of fresh w ater requ irem en ts by
– in tern al recircu lation an d in d irect coolin g
• m in im ization of solid w aste gen eration
– by m axim isin g th e recovery of su lp h u r as su lp h u ric acid an d /or oth er
by p rod u cts
Table 12 sh ow s th e ch aracteristics of variou s typ es of sm eltin g fu rn aces. Th e con -
tin u ou s Mitsu bish i p rocess w ill be d iscu ssed in m ore d etail later in th is ch ap ter
alon g w ith oth er con tin u ou s p rocesses.
Th e m atte grad e in flash sm eltin g is n ow ad ays easily raised to 75 %. Mg in
th e Table is an abbreviation for m agn etite. Magn esiu m h as n o effects on th e flash
smeltin g of cop p er. Th e p rod u ctivity valu es sh ou ld n ot be comp ared , becau se th ey
are calcu lated in d ifferen t w ays for th e variou s fu rn ace typ es.
In th e O u toku m p u flash sm eltin g p rocess it is p ossible to con trol th e m atte
grad e an d h eat balan ce in d ep en d en tly, w h ich allow s sm eltin g irresp ective of th e
com p osition of th e con cen trate. Becau se of th e h igh m ass an d h eat tran sfer rate in
su sp en sion th e reaction s take p lace very rap id ly an d th e reaction h eat of th e con -
cen trate can be totally u tilised in th e sm eltin g p rocess. Th is allow s th e u se of oxy-
gen en rich m en t in ord er to d ecrease th e gas volu m e of th e sm eltin g p rocess. Th e
ability to w ith stan d h igh tem p eratu res w ith ou t d estroyin g th e refractory lin in g is
in fact on e of th e m ain ben efits of th e flash sm eltin g p rocess w h ich en ables a lon g
cam p aign life, typ ically lon ger th an ten years w ith ou t m ajor rebrickin g /14/.
Low volu m e of gas an d con tin u ou s gas flow from th e p rocess facilitates h igh
su lp h u r recovery. Th ere is n o tiltin g of th e fu rn ace an d a lim ited am ou n t of op en -

45
in gs th rou gh w h ich fu gitive em ission s cou ld en ter th e w orkin g atm osp h ere. Be-
cau se th e fu rn ace is op erated at a sligh t u n d erp ressu re fu gitive em ission s are m in -
im al. Th ere is n o n eed for a h old in g fu rn ace w h ich is often a sou rce of fu gitive
em ission s in bath sm eltin g p rocesses. In fact all bath sm eltin g fu rn aces n eed a
h old in g fu rn ace or sep arate settler /14/.
Ta ble 12. Br ief specifica t ion of va r ious t ypes of sm elt ing fur na ces a ccor ding t o Ba ba a nd Hondo / 4 2/ .
Furna ce Type Product ivit y Furna ce Ma t t e Cha ra ct erist ics
2
T/ m * D Cha rge gra de %
1. Fla sh Sm elt ing
Out okum pu 8– 11 dr y conc. 55– 65 environm ent - friendly process
high flexibilit y for opera t ion
high pot ent ia lit y for expa nsion
high dust genera t ion
Inco 12 dr y conc. 45 pure oxygen sm elt ing
a ut ogenous opera t ion
low dust genera t ion
rest rict ion on Mg ( low Mg)
2. Ba t h sm elt ing
Nora nda 15 green conc. 65– 75 high flexibilit y for ra w m a t eria ls
( whit e m et a l)
short brick life of t uyere
Mit subishi 21 dr y conc. 55– 70 cont inuous process
short brick life
high energy cost s due t o
pressurized a ir
Tenient e 12 green conc. 70– 75 high flexibilit y for ra w m a t eria ls
short brick life of t uyere
Oxy- fuel reverb. 5 green conc. 40– 45 low Mg a nd product ivit y
Va nyukov 80 green conc. 45– 70 form sm elt ing
high product ivit y
low dust genera t ion
Isa sm elt 65 conc.pellet 55 com pa ct furna ce using subm erged la nce
low dust genera t ion due t o conc.pellet
short brick life
The average temperature in the furnace can be maintained at a reasonably low level
bu t th e con cen trate p article tem p eratu re can rise to very h igh figu res for a sh ort
p eriod of tim e before effective h eat tran sfer red u ces th e tem p eratu re of th e m elt-
ed p article. Du rin g th is p eriod it is p ossible for som e volatile im p u rities to tran s-
fer to th e gas p h ase. Th is m ean s th at im p u rity elim in ation in su sp en sion is very
effective. In bath sm eltin g p rocesses th e im p u rities d issolve rap id ly in to liqu id
p h ases as th e p rocess is sligh tly closer to th e th erm od yn am ic equ ilibriu m . H ow-
ever, in bath sm eltin g p rocesses th e gas volu m e is n orm ally m u ch h igh er an d th is
also en ables im p u rity elim in ation in to th e gas p h ase in bath sm eltin g p rocesses /
14/.
Th e bath in th e flash sm eltin g fu rn ace settler is relatively qu iescen t. Th is en -
ables th e sep arate tap p in g of m atte an d slag ou t of th e fu rn ace. It is also a p ossible
to skim slag an d tap matte or blister cop p er ou t of th e fu rn ace con tin u ou sly. In bath
sm eltin g p rocesses, h ow ever, th e reaction s take p lace in an agitated bath . In th ese
con d ition s th ere are better p ossibilities for th e m atte p articles to coalesce. After a
sep arate settlin g fu rn ace th e cop p er con ten t of th e slag m ay be closer to th e th er-
m od yn am ic equ ilibriu m . Slag red u ction is also easier in an agitated bath . Agita-
tion in bath sm eltin g is m ad e by blow in g a h igh p ressu re air-oxygen m ixtu re in to

th e bath or above it. In flash sm eltin g th ere is n o n eed to u se relatively exp en sive
h igh p ressu re gas /14/.
Th ere are also som e oth er d isad van tages in th e flash sm eltin g p rocess com -
p ared to bath sm eltin g p rocesses. In th e flash sm eltin g p rocess th e feed m aterial
grain size m u st be fin e en ou gh so th at th e p articles are able to h eat u p an d react
in th e su sp en sion before h ittin g th e bath in th e settler. In bath sm eltin g p rocesses
th e p article size is n ot critical at all. Th e sm all p article size in flash sm eltin g tod ay
is m u ch low er th an it u sed to be som e d ecad es ago /14/.
In th e flash sm eltin g p rocess th e con cen trate is d ried to a very low m oistu re
con ten t. O n e cou ld con sid er th is a d isad van tage. H ow ever, it can be easily d em -
on strated th at d ryin g at low tem p eratu res is m ost econ om ical becau se in th at case
th e en ergy loss is m u ch low er th an w h en w ater vap ou r is h eated u p to actu al
sm eltin g tem p eratu res /14/.
Th e Van yu kov fu rn ace h as on ly been u sed in Soviet areas. It exh ibits th e h igh -
est sm eltin g cap ability p er h earth area am on g th e oth er typ es of sm eltin g fu rn ac-
es, resu ltin g in m in im isin g th e cost of con stru ctin g th e sm elter fu rn ace. Th e fu r-
n ace is th ou gh en ou gh to p rovid e u n iform reaction con d ition s so th at lu m p s of
m aterial can be read ily p rocessed . Du st gen eration is low /38/.
In th e Mitsu bish i fu rn ace th e en ergy costs are h igh d u e to th e u se of p ressu -
rised air. Th e blen d ed feed is ch arged sequ en tially to th e smeltin g fu rn ace in batch -
es th rou gh ch arge tan ks an d con veyed p n eu m atically th rou gh feed p ip es to th e
fu rn ace. Th e feed p ip es are situ ated in feed lan ces d ow n w h ich oxygen -en rich ed
air is blow n at a velocity of 200 m /s /33/.
IsaSm elt, a com p act fu rn ace, h as still to solve su ch p roblem s as sp lash in g an d
th e sh ort brick life of th e fu rn ace for its fu tu re d evelop m en t /43/.
4.7 Slag Cleaning

4.7.1 Electric furnace
Cop p er sm eltin g fu rn ace slag is tap p ed th rou gh slag tap h oles alon g lau n d ers in to
the electric furnace. Coke and reverts are added through the furnace roof. Slag from
th e electric fu rn ace is tap p ed in to gran u lation an d tran sp orted to th e slag storage
area. Matte from th e electric fu rn ace is p eriod ically tap p ed th rou gh tap p in g h oles
an d lau n d ers in to lad les an d tran sferred by cran es to Peirce-Sm ith con verters for
fu rth er treatm en t.
Th ere are th ree or six electrod es in th e electric fu rn ace to su p p ly en ergy in to
th e fu rn ace. Electric p ow er is n eed ed for th e red u ction reaction s, h eat losses an d
sm eltin g of reverts. Th e red u ctive agen t is coke. Electric fu rn ace off-gases are first
bu rn ed in an in cin erator, th en cooled an d rou ted th rou gh a bag filter to th e stack.
4.7.2 Slag concentrator

Molten slag is tap p ed th rou gh tap h oles an d alon g lau n d ers in to lad les, w h ere th e
slag is cooled w ith w ater sp rayin g. After coolin g th e lad les are tran sp orted an d
u n load ed in to th e slag stockp ile. Th e slag is m oved by a fron t-en d load er from th e
stockp ile on to a grizzly w h ere oversized lu m p s are broken by h yd rau lic h am m er.
Metallic cop p er is sep arated as a grizzly oversize. Th e grizzly u n d ersize is tran s-
p orted by a belt con veyor to th e screen in g station w h ere lu m p s, p ebbles an d fin es
are sep arated in to sep arate bin s. Grin d in g con sists of au togen ou s lu m p m ills an d
p ebble m ills. Both grin d in g stages are equ ip p ed w ith h yd rocyclon es. Flotation is
carried ou t in th ree m ain stages. Recovered cop p er con cen trate is th icken ed an d

47
filtered by a p ressu re filter. Th e filtered con cen trate is con veyed in to th e d ryer. Slag
m ill tailin gs are p u m p ed in to a n earby tailin g area. Th e clarified w ater from th e
tailin g p on d is u sed as p rocess w ater.
Th e en ergy con su m p tion of th e slag con cen tration p lan t (60–65 kWh /t) is far
less th an th e en ergy con su m p tion of an electric fu rn ace. Th e slag con cen tration
p lan t op erates flexibly, ad ap tin g to great variation s in th e feed an d even a p ossi-
ble sh u td ow n of th e m ill d oes n ot affect sm elter op eration s. Th e electric fu rn ace
m igh t sh u t d ow n th e w h ole sm elter if d istu rban ces occu r. Cop p er recovery is very
h igh w ith low cop p er con ten t in th e tailin gs /51/.
4.8 Converting
Th e tech n ological in n ovation s in su lp h id e con vertin g h ave lagged beh in d th e
p rim ary sm eltin g p rocesses. Du rin g th e p ast few d ecad es n ew sm eltin g tech n olo-
gies h ave been d evelop ed , e.g. O u toku m p u flash p rocess, IN CO flash p rocess,
Mitsu bish i con tin u ou s sm eltin g p rocess, N oran d a reactor, d ry con cen trate in ject-
ed el Teniente process (CMT), ISASMELT process and CO NTO P. All these processes
h ave p roven th eir com m ercial viability. O n th e oth er h an d , th e Peirce-Sm ith con -
verter h as been th e u n d isp u ted con vertin g vessel /52/.
Th e Peirce-Sm ith con verter h as served th e in d u stry w ell sin ce its in cep tion .
It is, h ow ever, fast becom in g obsolete becau se of n ew d evelop m en ts in tech n olo-
gies an d very strin gen t en viron m en tal regu lation s /52/
Con tin u ou s con vertin g is ap p reciated as su p erior in p erform an ce as it p ro-
d u ces a stead y stream of h igh -stren gth SO 2 gas. It can also m eet p resen t an d fu -
tu re en viron m en tal regu lation s /52/.
O p eration w ith a very low m atte grad e close to th e n atu ral m atte grad e is n ot
econ om ical becau se, in th at case, th e laten t en ergy of th e con cen trate is n ot w ell
u tilised in th e p rim ary sm eltin g step an d excess fu el h as to be u sed to con trol th e
heat balance. As a matter of fact it is easier to operate with a high matte grad e which
is favou rable for feed in g to th e FCF-p rocess w h ich in fact, is th e on ly con vertin g
process which can be d ecoupled for a while from the whole smelting process chain.
Th is allow s h igh er on -lin e availability for th e w h ole p rocess /14/. Th e solid m atte
u sed also allow s h igh levels of oxygen en rich m en t /43/.
O p eration ally, th e con vertin g fu rn ace is easy to op erate an d becau se th e p roc-
ess is con tin u ou s, it d oes n ot requ ire cran es an d lad le tran sfer. Th u s corresp on d -
in g fu gitive em ission s in to th e w orkin g sp ace are avoid ed . In ad d ition to th is th e
lau n d ers u tilised to con vey th e m atte to gran u lation can easily be covered to col-
lect an d treat th e p articu lates an d fu m es /14/.
Th e flash con vertin g p rocess itself h as been su ccessfu lly p roven as an effec-
tive com m ercial m eth od of con vertin g m atte d irectly to blister cop p er /31/.
Table 13 is based on an article by Irsh ad A. Ran a &Co /52/, w h ich w as u p d at-
ed by O u toku m p u . It in d icates th at O u toku m p u -Ken n ecott an d Mitsu bish i con -
tin u ou s con verters are th e h igh est-ran ked p rocesses p rim arily becau se of sm aller
off-gas h an d lin g an d acid p lan t requ irem en ts, p lu s th eir ability to con tain fu gitive
em ission s an d m eet en viron m en tal requ irem en ts.
Gas flow in th e O u toku m p u -Ken n ecott p rocess is low er, becau se it is p ossi-
ble to u se h igh er oxygen en rich m en t (abou t 80 %) th an in th e Mitsu bish i p rocess
(32 %). O u toku m p u -Ken n ecott con vertin g also op erates in d ep en d en tly of th e
sm eltin g fu rn ace.

Ta ble 13. Com pa r ison of conver t ing syst em s / 52/ .
Crit eria Peirce- Sm it h Fla sh Mit subishi INCO fla sh ISA/ AUS
convert er convert ing convert ing convert ing convert er
Invest m ent cost – + + + – –
Opera t ing cost – + + + + –
Acid pla nt size – – – + + + + + + + +
Opera t ing m ode – – + + + + + + + +
Cont inuous/ ba t ch
Off- ga s cha ra ct erist ics – – – + + + – – + – –
Fugit ive em ission cont rol – – – + + + + + + – –
Opera t iona l flexibilit y + + – – – – +
Ma t eria l ha ndling – – – + + + + + + +
Sla g clea ning – – + + + + –
Fut ure expa nsion + – – – – – – –
Environm ent a l com plience – – – + + + + + + + – –
Im purit y rem ova l + + – + – +
Process sophist ica t ion – – – + + + + – –
Process m a t urit y + + + + + + + – – – – –
Genera lit y + + + – + – – – – – –
Scra p + + + – – – – – – – – +
Producing of revert s – – – + + + + + + + + + + + +
4.9 Anode Furnace

Blister cop p er is tran sferred to th e an od e d ep artm en t or fed in to th e an od e fu r-
n ace by blister lad les. It is refin ed by in jectin g oxygen -en rich ed air th rou gh tu y-
eres in ord er to rem ove su lp h u r from th e cop p er. Th en th e d issolved oxygen con -
ten t is red u ced to target levels by in jectin g a gaseou s red u ctan t (e.g. p rop an e or a
mixture of steam and natural gas). The refined anod e copper is then cast on a wheel
u tilisin g d ou ble m ou ld castin g an d au tom atic w eigh in g.
Fu rn ace gases are sen t to an in cin erator for com p lete com bu stion an d can be
scru bbed in an alkalin e scru bber before ven tin g th rou gh th e stack. An od e fu rn ac-
es are covered by a m ovable h ood con stru ction .
4.10 Gas Cooling

Recen t cop p er smelter in stallation s an d mod ern isation s in clu d e ap p lication s of th e
follow in g tech n ologies: th e O u toku m p u Flash Sm eltin g Process, th e IN CO Flash
Sm eltin g Process, th e Mitsu bish i Process, th e N oran d a Process, th e El Ten ien te
Process, th e IsaSm elt Process, an d th e Con top Process. Table 14 p rovid es a rep re-
sen tative list of th e typ e of gas h an d lin g system s associated w ith th ese sm eltin g
p rocesses /53/.
O u toku m p u Flash Sm eltin g an d th e Mitsu bish i Con tin u ou s Sm eltin g Proc-
ess u tilise h orizon tal w aste h eat boilers for coolin g th e off-gas an d ESP for p artic-
u late rem oval. Sin ce th e O u toku m p u p rocess u tilises oxygen -en rich ed air, a large
volume of off- gas containing consid erable heat exits from furnace. Recovery of this
available h eat is an im p ortan t econ om ical factor for th is p rocess /53/.
Th e IN CO Flash Sm eltin g Process is based on u sin g bu lk oxygen for sm elt-
in g w h ich resu lts in a very low off-gas volu m e w ith little sen sible h eat con ten t. A
p roven gas coolin g / clean in g tech n ology ap p lied to th is p rocess is a close-cou p led

49
satu ration tower for gas con d ition in g followed by a wet scru bbin g-based gas clean-
in g system /53/.
Th e N oran d a Process an d El Ten ien te Process u tilise an evap orative sp ray
coolin g ch am ber to con d ition th e fu rn ace gas p rior to th e h ot electrostatic p recip -
itator/53/. Th e CO N TO P Cyclon e Process is equ ip p ed w ith a vertical w aste h eat
boiler an d u ses an ESP for p articu late rem oval /53,40/. Th e IsaSm elt Process u tilis-
es a FLUXFLO W circu latin g flu id bed w aste h eat boiler follow ed by an ESP or a
vertical w aste h eat boiler follow ed by an ESP /53/.
Ta ble 14 . Review of sm elt ing pr ocess ga s ha ndling syst em s / 53/ . ESP = elect r ost a t ic pr ecipit a t or.
Fa cilit y Sm elt ing Conc. % O2 Furna ce off ga s Dust Ga s Ga s

ra t e
process t / da y in bla st Volum e Tem p. SO 2 % loa ding Cooling Clea ning
°C
3 6 3
Nm * 10 g/ Nm
BHP Copper Out okum pu 3800 50- 70 1400 1320 25 1100 Horiz.Boiler ESP
Kennecot t Out okum pu 3000 70- 90 670 - 44,8 - Horiz.Boiler ESP
P.D.Hida lgo Out okum pu 2200 35 1500 1300 22 2600 Horiz.Boiler ESP
Ha rja va lt a Out okum pu 1600 75- 95 350 1370 25- 50 3500 Horiz.Boiler ESP
Ta m a no Out okum pu 1360 35 880 1050 13,5 1200 Horiz.Boiler ESP
P.D.Chino Inco 2280 95 280 1200 80 3500 Sa t .Tower Scrubber
Inco Inco 3200 95 340 1260 70- 80 2800 Sa t .Tower Scrubber
KCML Mit subishi 1600 40- 45 570 1200 25 1100 Horiz.Boiler ESP
Nora nda Nora nda 1600 35- 40 2100 820 15 200 Spra y Cooler ESP
Ca let ones Tenient e 1600 28- 30 2200 820 15 200 Spra y Cooler ESP
Cyprus Mia m i Isa sm elt 2000 50 1300 1120 12 400 Vert ic.Boiler ESP
The gas hand ling systems mentioned above are the systems used in existing plants.
O th er gas h an d lin g systems can be u sed as w ell. Table 15 gives a comp arative su m-
m ary of altern atives in clu d in g ad van tages, d isad van tages an d d esign con sid era-
tion s. Th e table w as p rep ared by Paykan Safe an d David M. Jon es /53/.
Th ere is n o w aste h eat boiler in th e IN CO -p rocess. Som e Van yu kov p rocess-
es also lack w aste h eat boilers /14,38/.
In Jap an en ergy costs are very im p ortan t. Th e Jap an ese recover even a sm all
am ou n t of en ergy th rou gh th e w aste h eat boiler /14/.
4.11 Dust Separating

N on -ferrou s m etal p rocessin g p lan ts u se both w et an d d ry d u st, m ist or fu m e col-
lectors at variou s step s in th e gas clean in g p rocess. Follow in g th e roaster or sm elt-
er, a m ech an ical d u st collector, su ch as a cyclon e, is u tilised to red u ce d u st load in g
to a level of abou t 230 m g/m 3 /54/.
Electrostatic p recip itators are th e m ost com m on d u st or fu m e collection d e-
vices u tilised after th e h ot d u st collector to red u ce th e d u st bu rd en even fu rth er.
Th e gases are cooled d ow n to th e 420–450 °C ran ge p rior to th e ESP an d , in m an y
plants, heat recovery equipment has been found profitable. ESPs are typically sized
to rem ove p articu lates at 98 to 99 % efficien cy so th at th e off-gas leaves th e ESPs
w ith d u st load in gs of abou t 20 m g/m 3 to 50 m g/m 3 /54/.
If arsen ic rem oval from th e SO 2 lad en gas is n ecessary, a gas coolin g tow er is
u tilised to cool th e gases to arou n d 115 °C to con d en se ou t arsen ic fu m es. A fabric
filter is in trod u ced after th is step to rem ove th e arsen ic com p ou n d s an d m ost of
th e rem ain in g d u st from th e gas stream /54/.
Th e clean ed sm elter off-gases en ter th e gas clean in g section p rior to th e acid
p lan t.

Ta ble 15. Com pa r ison of ga s cooling a lt er na t ives / 53/ .
Alt erna t ives Wa st e Hea t Boiler a nd ESP Wet Syst em Spra y Cha m ber a nd ESP
Ga s Cooling Wa st e Hea t Boiler Sa t ura t ion Tower Spra y Cha m ber
Ga s Clea ning ESP Wet Scrubber ESP
Adva nt a ges st ea m genera t ion Minim um a ir infilt ra t ion dust segrega t ion
boiler is a good sulpha t ion ha ndling cold ga s m inim um equipm ent a nd
cha m ber high ca m pa ign life ca pit a l cost
reduces hea t loa d a nd good in pla nt low opera t ing cost s/
ga s volum e environm ent energy requirem ent s
dust segrega t ion rea sona ble ea sy t o im plem ent in
low pressure drop im plem ent a t ion ret rofit
Disa dva nt a ges pot ent ia l t ube lea ks m inim um dust no hea t rem ova l
m odera t e a ir infilt ra t ion segrega t ion high a ir infilt ra t ion
la yout difficult ies high energy high m a int ena nce
difficult in ret rofit a cid pipeline poor in- pla nt environm ent
need a ir a t WHB inlet for corrosion need for a ir/ O 2 upt a ke
sulpha t ion no hea t rem ova l for non- rot a r y process
high m a int ena nce due t o wa t er usa ge/ effluent vessels
build- up a t convect ion sect ion ha ndling
fa n noise
Design fouling of t ubes need a ft er burning of spra y pa t t ern/ droplet
considera t ions plugga ge of int erconnect ing S/ H 2 S eva pora t ion
flues hot / cold int erfa ce cont rols
ra pid build- up a t WHB build- up pot ent ia l of st icky
int erfa ce a cid resist a nt refra ct or y dust ha ndling
ra pping syst em s coa rse solid sepa ra t ion
expa nsion bet ween ra dia t ion vent ing of wea k a cid
a nd convect ion sect ion t a nks
4.12 Sulphur Fixation

Su lp h u r can be fixed in metallu rgical p rocesses by at least on e of th e follow in g fou r
p rocesses:
• Su lp h u ric acid p rod u ction
• Gas scru bbin g an d gyp su m p rod u ction
• Liqu id su lp h u r d ioxid e m an u factu re
• Elem en tal su lp h u r p rod u ction
All of th e p rocesses above ben efit from h igh su lp h u r d ioxid e con cen tration s in th e
gas stream, both econ omically an d in terms of con version efficien cies. Th e p rod u c-
tion of liqu id su lp h u r d ioxid e an d elem en tal su lp h u r both requ ire h igh su lp h u r
d ioxid e con cen tration s. Du e to th e u se of oxygen -n rich ed air in th e p rocesses th is
can easily be ach ieved .
Su lp h u ric acid p rod u ction is th e m ost w id ely u sed p rocess for tw o reason s.
Firstly it is th e easiest an d least exp en sive su lp h u r fixation m eth od w h ich d oes n ot
requ ire h igh su lp h u r d ioxid e con cen tration s in th e off-gas. Secon d ly th e m arket
for su lp h u ric acid is m u ch larger th an for th e oth er p rod u cts in m an y location s.
Th e p rod u ction of gyp su m th rou gh th e ad d ition of lim eston e to an am m on i-
u m su lp h ite solu tion , w h ich is p rod u ced from su lp h u r d ioxid e, is n ot as cost ef-
fective as su lp h u ric acid p rod u ction . It w ou ld also requ ire th e h an d lin g of m an y

51
ton n es of lim eston e, w h ich is requ ired as a reagen t in th e p rocess, an d of th e su b-
sequ en t large am ou n t of gyp su m p rod u ced .
Th e p rod u ction of liqu id su lp h u r d ioxid e w ou ld p rovid e a good retu rn on
in vestm en t if th ere w ere a large m arket d em an d . Elem en tal su lp h u r p rod u ction
requ ires a h igh su lp h u r d ioxid e con cen tration in th e off-gas. Th e feasibility of su ch
a p rocess requ ires a local m arket an d th e availability of a low cost red u ctan t.
Th e fu el an d en ergy requ irem en ts for th e fixation of su lp h u r from low su l-
p h u r d ioxid e con cen tration stream s can be fou n d in Table 16. Th e p rim ary en ergy
requ ired for an y su lp h u r fixation p lan t is th e en ergy n eed ed to op erate th e m ain
blow ers th at rou te th e gases th rou gh th e acid p lan ts. Th e m ost econ om ical p roc-
ess is th e p rod u ction of su lp h u ric acid from a con tin u ou s gas stream /55/.
Ta ble 16. Fuel a nd ener gy r equir em ent s for sulphur fixa t ion.
Per t onne of SO 2 fixed Sulphuric a cid produced from ( Gypsum )
Cont inuous Va ria ble Com bined Am m onia Elem ent a l
ga s st rea m convert er cont inuous dua l a lka li sulphur
ga s st rea m & va ria ble scrubbing product ion
Feed ga s ( SO2 % )
12 5– 8 va ria ble 9– 12 9– 10
Elect ric power for
m a in blower a nd
rela t ed equipm ent 118 219 152 175 350
kWh/ t onne
Coa l for reduct a nt
kg/ t onne – – – – 330
Na t ura l ga s, for
3
st a rt - up Nm / t onne 2,8 3,6 2,5 19,1 22,8
Acid neut ra liza t ion
Elect ric power for
pum ps, et c. 52 52 52 – –
kWh/ t onne
Tot a l power required
kWh/ t onne SO 2 fixed 170 271 204 175 350
Alth ou gh th e Su m itom o Toyo sm elter u tilises th e trad ition al O u toku m p u flash

sm eltin g p rocess an d Peirce-Sm ith con verters, it h as d istin ct d ifferen ces from oth -
er sm elters arou n d th e w orld w h ich u tilise th at sam e tech n ology. It is on e of th e
clean est sm elters in th e w orld . Th e su lp h u r fixation at Toyo is 99.9 %. Th is is ac-
com p lish ed th rou gh a fu gitive gas collection system , au tom ated ch argin g of con -
verters an d tail gas scru bbin g (Table 17). Man y facilities h ave recen tly in stalled
fu gitive gas collection an d treatm en t system s in ord er to red u ce em ission s to an
accep table level /14/.
Ta ble 17. Toyo sulphur dist r ibut ion.
It em Dist r ibut ion %
Sulphur ic a cid 95.8
Gypsum 2.9
Sla g 1.1
Wa t er t r ea t m ent 0 .1
Em ission 0 .1
Tot a l 10 0

At th e Toyo sm elter th e am ou n t of h eavy oil u sed as fossil fu el in th e sm elter h as
been su bstitu ted sequ en tially by less exp en sive coal /29/.
4.13 Acid Plant

Th e p erform an ce of a m etallu rgical acid p lan t is d ep en d en t on th e p erform an ce
of th e gas clean in g section . If th e clean in g system is n ot effective in rem ovin g im -
p u rities from th e in com in g gas, th e p erform an ce of th e con tact section w ill d ete-
riorate. Alth ou gh th e d esign of w et gas clean in g system s m ay d iffer w id ely, th ey
h ave th e follow in g requ irem en ts an d featu res in com m on :
• Solid con tam in an ts m u st be rem oved , givin g a fin al gas qu ality of 1–2 m g
solid /N m 3
• Th e su lp h u r trioxid e con ten t of th e gas m u st be red u ced to th e level of 15–
25 m g/N m 3
• Flu orid es an d ch lorid es m u st be rem oved to p reven t d am age to th e d ow n -
stream tow er brickw ork an d con verter catalyst
• Th e gas m u st be cooled to a tem p eratu re of ap p roxim ately 35-40°C to satisfy
th e acid p lan t w ater balan ce
O p eratin g at a gas stren gth of 14 % SO 2 red u ces equ ip m en t sizes, d u e to th e re-
d u ced gas volu m e. It is estim ated th at th e red u ction in cap ital cost is 25 % an d th e
m ain com p ressor h orsep ow er is red u ced by 40 %, even com p ared to a p lan t d e-
sign ed for 10 % gas. Moreover, p u m p in g p ow er w ill also be red u ced by virtu e of
th e low er circu lation rates in th e h igh efficien cy d ryin g an d fin al absorber tow ers
/57/.
Ta ble 18 . Acid pla nt size wit h oxygen enr ichm ent va r ia t ion ( Ma t t e gr a de a t 60 % ) .
Oxygen enrichm ent 35 % 49 % 55 % 65 % 70 %
Concent ra t e sm elt ed t / d 2424 2424 2424 2424 2424
Ma t t e t / d 1486 1486 1486 1486 1486
Oxygen t / d 343 405 420 436 442
FSF process ga s
Volum e kNm 3 / h ( wet ) 43.7 28.3 24.7 20.4 18.9
SO2 % 19.6 30.2 34.6 41.7 45.2
FSF process ga s t o a cid pla nt
Volum e kNm 3 / h ( wet ) 78.8 53.5 47.6 40,6 38.0
SO2 % 10.9 16.0 17.9 21.0 22.4
Peirce- Sm it h convert er process
Ga s ( a vg.) t o a cid pla nt
Volum e kNm 3 / h ( wet ) 175.1 175.1 175.1 175,1 175.1
SO2 % 4.9 4.9 4.9 4.9 4.9
Avg. process ga s t o a cid pla nt
Volum e kNm 3 / h ( wet ) 253.8 228.6 227.7 215.8 213.2
SO2 % 6.8 7.5 7.7 8,0 8.1
Convert er scheduling
Volum e kNm 3 / h ( wet ) 366.3 341.0 335.1 328.1 325.5
Acid pla nt ca pa cit y, 10 %
Design fa ct or, kNm 3 / h ( wet ) 400.4 375.1 369.2 362.2 359,6
Rela t ive ca pit a l cost fa ct or 104 % 100 % 99 % 97.9 % 97.5 %

53
With flash sm eltin g tech n ology an d a sligh tly revised con tact section , th e gas
stren gth an d volu m etric savin gs can be p u sh ed even h igh er. At th e O lym p ic Dam
site in Au stralia (d irect blister p rod u cin g), a p recon verter w as u sed to allow op er-
ation at 18 % SO 2. In th is case, th e aim w as h igh er cap acity, w h ile m ain tain in g th e
stan d ard 99.7 % con version /57/.
O n e of th e op p ortu n ities of h igh gas stren gth is th e excess h eat it makes avail-
able. In th e m od ern sm elter su lp h u ric acid p lan t, th is h eat rep resen ts p oten tial
in com e in th e form of electrical p ow er /57/.
Su lp h u r d ioxid e em ission s can be m ain tain ed at less th an 100 p p m rep resen t-
in g 99.95 % collection efficien cy of th e 14 % SO 2 in th e feed gas. Un d er n orm al
op eratin g con d ition s SO 2 emission s are in th e 30–60 p p m ran ge /31/. Table 18 sh ows
th at in creasin g en rich m en t is accom p an ied by a corresp on d in g d ecrease in th e off
gas volu m e from th e flash fu rn ace. Sin ce m atte grad e is in th is exam p le h eld con -
stan t at 60 %, th e gas volu me to th e acid p lan t from th e con verters d oes n ot ch an ge
/59/.
Th e Ken n ecott Garfield sm elter is said to be th e clean est sm elter in th e w orld .
It u ses O u toku mp u Flash Smeltin g an d th e O u toku mp u -Ken n ecott Flash Con vert-
in g system . Th eir SO 2 em ission rate is 2.6 kg/ton n e of cop p er. To ach ieve th is val-
u e th ey h ave also a very m od ern acid p lan t.
Dyn a Wave scru bber system s w ere selected becau se of th eir h igh collection
efficien cy an d op en , robu st d esign . Th e gas clean in g system con sists of tw o stag-
es of Reverse Jet scru bbin g follow ed by tw o stages of m ist p recip itators /57/.
Th ere are som e gas booster blow ers in ord er to m eet th e extrem ely strin gen t
p rod u ct qu ality requ irem en ts, esp ecially w ith regard to h eavy m etals /57/.
Th e con tact section of th e acid p lan t gen erally follow s th e w ell-p roven Mon -
san to En viro Ch em 3:1 IPA arran gem en t. Caesiu m is u sed as catalyst. With th is
d esign an d th e oxygen -en rich ed feed gas, con version s of 99.9 % can be reach ed .
Th is tran slates to a gas efflu en t w ith less th an 100 p p m of SO 2 /57/.
Th e acid p lan t em p loys a boiler an d su p erh eater to recover sen sible h eat an d
a Mon san to H eat Recovery System to recover th e absorp tion h eat. Th e h eat recov-
ery tow ers h ave p roven to be easy an d safe to op erate /57/.
4.14 Tail and Secondary Gas Cleaning and Scrubbing

Acid p lan t in stallation s w ith tail gas scru bbin g are becomin g common /14/. Secon d -
ary em ission s are gases an d d u st from tap h oles, tran sfer p ots, etc. It is p ossible to
con trol th ese em ission s so th at th ey con tain su lp h u r less th an 0.1 % of th e in p u t
of th e sm elter. It is also n ecessary to recover d u st em ission s. To ach ieve su ch lev-
els, a m yriad of exh au st ven ts, blow ers an d au xiliary equ ip m en t m u st be ad d ed
which further increase the energy consumption. As an example of the requirements
n eed ed for su ch a “clean ” op eration , an en gin eerin g stu d y w as mad e on a 150,000–
200,000 ton n e/year cop p er p lan t. Table 19 gives th e en ergy requ irem en ts for su ch
an op eration w ith resp ect to th e sm elter area alon e /55/.
Th ese fu gitive em ission s com e from feed h an d lin g equ ip m en t, th e d ryer, fu r-
n aces, m atte an d slag gran u lation system s etc. Th ey can be treated w ith bag filters
an d scru bbers. O n e p ossibility is to u se calciu m h yd roxid e Ca(O H )2 w h ich h as a
h igh su rface area as an absorbin g agen t. Th e reaction p rod u ct is recircu lated sev-
eral tim es to exp loit it as far as p ossible. Th e en d p rod u ct is a m ixtu re of d u st, cal-
ciu m su lp h ate as well as ad d itive resid u e wh ich is fed to th e flash smeltin g fu rn ace.
A clean ed gas d u st con ten t of less th an 1 m g/N m 3 can be ach ieved in th e clean ed
off- gas from th e con n ected bagh ou se /47/.
All of th e en viron m en tal con trol equ ip m en t m u st be con tin u ou sly m on itored
to en su re com p lian ce.

Ta ble 19. Ener gy r equir em ent s for cont r ol of fugit ive em issions.
Design Ca pa cit y Tot a l Annua l
of exha ust fa n energy consum pt ion
Sm elt er Area Nm 3 / h kWh/ yea r
Concent ra t e a nd flux
receiving a nd ha ndling 377 000 1 080 000
Sm elt ing furna ce, hood,
la dle pit s, la under covers, et c. 187 000 750 000
Sla g ret urn la under hood 374 000 220 000
Tot a l power required for fugit ive
em ission cont rol for sm elt er a rea a lone 2 050 000
4.15 Waste Acid and Water Treatment

Th e w eak acid gen erated in th e gas clean in g section typ ically con tain s 1–20 %
H 2SO 4. H alid es w ill be p resen t as H Cl (10–1,000p p m ) an d H F (10–1,000 p p m in -
clu d in g H 2SiF6). Th e acid m ay also con tain m etals su ch as cop p er, zin c an d iron
(each u p to 2,500 p p m ), m ercu ry (u p to 1,900 p p m ) an d lead (u p to 50 p p m ). Ar-
sen ic m ay be p resen t u p to levels of 10,000 p p m . O th er elem en ts, su ch as alu m in -
iu m , n ickel, ch rom iu m , cad m iu m , bism u th , an tim on y, etc. m ay also be p resen t
d ep en d in g on th e con tam in an ts p resen t in th e sm elter feed . Th e w eak acid w ill
also be satu rated w ith SO 2 (typ ically betw een 2,000 an d 5,000 p p m d ep en d in g on
th e SO 2 stren gth ) /56/.
A typ ical m eth od for rem ovin g arsen ic from d ilu te su lp h u ric acid is to ad d a
ferric salt an d an oxid an t to p recip itate ferric arsen ate at a p H valu e betw een 2.5
an d 3.0 (< 0.5 % H 2SO 4) /56/.
Most of th e selen iu m w ill be volatilised d u rin g roastin g or sm eltin g. Un d er
oxid isin g con d ition s, selen iu m w ill en ter su lp h u ric acid as selen iou s acid . H ow-
ever, it is rap id ly red u ced to elem en tal selen iu m . Selen iu m is recovered from th e
w eak acid by filterin g /56/.
Weak acid can be u sed in h yd rom etallu rgical leach in g p rocesses an d in flota-
tion p rocesses. Th e m ost com m on treatm en t for w eak acid efflu en t, w h ich can n ot
be u sed elsew h ere, is lim e n eu tralisation . Th is p rod u ces large am ou n ts of gyp su m
w h ich is frequ en tly con tam in ated w ith p oten tially toxic m etal com p ou n d s an d
th erefore m u st be stored or d isp osed of. Th e ad van tage of th is ap p roach is th at it
is w ell establish ed an d u ses relatively straigh tforw ard equ ip m en t. Th e acid p ass-
es in to reaction vessels in to w h ich lim e slu rry is ad d ed to form solu ble calciu m
su lp h ate an d in solu ble h yd roxid es of m etals su ch as lead , zin c an d cop p er. Air an d
a ferric salt m ay be ad d ed to p rom ote th e p recip itation of ferric arsen ate. Th e p res-
en ce of ferric ion s also assists in th e rem oval of m ercu ry. Flu orid es w ill be p recip -
itated as calciu m flu orid e bu t ch lorid es w ill rem ain in solu tion . Th e slu rry is th ick-
en ed an d th e overflow is d isch arged to th e en viron m en t. In ord er to ach ieve op -
tim u m p erform an ce of th e n eu tralisation system , it is im p ortan t to m ain tain p H
con trol an d to m on itor an d con trol th e ratio of certain com p on en ts /56/.
Th e d isad van tage of th e n eu tralisation p rocess is th at th e gyp su m w h ich is
produced is usually not of a quality high enough to be sold. Therefore the produced
gyp su m h as trad ition ally been stored /56/.
H ow ever, in m an y location s, storage sp ace is lim ited an d con cern s exist th at
potentially toxic contaminants in the gypsum may leach to the groundwater. There-
fore, th ere is a grow in g ten d en cy to en cap su late th e gyp su m in th e fu rn ace slag
eith er via extern al ad d ition of th e gyp su m to th e m olten slag or by recyclin g th e
gyp su m slu d ge to th e sm eltin g fu rn ace /56/.

55
Man y p lan ts h ave an efflu en t treatmen t p lan t w h ich can treat acid ic d isch arg-
es, p rocess w ater an d con tam in ated site w ater. Metals are p recip itated w ith sod i-
u m h yd roxid e or lim e. Th e slu d ge form ed is led to clarification basin s. Th e filtered
overflow can be d isch arged to th e w aterw ays. Th e m etal p recip itates can be fed
to th e sm eltin g fu rn ace.
4.16 Comparison of Copper Smelting Processes

In form ation on cop p er sm elters h as been collected in Table 20. Th e d ata is from
1995 an d h as been taken from CRU rep orts. It is very d ifficu lt to com p are p lan ts
in variou s cou n tries an d geograp h ic location s. For exam p le labou r legislation , cli-
m atic con d ition s, in -p lan t tran sp ort costs, en ergy availability, available in frastru c-
tu re, sp ecial en viron m en tal p rotection requ irem en ts etc. in flu en ce on op eratin g
costs. H ow ever, m an y in terestin g tren d s can be seen . Th e w h ole sm eltin g p rocess
is in clu d ed in th e figu res in Table 20 begin n in g from th e d ryin g of th e con cen trate
u p to th e acid p lan t.
Th ere are h u ge d ifferen ces in th e am ou n t of m an -h ou rs n eed ed to p rod u ce
on e ton of cop p er. In on e p lan t on e m an -h ou r is n eed ed an d in an oth er 285 m an -
h ou rs. It seem s th at th ere are m an y w orkers in th e p lan ts in th e form er Soviet
Un ion an d very few in Jap an . O n e im p ortan t th in g is tod ay ’s tren d of ou tsou rc-
in g. Does th e p lan t em p loy all th e p eop le w orkin g for th em or d oes it bu y som e of
th e services n eed ed from ou tsid e com p an ies? In th e latter case th e am ou n t of
em p loyees is m u ch sm aller.
Th e total electricity u sed in th e sm elter varies from 380 to 867 kWh /ton n e of
con cen trate. Th e average is abou t 700 kWh . Th e Mitsu bish i p rocess h as th e h igh -
est con su m p tion . O n e p lan t w ith th e com bin ation of reverbatory fu rn ace, El
Ten ien te an d Peirce-Smith con verters u ses on ly 425 kWh /ton n e of con cen trate, bu t
its su lp h u r recovery is on ly 5 %!
It w as m en tion ed earlier in th is ch ap ter th at su lp h u r recovery can be im -
p roved by ad d in g tail gas scru bbin g p roced u res. It is in terestin g to com p are th e
p ercen tage of su lp h u r recoveries in th e p lan ts w h ich u se O u toku m p u flash sm elt-
in g, as m ost p lan ts w ith d ou ble con tact acid p lan ts recover 98 % or m ore. O f th e
sin gle con tact p lan ts on e recovers 95 % an d th e tw o oth ers 50 an d 75 %.
O n ly som e SO 2 em ission s are given in Table 20. Th e O u toku m p u -Ken n ecott
flash sm eltin g-flash con vertin g p lan t em its less th an 3.5 kg SO 2/ton n e of cop p er.
Th e Mitsu bish i p rocess em ission s are abou t 14 kg SO 2/ton n e of cop p er. Tw o oth er
p lan ts u sin g O u toku m p u flash sm eltin g an d Peirce-Sm ith con vertin g em it 18 an d
26 kg SO 2/ton n e of cop p er.
Figu re 8 sh ow s th e SO 2 em ission s in th e in tegrated H arjavalta p lan t. Th e
u p p er p art of th e figu re p resen ts th e total em ission s an d th e low er p art th e sp ecif-
ic em ission s p er ton n e of m etal p rod u ced . Th e p erm it lim it sin ce 1.1.1997 is 4,500
t/a. Th e big d ecreases in th e am ou n t of SO 2 are all d u e to h avin g m ore cap acity in
th e acid p lan t. Th e d ou ble con tact acid p lan t w as bu ilt in 1994. After th at SO 2 em is-
sion s d ecreased from 5,000 ton s to 3,300 ton n es p er year. Th e d ecrease from 9,000
to 5,200 ton n es p er year in 1991 was d u e to ch an gin g th e d ryin g meth od of th e con -
centrate. Earlier the concentrates were d ried in a higher temperature, which caused
SO 2 em ission s. In 1997 th e sp ecific em ission of SO 2 w as on ly 16 kg/t of m etal d e-
sp ite th e exp an sion of th e p rod u ction of cop p er an d n ickel /68/.

Ta ble 20 . Com pa r ison of copper sm elt er s.
New anode Capacity O2-enrichm. Natural gas Fuel oil Matte O2-enrichm. Oxygen
Concepts t t/h of smelting m3/t conc. kg/t conc. grade of converting consumption
% % % kg/t new Cu*
Stea m coil, OK fla sh smelter ( direct blister) , 61 000 13 75-95 56
electric furna ce, double conta ct
Rota r y dr yer, OK fla sh smelting, electric furna ce, 144 000 65 46 85
Hoboken converter ( 3) , double conta ct
Rota r y dr yer, OK fla sh smelting, sla g flota tion, 268 000 85 65-75 26 75 65-75 1700
OK fla sh converting, Monsa nto double conta ct
OK fla sh smelting, sla g flota tion, 351 000 115 43 54 65 21 800
P-S converter ( 5) ,double conta ct
Rota r y dr yer, OK fla sh smelting, electric furna ce, 210 000 97 40-45 44 60 23.5 700
P-S converter, double conta ct
Stea m dr yer( 2) , OK fla sh smelting, sla g flota tion, 104 000 90 95 24 68 26
P-S converter ( 3) double conta ct
Rota r y dr yer, OK fla sh smelting, electric furna ce, 196000 80 35 40 58 26
P-S converter ( 3) Chemico double conta ct ( 210 000* ) ( 67* )
Rota r y dr yer, OK fla sh smelting, electric furna ce, 178 000 80 60-70 40 58 25
P- S converter ( 3) ,double conta ct
Rota r y dr yer,OK fla sh smelting,electric furna ce, 182 000 80 55 60 24 750
P-S converter ( 3) , double conta ct
Rota r y dr yer, OK fla sh smelting, settling cha mber, 189 000 75 27 40 50 21
P-S converter ( 4) , double conta ct ( 192 000* ) ( 58-60* )
Rota r y dr yer, OK fla sh smelting, electric furna ce, 350 000 70 42 40 60 24
P-S converter ( 3) , double conta ct ( 3)
Rota r y dr yer ( 2) , OK fla sh smelting ( 2) , settling 312 000 2* 70 32 40 60 21-26
cha mber, P-S converter ( 6) ,double conta ct ( 3)
P-S converters ( 3) , double conta ct ( 3)
Fla sh dr yer, OK fla sh smelting, settling cha mber, 212 000 72 34 57 61 25
P-S converter ( 3) , Monsa nto double conta ct
P-S converter ( 2) , single conta ct
Rota r y dr yer, OK fla sh smelting, electric furna ce, 165 000 70 60 44 60 24 800
Hoboken converter ( 3) , double conta ct
OK fla sh smelting, sla g disca rd, P-S converter ( 3) 115 000 55 47 60 850
single conta ct
Rota r y dr yer ( 2) , OK fla sh smelting, sla g flota tion, 28 000 120 50 37 50 25
P-S converter ( 3) , single conta ct, double conta ct
Rota r y dr yer, OK fla sh smelting, sla g flota tion, 10 000 33 50
P-S converter
Rota r y dr yer, OK fla sh smelting, electric furna ce, 105 000 36-40 44 52.5
Rota r y dr yer, OK fla sh smelting, sla g clea ning furna ce, 15 000 9 40 50
P-S converter ( 2) ,single conta ct
Rota r y dr yer, OK fla sh smelting, sla g flota tion, 33 000 36 42 47
Rota r y dr yer, OK fla sh smelting, sla g flota tion, 32 000* 93 50
Fluid bed dr yer ( 2) , Inco fla sh ( 2) , sla g disca rd, 114 000 2* 83 100 28 49
MK furna ce, Monsa nto double conta ct
Fluid bed dr yer, Inco fla sh, settling furna ce, 160 000 63 95 29 60 21 900
Fluid bed dr yer ( 2) , Inco fla sh, disca rd sla g, 157 000 80 90 23 50 23 1100
Rota r y dr yer, Mitsubishi continuous, electric 122 000 70 48-50 61 67 32 900
furna ce, Mitsubishi continuous, double conta ct ( 40-45) ( 68-69) ( 30-35)
Rota r y dr yer, Mitsubishi continuous, electric furna ce, 202 000 120 43 35 69 28
Mitsubishi continuous, single conta ct ( 2)
No dr yer, Nora nda rea ctor, sla g flota tion, 220 000 100 35-40 51 71 21 1000
Fluid bed dr yer, reverbera tor y, El Teniente converter ( 2) , 180 000 40 30 35 47 30 730
Rota r y dr yer ( 3) , OK fla sh smelting, sla g flota tion, El 442 000 47 50 900
Teniente ( 2) , P-S converter ( 5) , single conta ct, double conta ct
Rota r y dr yer, Isa smelt,electric furna ce, 147 000 50* 57 52 21 800
Hoboken converter, double conta ct ( 58-60* )
Hyperba ric filters, reverbera tor y, Isa smelt, 136 000 67 60
P-S converter ( 3)
Fluid bed dr yer, Contop, settling furna ce, 100 000 43 70 21 1150
Rota r y dr yer ( 2) , Va nya kov ( 2) , settling, P-S converter ( 8) 300 000 25-35 23 55 21

57
Ta ble 20 . Com pa r ison of t he sm elt er s ( cont inued) . Man-h/ Electricity use Electricity use Electricity use Electricity use Acid SO2 Sulphur Operating
Concepts t new smelting acid pl oxygen total in smelter plant emissions Capture cost 1995
anode kW h/ t conc kW h/ t conc kW h/ t conc kW h/ t conc feed gas kg SO2 / % $ c/lb Cu
SO2 %* t Cu
St ea m coil, OK fla sh sm elt er ( direct blist er) , 3.2 50 95 350 495 97 6.3
elect ric furna ce, double cont a ct
Rot a r y dr yer, OK fla sh sm elt ing, elect ric furna ce, 9.2 110 170 450 730 95.5 15.2
Hoboken convert er ( 3) , double cont a ct
Rot a r y dr yer, OK fla sh sm elt ing, sla g flot a t ion, 4.8 60 110 450 620 34 ~ 3.5 99 8.8
OK fla sh convert ing, Monsa nt o double cont a ct
OK fla sh sm elt ing, sla g flot a t ion, 2.3 220 99 284 603 8-10 ~ 26 98 11
P-S convert er ( 5) ,double cont a ct
Rot a r y dr yer, OK fla sh sm elt ing, elect ric furna ce, 5 140 135 450 725 8 98 12.6
P-S convert er, double cont a ct
St ea m dr yer( 2) , OK fla sh sm elt ing, sla g flot a t ion, 4.5 61 99 220 380 ~ 18 98.1 13.7
P-S convert er ( 3) double cont a ct
Rot a r y dr yer, OK fla sh sm elt ing, elect ric furna ce, 1.8 150 163 450 763 ( 13* ) 98.4 21.9
P-S convert er ( 3) Chem ico double cont a ct ( 99.9* )
Rot a r y dr yer, OK fla sh sm elt ing, elect ric furna ce, 3.6 50 144 450 644 98 7.7
P- S convert er ( 3) ,double cont a ct
Rot a r y dr yer,OK fla sh sm elt ing,elect ric furna ce, 8.8 200 101 370 671 10 90 5.3
P-S convert er ( 3) , double cont a ct
Rot a r y dr yer, OK fla sh sm elt ing, set t ling cha m ber, 3.1 145 193 450 788 96 8.7
Rot a r y dr yer, OK fla sh sm elt ing, elect ric furna ce, 1 130 163 400 693 99.5 19.7
P-S convert er ( 3) , double cont a ct ( 3)
Rot a r y dr yer ( 2) , OK fla sh sm elt ing ( 2) , set t ling 1.2 144 163 450 757 99.3 22.9
cha m ber, P-S convert er ( 6) ,double cont a ct ( 3)
Rot a r y dr yer, OK fla sh sm elt ing, elect ric furna ce, 4.7 130 163 450 743 97.5 12.5
P-S convert ers ( 3) , double cont a ct ( 3)
Fla sh dr yer, OK fla sh sm elt ing, set t ling cha m ber, 1.5 142 163 450 755 98 23.9
P-S convert er ( 3) , Monsa nt o double cont a ct
Rot a r y dr yer, OK fla sh sm elt ing, elect ric furna ce, 2.7 120 160 450 730 99 27.5
P-S convert er ( 2) , single cont a ct
Rot a r y dr yer, OK fla sh sm elt ing, elect ric furna ce, 6.1 140 140 450 730 10 92 9.6
Hoboken convert er ( 3) , double cont a ct
OK fla sh sm elt ing, sla g disca rd, P-S convert er ( 3) 7 100 150 450 700 8 93 15.1
single cont a ct
Rot a r y dr yer ( 2) , OK fla sh sm elt ing, sla g flot a t ion, 55.7 95 100 400 595 90 10.4
P-S convert er ( 3) , single cont a ct , double cont a ct
Rot a r y dr yer, OK fla sh sm elt ing, sla g flot a t ion, 285 70 140 450 660 90 81.6
P-S convert er
Rot a r y dr yer, OK fla sh sm elt ing, elect ric furna ce, 6.3 70 120 98
Rot a r y dr yer, OK fla sh sm elt ing, sla g clea ning furna ce, 56 140 111 450 701 75 34.7
P-S convert er ( 2) ,single cont a ct
Rot a r y dr yer, OK fla sh sm elt ing, sla g flot a t ion, 37.8 140 197 450 787 50 31.2
Rot a r y dr yer, OK fla sh sm elt ing, sla g flot a t ion, 38.6 90 120 95
Fluid bed dr yer ( 2) , Inco fla sh ( 2) , sla g disca rd, 4.4 130 130 450 710 98 15.6
MK furna ce, Monsa nt o double cont a ct
Fluid bed dr yer, Inco fla sh, set t ling furna ce, 4.7 155 120 450 725 8-10 97 13.1
Fluid bed dr yer ( 2) , Inco fla sh, disca rd sla g, 4.6 130 135 450 715 8-10 95 11.4
Rot a r y dr yer, Mit subishi cont inuous, elect ric 3 227 240 400 867 13 ~ 14 99 9.7
furna ce, Mit subishi cont inuous, double cont a ct
Rot a r y dr yer, Mit subishi cont inuous, elect ric furna ce, 2.9 144 193 450 787 10.5* * 99 24.6
Mit subishi cont inuous, single cont a ct ( 2)
No dr yer, Nora nda rea ct or, sla g flot a t ion, 7.2 150 107 450 707 7-10 75 12
Rot a r y dr yer, reverbera t or y, El Tenient e convert er ( 2) , 6.5 80 95 250 425 4.2 5 7.3
Rot a r y dr yer ( 3) , OK fla sh sm elt ing, sla g flot a t ion, El 4.9 100 140 450 690 10.2 68 8
Tenient e ( 2) , P-S convert er ( 5) , single-, double cont a ct
Rot a r y dr yer, Isa sm elt ,elect ric furna ce, 3.8 123 164 461 748 8.3 98.4 9.9
Hoboken convert er, double cont a ct ( 7.5* )
Hyperba ric filt ers, reverbera t or y, Isa sm elt , 3.6 95 350 0 9
P-S convert er ( 3)
Fluid bed dr yer, Cont op, set t ling furna ce, 4.7 100 150 450 700 4-8 96 15.3
Rot a r y dr yer ( 2) , Va nya kov ( 2) , set t ling, 15.8 100 200 400 700 80
P-S convert er ( 8)

SO 2 emission t/a
25000
A
20000
15000
10000
5000
0
1950 1960 1970 1980 1990 1991 1992 1993 1994 1995 1996 1997
Year
Specificemission kg SO 2/t metal

1200
1000 B
1000
800
600
330
400 270
140
200 80 45 35 36 41 31 18 16
0
1950 1960 1970 1980 1990 1991 1992 1993 1994 1995 1996 1997
Year
Figure 8. Sulphur dioxide emissions in H arjavalt a in t he years 1950–1997. A. Tot al emis-

sions. B. Specific emissions /68/.
Th e op eratin g costs also vary qu ite a lot, from 5.3 to 81.6 Usc/lb Cu . Th e h igh est
figu re of cou rse belon gs to th e p lan t w ith m an y m ore w orkers th an th e oth ers. In
th e O u toku m p u -Ken n ecott flash sm eltin g-flash con vertin g p lan t th e costs are 8.8
USc/lb Cu , in th e p lan ts u sin g th e Mitsu bish i p rocess from 9.7 to 24.6 USc/lb Cu
an d in th e Isasm elt p lan ts 9 an d 9.9 USc/lb Cu .
H.Soh n h as com p ared cop p er sm eltin g p rocesses an d w rites /43/:
• Th e Ken n ecott-O u toku m p u Flash Con vertin g p rocess: Th e solid ification of
m atte from th e sm eltin g fu rn ace h as p roven to be an effective ap p roach to
m axim isin g th e in h eren t flexibility of th e sm elter by avoid in g th e p roblem s
of main tain in g an d regu latin g con tin u ou s metal flow s. Th e solid matte allow s
h igh levels of oxygen en rich m en t, an d w ith th e w ell-p roven fu rn ace d esign
O u toku m p u th e p rocess can be d esign ed for a w id e ran ge of sm elter cap aci-
ties. Environmental control is exceptional with emissions less than 3.5 kg (SO 2)/
ton n e of cop p er or 99.9+ su lp h u r recovery, th e low est em ission rate in th e
w orld .
• Th e Mitsu bish i p rocess is su itable for cop p er p rod u ction of u p to 200,000
ton n es p er year of n ew m etal.
• Bath sm eltin g p rocesses in clu d in g th e N oran d a p rocess an d th e closely allied
Caleton es Matte Treatm en t (CMT) p rocess h ave n ot yet been d em on strated
to m eet th e h igh est levels of em ission con trol.

59
• Th e Van yu kov foam -bath sm eltin g p rocess for both cop p er an d n ickel h as
been ap p lied at N orilsk, Balkash , an d Sred n eu ralsk sm elters, bu t it h as n ot
been ad op ted ou tsid e th e CIS cou n tries.
• Th e IsaSm elt Process an d th e closely related Au sm elt (also Sirosm elt) p roc-
ess ap p ear to be a good op tion for sm aller p lan ts, p articu larly on es w ith a
sou rce of secon d ary feed w h ich can easily be sm elted in th e reactor.
• Th e Con top , w h ich stan d s for CO Ntin u ou s smeltin g an d TO P blow in g, p roc-
ess h as resu lted in 98 % su lp h u r recovery. Th e p rocess w ill be closed d ow n
in 1999.
Th e Mitsu bish i p rocess em p loys bath sm eltin g as a con tin u ou s p rocess w ith h igh
reaction u n iform ity. Th is p rocess allow s a com p act facility w ith h igh p rod u ctivity.
Th e d isad van tage is th at th e brick of th e fu rn ace ceilin g is likely to be su bstan tial-
ly d am aged ow in g to th e calciu m ferrite slag em p loyed in th is p rocess an d sp lash
erosion resu ltin g from bath sm eltin g. Th erefore, it is d ifficu lt to keep a h igh qu al-
ity w orkin g en viron m en t. Ad d ition ally, th e em ission load to th e p erip h ery of th e
sm elter is relatively h igh . Th e brick of th e fu rn ace bod y as a reaction vessel is also
su scep tible to fu sion loss. A large am ou n t of w ater coolin g blocks are u sed to over-
com e th is p roblem , resu ltin g in large en ergy losses. Th e fu rn ace fu rth er requ ires
a large am ou n t of en ergy to cap tu re fu gitive gases, w h ich is also a d isad van tage.
4.17 Electrolytic Refining

In th e electrolytic refin in g of cop p er it is p ossible to u se p erm an en t cath od e tech -
n iqu es in stead of cop p er starter sh eets. Th e ISA p rocess u ses stain less steel p lates,
from w h ich th e cop p er cath od es are strip p ed w ith au tom atic strip p in g m ach in es.
An oth er m od ern electrolytic refin in g con cep t is th e Falcon brid ge/Kid d Creek p er-
m an en t cath od e ap p roach . Th is tech n iqu e is very sim ilar to th e ISA p rocess. Th e
m ain d ifferen ce is th e fact th at Kid d Creek d oes n ot u se sid e an d bottom w ax an d
th erefore th e cop p er d ep osits on both sid es of th e cath od e p late grow togeth er at
th e bottom /2/.

B est A v a i l a b l e Tech n i q u e
○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
In th e last ch ap ter th e variou s p rocess step s in p yrom etallu rgical cop p er p rod u c-
tion w ere d iscu ssed . It is easy to con clu d e th at th ere is n o u n am bigu ou s best avail-
5
able tech n iqu e. Th e best available tech n iqu e con sists of op tim ised u n it p rocesses.
Th ese u n it p rocesses m u st be d esign ed in su ch a w ay th at th ey fit togeth er. All
p articu late an d gaseou s em ission s m u st be kep t in strict con trol.
Th e best available tech n iqu e con sists of th e follow in g u n it p rocesses:
• Th e con cen trates are stored in w areh ou ses.
• Th e con cen trates are d ried in m u lticoil steam d ryers.
• A loss-in w eigh t feed in g system is u sed to feed th e con cen trate in to th e flash
sm eltin g fu rn ace.
• Th e con cen trate is sm elted in th e flash sm eltin g fu rn ace u sin g a h igh oxygen
en rich m en t of air (65–75 %). Th e gas p rod u ced in th e reaction s in th e reac-
tion sh aft is cooled an d clean ed in a w aste h eat boiler an d electrostatic p re-
cip itator before p assin g th rou gh gas scru bbers to th e acid p lan t. All d u st col-
lected in the electrostatic precipitators is recycled to the flash smelting furnace.
• Th e h igh grad e m atte is gran u lated d irectly from th e flash sm eltin g fu rn ace
w ith ou t an y lad le tran sp ort. Th e slag is cooled , cru sh ed an d grou n d before
flotation for cop p er recovery. Th e slag con cen trate is fed in to th e flash sm elt-
in g fu rn ace togeth er w ith th e p rim ary con cen trate. Th e oth er op tion is to u se
an electric fu rn ace for slag clean in g.
• Cop p er m atte is sm elted in th e flash con vertin g fu rn ace u sin g h igh oxygen
en rich m en t. Th e gas p rod u ced in th e reaction s in th e reaction sh aft is cooled
an d clean ed in a w aste h eat boiler an d electrostatic p recip itator before p ass-
in g th rou gh gas scru bbers to th e acid p lan t. All d u st collected in th e electro-
static p recip itators is recycled to th e flash sm eltin g fu rn ace or th e flash con -
vertin g fu rn ace.
• Th e m olten blister cop p er is tap p ed from th e flash con vertin g fu rn ace via
lau n d ers d irectly in to th e an od e fu rn ace.
• Blister cop p er is refin ed in th e an od e fu rn ace an d cast in to an od es.
• Cop p er an od es are electrorefin ed to cop p er cath od es by th e p erm an en t cath -
od e tech n iqu e.
• Th e clean ed gas stream from th e fu rn aces is rou ted to a m od ern d ou ble con -
tact acid p lan t for th e p rod u ction of su lp h u ric acid .
• Th e p lan t is equ ip p ed w ith good en viron m en tal con trol equ ip m en t:
1. All feed h an d lin g equ ip m en t is ven ted th rou gh h igh -efficien cy bag fil-
ters.
2. Dryer gas, after clean in g in a bag filter, p asses th rou gh a d esu lp h u risa-
tion gas scrubber, before being d ischarged to the atmosphere through the
stack.
3. Secon d ary gas, p rim arily from th e fu rn ace lau n d er ven tilation system s,
is exh au sted th rou gh a fou r-com p artm en t bag filter, scru bbed u sin g so-
d iu m h yd roxid e an d d isch arged th rou gh th e stack.
4. An od e fu rn ace com bu stion an d refin in g gases are p rocessed th rou gh
d esu lp h u risation scru bbers w h ich , in ad d ition to con trollin g SO 2 em is-
sion s d u rin g th e fu rn ace oxid ation p rocess, also rem ove th e fin e p artic-

61
u lates from th e fu rn ace gas. Th e clean ed gas is d isch arged to th e atm os-
p h ere th rou gh th e stack.
5. Th e exh au st gases from th e matte an d slag gran u lation systems are p roc-
essed th rou gh th e secon d ary gas h an d lin g system .
Ken n ecott Corp oration ’s Magn a sm elter in th e Un ited States u ses th is Ken n ecott-
O u toku m p u Flash Sm eltin g Flash Con vertin g p rocess ju st as it is d escribed in th is
ch ap ter. Th e p lan t h as been d esign ed to treat 1,000,000 ton n es of con cen trates a
year. Its SO 2 em ission levels h ave been u n d er 3.5 kg SO 2 p er ton n e of cop p er, th e
low est em ission rate in cop p er sm eltin g p lan ts in th e w h ole w orld . With cu rren t
em ission an d cop p er p rod u ction rates, th e em ission rate is 2.6 kg SO 2 p er ton n e of
cop p er.
Perm it level for p articu late m atter PM10 is 400 ton n es/year. Th e actu al last 12
m on th s PM em ission s h ave been 276 ton n es.
Th e Flash Sm eltin g Flash Con vertin g p rocess h as th e follow in g ad van tages:
• Low in vestm en t an d op eration costs for th e w h ole sm elter in clu d in g sm elt-
in g, con vertin g an d acid p rod u ction
• H igh p rocess en ergy efficien cy
• H igh on -lin e availability
• Flexibility to treat a w id e ran ge of raw m aterials
• H igh su lp h u r fixation from con tin u ou s h igh SO 2 gas flow, e.g. m in im u m
em ission s to th e en viron m en t an d w orkin g atm osp h ere
• Elim in ation of u n n ecessary m olten m aterial tran sp ortation , e.g. m in im u m
em ission s of fu m es an d SO 2 to th e en viron m en t an d w orkin g atm osp h ere
• Low revert form ation rate
• Low m etal con ten t in vitrified silicate slag
• H igh d egree of au tom ation .

Em er g i n g Tech n i q u es
○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
It is qu ite d ifficu lt to d eterm in e th e d ifferen ce betw een available an d em ergin g

tech n iqu es. In th is stu d y “available” m ean s th at an op eratin g com p an y, follow in g
6
issu e of a com m ercial in vitation to ten d er to a m etallu rgical en gin eerin g d esign
con tractor for th e con stru ction of a fu ll scale p lan t, cou ld exp ect to receive an of-
fer cap able of accep tan ce, in clu d in g tech n ical an d com m ercial p erform an ce gu ar-
an tees. If su ch an offer w as u n likely to be forth com in g th e p rocess/p lan t sh ou ld
be con sid ered as “em ergin g”. Em ergin g tech n iqu es h ave, h ow ever, been tested on
p ilot scale an d th e resu lts an d p rocess calcu lation s seem p rom isin g.
6.1 Pyrometallurgical Processes

In ten sive p rocess d evelop m en t is goin g on in th e cop p er sm eltin g p rocesses. O n e
em ergin g flash sm eltin g p rocess is th e Kivset p rocess, w h ich is in u se in Kazak-
stan . Th e N oran d a-Mitsu bish i con tin u ou s sm elter w ill start in 1999. In th is p roc-
ess th e p lan t h as been retrofitted by com bin in g th e N oran d a reactor w ith a con -
tin u ou s Mitsu bish i typ e con vertin g fu rn ace. It m akes p ossible a p ractically con tin -
u ou s op eration from con cen trate to blister sm eltin g. Th e op eration of th e sm elter
an d th e em ission valu es obtain able w ill be seen in th e fu tu re.
Research ers alread y h ave som e vision of th e cop p er sm elter of tom orrow. It
goes fu rth er th an tod ay ’s con cep t of flash sm eltin g-flash con vertin g. Th e sm elter
w ill h ave on ly on e sin gle fu rn ace w h ich p rod u ces d irectly blister cop p er, d iscard
slag an d h as on ly on e con tin u ou s off-gas stream . It cou ld be as follow s:
• Th e flash sm eltin g fu rn ace h as tw o reaction sh afts, on e for sm eltin g con cen -
trates to m atte an d on e for sm eltin g m atte an d h igh grad e con cen trates to
blister. Du e to SO 2 recircu lation it is p ossible to u se p u re oxygen in sm eltin g.
• Th e slag from th e blister cop p er sm eltin g p art ru n s in to a sm eltin g settler an d
is red u ced . Th e blister is tap p ed ou t con tin u ou sly an d is p ossibly refin ed be-
fore th e an od e fu rn ace.
• Th e m atte from th e p rim ary sm eltin g p art is con tin u ou sly tap p ed an d gran -
u lated . Th e cop p er con ten t of th e slag is red u ced in th e slag clean in g u n it
located at th e oth er en d of th e fu rn ace so th at th e con tin u ou sly skim m ed slag
can be d iscard ed .
• Th e low d u st-con tain in g p rocess gas p asses th rou gh a gas coolin g u n it an d
th rou gh d u st sep aration to a n ew gen eration acid p lan t, w h ich is able to p ro-
d u ce su lp h u ric acid w ith ou t d ilu tion of th e h igh stren gth p rocess gas. Sep a-
rated d u st is treated so th at im p u rities are bled off in con cen trated saleable
or in ert form . Resid u e from th e treatm en t u n it is th en circu lated back in to th e
p rim ary sm eltin g u n it.
6.2 Hydrometallurgical Processes

O f th e m an y p rocesses th at h ave been p rop osed for th e h yd rom etallu rgical p ro-
d u ction of cop p er, th e m ajority h ave been d evelop ed on ly as far as ben ch scale.

63
Th e d rivin g force beh in d h yd rom etallu rgical p rocesses is en viron m en tal p rotec-
tion , w h en n o SO 2 is p rod u ced from su lp h id e con cen trates, bu t su lp h id es are ox-
id ised to w ater solu ble su lp h ates or p referably to elem en tal su lp h u r, w h ich is in -
ert an d can be stored safely /26/.
Most su lp h id ic con cen trates also con tain iron . Th e p roblem s of iron d isp osal
can be illu strated by th e zin c in d u stry, w h ere jarosite, goeth ite an d h aematite p roc-
esses h ave been u sed for a lon g tim e. Th e key requ irem en ts for a h yd rom etallu r-
gical su lp h id e con cen trate p rocess are n ot d ictated by th e qu ality of cop p er, w h ich
is easy to ach ieve w ith SX-EW, bu t rath er th e fates of th e m ajor by-p rod u cts, su l-
p h u r an d iron . Th ese p roblem s h ave n ot yet been solved w ell en ou gh .
Th e leach in g p rocesses d evelop ed far en ou gh th at th ey can be p resu m ed to
be em ergin g tech n iqu es, are th e In tec p rocess an d Com in co´ s CESL p rocess. Th e
d evelop m en t of th e bioleach in g of ch alcop yritic cop p er con cen trates is also p ro-
ceed in g fast, as Billiton is d evelop in g a “Biocop ”-p rocess.

Con cl u si on s a n d R ecom m en d a t i on s
○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
Abou t 90 % of th e w orld ’s cop p er p rod u ction from ores is n ow man u factu red from
su lp h id ic ores by p yrom etallu rgical tech n iqu es. H yd rom etallu rgical cop p er p ro-
7
d u ction h as, h ow ever, becom e m ore im p ortan t d u rin g th e last d ecad e. In th e year
2000 m ore th an 20 % of cop p er is exp ected to be p rod u ced by th e leach in g of cop -
p er ores or con cen trates.
O n ly th e p yrom etallu rgical cop p er p rocess is u sed in Fin lan d to recover cop -
p er from cop p er con cen trates. Selen iu m , tellu riu m , silver, gold , p latin u m an d p al-
lad iu m are recovered in th e p rocess as by-p rod u cts.
Th e p yrom etallu rgical treatm en t of cop p er su lp h id e con cen trates com m on -
ly includes two types of operations, smelting and converting. In the smelting phase,
p art of th e su lp h u r an d iron in th e con cen trate feed is oxid ised w ith oxygen -en -
rich ed air at abou t 1,200°C an d a m olten su lp h id e p h ase (m atte) rich in cop p er is
p rod u ced . Cop p er con vertin g con sists of air oxid ation of th e m olten m atte from
sm eltin g. Con vertin g rem oves th e iron an d su lp h u r from th e m atte an d p rod u ces
cru d e m olten m etallic blister cop p er. Th e slag form ed is d iscard ed after a p u rifica-
tion step . Blister cop p er is fire-refin ed an d cast in to an od es. Th e an od es are elec-
trorefin ed to p u re cop p er cath od es. Th e rem ain in g an od e slim e is fu rth er treated
to recover th e rem ain in g m etals.
Th e m ain solid w aste from th e p rocess is th e rem ain in g slag w h ich h as to be
stored in a tailin gs area. Liqu id efflu en ts from p yrom etallu rgical p rocesses are of
m in or im p ortan ce becau se th ese p rocesses are essen tially d ry. Liqu id efflu en ts
resu lt from th e coolin g w ater system , from th e su lp h u ric acid p lan t attach ed to th e
sm elter an d from w et gas clean in g system s. Wet gas clean in g system s p rod u ce a
w eak acid . Th ey also collect arsen ic, m ercu ry, selen iu m an d fin e d u st p articles
con tain in g oth er im p u rities. Th e m ajor en viron m en tal p roblem resu lts from th e
release of SO 2 an d p articu late em ission s.
Th e best available tech n iqu e to p rod u ce cop p er from su lp h id ic con cen trates
con sists of th e follow in g u n it p rocesses:
• Th e con cen trates are stored in d oors an d d ried in m u lticoil steam d ryers.
• A loss-in -w eigh t feed in g system is u sed to feed th e con cen trate.
• Th e flash sm eltin g flash con vertin g p rocess is u sed .
• Th e slag is clean ed .
• Blister cop p er is refin ed in th e an od e fu rn ace an d cast in to an od es.
• Cop p er an od es are electrorefin ed to cath od es u sin g p erm an en t cath od es.
• Th e clean ed gas stream from th e fu rn aces is rou ted to a m od ern d ou ble con -
tact acid p lan t.
• Th e p lan t is equ ip p ed w ith a good en viron m en tal con trol system .

65
Li t er a t u r e
○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○
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p p .493-501.

67
38. Bystrov V. P. an d Kom kov A. A. O p tim izin g th e Van yu kov p rocess an d fu rn ace for
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Green field cop p er sm elter, EPD Con gress 1996, Proceed in gs of session s an d Sym p osia
sp on sored by th e extraction an d p rocessin g d ivision , h eld at th e TMS An n u al Meet-
in g in An ah eim , Californ ia, Febru ary 4-9,1996, p p .875-891.
42. Baba K. an d H on d o K. Th e fu tu re of th e flash sm eltin g p rocess in Jap an an d Asia,
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1996, p p .393-407.
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sym p osiu m h eld at th e 1998 TMS An n u al Meetin g, San An ton io, Texas, Febru ary 16-
19,1998, p p .3-37.
44. Ven katesh S.V., Sh arm a,A.K. an d Kh an d elw al K.C.D. Dah ej sm elter com p lex- an over-
view. Proceed in gs of th e Eigh th In tern ation al Flash Sm eltin g Con gress, U.S.A., 13-
18.10, 1996, p p .45-56.
45. Yaom in g Z. an d Ju n Z. Review of Jin lon g cop p er flash sm elter, Proceed in gs of th e
Eigh th In tern ation al Flash Sm eltin g Con gress, U.S.A., 13-18.10,1996, p p .57-65.
46. Jon es D.M. an d Gon zales T.W. Up d ate on th e first cam p aign of th e BH P San Man u el
sm elter. Proceed in gs of th e Eigh th In tern ation al Flash Sm eltin g Con gress, U.S.A., 13-
18.10, 1996, p p .183-198.
47. Gern erth S. an d Willbran d t P. Presen t ch an ges at N ord d eu tsch e Affin erie’s cop p er
sm elter, Proceed in gs of th e Eigh th In tern ation al Flash Sm eltin g Con gress, U.S.A, 13-
18.10, 1996, p p .95-111.
48. An d ersin E., An jala Y. an d Lah tin en M. O p tion s in cop p er flash sm elter exp an sion
an d m od ern ization . Proceed in gs of th e Eigh th In tern ation al Flash Sm eltin g Con gress,
U.S.A., 13-18.10, 1996, p p .373-391.
49. Gon zalez P., Bon ifaz R. an d Su biabre R. Start-u p exp erien ce at Ch agres sm elter. Pro-
ceed in gs of th e Eigh th In tern ation al Flash Sm eltin g Con gress, U.S.A., 13-18.10, 1996.
p p .27-44.
50. Takah ash i M. Th e d evelop m en t h istory of flash d ryer for cop p er con cen trates. Pro-
ceed in gs of th e Eigh th In tern ation al Flash Sm eltin g Con gress, U.S.A., 13-18.10, 1996,
p p 163-175.
51. H im m i M., Saari M. an d Vartiain en A. Slag Clean in g of H arjavalta Cop p er Flash
Sm elter. Au fbereitu n gstech n ik in H u etten w erken H eft 54,1989, p p . 163-174.
52. Ran a I.A., N ah as W.N . an d an d Allee R.E. Con vertin g altern atives for cop p er sm eltin g
p rocesses, Con vertin g , fire refin in g an d castin g, Proceed in gs of a sym p osiu m sp on -
sored by th e Extraction an d Processin g Division Pyrom etallu rgical Com m ittee, h eld at
th e 1994 TMS An n u al Meetin g an d Exh ibition in San Fran cisco, Californ ia, Febru ary
27-March 3, 1994, p p .91-105.
53. Safe P. an d Jon es D.M. Process off-gas coolin g d esign con sid eration s for n on -ferrou s
m etallu rgical p rocesses, Su lfid e Sm eltin g’98 Cu rren t an d Fu tu re Practices, Proceed -
in gs of th e sym p osiu m h eld at th e 1998 TMS An n u al Meetin g San An ton io, Texas,
Febru ary 16-19,1998, p p .401-415.
54. Ku m ar K.S. an d Man sou r A. A review of recen t d evelop m en ts in p articu late con trol in
th e cop p er an d n ickel in d u stry, Su lfid e Sm eltin g’98 Cu rren t an d Fu tu re Practices,
Proceed in gs of th e sym p osiu m h eld at th e 1998 TMS An n u al Meetin g San An ton io,
Texas, Febru ary 16-19,1998, p p .443-450.
55. Lam on tagn e E.M. an d Pickles C.A. En ergy an d en viron m en tal con sid eration s in n ick-
el sm eltin g p rocesses. Proceed in gs of th e N ickel-Cobalt 97 In tern ation al Sym p osiu m -
Volu m e II,I Au gu st 17-20, 1997, Su d bu ry, O n tario, Can ad a, p p .397-413.

56. Law ler D. W., Evan s C. M., Lyn e E. G. C. an d Th om p son J. Metallu rgical gas clean in g
efflu en t d econ tam in ation an d acid recovery, Su lfid e Sm eltin g’98 Cu rren t an d Fu tu re
Practices, Proceed in gs of th e sym p osiu m h eld at th e 1998 TMS An n u al Meetin g San
An ton io, Texas, Febru ary 16-19,1998, p p .473-489.
57. Pu ricelli S.M., Gren d aj R.W. an d Fries R.M. Pollu tion to p ow er: A case stu d y of th e
Ken n ecott su lfu ric acid p lan t, Su lfid e Sm eltin g’98 Cu rren t an d Fu tu re Practices, Pro-
ceed in gs of th e sym p osiu m h eld at th e 1998 TMS An n u al Meetin g San An ton io, Texas,
Febru ary 16-19,1998, p p .451-462.
58. Tjerkstra M. an d Ph illip s P. Kalgoorlie n ickel sm elter en viron m en tal Project, Su lfid e
Sm eltin g’98 Cu rren t an d Fu tu re Practices, Proceed in gs of th e sym p osiu m h eld at th e
1998 TMS An n u al , San An ton io, Texas, Febru ary 16-19,1998, p p .93-109.
59. Ran a I.A. Acid p lan t size d eterm in ation for a m od ern cop p er sm elter, Extractive m et-
allu rgy of cop p er, n ickel an d cobalt. Proceed in gs of th e Pau l E .Q u en eau In tern ation al
Sym p osiu m , sp on sored by th e Extraction an d Processin g Division of TMS an d th e
Metallu rgical Society of th e Can ad ian In stitu te of Min in g, Metallu rgy an d
Petroleu m (CIM), volu m e II, p p .1613-1631.
60. Viveros J.H.M. an d Velazqu ez Vald ez J.M. Exp an sion p roject at Mexican a d e cobre
sm elter. Proceed in gs of th e Iflash Sm eltin g Con gress, U.S.A., 13-18.10, 1996 p p .79-85.
61. CRU Rep orts, 1995
62. N ym an B. Yllö E. an d Lan tto T. In n ovative Cop p er Recovery by O u toku m p u ´ s VSF
Tech n ology. Pap er p resen ted at 1995 SME An n u al Meetin g, March 6-9, 1995, Den ver,
Colorad o, USA.
63. N ym an B., Ku u sisto R. an d N atu n en H. Th e First Com m ercial O u toku m p u CSF Sol-
ven t Extraction Ap p lication at Com p an ia Min era Zald ivar Cop p er Min e in Ch ile. Pa-
p er p resen ted at ALTA 1995 Cop p er H yd rom etallu rgy Foru m , Sep tem ber 18-19, 1995,
Brisban e, Au stralia.
64. N ym an B. Yllö E. an d Lan tto T. In n ovative Cop p er Recovery by O u toku m p u ´ s VSF
Tech n ology. Pap er p resen ted at Cop p er 95-Cobre 95 Con feren ce, N ovem ber 26-
29,1995, San tiago, Ch ile.
65. N ym an B., Yllö E. an d Ku u sisto R. Asp ects of Design of Large VSF Cop p er Mixer-Set-
tler Un its. Pap er p resen ted at 1996 SME An n u al Meetin g, March 11-14, 1996, Ph oen ix,
Arizon a, USA.
66. N ym an B., Ku u sisto R., Taip ale P. an d Lyyra J. Em p h asis of Feed an d Settlin g in
O u toku m p u ´ s Cop p er VSF Mixer-Settler. Pap er p resen ted at ALTA 1996 Cop p er H y-
d rom etallu rgy Foru m , O ctober 14.15,1996, Brisban e, Au stralia.
67. Taip ale P., N ym an B., Ku u sisti R., Lyyra J. an d Kah ikko A. Im p lem en tation of
O u toku m p u ´ s VSF Cu Solven t Extraction Plan t Project at Cod elco´ s Rad om iro Tom ic
Min e, Ch ile. Pap er p resen ted at Cop p er H yd rom et Rou n d table´ 97 Con feren ce, 2-5
N ovem ber, 1997, Van cou ver, Can ad a.
68. Ran talah ti R. Person al com m u n ication , Decem ber, 1998.

69
D ocu m en t a t i on p a g e
Publisher Finnish Environment Institute D ate
June 1999
Author(s) Marja Riekkola-Vanhanen
Title of publication Finnish expert report on best available techniques in copper production and by-production of precio-
us metals
Parts of publication/
other project
publications
Abstract The main objective of this BAT report is to identify available techniques for the reduction of emissions
and energy use in the primary copper production in Finland. Copper is recovered from sulphide con-
centrates with the pyrometallurgical flash smelting process. The smelting takes place without any ex-
ternal fuel addition, i.e. the chemical energy of the concentrate is utilised for smelting. First, part of
the sulphur and iron in the feed are oxidised to form copper matte and slag. Matte is further oxidised
in converters to blister copper. The slag formed is discarded after a purification step. Blister copper is
fire-refined and cast into anodes. The anodes are electrorefined to pure copper cathodes. The remai-
ning anode slime is further treated to recover the remaining metals.
The main solid waste from the process is the purified slag, which is stored in a tailings area. Liquid ef-
fluents result from the cooling water system, from the sulphuric acid plant attached to the smelter
and from wet gas cleaning systems. The major environmental problem results from the release of SO 2
and particulate emissions.
Keyw ords copper production, precious metals production, best available technique
Publication series The Finnish Environment 316

and number
Theme of publication Environmental protection
Project name and

number, if any
Financier/
commissioner
Project organization
ISSN ISBN
1238-7312 952-11-0506-2
N o. of pages Language
72 English
Restrictions Price
Public 66 FIM
For sale at/ Edita Ltd, phone + 358 9 566 0266, telefax + 358 9 566 0380
distributor
Financier Finnish Environment Institute, P.O. Box 140, FIN-00251 Helsinki, Finland
of publication
Printing place and year

Edita Ltd, Helsinki 1999

K u v a i l u l eh t i
Julkaisija Suomen ympäristökeskus Julkaisuaika
Kesäkuu 1999
Tekijä(t) Marja Riekkola-Vanhanen
Julkaisun nimi Suomalainen asiantuntijaraportti parhaimmista käytettävissä olevista tekniikoista kuparin ja sen si-
vutuotteina syntyvien jalometallien tuotannossa
Julkaisun osat/
muut saman projektin
tuottamat julkaisut
Tiivistelmä Tässä BAT raportissa esitellään menetelmät, joita käyttämällä voidaan vähentää päästöjä ja energian
kulutusta primäärisessä kuparin tuotannossa Suomessa. Kuparia valmistetaan sulfidisista rikasteista
käyttämällä pyrometallurgista liekkisulatusprosessia. Se ei tarvitse ulkoista energiaa, vaan tuottaa itse
energiansa polttamalla rikkiä ja rautaa. Ensimmäisessä vaiheessa osa syötteen rikistä ja raudasta ha-
petetaan, jolloin saadaan kuparikiveä ja kuonaa. Kivi hapetetaan edelleen konverttereissa blister-ku-
pariksi. Puhdistettu kuona jää jätteeksi. Blister-kupari puhdistetaan raffinoimalla ja valetaan anodeik-
si. Anodeista tehdään puhdasta katodikuparia elektrolyysin avulla. Jäljelle jääneestä anodiliejusta
erotetaan siihen jääneet metallit.
Prosessissa syntyvät kiinteät jätteet ovat lähinnä kuonahiekkaa, joka varastoidaan läjitysalueelle.
Liuenneet epäpuhtaudet tulevat jäähdytysvesisysteemistä, sulattoon liitetyltä rikkihappotehtaalta ja
kaasunpesulaitteistoista. Rikkidioksidi- ja hiukkaspäästöt ovat pahin kuparinvalmistuksen ympäris-
töön kohdistuva haitta.
Asiasanat Kuparin tuotanto, jalometallien tuotanto, BAT
Julkaisusarjan nimi Suomen ympäristö 316

ja numero
Julkaisun teema Ympäristönsuojelu
Projektihankkeen nimi
ja projektinumero
Rahoittaja/
toimeksiantaja
Projektiryhmään
kuuluvat organisaatiot
ISSN ISBN
1238-7312 952-11-0506-2
Sivuja Kieli
72 englanti
Luottamuksellisuus H inta
Julkinen 66 mk
Julkaisun myynti/ Oy Edita Ab, puh. (09) 566 0266, telekopio (09) 566 0380
jakaja
Julkaisun kustantaja Suomen ympäristökeskus, Pl 140, 00251 Helsinki
Painopaikka ja -aika Oy Edita Ab, Helsinki 1999

71
P r esen t a t i on sb l a d
U tgivare Finlands miljöcentral D atum
Juni 1999
Författare Marja Riekkola-Vanhanen
Publikationens titel Finsk Expert rapport om den bäst användbara tekniken i koppar produktion och biproduktion av
ädelmetaller
Publikationens delar/
andra publikationer
inom samma projekt
Sammandrag Målet med den här BAT raporten är att identifiera tillgänglig teknik för reduktion av emission och
energianvändning i primär koppar produktion i Finland. Koppar raffineras från sulfidiska koncent-
rat med flamsmältningsprocessen. Smältningen av koncentratet genomförs utan tillförsel av extern
energi eftersom koncentratets kemiska energi kan användas till godo vid smältningen. Först oxideras
en del av svavlet och järnet i ingångsmaterialet så att det uppstår en kopparslig och en slagg. Sligen
oxideras vidare i konvertrar för att forma blisterkoppar. Slaggen avsätts efter en reningsraffination.
Blisterkoppar eldraffineras och gjuts till anoder. Anoderna elektroraffineras till rena kopparkatoder.
Det kvar varande anodslammet behandlas vidare för att ta till vara på övriga metaller.
De huvudsakliga fasta biprodukterna från processen är slaggen som lagras på området. Avloppsvat-
ten uppstår från processens kylsystem, från svavelsyre-enheten och från det våta gas reningsverket.
För de stora miljöutmaningarna står svaveldioxid och partickel emissionerna.
N yckelord Koppar produktion, biproduktion av ädelmetaller, BAT
Publikationsserie Miljön i Finland 316

och nummer
Publikationens tema Miljövård
Projektets namn
och nummer
Finansiär/
uppdragsgivare
O rganisationer
i projektgruppen
ISSN ISBN
1238-7312 952-11-0506-2
Sidantal Språk
72 Engelska
O ffentlighet Pris
Offentlig 66 FIM
Beställningar/ Oy Edita Ab, tel. (09) 566 0266, telefax (09) 566 0380
distribution
Förläggare Finland miljöcentralen, Po Box 140, FIN-00251 Helsingfors, Finland
Tryckeri/ Oy Edita Ab, Helsingfors 1999

tryckningsort och -år

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Th e Fi n n i sh En vi r o n m e n t 316

Fin n ish exp ert rep ort on

Phot o: Out okum pu Oyj

Helsinki 1999 Helsingfor s

2 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ The Finnish Environment 316

The Finnish Environment 316 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

2 Applied Processes and Techniques.......................................... 10

3 Present Consumption and Emission Levels............................. 30

The Finnish Environment 316 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

5 Best Available Technique ........................................................ 61

7 Conclusions and Recommendations ....................................... 65

6 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ The Finnish Environment 316

Metallic cop p er h as been fou n d at several location s in th e w orld . It w as kn ow n to

Ta ble 1. Copper pr oduct ion 1997 in 10 0 0 t ons of copper / 2/ .

Ar ea Mine Sm elt er Refiner y

NonEU Eur ope 1 135 1 310 1 271

Am er ica 6 952 4 58 6 6 000

An n u al refin ed cop p er p rod u ction in th e EU reach ed 1,854,000 ton n es in 1997

The Finnish Environment 316 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

Tot a l EU 239 959

Ta ble 3. Pr im a r y r efined copper pr oducer s in EU.

Count r y Com pa ny Loca t ion Ca pa cit y t / y

Spa in At la nt ic Copper S.A. Huelva 250 0 0 0

Finla nd Out okum pu Ha r ja va lt a Met a ls Oy Ha r ja va lt a , Por i 125 0 0 0

8 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ The Finnish Environment 316

The Finnish Environment 316 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

Ap p roxim ately 90 % of th e w orld cop p er p rod u ction from ores is n ow m an u fac-

Ta ble 4 . Wor ld copper sm elt er ca pa cit ies a nd pr oduct ion in 1995.

Pr im a r y Copper Ca pa cit y Mt Pr oduct ion Mt Num ber of Num ber of

t his Technology only t his Technology

Out okum pu Fla sh Sm elt ing 4 .1 3.5 26 25

Modified El Tenient e Conver t er Conver t er 0 .9 0 .8 7 0

INCO Fla sh Sm elt ing 0 .5 0 .4 3 2

10 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ The Finnish Environment 316

Smelting to Matte Solvent Extraction

Electrorefining to Cathode Electrowinning

Figure 1. Flowsheet of primary copper product ion.

2.1 Pyrometallurgical Copper Production

The Finnish Environment 316 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○

2.1.2.1 Reverbatory Furnace Smelting

2.1.2.2 Other smelting processes

12 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ The Finnish Environment 316

2.1.4 Slag cleaning

2.1.4.1 Electric furnace

2.1.4.2 Slag concentrator

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2.1.5 Copper refining, anode casting and electrorefining

2.2 Single Furnace Coppermaking

2.3 Continuous Converting

14 ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ ○ The Finnish Environment 316

2.4 Outokumpu Flash Smelting Process at Harjavalta

2.4.1 Raw material reception and storage

2.4.2 Blending and drying of the concentrate

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2.4.4 Gas cleaning

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Steam Steam O ff gas Bag O ff gas to stack

tapholes and SO 2 plant Liquid SO 2

Slag Flux Bag O ff gas to stack

Figure 2. Flowsheet of t he H arjavalt a copper smelt er.

2.4.5 Copper converting

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