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 IC 9002

Bureau of Mines Information Circular/1985

c
^^V

Production of High-Purity Gold From Zinc

Precipitates and Steel Wool Cathodes
by Hydrometallurgical Refining

By G. E. McClelland, M. D. Wroblewski, and J. A. Elsele

UNITED STATES DEPARTMENT OF THE INTERIOR 75^

AMINES 75TH AV5J^
I r^-for f^iOL-K c^ c i^culcLT
\
( UA red Stoies .
S^nreau o-f Mi'^tes )

Information Circular 9002

Production of High-Purity Gold From Zinc

Precipitates and Steel Wool Cathodes
by Hydrometallurgical Refining

By G. E. McClelland, M. D. Wrobiewski, and J. A. Eisele

UNITED STATES DEPARTMENT OF THE INTERIOR

William P. Clark, Secretary

BUREAU OF MINES
Robert C. Norton, Director
 (\^
/r\^
]}}< .kO^
Op-

fj
&

Library of Congress Cataloging in Publication Data:

McClelland, G. E
Production of high-purity gold from zinc precipitates and steel wool
cathodes by hydrometallurgical refining.

(Information circular / United States Department of the Interior, Bu-

reau of Mines 9002)
;

Bibliography: p. 11.

Supt. of Docs, no.: I 28.27:9002.

1. Gold— Metallurgy.
2. Hydrometallurgy. 3. Precipitation (Chem-
istry). Zinc. 5. Cathodes. 6. Steel. I. Wroblewski, M. D. (Matt D.).
4.
II. Eisele, J, A. (Judith A.). III. Title. IV. Series: Information cir-
cular (United States. Bureau of Mines) 9002. ;

TN295.U4 [TN769] 622s [6(59'. 22] 84-600263

 CONTENTS
Page

Abstract 1

Introduction 2
Experimental procedure. 2
Acid pretreatment 3
Precipitation of sliver 3
Aqua regla dissolution of gold 3
Precipitation of metallic gold 3
Refining of precipitated gold. 4
Cyanldatlon of acld-leached residues for recovery of residual precious metals 4
Results and discussion 4
Acid pretreatment 4
Precipitation of silver 4
Aqua regla dissolution of gold 5
Precipitation of metallic gold 5
Refining of precipitated gold 7
Cyanldatlon of acid leached residues for recovery of residual precious metals 7
Slurry solids for acid leaching procedures 8
Recommended procedure for zinc precipitates 8
s Recommended procedure for steel wool cathodes 10
Handling and disposal of acid solutions and acid wastes 10
Summary and conclusions 11
References 11

ILLUSTRATIONS

1. Flowsheet for chemical refining zinc precipitates. 8

2. Flowsheet for chemical refining steel wool cathodes 9

TABLES

1. HNO3 pretreatment of zinc precipitates.. 5

2. Precipitation of silver from HNO3 leaching solutions 5
3. Results of aqua regla leaching of HNO3 residues,. 6
4. Precipitation of gold by reduction with (C00H)2 6
5. Precipitation of gold by reduction with SO2 7
6. Results of flre-ref Inlng precipitated gold 7
7. Results of cyanide leaching of aqua regia-leached residue 8
 UNIT OF MEASURE ABBREVIATIONS USED IN THIS REPORT

°c degree ce Lsius mg/L milligram per liter

g gram min minute

h hour ml, milliliter

kg kilogram oz/ton ounce per ton

L liter pet weight percent

M molar
 .

PRODUCTION OF HIGH-PURITY GOLD FROM ZINC PRECIPITATES AND STEEL WOOL

CATHODES BY HYDROMETALLURGICAL REFINING

By G. E. McClelland/ M. D. Wroblewski,^ and J. A. Eisele^

ABSTRACT

The Bureau of Mines Investigated chemical methods for producing high-

purity gold from precious-metal-bearing zinc precipitates and steel wool
cathodes. Precious-metal-bearing zinc precipitates and steel wool cath-
odes are unrefined products from conventional cyanidation and heap
leaching-cyanidation operations. The zinc precipitates contained 14.40
pet Au and 0.35 pet Ag. The precious-metal-bearing steel wool cathodes
contained 20.65 pet Au and 4.84 pet Ag. The precipitates and cathodes
were treated with dilute acid to solubilize the silver and/or base met-
als. The gold-bearing residue was leached in dilute aqua reqia to solu-
bilize the gold. High-purity gold was precipitated from the aqua regia
solution with oxalic acid, sulfurous acid, sodium bisulfite, and gaseous
sulfur dioxide. The leaching-precipitation experiments recovered 99.9
pet of the gold. The gold precipitates ranged in fineness from 997 to
999 fine.

The chemical refining method provides a viable technique for the

smaller operator to produce high-purity gold without using pyrometallur-
gical refining methods.

^Metallurgist, Reno Research Center, Bureau of Mines, Reno, NV (now with Hienen-
Lindstrom Associates, Sparks, NV)
^Physical science technician, Reno Research Center, Bureau of Mines, Reno, NV.
^Supervisory chemical engineer, Reno Research Center, Bureau of Mines, Reno, NV.
 INTRODUCTION

The increase in precious metals prices
since 1975 has stimulated extensive ex-
ploration programs. Concurrently, the
Bureau of Mines (_3, 8^)^ has devised im-
proved leaching technology for processing
gold-silver ores. Many of the precious
metal resources are too small to warrant
expenditure of large amounts of capital
to recover the contained values. The
operators of small properties are limited
in processing technology to low-cost
heap leaching or small-scale agitation
cyanidation.
Regardless of the leaching technology
employed, the dissolved precious metals
are recovered from the pregnant solution
either by precipitation on zinc dust
(J^, _5,
9-10) or by carbon adsorption-
desorption-electrowinning 0-2, A~5» 11~
12). In larger scale operations, the
precious-metal-bearing zinc precipitates
and steel wool cathodes are fire-refined
to obtain dore bullion. The dore bullion
is either sold to a refiner or refined on
site to obtain pure gold and silver
bullion.
The operators of small mining proper-
ties in many instances cannot afford to
construct a precious metal refinery and
must sell their zinc precipitates or
steel wool cathodes to a custom refiner.
Marketing their product in this manner
decreases the small operators' profits
because of loss of interest on the price
of the metal while it is idle, assay
charges, costs for packing, shipping, and
insurance while in transit, and the re-
finers' fees and profits.
The objective of this investigation was
to develop a hydrometallurgical refining
procedure to enable the smaller operator
to produce high-purity precious metal
products from zinc precipitates or steel
wool cathodes. The chemistry used in
this procedure is essentially the same as
used for chemically refining jewelry or
dental scrap (6-7).

EXPERIMENTAL PROCEDURE

Gold- and silver-bearing zinc precipi- were made by fire assay, atomic absorp-
tate used in the experiments was obtained tion, and wet-chemical methods. Spectro-
from a large operating gold mine. Anal- graphic analysis showed that the zinc
ysis of the zinc precipitate was as precipitate contained small amounts of
follows: other metals.
Element pet
The wet zinc precipitate was air-dried
Ag 0.35 at room temperature for 120 h. The dry
Au 14.40 precipitate was sized on a 100-mesh
CaO 10.2 screen. The oversize was ground to pass
CO2 and others 16.45 100 mesh and mixed with the minus 100-
Cu 9 mesh material in a glass bottle by roll-
Hg 6 ing and tumbling.
Pb 2.1
S 4.6 A precious metal-bearing steel wool
Si02 25.7 cathode was generated from the Bureau's
Zn 9.4 carbon stripping-electrowinning pilot
Other metal oxides.. 15.3 demonstration unit (PDU) in Reno, NV.
The cathode was oven-dried and weighed.
Analyses for specific elements and com- Pieces were cut from different regions of
pounds contained in the zinc precipitate the cathode and hand-blended to make a
head sample. The sample was assayed by
^Underlined numbers in parentheses re- conventional fire assay methods. The
fer to items in the list of references at steel wool cathode assayed 20.65 pet Au,
the end of this report. 4.84 pet Ag, and 0.14 pet Cu.
 Solid products (residues, Au sponge,
AgCl precipitate, etc.) from all experi-
ments were analyzed by fire assay for
precious metal values. Solutions were
analyzed by atomic absorption spectropho-
tometry for metal values.
ACID PRETREATMENT
Acid pretreatment experiments were con-
ducted on 25-g charges of zinc precipi-
tate which were agitated for 2 h at 80° C
in 200 mL of 6M acid. Acids used were
H2SO4, HCl, and HNO3 . After leaching,
the pulps were filtered, and the residues
were washed with 100 mL of deionized wa-
ter. Residues were dried, weighed, and
analyzed for residual metal values.
A multistage HNO3 pretreatment experi-
ment was conducted on a 25-g charge of
zinc precipitate to improve silver recov-
ery. The zinc precipitate was agitated
for 2 h at 85° C in 100 mL of 6M HNO3
After pretreatment, the pulp was filtered
and the filtrate was analyzed for silver
and base metal content. The residue was
leached three times. The final residue
was washed with 400 mL H2O and was as-
sayed for silver,
A 62-g steel wool cathode was digested
at 90° C for 1 h in 1 L of 5M HCl to dis-
solve excess iron. The solids were sepa-
rated from the acid solution by filtra-
tion. The solids were washed with dis-
tilled water, dried, and saved for aqua
regia leaching to recover the contained
gold values.
PRECIPITATION OF SILVER
Silver precipitation experiments were
conducted by adding known quantities of
NaCl to slowly agitated silver-bearing
HNO3 pregnant solution at room tempera-
ture. When initial AgCl precipitation
ceased, 1 g of additional NaCl was added
and the solution was gently agitated. If
further AgCl precipitation was observed,
additional NaCl was added in 1-g incre-
ments until precipitation was complete.
The AgCl precipitate was separated from
the acid solution by filtration, washed
with distilled water, and dried.
AQUA REGIA DISSOLUTION OF GOLD
The gold-bearing residues from acid-
preleaching zinc precipitates and steel
wool cathodes (10 to 15.7 g) were agi-
tated at 90° C for 1 h in dilute aqua
regia. ^ After leaching, the slurries
were filtered on glass fiber filter paper
and washed with distilled water.
A simulated two-stage aqua regia leach-
ing experiment was conducted on an HNO3-
leached residue. Ten grams of residue
were agitated at 90° C for 1 h in 175 mL
of dilute aqua regia. The pulp was fil-
tered, and the filtrate was used to leach
a fresh 10-g charge of residue at 90° C
for 1 h. The slurry was filtered, and
the washed residue was leached with di-
lute aqua regia.
PRECIPITATION OF METALLIC GOLD
One-hundred milliliters of gold-bearing
dilute aqua regia solution was heated
to 80° C. The stoichiometric amount of
oxalic acid (0,69 g (C00H)2 per gram Au)
required to precipitate the contained
gold was added slowly and gently agi-
tated. The solution was digested at
temperature until gold precipitation
stopped. Additional (C00H)2 was added
to the solution in 1-g increments until
precipitation stopped and the bright yel-
low color of the solution disappeared.
The acid solution was decanted and al-
lowed to stand overnight at room tempera-
ture for additional gold precipitate to
form. The gold products were combined,
washed with distilled water, dried, and
assayed.
A second method for gold precipitation
was to slowly bubble SO2 gas through a
fritted glass dispenser into 100 ml of
gold-bearing aqua regia solution at room
temperature for periods ranging from
15 min to 1 h. The gold precipitate was
washed with distilled water, dried, and
assayed.
^Dilute aqua regia refers to a solution
containing 75 mL of 36.5-pct HCl and 50
mL of 70.0-pct HNO3 per liter of water.
 The third method evaluated was sodium
bisulfite or sulfurous acid precipitation
of gold from 100 mL of gold-bearing aqua
regia solution. The sodium bisulfite
(1.8 g NaHS03 per gram Au) or sulfurous
acid (2.5 g H2SO3 per gram Au) was added
to the solution in one increment. The
mixture was gently stirred for 15 min at
80° C. Precipitation was complete when
no additional precipitation was observed
and when the yellow color of the solution
disappeared. The barren solution was an-
alyzed for residual gold. The precip-
itate was filtered, washed, dried, and
assayed,
REFINING OF PRECIPITATED GOLD
Separate charges of gold precipitated
by (C00H)2 or by SO2 gas were mixed with
nitre (KNO3), silica (Si02), and borax
(Na2B4 07) and heated in clay crucibles to
1,000° C for 1 h. The molten charges
RESULTS AND DISCUSSION
The chemical technique for refining
zinc precipitates differs from the pro-
cess for steel wool cathodes. For refin-
ing zinc precipitates, the silver and
base metals must be separated from the
gold and silica. Since the steel wool
cathodes contained no silica, separation
of the gold from the silver by acid pre-
leaching was not necessary. The residue
generated from the aqua regia leaching of
the HCl pretreated steel wool cathodes
was a nearly pure AgCl product which
assayed 74 pet Ag.
ACID PRETREATMENT
Preliminary tests showed that HNO3 was
the only effective acid for dissolving
the silver from the zinc precipitates.
The results of HNO3 leaching experiments
are shown in table 1. The data show that
leaching with 6M HNO3 for 6 h dissolves
76 pet of the silver and most of the base
metals and that multiple leaches are not
justified.
HCl pretreatment of the steel wool
cathodes generated an acid filtrate which
were poured into cast iron molds and
cooled. The gold beads were fire-assayed
for fineness, and the slags were fire-
assayed for residual gold content.
In a separate experiment, gold precipi-
tated with SO2 was upgraded in purity by
digesting in 5M HNO3 at 90° C for 4 h.
The gold sponge was washed with distilled
water, dried, and assayed.
CYANIDATION OF ACID-LEACHED RESIDUES
FOR RECOVERY OF RESIDUAL
PRECIOUS METALS
Gold- and silver-bearing siliceous
residue from aqua regia leaching of zinc
precipitates (~7.5 g) was agitated at
room temperature for 24 h in 100 mL H2O
containing 0.3 to 1.0 g NaCN and 0.2 g
CaO. The cyanide leached residues were
filtered, washed, and dried.
contained 99 pet of the Fe, 28 pet of the
Cu, 0.016 pet of the Au, and 1.7 pet of
the Ag. The leached residue was 80.5 pet
Au, 19.0 pet Ag, 0.4 pet Cu, and <0.1 pet
Fe.
PRECIPITATION OF SILVER
Silver can be precipitated as AgCl
chloride from the HNO3 leaching solutions
with NaCl according to the following equ-
ation:
NaCl + AgN03 ^ AgCl(s) + NaN03 . (1)
The amount of silver contained in the
HNO3 leaching solutions must be known to
ensure the addition of the proper amount
of NaCl. The results of NaCl precipita-
tion of silver from HNO3 leaching solu-
tions with stoichiometric and excess NaCl
are shown in table 2. The silver was
precipitated, but a large excess of NaCl
was needed.
The dry AgCl precipitate is suitable
for fire refining, or is marketable if it
contains between 70 and 75 pet Ag.
 TABLE 1. - HNO3 pretreatment of zinc precipitates

Acid leaching HNO3, Extraction, pet

number M Ag Cu Fe Pb Zn
SINGLE LEACHING WITH 200 mL OF SOLUTION
1.5 50.2 97.8 92.0 72.4 97.9
3.0 >99
45.5 >99 81.9 >99
6.0 >99
64.8 >99 85.7 >99
6.0 >99
69.1 >99 86.3 >99
6.0 >99
69.8 >99 85.9 >99
MULTIPLE LEACHING WITH 100 mL OF SOLUTION
1 6.0 17.0 86.9 48.5 48.2 89.4
2 6.0 61.1 12.1 45.6 27.9 10.2
3 6.0 .1 .9 5.8 20.0 .3
Total NAp 78.2 >99 >99 96.1 >99
SINGLE LEACHING WITH 200 mL OF SOLUTION, 6 h
1 6.0 75.9 >99 >99 196.0 >99
NAp Not applicable.

—
NOTE. Leaching time = 2 h, multiple leaching to-
taled 6 h.

TABLE 2. - Precipitation of silver from HNO3

leaching solutions

Pet of Silver, mg/L Silver

stoichiometric In pregnant In barren precipitated,
NaCl solution solution pet
100 120 110 8.3
500 120 95 20.8
1,000 180 56 68.9
1,500 120 20 83.3
3,000 120 2.1 98.3

AQUA REGIA DISSOLUTION OF GOLD A two-stage leach produced a pregnant

Dilute aqua regia leaching experiments
were conducted to determine if gold could
be extracted from residues from the HNO3
pretreatment of zinc precipitates and HCl
pretreatment of steel wool cathodes.
The amounts of HCl and HNO3 used were
150 to 300 pet in excess of the stoichio-
metric amounts required by the following
equation:
AUCI3 solution low in residual HNO3,
which improves the precipitation of gold
from the aqua regia leaching solution.
PRECIPITATION OF METALLIC GOLD
(C00H)2 was added to the pregnant di-
lute aqua regia solution to precipitate
gold as metallic crystals, according to
equation 3:

Au + 3HNO3 + 4HC1 3(COOH)2 + 2HAUCI4

-> HAUCI4 + 3NO2 + 3H2O. (2) -> 2Au + 6CO2 + 8HC1. (3)

The experimental results are shown in ta- The experimental results for the chemi-
ble 3 and indicate that agitated leaching cal reduction of gold with (C00H)2 are
in hot dilute aqua regia dissolved metal- shown in table 4.
lic gold from the acid-leached residues.
 . , 2

TABLE 3. - Results of aqua regia leaching of HN03-leached residues

Pretreated Volume of Au Au
36-pct HCl/70-pct HNO3, mL^ residue dilute recovered extracted, Residual
weight, g aqua regia g pet HNO3, M
used, mL
Single leaching:
10/7 , 5l2 175 3.51 91.6 >0.5
15/10 ,
^12 175 3.74 99.9 >.5
2-stage leaching:
Stage 1, 15/10 ,
310 175 3.19 99.9 .48
Stage 2, NAp , Mo 175 6.63 97.9 <.l
Leaching of 2d-stage resi-
due, 15/10 , NAp 175 .14 100 .88
(total)
Residue from HCl leach of
steel wool cathodes, 50/30. 15.7 500 12.77 99.75 >.5
NAp Not applicable.
^Pairs of figures in column entries are the respective amounts of 36-pct HCl and
70-pct HNO3; e.g., 10/7 = 10 mL HCl and 7 mL HNO3.
^Residual HNO3 determined by chemical analysis.
^Residue from HNO3 leaching of zinc precipitate.

TABLE 4. - Precipitation of gold by reduction with (C00H)2

Test 1 Test 2 Test 3^ Test 42 Test 5^ Test 6^

(C00H)2 added g.. 15 20 5 15 10 11.6
Gold precipitated g. 1.48 5.20 1.05 3.22 3.14 5.50
Gold precipitated pet. 96.54 98.95 99.91 99.43 99.99 99.95
Fineness 999 995 999 997 998 998
Gold in barren mg/L. 200 300 5 110 3 4
Urea added g.. 2 8
NaOH added g. 14 3
Retention time h. 24 24 24 24 2 2
Residual HNO3 .M. 0.5 0.5 <0.1 <0.1 <0.1 <0.1
Final pH <0 <0 <0 <0 1.7 1.0
'Pregnant solution generated by dilute aqua regia leaching of pretreated zinc
precipitates.
2 Pregnant solution generated by 2-stage dilute aqua regia leaching of pretreated
zinc precipitates.
Pregnant solution generated by dilute aqua regia leaching of pretreated steel wool
cathode.

NOTE. —All tests made at 70° to 80° C.

The data show that reduction with O.IM HNO3. Residual HNO3 could also be
(C00H)2 precipitated high-purity gold decreased by adding urea according to
(998 to 999 fine) from dilute aqua regia equation 4,
leaching solutions. Five-tenths molar
residual HNO3 in the leach solution re- 6HNO3 + 5CO(NH2)2
sulted in slightly less precipitation of
gold. Gold precipitation was higher from -> 8N2 + 5C02 + I3H2O, (4)
aqua regia leaching solutions from the
second stage of the two-stage leaching increasing the percent of gold precip-
experiment, which contained less than itated. Increasing the pH with NaOH
 .

TABLE 5. - Precipitation of gold by reduction with SO2

Test 1 Test 2 Test 3 Test 4 Test 5

SO2 source Gas Gas Gas NaHS03 H2SO3
Quantity used Excess Excess Excess ^2.9 I3
g.
Gold precipitated g. 2.39 1.55 2.23 1.61 1.15
Gold precipitated pet,. 99.63 99.62 99.61 99.44 99.72
Fineness 988 983 985 979 970
Gold in barren mg/L. 59 42 67 71 33
Reaction time min. 15 15 60 15 15
Residual HNO3 M» • 0.5 <0.1 <0.1 0.5 0.5
^Weight of pure substance,

—
NOTE. Pregnant solutions were generated by the aqua regia leach-
ing of Zn precipitates. Tests using SO2 gas were carried out at
room temperature (25° C). Tests using NaHS03 and H2SO3 were heated
to 80° C.

decreased the time required to precipi- necessary, to 999.9 fine by fluxing with
tate the gold. The crystalline gold pro- nitre, borax, and silica at 1,000° C,
duced by (GOGH) 2 reduction is bright and
lustrous. TABLE 6. - Results of fire-refining
precipitated gold'
SO2, NaHS03 or H2SO3 was added to pre-
,

cipitate gold as metallic sponge, accord- Test 1 Test 2 Test 3

ing to equation 5, Weight, g:
Nitre (KNO3).... 2.9 3.4 3.4
2AUCI3 + 3S02 + 6H2O Borax (Na2B4 07). 3.8 3.2 3.2
Silica (Si02)... 2.9 2.4 2.4
-»-
2Au + 6HC1 + 3H2SO4. (5) Au bead. ........ 0.99 0.99 0.99
Fineness:
The experimental results for the reduc- Before. ......... 979 990 995
tion of gold with S02-producing compounds After 997 999.9 999.9
are shown in table 5. The gold precipi- '
1-g gold samples,
tate was not as pure as gold precipitated
with (C00H)2 and did not have the lus- CYANIDATION OF ACID LEACHED RESIDUES
trous appearance. FOR RECOVERY OF RESIDUAL
PRECIOUS METALS
REFINING OF PRECIPITATED GOLD
The siliceous residues from leaching
If the precipitated gold is not of high zinc precipitates contained residual pre-
enough purity, refining by smelting or cious metals. The results of cyanidation
leaching with hot HNO3 may be necessary. to recover the precious metal values are
Gold precipitated by SO2 was upgraded by shown in table 7, Approximately 96 pet
digestion in hot HNO3 from 985 to 998 of the gold and silver in the residues
fine. The experimental results obtained was recovered by leaching in alkaline
from melting (C00H)2- or S02-precipitated cyanide solutions. The precious-metal-
gold with nitre, borax, and silica are bearing residues could be recycled to the
shown in table 6. Gold produced by plant's cyanide leaching circuit.
chemical refining can be purified, if
TABLE 7. - Results of cyanide leaching of SLURRY SOLIDS FOR ACID
aqua regia-leached residue LEACHING PROCEDURES

Test Test Test The slurry solids recommended for all

1 2 3 the acid-leaching procedures are very low
NaCN g. 1.0 1.0 0.2 and depend on the amount of gold and/or
Gold, oz/ton: silver contained in the specific feed.
Feed 2.90 14.00 33.00 If the pulp solids are too high, the
Tailing 0.13 0.51 1.00 solubility limits for gold, silver,
Gold extracted, ., ,pct. 95.52 96.36 96.97 and other metals in the specific acid-
Silver, oz/ton: leaching liquor may be attained, and pre-
Feed 171.2 118.1 196.8 mature precipitation of precious metals
Tailing 1.9 1.7 8.6 and other metals may occur. The recom-
Silver extracted. .pet. 98.89 98.56 95.63 mended pulp solids should be used unless
Time h. 24 24 1 it is determined by metallurgical testing
that the slurry solids can be changed.

RECOMMENDED PROCEDURE FOR ZINC PRECIPITATES

The recommended flowsheets based on the precipitates is required to dissolve the

results of this study are shown in fig- silver and base metals and leaves a gold-
ures 1 and 2. Acid pre treatment of zinc bearing siliceous residue. One kilogram

Zinc precipitates

HNO: Acid
pretreatment,
H2O 85° C, 6 h

Residue
HgO
n Filtration
Filtrate

1
Aqua regia
Silver
leaching , NaCI precipitation
90° C. I h

H2O
Residue -^
recycle to
cyanide
Filtration
AgCI
product
H2O
U Filtration
Filtrate
to waste
leaching
Filtrate H2O

Urea- Precipitation of
Gold sponge
Oxalic acid- nnetallic gold,
NaOH- 80° C Barren Gold
acid to product
waste
FIGURE 1. - Flowsheet for chemical refining zinc precipitates.
 steel wool cathode

HCI Acid
pretreatment,
HgO 85" C, 6 h

H2O

Residue
-
n Filtration -Filtrate
to waste
I
Aqua regia
leaching,
90' C, h

O
I

H2O

Filtration ^ AgCI residue product

Filtrate H2O

Gold sponge
Urea Precipitation of
Oxalic acid metallic gold,
NaOH 80* C •Barren Gold
acid to product
waste
FIGURE 2. - Flowsheet for chemical refining steel wool cathodes.

of zinc precipitate is slowly added to cases a 30-fold excess of NaCl may be re-
10 L of 6M HNO3. The slurry is heated to quired. The AgCl product is washed with
85° C, agitated, digested at temperature distilled water and dried at low tempera-
for 6 h, and filtered hot. The residue ture (<100° C).
is washed with water. The wash water and
acid filtrate are combined and saved for Gold is recovered from the HNO3-
silver recovery. preleached siliceous residue by leaching
with aqua regia. The HN03-leached resi-
The silver contained in the acid fil- due is divided into two equal charges.
trate and wash water is precipitated as One charge is slurried with dilute aqua
AgCl by the addition of NaCl. A tenfold regia. For every 100 g of charge, 2 L of
stoichiometric excess of NaCl is added to dilute aqua regia containing 150 mL of
the HNO3 leaching solution at room tem- 36.5-pct HCI and 100 mL of 70-pct HNO3
perature. (The stoichiometric amount of are used. The solution is heated to
NaCl is 0.54 g NaCl per gram of silver in 90° C and digested with continuous agita-
solution.) The solution is agitated tion for 1 h. The slurry is filtered hot
gently for 5 min and filtered. One gram on glass fiber filter paper. The acid
of NaCl is added to the filtrate. If filtrate is removed, and the residue is
additional AgCl precipitation is ob- washed with distilled water until no yel-
served, the above procedure is repeated, low color can be seen in the filtrate.
NaCl is added in the above manner until The washes are combined with the acid
no precipitation is observed. In some filtrate. The first aqua regia-leached
10
residue is saved for recycle to cyanide
leaching. The acid filtrate is slurried
with the second charge of HN03-leached
residue and treated as above. The second
aqua regia leached residue is saved for
further dilute aqua regia leaching.
Metallic gold is precipitated from the
aqua regia leaching solution by (C00H)2.
The pregnant AUCI3 solution (dilute aqua
regia leaching solution) is heated to
80° C and treated as follows:
1. Slowly add urea prills in 1-g
increments until gas evolution stops.
Add the stoichiometric amount of (C00H)2
required to precipitate the known or
estimated amount of gold contained in
the pregnant solution (0.69 g (C00H)2 per
gram of gold in solution) . Precipita-
tion should start within 10 min. If
precipitation does not start, or if it
RECOMMENDED PROCEDURE FOR STEEL WOOL CATHODES
HCl pretreatment of the cathodes is re-
quired to dissolve the steel wool. One
kilogram of steel wool cathode is slowly
added to 10 L of 5M HCl, which is heated
to 90° C while stirring. The slurry is
digested at temperature for 1 h, filtered
hot, and washed with water.
The HCl-pretreated cathode residue is
leached with dilute aqua regia to recover
the gold and silver. The HCl leach resi-
due is divided into two equal charges.
One charge is slurried with dilute aqua
regia. For every 100 g of charge, 2 L of
dilute aqua regia containing 150 mL of
36.5-pct HCl and 100 mL of 70-pct HNO3
are used. The pulp is heated to 90° C,
digested, and agitated for 1 h. The hot
slurry is filtered on glass fiber filter
HANDLING AND DISPOSAL OF ACID SOLUTIONS AND ACID WASTES
The acid solutions used are corrosive
and should be handled with extreme care.
All leaching must be done in vessels that
will not be corroded. The solutions
should not contact the skin or eyes.
Protective clothing should be worn to
prevent accidental contact. Should the
acid solution contact a person's skin or
eyes, flush with cold water for a minimum
of 15 min and consult a physician.
stops, add enough 30-pct NaOH solution to
bring the pH to 1,0, Digest the solution
at 80° C until precipitation stops.
2. Add 10 pet of the previously calcu-
lated amount of (C00H)2. If precipita-
tion is not observed, or if it stops, add
enough NaOH to bring the pH up to 1.0,
Digest the solution until precipitation
stops. Repeat until the yellow color of
the solution disappears. Combine the
gold precipitate into a single sponge by
using a spatula to free entrained gases
and to scrape the sides and bottom of the
vessel. When all of the gold has been
collected, decant the barren solution and
analyze for residual gold,
3, Wash the gold sponge with distilled
water and dry at 100° C, The dry gold
sponge should assay between 997 and 999
fine.
paper, and the acid filtrate is removed.
Displacement washing of the residue with
distilled water is continued until no
yellow color is visible in the filtrate.
The washes are combined with the acid
filtrate. The residue from the first
aqua regia leach is an AgCl product which
should contain 70 to 74 pet silver. The
second charge of HCl-leached residue is
slurried with the combined filtrate and
treated as above. The second aqua regia-
leached residue is saved for further di-
lute aqua regia leaching.
The procedure for precipitating me-
tallic gold from the resultant solution
with (C00H)2 is the same as for zinc
precipitates.
The fumes from the acid solutions and
chemical reactions with the solutions can
be very hazardous. All operations should
be conducted in a fume hood or in a well-
ventilated area. If a fume hood is not
available, ensure good outside ventila-
tion and wear an appropriate chemical
respirator and full protective clothing
at all times.
 ,

11

The acid waste solutions should be neu- prevent an uncontrollable reaction. The
tralized with alkaline solutions before pH of the neutralized acid waste should
disposal. Violent reactions may occur be between 6 and 7. The neutralized
when mixing acid solutions with alkaline solutions should be disposed of accord-
solutions. Extreme care should be taken. ing to local, State, and/or Federal
The solutions should be slowly mixed to regulations.

SUMMARY AND CONCLUSIONS

The experimental results showed that
zinc precipitates and steel wool cathodes
can be chemically refined to produce a
pure metallic gold and an AgCl precipi-
tate. Chemical refining of zinc precipi-
tates and steel wool cathodes recovered
99.9 pet of the contained gold. HNO3
preleaching separated silver and base
metals from the gold in zinc precipi-
tates. Silver in the HNO3 leaching solu-
tion was recovered as AgCl by precipita-
tion with NaCl. HCl leaching separated
base metal from the gold and silver con-
tained in steel wool cathodes. Silver
was recovered as an AgCl precipitate
which contained some gold.
Aqua regia leaching dissolved gold in
the residues from HNO3 and HCl preleach-
ing. (C00H)2 and SO2 precipitated metal-
lic gold from the aqua regia leaching
solutions. The gold produced by (C00H)2
reduction was 998 to 999 fine. Gold pro-
duced by SO2 reduction was 970 to 988
fine, but was upgraded to 998 fine by di-
gestion in HNO3 . The gold can be puri-
fied to 999.9 fine by fire refining.

REFERENCES
1. Adams on, R. J. Gold Metallurgy in International, 300 North Zeeb Road, Ann
South Africa. Chamber of Mines of South Arbor, MI 48106.
Africa, 1972, pp. 203-255.
7. Lowen, R. The Worshipful Company
2. Hall, K. B, Homes take Carbon- of Goldsmiths (London), Tech. Rept. 44/1,
In-Pulp Process. Pres. at Am, Min, Cong. 1980, 22 pp.
Mtg., Las Vegas, NV, Oct. 7-10, 1974, 16
pp.; available upon request from Home- McClelland, G. E.,
8. and J. A.
stake Mining Co., Lead, SD. Eisele. Improvements in Heap Leaching To
Recover Silver and Gold From Low-Grade
3. Heinen, H. J., G. E. McClelland, Resources. BuMines RI 8612, 1982, 26 pp.
and R. E. Lindstrom. Enchancing Perco-
lation Rates in Heap Leaching of Gold- 9. Merrill-Crowe. Merrill-Crowe Pre-
Silver Ores. BuMines RI 8388, 1979, —
cipitation Process Details of Operation.
20 pp. Undated, 9 pp.; available upon request
f rom M. D. Wroblewski, BuMines, Reno, NV.
4. Heinen, H. J. D. G. Peterson, ,and
R. E. Lindstrom. Processing Gold Ores 10. Pickett, D. E. Milling Practice in
Using Heap Leach-Carbon Adsorption Meth- Canada. Can. Inst. Min. and Metall.
ods. BuMines IC 8770, 1978, 21 pp. spec. V. 16, 1978, pp. 45-78.

5. Hinds, H. L. and F. Mosely. Re-

, 11. Potter, G. M. Design Factors for
fining Gold at Homes take. Undated, 8 pp; Heap Leaching Operations. Min. Eng,
available upon request from Homestake Mar. 1981, pp 277-281.
Mining Co., Lead, SD.
Zadra, J. B.
12. A. L. Engel,
, and
6. Hoke, C. M. Refining Precious H. Heinen.
J. Process for Recovering
Metal Wastes. Metallurgical Publ. Gold and Silver From Activated Carbon
Co., New York, 1940; 355 pp.; re- by Leaching and Electrolysis. BuMines
prints available from Univ. Microfilms RI 4843, 1952, 32 pp.

*U.S.CPO: 1985-505-019/5092 INT.-BU.OF MINES, PGH., PA. 27847

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