Europaisches P a t e n t a m t

J )

European Patent Office

(J3 Publication number:

EUROPEAN

176

A1

Office europeen des brevets

PATENT

APPLICATION

Int. CI.4: C 22 B 1 1 / 0 2
C 22 B 7 / 0 0

Application number: 85850294.1

Date of filing: 25.09.85

Priority: 28.09.84 SE 8404862

Applicant: Boliden Aktiebolag

Box 5508
S-11485Stockholm(SE)

@ Date of publication of application :

02.04.86 Bulletin 86/14

Inventor: Berg, Hans Gunnar

Takdroppsgatan 10
S-931 52 Skelleftea(SE)

@ Designated Contracting States:

AT BE CH DE FR GB IT LI LU NL

inventor: Holmstrom, Sven Ake

Kadettgatan 40
S-930 30 Ursviken(SE)
Inventor: Johansson, Leif
Vintergatan 35
S-932 00 Skelieftehamn(SE)
IQj) Representative: Lundin, Bjorn-Eric et al,
Boliden Aktiebolag Box 5508
|
S-114 85Stockholm(SE)

A method for recovering precious metals.

(g) The invention relates to a method for pyrometallurgically recovering the precious metal content, such as gold, silver
and platinum metals, of halogen-bearing materials rich in
silver. The material is caused to rapidly disperse in or be
finely distributed throughout an at least partially molten
charge containing a non-oxidic metal-containing phase
having the ability to dissolve precious metals and to
substantially lower their chemical activity. The halogen
content of the material herewith reacts with any fluxes or
metals of high chemical activity present in the furnace
charge, while forming metal halogenides. The halogenides
formed are separated by slagging and or
or volatilization, and
the precious metals are recovered from the molten charge,
depleted of halogens, in a conventional manner and with
regard to the charge phases.

Croydon Printing Company Ltd

491

The present invention relates generally to a method for recovering p y r o m e t a l l u r the p r e c i o u s - m e t a l

gically

materials

of h a l o g e n - b e a r i n g
relates
being

with regard

the

precious

hitherto

but

from

metals,

chlorides.

considered

of

treatment
with

together

'Since

as their

such

silver

materials
for

halogens,

materials

these

their valuable metal contents,

ashes,

risk

the

these

products

unattractive
processes.

metal products

a prohibitive

of

factor.

and

in chloride

example

deriving
other

form,

can

in conventional p y r o m e t a l l u r g i c a l c o p p e r
often highly a t t r a c t i v e with regard t o

are

and also with regard to their high precious m e t a l

is need

there

content,

of precious

losses

silver

containing

for a process

enable such valuable and precious metals to be recovered

without

invention

economically

Ashes and other

only be worked-up to a l i m i t e d e x t e n t

content,

chloride

metals,

the

specifically,

the ashes by means of p y r o m e t a l l u r g i c a l

silver

metallurgical

smelters.

More

silver-rich

and platinum

silver,

also relates in particular to a method for recovering silver p y r o -

metallurgically
from

available

to working-up

The invention

in silver.

rich

for working-up

to a method
commonly

such as gold,

content,

metals

the

to

gases in general

Halogen-bearing

which

in g r e a t e r

will

quantities,

surroundings

becoming

also represent

a hazard

to the environment. Moreover there is also the risk of releasing toxic h a l o g e n i d e s

to the surroundings.
One possible
materials

is

although

there

alternative
the

to the

method

pyrometallurgical
method,

hydrometallurgical

are only a limited

such

as

of working-up
for

leaching

of h y d r o m e t a l l u r g i c a l

number

cally

with

often

already

precious

pyrometallurgical
incorporate

smelter.

content

chlorine

stages

which

In addition,

enable

silver,

these
gold

plants

economismelters
and

other

in large yields from the raw materials w o r k e d -

Consequently,

of the

smelters.

copper

process

metals to be recovered

-up in the
metal

the

example,

copper

available on a worldwide basis and such plants are unable to compete

such

if it were

bearing

possible

materials

to transfer

the p r e c i o u s

in the

introduction

discussed

to the metal to be recovered without suffering significant losses of said p r e c i o u s

metals in the halogenides f u m e d - o f f ,
metallurgically

in

highly

these materials

advantageous

processes particularly a t t r a c t i v e .

fashion,

could be worked-up p y r o therewith

rendering

such

there

art

In the prior

of p r e c i o u s - m e t a l

types

since long known processes

are

with

in a

their ores
lead.

molten

the

with

smelting
litharge

metals.

precious

for

as collector

the

reverberatory

smelting

hydrometallurgical

products

reductant

and

sulphur

and

discloses

US-A-1 415 526

of the

elements

Se and other

for separating

teaches

different

silver and gold are r e c o v e r e d

comprising

process

mixed

metals

from

lead

formed

two-stage

US-A-815851

precious

containing

using lead

Thus, in US-A-718087

precious metals recovered.

from

materials

containing

for processing

cupelling
a process
metals

and noble

group

from each other by fusion with a collector, such as lead, for the noble m e t a l s .
extraction

of precious

ashes

copper

GB-A-689824

discloses

for

goldsmith's

examples

is mixed with a
type.

with lead

electrolysis

compound and introduced

lead

relates

GB-A-1574274

furnace

and

from

metals
into

ashes or r e s i d u e s ,
The

sludge.

a molten

slag of f a y a l i t e

to reducing smelting of waste products

oxide and coke to form a lead smelt

material
in a b l a s t

containing any p r e c i o u s

metals.
Also

copper

is

used

as

precious

metal

such

collector,

as

disclosed

in

GB-A-1601450, in which precious metal wastes of metallic type, such as s w e e p s ,

are smelted
as lime,

iron

with copper sulphide or a copper sulphide precursor and flux, s u c h

oxide

and silica

and/or

an alkali

metal

carbonate

and

chloride

flux, such as a sodium carbonate and sodium chloride flux.

None of the prior art processes using lead or another metal collector for p r e c i o u s
metals

discloses

processing

fact that such materials,

play a

very important

reason

is of course

of any h a l o g e n - b e a r i n g

in spite

of t h e

as follows from the introduction of this s p e c i f i c a t i o n ,

economical

that

materials

they

part

on the smelting

are t r o u b l e - s o m e

material

market.

The

to process p y r o m e t a l l u r g i c a l l y

due to risks of losses and toxic pollution, as already indicated a b o v e .

The present invention, however, provides a method which enables h a l o g e n - b e a r ing materials

rich in silver to be worked-up p y r o m e t a l l u r g i c a l l y in the a b s e n c e

of those technical, economical and environmental drawbacks hitherto a s s o c i a t e d

with

pyrometallurgical

class intended h e r e .

processes

intended

for

working-up

materials

of

the

The invention is c h a r a c t e r i z e d by the procedural steps set forth in the following

claims.
material

The h a l o g e n - b e a r i n g

rich in silver is supplied to an at least

furnace

charge

example

metal,

matte,

material

is finely dispersed or distributed

molten

in the

non-oxidic

a non-oxidic

containing

in a manner

speiss or similar,

throughout

phase

metal-containing

metal-containing
which

as quickly

phase,

for

that

the

ensures

the charge

partially

and d i s s o l v e d
The

as possible.

charge

is selected so that at least one of the precious metals contained in the m a t e r i a l

is absorbed by and dissolved in the non-oxidic m e t a l - c o n t a i n i n g phase at p r e v a i l in conjunction with finely distributing or dispersing the m a t e -

ing t e m p e r a t u r e s

rial throughout said charge. The chemical activity of the precious metal c o n t e n t
is greatly
is

lowered

"thinned".

those

in this way in proportion

Halogen
in

metals

the

non-oxidic

will

charged

metal-containing

than the precious metals.

activity

material

in the

present

to the extent to which the c h a r g e

then

which

phase

react

have

with

greater

Appropriate phases in this respect are m e t a l s

as lead, copper and zinc or sulphides or speisses containing the same. D e p e n d i n g

upon

the

slag

phase

and

and form slag.

phase

will

precious
form.

of the

temperature

be

metal

The

its

composition,

Consequently
depleted

of

the

and the

charge
metal

halogenides

during this stage

chlorine

possible
formed

the non-oxidic

to a progressively

presence

of a

will v o l a t i l i z e

metal-containing

increasing

extent,

and

dissolved in said phase will be unable to f u m e - o f f in h a l o g e n i d e

non-oxidic

recover the precious

mainly of lead,

furnace

is then

phase

processed

metals therefrom.

Parkes-process

mainly

of copper

for

or copper

example.

When the
the

matte,

manner,

to

When the non-oxidic phase is c o m p r i s e d

then silver and other precious

by the

in a conventional

whole

metals are recovered t h e r e f r o m

non-oxidic
of the

phase

is c o m p r i s e d
metal

precious

content

is obtained in the form of a p r e c i o u s - m e t a l sludge when e l e c t r o l y t i c a l l y r e f i n i n g

the copper
tional

or the copper obtained

techniques,

this

sludge

from the

being

matte in a c c o r d a n c e

subsequently

worked-up

with c o n v e n -

separately

with

the aid of known m e t h o d s .

The course followed by the reactions taking place when adding the h a l o g e n - b e a r ing material

to the furnace charge can be illustrated by the following r e a c t i o n

in which

formulae,

of the material

for

the

sake

of simplicity

the silver and halogen

content

is assumed to exist solely in the form of silver chloride (AgCl)

and the furnace charge is assumed to be lead and an oxidic slag l a y e r .

The silver chloride will thus be taken-up in the lead bath, while forming t h e r e i n
metallically dissolved silver and free chlorine, which probably exists t e m p o r a r i l y
in the
with

in an atomic

bath
the

gaseous

lead

present

lead

chloride

state.

Atomic

form

to

lead

(PbC12),

chlorine,

which

chloride,

depending

the

upon

will quickly

however,
in turn

react

is f u m e d - o f f
of the

temperature

as

bath.

of chlorine f u m e d - o f f in this way has been indicated in f o r m u l a

The p e r c e n t a g e

(3) by the symbol X, the value of which lies close to zero at the melting p o i n t
of lead chloride,
remainder

but approaches

of the

chloride

1 as the smelting

formed

temperature

will be t a k e n - u p

by any

increases.

slag which

The
might

be present, or will form its own slag p h a s e .

Consequently,

the

during

dissolution

phase

the

of the silver

activity

present,

and therewith also its partial pressure, will come closer to z e r o .

That

which

has been said

to a furnace
taining
therein

charge

will

obtain

proportionally
of respective
then

to

respect

to lead

also a p p l i e s

of dissolving silver and with which any silver dissolved

a low
the

activity.

prevailing

halogenide.

be recovered

with

aforegoing

containing large quantities of other non-oxidic m e t a l - c o n -

capable

phases

in the

bath

The halogen

therefrom

Metal

halogenides

temperature
and metal

by subjecting

said

and

content
phase

formed
the

will

fume-off

vapor

pressures

of the gas phase c a n

to a conventional

gas

wash.
Dispersion

of

the

halogen-bearing

material

throughout

the

furnace

charge

is suitably effected by utilizing a reactor vessel capable of vigorously a g i t a t i n g

the burden, such as a K a l d o - t y p e top-blown rotary c o n v e r t e r .

The material can also be dispersed and smelted in a flame using o x y g e n - c o n t a i n ing gas. Thus, the dispersion is rapidly obtained. Flame dispersion and s m e l t i n g
is applicable

in connection

to top-blown

mainly

and f l a s h -

converters

rotary

-smelting f u r n a c e s .
material

The

molten

pletely

or

throughout

tion of the precious

metal

the
from

of the

invention

present

the silver

chloride,

and therewith

while simultaneously

content,
halogenides

silver

is c o m for

techniques

metallurgical

the furnace charge,

precious-metal

scope

charge

into molten baths. This ensures extremely rapid d i s p e r -

sion of the material

of

known

so, by applying

nearly

injecting solid materials

losses

at least when the furnace

can also be dispersed,

due

to

chloride

avoiding u n n e c e s s a r y
It

fuming-off.
the

to apply
being

also dissolu-

method

lies

also

within

for producing

silver

to a molten lead b a t h .

charged

In this case fuming-off of the chloride should be avoided, and hence the t e m p e r a ture of the lead bath is preferably maintained as close as possible to the m e l t i n g
of the lead

point

is consumed

possible

( 500C).

chloride

this

at

bath

In order

to ensure
the

temperature,

as little

that

ratio

weight

lead

as

of lead

to

silver chloride is about 3:1.

The invention will now be described in more detail with reference to a p r e f e r r e d
embodiment
carried

as

when

applied

out in a top-blown

silver-rich

processing

chlorine-rich

of the Kaldo-type,

converter

rotary

and

ashes

and with r e f e -

rence to working e x a m p l e s .
Ash rich
lead

in silver

and chlorine

is charged

oxide/sulphate

pellets

or lead

all

charge

constituents

fluxing

agents,

to a Kaldo converter

concentrate
well

together

mixed

with

together.

together

with

reductants

and

mixture

The

is

smelted progressively while supplying heat from an oil-oxygen burner, t h e r e w i t h

to

form

which

a charge

comprises

a molten

lead

phase

during

the

500-800C,
of

the

becomes

initial
and

smelting

stage
the

of

charge

cycle

the

smelting

cycle

is consequently

a temperature

which

in the smelting cycle. Thus,

the

is as low

temperature

only partially

is reached

and

of the charge lies b e t w e e n

is at least partially molten initially. The t e m p e r a t u r e

500 and 1200C, depending upon the point reached

and slag

at

which

molten.
the

At the

whole

as
end

charge

molten, inter alia to enable the slag to be tapped from the c o n v e r t e r .

The smelting
such

the

that
in

formed,
the

solid

the m a n n e r

material

will

is rapidly

the converter

dissolve

described.

previously

material

silver-rich

elements

and other

in the

halogens,

iron for example,

pellets

bearing

silver

out while rotating

Thus,

dispersed

in the

rapidly
by

in a m a n n e r
the

rotating

throughout

lead

the

bath

furnace

lead

bath

Chlorine r e l e a s e d as silver dissolves in the molten lead will then r e a c t

formed.
with

iS carried

process

bath

of high activity
elements

these

which may

although
furnace

the

c h a r g e is based

charged

on lead

to c h l o r i n e

affinity

in addition

in substantial

in ash form.

of chlorine

amount

comprising,

be present

and lead c o n c e n t r a t e ,

and of great

to lead,

zinc

and

in both l e a d

quantities

Metal chlorides will then f u m e - o f f ,

in ash

form

pellets - relatively

is - at

least

restricted

when

the

in relation

to

the total chlorine content of the furnace charge, because of the chlorine c o n t e n t
of the lead

containing about 3%

if the

For example,

material.

mixture

incorporates

5% of an ash

Cl this will r e p r e s e n t a sole increase in the total c h l o r i n e

content of t h e c h a r g e of about 15%, with respect to the normal chlorine c o n t e n t

of lead pellets, and dusting will thus only increase marginally. The c h l o r i n e - c o n taining

dust

is e x t r a c t e d

from

the

process

gas

in the

gas

cleansing

system

of the K a l d o - f u r n a c e c o m p l e x .
Example 1
A first

series

of tests

was carried

in order

AgCl-Pb

system,

of silver

to the lead phase

out with the simplest

to illustrate,

inter

and the small

alia,

metal

system,

the surprisingly

i.e. a single
good yield

losses which can be o b t a i n e d

through f u m i n g - o f if found d e s i r a b l e .
The tests w e r e c a r r i e d out on a laboratory scale and the amount of silver c h l o ride used in e a c h t e s t

was 70 g. In tests 1 and 2 pulverized lead and silver c h l o -

ride were mixed together as thoroughly as possible prior to charging the m i x t u r e

to a crucible,

in which the mixture was smelted.

In test 3 first lead and t h e n

chloride were charged to the crucible, while in test 4 the chloride was c h a r g e d
to the bottom of the crucible. The following results were obtained in the t e s t s .

The amount of l e a d - c h l o r i d e phase formed can be compared with the t h e o r e t i c a l

quantity

69.2 g capable

observed

that

of being

formed

purely

the

amount

of silver

An ash containing

3% Cu,

22% Zn, 5% Fe,

stoichiometrically.

to the lead

yielded

phase

It will be

was e x t r e m e l y

high.
Example 2
was

mixed

with

1.1% Ag, 60 g/t

of an oxidic-sulphatic

pellets

lead

Au and 3.3%

material

raw

Cl
the

having

following c o m p o s i t i o n :
4.0% Pb, 12% Zn, 1.1% Cu, 8% Sand 1.5% C l
such as to form a furnace charge of the following major c o m p o s i t i o n :
36% Pb, 13% Zn, 1.3% Cu, 0.1% Ag, 6 g/t Au, 7.2% S and 1.7% Cl
25 tons of the
of coke
the
with

and

furnace
the

mixture

fluxing

were

burner

molten lead bath and a slag.

to have
Au were

melted,

8.5 tons

removed

from

charge

to melting

was

together
heated

said

while

charge

temperature,

such

with 2 tons
rotating

being h e a t e d
as to form

When the whole of the furnace charge was found

of raw
the

the

of 150 minutes,

for a period

aid of an oil-gas

to a K a l d o - f u r n a c e

whereafter

agent,

at 10 rpm

charged

molten

furnace,

lead

together

containing
with

0.29% Ag and 18 g / t

13 tons

of slag c o n t a i n i n g

0.3% Cl. Thus, 99.5% of the silver charged and practically all of the gold c o n t e n t
had been absorbed by and dissolved in the lead. Of the chlorine charged,
90% had

fumed-off

absorbed in the slag.

in the

form

of different

metal

chlorides

and about

about
10%

1.

A method for p y r o m e t a l l u r g i c a l l y

such

as

silver

gold,

in silver,

characterized

or dispersed

throughout

a non-oxidic
metals
the

and

and

halogen

platinum

an at least partially
phase

lower

appreciably

content

of

metals,

materials

halogen-bearing

rich

by causing the material to be rapidly finely d i s t r i b u t e d

metal-containing
to

recovering the precious metal c o n t e n t ,

the

having

the

material

of the

molten

chemical

reacts

with

furnace

charge c o n t a i n i n g
dissolve

to

ability
activity

precious
wherewith

thereof,

any fluxes or metals

of high

chemical activity present in the charge to form metal halogenides; by s e p a r a t i n g

the

halogenides

the

precious

formed

metals

and/or

by slagging

from

molten

the

and

volatilization;

charge

thus

by r e c o v e r i n g

of chlorine

depleted

in a

conventional manner selected with respect to the choice of molten c h a r g e .

2.

A method

according

to claim

1, c h a r a c t e r i z e d

in that

the

material

is

the

material

is

material

is

dispersed in the charge with the aid of injection t e c h n i q u e s .

3.

A method

according

to claim

1, c h a r a c t e r i z e d

in that

dispersed in the charge by vigorously agitating the furnace c h a r g e .

4.

A method

dispersed

and

according

smelted

to claim

in a flame,

1, c h a r a c t e r i z e d
such

in that

as in a top-blown

the
rotary

converter

3 and 4, c h a r a c t e r i z e d in that

agitation

or a f l a s h - s m e l t i n g f u r n a c e .
5.

A method

according

to claims

of the furnace charge is carried out by employing a top-blown rotary c o n v e r t e r .

6.

A method

according

claims

to

1-5,

characterized

in that

the

furnace

charge incorporates

a molten lead bath; and in that the precious metal c o n t e n t

is

the

recovered

from

lead

metal

by known

de-silvering

processes

and

the

Parkes-process.
7.

A method

charge

according

incorporates

a copper

to

claims
phase

1-5,

characterized

or a copper

matte

in that

phase;

the

furnace

and in that

the

precious metal content is recovered in a known manner by electrolysis of c o p p e r

anodes.

8.

A method

according

to claim

1, in which the silver-rich

material

com-

prises mainly silver chloride and the furnace charge contain molten lead, c h a r a c terized

in that

is recovered

the

from

oxygen; and in that

-metal phase.

lead

chloride

phase

formed

the l e a d - s i l v e r

phase

by oxidizing

the l e a d - o x i d e

phase formed

is s l a g g e d - o f f ;
the lead

is s e p a r a t e d

in that

silver

with air a n d / o r
from

the s i l v e r -