190

THE SEPARATION OF PLATINUM, PALLADIUM, RHODIUM AND GOLD

FROM ORES AND CONCENTRATES BY AQUA REGIA EXTRACTION
AND BY HIGH-TEMPERATURE CHLORINATION FOLLOWED BY
ACID LEACHING
By ILDIKO PALMER, R. PALMER, and T. W. STEELE

From the outset of the investigations into the recovery and analysis of the noble
metals, it was realized that the absence of any internationally recognized standard
platinum ore, although not hampering relative studies of the variables affecting such
factors as recovery, would present a problem in the determination of absolute values
for samples. The need for comparative data was therefore of paramount importance,
the inference being that a high recovery is synonymous with a higher collection
efficiency and would possibly indicate where further work was required to increase
the efficiency of collection of noble metals by simpler procedures.
Two possible alternati-'lcS to the collection of noble metals by fire .. n.ssn.y techniques
are chlorine roasting followed by acid extraction, and a straight aqua regia attack of
ores. It was hoped that these 1\vo procedures would rcducc or eliminate the losses
which are known to occur at the various stages ill the fire-assay procedure.
In 1929 Copper and Watson 1 examined chlorine roasting followed by aqueous
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or acid leaching of the roast, with the object of developing a new industrial process
for the sf'paration of noble metals from ores in which the platinum was present as
as sperrylite or as a disulphide, neither of which was readily soluble in aqua regia.
Almost forty years later, Grimalde and Schnepfe 2 user! extraction with aqua regia to
determine the acid-soluble platinum and palbdium in ores. Both these procedures
were examined at the National Institute for Metallurgy (NIM) for their applicability
to ores from the Merensky Red. At that stage of the inveE'tigations no analyses were
carried out for ruthenium, iridium, and osmium because methods of suitable sensi-
tivity were not available. However, as platinum and palladium are the major noble-
metal constituents of Mcrensky Reef ores, these omissions are perhaps of relatively
little consequence.

Experimental methods. As both procedures are likely to produce leach liquors

containing large amounts of base metals, and as it had already been established that
almost every method of analysis available was subject to either mutual-interference
or matrix interference effects, some mQa_ns for the separation of the noble metals from
the base metals was required. Possible means of separation were ion exchange,
liquid-liquid extraction, and co-precipitation with carriers such as tellurium, selenium
or reduction to the metal with copper or zinc. Separation of the base metals with
cation exchange was not thought to be feasible, although ultimately S this procedure
was shown to be effective for all the elements except ruthenium and osmium. \Vhen
dealing with residues from nickel sulphide buttons where the ratio of base metals

JOURNAL OF THE SOUTH AFRICAN CHEMICAL INSTITUTE 1972, Vol. XXV

 The Se/,ah1fum of Platmum. Pallad1!lm. r,'I"xlllml and Gold from OYCS and Concentr"le' 191

to noble metals 1S lower, liquid-liquid extractiuIl as practised at NGVI was found to be

subject to interference by relati\'ely small amounts (~ to;) l1lg) of base metals.
Examination of Grimaldi and Schnepfe's procedure of co~precipitation with tellurium
for the sep;J.ration of acid-soluble platinum and paUauium showed that platinum,
palladium, gold and rhodium were (Iuantitatively precipitated. The precipitation was
carried out by the addition of;) mg of tellurium (as tellurite) to the leach liquor,
followed by the addition of stannuus chloride as the reductant. The precipitated noble
metal tellurite and the tellurium carri!'r were filtered under vacuum and washed with
molar hydrochloric acid. AftC'r being dried, thc fitter paper and contents wcrc treated
by one of two proccdurcs. (I) They were ig'nited in a porcelain crucible, reduced to the
metal with hydrogen, and dissolyed in aqua regia. (2) They 'were treated in a bea.ker
with a mixture of nitric and perchIoric acids, which destroyed the filter paper. The
perchloric acid was evaporated off, and the perchIorates ,vere converted to chlorides
by repeated ~vaporation with hydrochloric acid.
The resulting solutions are then suitable for analysis by atomic-abosrption
spectrophotometry 5 or by spectrophotometric vrocedurcs. J
As a test of the efficiency of the two separation methods being examined, it was
necessary to determine which noble metals arc ret ainC'd in the residue. If thc starting
material is :?S g of ore, which will contain ca. :250flg of total noble metals, the total
noble metals likely to be found in the rcsidue, lf the extractiun procedures are effective,
will be 1 to 5fLg or less and the individual metals likely to be found will probably
be less than l}J-g. So that the residual amuunt::. CQuld be determined effectively. a
number of residues were collected hy the fire-assay (lead fusion) method. As the
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amounts to be deterIllinl~d were small and represen ted a combined total of six residues,
any error in this pmcedure would have a relatively small effect on the absolute value
for the noble metals. Before fire assay and low-temperature cupellation, the residues
0
were dried un a hot-plate and th<!n roa::.ted at 600 for one hour. Sih.'f!r (O,5mg) was
added to serve as a collector. The resulting pnlls were dissolved by a dosed-tube
chlorinZl.tion procedure, 6 with hydrochloric acid and fuming nitric acid under pressure.
The noble metals now in solution were converted to chloride by repeated evaporation
with hydrochloric acid, sodium or lithium chloride being added to prcwnt the re-
duction of gold on evaporation, Because atomic-absorption methods lack adequate
sensitiyity for small amounts of noble metals, liquid-liqnid-cxtraction procedures in
conjunction with spectrophotometric methods were used in the analysis of these
solutions.

Chlorine roasting. The procedure employed was briefly as follows:- A 25 g

sample of are or a IO g sample of concentrate was mixed (by hand) 'with an appropriate
amount of sodium chloride in a silica roasting dish, and masted for 1 hour at 600°.
The pre-roastEd :ample was then transferred to a Pyrex tube, 45 cm long and 2 ell
in diameter, having a glass-wool plug at the lower part of the tube to hold the sample.
"Quickfit" sockets and cones at each end served respectively as the inlet and outlet
tubes for the chlorine-gas supply. The sample was loo~ely packed to allow a free
passage of chlorine, the flow-y::tte of which was adjusted to give one or two bubbles

JOERNAAL VAl\' DIE SUlD-Al'IUJo;AANSE CB'EMIESE INSTITUUT 1972, Band XXV

 192 !ld/ko Pulmer, R. Palmer, and T. W. Steel.

per second thrOllgh an outlet bubbler. Temperature was controlled between 0 and
600° by use of a pyre-meter.
Several v8riables in the roasting procc~s were examined, namely the effects of
temperature of chlorination, the time of contact with chlorine, and the amount of
fluxing material needed. With respect to the extraction of the noble metals, the
strength and temperature of the extracting acids were examined.
Under the following fixed conditions the effect of the strength of extracting acid
(hydrochloric) \\ as examined (figure 1) for platinum, palladium and rhodium: 25 g
of sample, 5% (m/m) of sodium chloride, and a temperature and time of chlorination
of 380±20° and 1 hour respectively. The concentration of gold was too low to be
determined accurately by atomic absorption.

'"

..
~
\
~

'.
\
0
~

·~

·"
~
Reproduced by Sabinet Gateway under licence granted by the Publisher (dated 2012)

·"
Q

----==~'~~~~~~~>.LL.OIU.
-------------=- _
11 ------- , "Ii I!o 10 12
"lATINlJ~
RHOC~U~

tJol .."U1Y OF ~n~"'{"H""G . . clo (Ht;\)

Fig. 1. Effect of sltcngth of extracting acid on recoveries from chlorine rOilsten ore

For acid strengths ranging from 1 to 12M, it appears that the d~crease in residual
noble metals becomes asymptotic at approximate 6M hyurochloric acid for all threc
clements. The strength of the extracting acid was fixed at GM for all further tests.
The effect of temperature and time of leac:hing were studied, particularly with
respect to the separation of silica from solution. Any solids present in solution must be
filtered before co-precipitation of the noble metals with tellurium. Leaching by
digestion for 4- hours on a stearn-bath, with the· temperature of the leaching solution
maintained between SO and 85° caus~d any silica dissulved by the strong acid to
co<:gulate readily and give a residue which was easily filtered and washed. At lower
temperatures-·50 to 600~the silica was present as a colloidal precipitate which was
almost impossible to filter. The best filtration was obt:l1ned after the solution had
been heated on a boiling steam-bath (92°) for four hours. Prolonged heating on a
steam-bath led to a further separation of colloidal silica, which again made filtration
difficult.

JOURNAL OF THE SOUTH AFRICAN CHEMICAL. INSTITUTE 1972, Vol. XXl'

 The Sepa.atlOn nf Pta/Plum, P,llladiu1n, Rhodntm aHd Gold from Ores ,wd Concentrates 193

After the leaching conditions had been established, those affecting the chlorina-
tion roasting procedure were examined. The effect of sintering with increasing amounts
of sodium chloride was first determined. Temperature and time of chlorination were
kept constant as for the prcdous test, and the leaching conditions were the same as
those outlined above, The amount of sodium chloride added ranged from 0 to 20
per cent (m/m). Figure 2 shows the effect of sodium chlonde on the extraction from
the chlorinated are, Th('rc is a rapid decrease in residual platinum and palladium wIth
increasing sodium chloride additions up to e,l. 10%, any further change with larger
amounts of sodium chloride being small-ca. 1 %. The optimum addition of sodium
chloride was taken to be 10%. The change for rhodium ,vas small but showed a steady
decrea~e over the range of sodium chloride additions.

"

I.
...~ ----------------- P'.UlAOIIJIoI
Reproduced by Sabinet Gateway under licence granted by the Publisher (dated 2012)

/!:HOOIIJM

- - - - - - - - - - - Pl A H"'u~

I0 ~ ~ 2 (I
Ai1.o~D h~l. fJ/., (m/m)

Fig. 2. The additIOn, of NaCl and Its effect on the extraction of noble metals from a chlonnated ore.
Concentration of HCl =<'M

The effect of temperature of the chlorine roasting was studied over the range
0
200 to 600 with the following fixed conditions: time of chlorination 1 hour, strength
of extracting acid 6M, and addition of sodium chloride 10% (m/m) , The changes
observr:d (Figure 3) for platinum and rhodium are small-ca. 1 %-and cannot be
conSIdered to be significant in rdation to the experimental error of determination,
i.e. 2 to 3%. The change in residual palladium shows an in!:TP'Rse with increasing
temperature up to 350°, followed by a sharp decrease down to 600°, where the residual
palladium amounts only to some 3% of the total present. Accordingly, the temper-
ature of roasting wa" set at 550±1O°.
Increasing time of chlorination at this temperature produced a decrease in the
amount of residual noble metals for times of chlorination of up to 30 minutes (Figure
4). After that hme Lny cha.nges observed were well within the ~xperimental crror of
the method of determination. A chlorination period of 60 minutes was therefore
adopted so that some possible compensation would be made for the effects of different
mineral compositions.

JOI1RNA.A.L VA.N DIE. SUln·I\FRlKAANSE. CHEMl£SE INSTITUUT 1972, Bana Xx. V

 194 IldlRO Palmer, R. Palmer, and T. W. Steele

,.,. ... lINUIooI

----->..,~-":HODIU ...

IPALL"OrUI.l

"0 ". 'DO

." ... '00

Fig. 3. Effect of chlorine roasting temperature on the extraction of the chlorinated ore.
Concentration of HCI =6M

Finally, the necessity for the pre-roasting of the sample was determined from a
comparison of percentage recoveries under the established conditions with and without
pre-roasting (Table 1). All the recoveries improved when the samplp,s had been pre-
roasted.
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Throughout these tests, solutions from the bubbler at the chlorination-tube exit
were saved and combined, so that their noble-metal content could be detennined as
an indication of whether there was any degree of volatilization or carry-over. No
noble metals were found in any of these solutions, suggesting that losses due to these
factors were minimal.

m
,
o

" ,'" ",

Fig. 4. Effect of chlorination time on the extraction from the chlorinated are.
Concentration of HCI =6M

JOURNAL OF THE SOUTH AFRICAN CHEMICAL INSTITUTE 1972, Vol. XXV

 The Seprnat;un of l'ia/illum, P"ll,ul Uflll , RhfJdllllll <llld Guld fYoHI OYes lllld Concojfralfs 195

TABLE]
The effects of pre-roast~ng on ~euoveyy of the noble metals

Pre-treatment Recov"ry, %
-P-]-a-ti-n-u-m- I Palladium I-R-ho-d-i-u-m-

None llU% NaClJ 79 84 87

Roa~ted at 600'
for Ih in presence 96 96 98
of 10% NaCI

Extraction wtth aqua regia. Extraction with lOOml of aqua regia after pre-roasting
at 6000 for the removal of volatile constituents was carned oui on 35g of are sample
for 4 hours on a steam-bath. After removal of the excess acids, the noble metals were
converted to their chloro-complexes by repeated evaporation with concentrated
hydrochloric acid. The sample was then digested with molar hydrochlnric acid on a
steam-bath for 3 to 4 hours, after which the soluilO11 was filtered by decantation
through a Buchner funnel. The insoluhle mate'nal was washed with hot molar hydro-
chloric acid until the washings were colourless. The residue was then set aside for
combination with other residues and subsequent fire-assay treatment. After the noble
metals had been separated. from the filtrate by co-precipitation with tellurium, the
Reproduced by Sabinet Gateway under licence granted by the Publisher (dated 2012)

precipitate was ignited and reduced, and the acid solution was analysed by atomic-
absorption spectrophotometry.
A comparison of results ohtaincd for individual noble metals after chlorine
roasting, acid extraction, and collection by lead and nickel fire-assay procedures is
given in Table II.
For each sample, the platinum recoveries were higher by either of the two pro-
cedures discussed than that obtained by fire-assay lead collection, by some 15%
for the ore sample and chromite ore, and by 4% for the concentrate. The comparison
for palladium was good, except for the chromite. when IO'wer results were obtained
for the acid-extraction method. The detennined rhodium compared satisfactorily
for the ore and concentrate by both methods but was low for the chromite. For gold
the agreement was acceptable.
Fire assay using nickel as a collector gives values for the three samples which,
except for platinulll iu both LIte ore amI cUIlcentrate, are generally in accord "'ith
those obtained by chlorination and roasting. The values obtained for platinum in
these samples are intermediate between those for leaq collection and those for the
two procedures under dIscussion.

DISCUSSION

The value uf the investigation lies in the fact that, although the acid-extractinn and
chlorination and roasting procedures have little to commend them for routine analysis,

JOERNAAL \,,'>.N DIE SUlLo-Al;Rll<AAJ':SE CHEMlESE IJ':S"IlTUUT 1912, Band XXt"

 .....c
~

TABLE II
.....
Results for noble metals obtmned by vanou, procedures. <>:
".
c
't:
Pt
p.p.m.
Pd
p.p.m.
Rh
::l.p m.
Au
p.p.tn.
No. of
d~terminahons
~
"?::
""
Chromite Pb collection 3,11 ±O,07 1,39±O,O2, O)53±O,OI U,lO±O,OI 8
.,'1::;
• Acid extraction 3,70±O,15 1,26±O,0l o,:n ±O,Ol O,12±O,OI 18 ~
~
·Chlorine & roast 3,50±O,lO 1,45±O,Q;' O,:53±O,OI 12 '"
~
,,is collection 3.33±O,O9 1,42±O,Ul O,:56±O,O2 O,03±O,OI 4 :-;
"
Ore Pb collection 5,38±O,lD O,89±O,O~-I O,:37±O,O2 0,21 ±O,Ol 6 If;
Reproduced by Sabinet Gateway under licence granted by the Publisher (dated 2012)

c;;-
'"
Acid extractlOn

Chlorine & roast

6,10±O,24

6,27±O.ZO
O,92±O,02

1,03 ±ll,O~-I
0,:37 ±O,Ol

OA5±O,O~
0,17±O,Ol 36

12
"
NiS collection S,86±O,OS 0,92 :::0,07 O,.36±0,02 O,16±0,03 12

Concentrate Pb collection 79±I,S 51±1,0 13±O,4 2,50±O,IO 14

Acid extraction 81 ±0,8 47±1,4 10±0,2 2,30±O,tO 12

Chlorine & roast 81 ±3,2 48±1,8 10±0,3 12

NiS collection 79±2.4 49±1,5 13±O,2 2,20±O,20 12

~ The values obtained by these two methods represent the sum of the metal extracted plus that found in the residue.
~ = not detennined.
 the IT~nlh nht:ll1wd dn ohrJ\\' that, wIth tIl" 1·,1' cihlf' cxu"pti()J1 ()f pLttlllum, the
reco\'l'ril'o; from tIll' typ's IIf ,,::j11] ,I. S , X:ll;,i;", <l ;n(' ('(,mllambl,' \\'ith th()~f' obtain cd
by nickel ,nlpJddc colledi"n. sngg' stmg th:1t thc~{' f('f'(,\','rJo S lll:1y repn'st'nt tht.' true
valuf's for th('~(' s;,ul1I,j, '. t'ilful tuned, 1)" J'fI L·(1.i,'ch,'wil,,1l tl'~'ts 11:1\'1' lW('tl satis-
bct()rily C:1rn (1 (,nt t'l d 't"rll1iT'" tIl<' I """~; "f j l ,til'ul1l at the yariOU5 ~tag ... s ,;f the
nickd sulphide C'nll,·ctl{J'l I'rrll','dll,", ~"Illi' tl' t" 118\'" hf'('n I'arri, d ('ut <In thl' H'-
fusing I,f ,·{,mhn nl ,l.'g'- fn,m "('\Tr;,l ,~mj'l' ~ "f ~1{'I(·mh.y ',n'. SI1l.111 dillOllllb of
nohle ]11<'t[l]'" \\', rt' [("'DYl n (1, ~1l1d th:,t f, r l.l:,ti: llITl JIllllunt, d t.l Illlly 2 to :~n~ of the
cont"ll! III Cd. I,JI' -thile! (,f ill" dirkr']1U h'tWl'('I1 Ow H'l'(\\Tnl'" hUJIl the nH h'l
su11'liHl,' and I'ldllrin" t il>l' llll'[ h, ,d". l' I1til I lull' 'l'IH'mical tl'"ts ha\'e heen d, '11<' as cfln-
fiIIllati()ll <If thl' 1.,\C, 1 <If th,' 10,01'0, tlii" an, mz:ly must nmain.
TI1I' n,'", ,f a )'I,t;,lil'g s81npk flf fluirllwrllmghl fnrtlwr incrc:1;.,f' thr· r('con'r~' of
tIl(' ll"hl,' md;ils, p"\\·P\"T. ('''!'l'ef cd:,] \Y,lt~(,l' 1 f',Ul:(l that nkltil)n (If the ::alllpk
rluring' dJ!lIriJldill'll f;,il,'d tl! impl'o\'(' thl' ff'I'()\"'ri,,, ,','('11 thongh,:1s tlll'Y ~ubser]l[('ntly
fuunu. the n ell\·,'ry \\'as 1I1n'T~dy l'I'lIj1<>rtl,oJl;}1 to t 111' number flf rC'volutions per
treatnwn1. In tli(' ~lri(I-(,xLracti'm mcthtHl, tl1(' kl'(kncy for ~ljghtly l()\n~r value" fnr
pdl;}dlU111l1li~ht JIl c"llW \\', Y hl' f! Jakel to til,' f tet that in lW,lrly all tIl<' paramd('r
tests tlw fI'!':Hlllril p:dhulilll11 \\';~s, "n ,1 " h("P(.lg(' b:lq~, gr\'akr than the nthcr lhr('\'
ell-Ill"llts, ]H"'~ihly ,l~ a l't'-nlt "f a tlifkrl'lit (1"1111' (f IICCJUfI·IlCl'. Tn(l, crI, GrimalJI
and ~I'hn, '1 ,f,' , h,IV(, :--hl )\\'n tl[,lt Th,,, hnm ,mel l,]a 1in urn nny IlCcur within t lIt' cltn IInik
lattiCi', ,,'llIdl r<,nd,'l's ree!}\'!'ry llifficult ,ll~cl palLtclium m~y be similarly buund \\'ithin
tht'l:iti)(,r",
Reproduced by Sabinet Gateway under licence granted by the Publisher (dated 2012)

Tit,' ["~llib "btained l',~· tIl" Lw" ('xtractlOJl pnle,'duTP" an' g~l1l'rally in ag-ree-
TTlI'nt \\-ith tl!flc" "ht.ll!H',l by til" fin'-<LOi'<ry t('Chlli'lUC5. T1w I1l:1ill ('xcl'j,tion being the
rCC<J\'( -ry "f pl.l j Illum wlill'll t, '11' 1~ t (\ 1,,· hil.:I I' 'r by (11,' l 'x t ra( ti,)J1 (C,hllil [llC :1nd mark('ri-
ly so in till' ca'\" "f tb,' nrl' TIll' :lfjua 1'I'gla ('xlradllJll ()f chrllllut(' '-:tIll1']CS rcsull>, in
low r"C';\Tri,'~ uf all tlw nnbk !lil'tab l',c"1-,t platinum, CI,,);;{"~t Z1gr<"Tll,'nt t,) tIll'
I'xtractWTl Tt'~\llt ~ is by ih" lllckd ~ll(l .hidp c()lkctlOl1 proc('durf'.

Natl<:Jllal In:-.htUk fvr l\1ddllurgy,

Private ndg 7.
Auckl.'md l"lrk,
Tr:1nsyaal.

REFERENCES

1 I{. A C()l'p~r and F" \V, \Vat~on, Chem Met & Mintnt Soc., S,,~., Apr. W2~), 220.
• F. S (;nmald, and M .\1. Scllllcpfe, U.S. (;e(ll. Su;'vcy. Prof. Papa 600-B, 1968. B99"
" R_ Palmer, K. Dlx,on and T \V. Steele. Johanll<'sburg, NatIOnal Institute for Metallurgy.
Rctnyl x', 112·1, 29tl, Od., 1971.
• E \\', Fowler, et al., Johat\u"sburg, Natio[4'1.1 Institute for Metallurgy, Report No. 97], :''ith
June, 1970
6 R. C. Mallett, ct al , johal\l\c~hurg, 0!atinnal InstItute for Metallurgy. Report No. 970, 5th
june, Hl70"
• R. Breckenridge, D Pearton, r. Palmer and K. Dixon, johanul'sburg. National Tr:.stitut~ for
Metallurgy, to be publtshed,
, F. S. GrimaldI and !\1, M, Schnepfe, U.S. (;e"l, Suyvey, PYOf Paper 650·C, 1969, C. ]49.

)OERNAAI. VAN DIE ~t:Jl)-AFRrj;,\,\XSE CHEAlIE~)" INSTlTUUT W7::!, lJ<lnd .\.\T