United States Patent (19) (11) 4,149,880

Prater et al. 45) Apr. 17, 1979

54 RECOVERY OF COPPER FROMARSENIC Primary Examiner-G. Ozaki
CONTAINING METALLURGICAL WASTE Attorney, Agent, or Firm-Mallinckrodt & Mallinckrodt
MATER ALS (57) ABSTRACT
(75) Inventors: John D. Prater, Salt Lake City; Barry Highly toxic metallurgical waste materials from copper
A. Wells, Centerville, both of Utah smelting and/or refining operations are processed on a
73) Assignee: Kennecott Copper Corporation, New cyclic basis for recovering copper values therefrom
York, N.Y. while protecting the environment from contamination.
21 Appl. No.: 925,969 The waste materials, usually smelter flue dust and/or
refinery sludge containing copper values and princi
(22)Filed: Jul.19, 1978 pally arsenic, bismuth, lead, antimony, and cadmium, as
51)Int. C.’.............................................. C22B 15/12 toxic values, with or without added sulfuric acid, are
52 U.S. C. .......................................... 75/117, 75/99; reacted in an autoclave at an overpressure atmosphere
75/109; 75/120; 75/121; 75/101 R; 423/41 of O2. The resulting solution, pregnant with copper and
58) Field of Search .................... 423/41; 75/117, 109, still containing a significant amount of arsenic, i.e. from
75/101 R, 99, 120, 121 about 0.5 to about 2.0 grams per liter, is subjected to
56) References Cited copper cementation on metallic iron to recover copper
and to provide iron values in the solution while substan
U.S. PATENT DOCUMENTS tially eliminating residual toxic constituents, surpris
2,686,114 8/1954 McGauley et al. ............... 75/117 X ingly without the evolution of arsine gas. The copper
3,330,650 7/1967 Zimmerley et al. ................... 75/104 barren but iron-containing solution is then recycled to
3,455,677 7/1969
Litz ........ 75/117 X the leaching step. The cement copper precipitate is
3,880,650 4/1975
Pemsler ............. 75/117 X smelted along with copper ore concentrates, while the
3,902,896 9/1975 Borbely et al. ........................ 75/109 solid residue from the leaching step is discharged to a
3,929,599 12/1975 Johnson et al..................... 75/117 X tailings pond or the like as an environmentally safe,
4,026,988 5/1977. Wells et al. ... ... 75/101 BE insoluble residue.
4,071,357 1/1978 Peters ............. ... 42.3/105 X
4,071,421 1/1978 Masters et al. ... 75/117 X
4,076,605 2/1978 Bilson .................................. 77/99 X 9 Claims, 1 Drawing Figure

IOUD-SOLDS
SEPARATION

METALIC

RECYC LIQUID-SOLDS COPPEr

SOLUTION SEPARATION CEMENTATION

CACUM MOYOAfE
2INC AND CADMUM
PRECIPITATE

WAER QUID-SOLIDS ZANC YoROXIDE

RAMENT SEPARATION
 4,149,880 2
1
smelter flue dusts and refinery sludges in a cyclic, envi
RECOVERY OF COPPER FROMARSENIC ronmentally protective procedure.
CONTAINING METALLURGICAL WASTE DETAILED DESCRIPTION OF THE
MATERALS ILLUSTRATED EMBODIMENT
BACKGROUND OF THE INVENTION In the illustrated application of the invention, highly
1. Field: toxic smelter flue dust, formed incidentally to the smelt
The invention is in the field of treatment of smelter ing of flotation concentrates of a low grade, copper
flue dusts, refinery sludges, and like metallurgical waste prophyry ore, such as that obtained from the Bingham
materials containing highly toxic ingredients, for the 10 Canyon open pit mine of the Utah Copper Division of
recovery of copper values. Kennecott Copper Corporation, is treated on a cyclic
2. Objective: basis for the recovery of copper and other desired val
In the making of the invention it was a major objec ues contained therein while protecting the environment
tive to protect the environment from highly toxic con 15
from highly toxic constituents thereof, chiefly arsenic
stituents of such waste materials, while recovering cop but also including bismuth, lead, antimony, and cad
per values therefrom in a more economical manner than mium as principal potential contaminants of the envi
theretofore. ronment. Refinery sludge may also be fed into the sys
3. State of the Art: tem, as indicated, or may be similarly treated indepen
It has been proposed heretofore (U.S. Pat. No. dently of smelter flue dust if for some reason it becomes
2,686,114) to recover various metal values from ore 20 desirable to do so.
concentrates high in arsenic by leaching such ore con A typical flue dust will analyze, by weight:
centrates at elevated temperature (250-650 F) and
pressure (100-560 psi.) According to the examples: 13.6% copper 13.5% arsenic 0.2% antimony
given in that patent, use of the specified higher tempera 25 0.9% molybdenum
2.1% zinc
1.71% bismuth 0.2% cadmium
14.7% lead 3.8% iron
tures and pressures results in removal of essentially all
of the arsenic values from the leach solution during the
leach, resulting in a substantially arsenic-free solution The flue dust and refinery sludge if desired are
which may be treated in a variety of ways, including formed into a slurry by the addition thereto, in appro
cementation techniques, for the recovery of desired 30 priate mixing equipment, of the aqueous recycled solu
metal values, such as copper. The important factor is tion from the copper cementation stage of the process.
that there be sufficient iron or alkaline earth metal val The slurry will usually have an iron content of from 15
ues present during the leach to render essentially all of to 35 grams per liter due to iron in the recycled solution.
the arsenic values insoluble during the leach. This re It will also have a pH that is usually below 2 due to the
quires the addition of iron or alkaline earth metal values 35 acid formed when the aqueous solution is added to the
to the each feed material when the total available flue dust and because of the acid in the recycled solu
therein is less than or even merely the equivalent of the tion. Additional sulfuric acid may be added to the
arsenic values present therein. slurry, if necessary, to bring it to the desired level for
Unless essentially all of the arsenic values are re satisfactory copper recovery.
moved from the solution, common experience in the art The aqueous, acidic slurry is introduced into an auto
indicates that the application of cementation procedures clave. Leaching is carried out in the autoclave within
to the resulting pregnant leach solution will be accom the lower temperature end of the range previously men
panied by the undesirable evolution of arsine gas and tioned herein for the prior art proposal, typically at
that such cementation procedures should be avoided in about 140 C. (284. F.) and at a considerably lower
the absence of essentially complete removal of arsenic 45 oxygen overpressure than is within the range previously
values from the leach feed material. mentioned herein for the prior art proposed, typically at
about 50 pounds per square inch. The resulting slurry is
SUMMARY OF THE INVENTION subjected to liquid-solids separation, usually by filtra
In achieving the aforesaid major objective of the tion, to separate the copper-bearing solution from resid
invention, we have found unexpectedly that during the 50 ual solids, which include precious metal values along
cementation of copper with metallic iron from leach with arsenic, bismuth, lead, and antimony values in
solutions derived in the manner of the aforesaid U.S. insoluble form. These are washed and passed to waste,
Pat. No. 2,686,114, but still containing significant e.g. to the usual tailings pond following recovery of the
amounts of arsenic values, i.e. from about 0.5 to about precious metals by conventional techniques. Because of
2.0 grams per liter, arsine gas is not evolved during the 55 their aqueous insolubility, there is no danger of harming
cementation procedure, which enables the leaching to the environment.
be carried out at lower and more economical tempera It is usually desirable, though not necessary, to pass
ture and pressure and without the extra step of adding the pregnant leach solution through a molybdenum
iron or alkaline earth metal values to the leach feed recovery circuit (see Wells et al. U.S. Pat. No.
material. Accordingly, the present disclosure enables 60 4,026,988), as indicated, for salvaging molybdenum
the art to avoid the costly requirements insisted upon by values. In any event, it is passed to a conventional cop
said patent, while attaining equivalent results. per cementation stage, where the copper is precipitated
on metallic iron. Surprisingly, despite the fact that the
THE DRAWING flue dust leach stage described above leaves a significant
The accompanying drawing constitutes a flow sheet 65 amount of the arsenic values, i.e. from about 0.5 to
representing the best mode presently contemplated of about 2.0 grams per liter and typically 1.0 gram per liter,
applying the process of the invention to the recovery of in the leach solution subjected to cementation of copper
copper and other desired metal values from highly toxic on metallic iron for recovery of the copper values, there
 4,149,880
3 4.
is substantially no evolution of highly toxic arsine gas one hour leach at 140° C. The lower temperature limit
during the cementation stage. thus depends on the time available for each leach cycle.
Some of the arsenic remaining in solution is precipi The oxygen overpressure is also noncritical. The
tated with the copper in the cementation stage. Copper preferred range is between 20 and 50 pounds per square
is generally precipitated first, however, so that the 5 inch. Copper extraction of 93% and arsenic in solution
amount of arsenic precipitated with the copper can be of 5% (about 1.5 grams per liter) remain approximately
held at a very low level by holding copper recovery in constant in this pressure range at a leaching time of one
the cementation stage to about 95%. Overall copper hour. When oxygen overpressure drops below 20 psi,
recovery is not affected by this, since the solution is copper extraction remain approximately constant, but
recycled. 10 the amount of arsenic in solution increases rapidly to
Following separation of the liquid and solid phases, as about 20% arsenic at 5 psi overpressure with a leaching
by a conventional filtration step, the precipitate copper time of one hour. Thus, the upper limit is determined by
solids are preferably recycled to the smelter, while economic considerations and the lower limit depends
barren solution is recycled for use in slurrying the upon temperature and time.
smelter flue dust and as a diluent for the copper-bearing 5 A typical laboratory example is as follows:
solution sent to the cementation stage. It should be
noted that this supplies iron values additional to those EXAMPLE
contained in the autoclave feed material, which is desir A series of cyclic tests were made wherein, for each
able. cycle, 250 grams of flue dust were leached in a 2 liter
It is usually advantageous to control impurity build 20
Parr autoclave at 140 C. and 50 psig oxygen pressure
up in the solution and to recover zinc and cadmium for one hour in 1 liter of solution. Copper was precipi
values by establishing a quantitatively minor bleed tated by cementation on scrap iron, and the solution
stream of the barren solution and neutralizing such after copper removal was recycled to the autoclave to
bleed stream by the addition of sodium carbonate or leach a new sample of dust. Sulfuric acid concentration
hydroxide thereto to precipitate zinc values as zinc 25 was adjusted in each cycle to 44 g/l in the solution fed
hydroxide. The cadmium values come out with the zinc to the autoclave. Iron concentration was not adjusted
values. Following filtration, the liquid phase may be and was variably dependent upon the dilution of the
sent to waste or to a water treatment plant. leach solution. Results are shown in the Table.
The total sulfuric acid content of the leach solution is Table
determined by optimum recovery of copper values. 30 Copper and Arsenic Recovery From
With flue dust feed analyzing as above indicated, the Flue Dust Sample in Cyclic Tests
leach solution will have a pH of about 2.0 without the Fe
addition of any acid and copper recovery will be within Cycle Concentration Extraction, Percent
the range of about 80 to 87%. With the addition of No. to Leach g/ Cu As
sulfuric acid to bring sulfuric acid concentration to 35 18.8 92.7 4.0
about 44 grams per liter (2.5 volume percent), about 2 16.1 97.7 10.7
93% of the copper is leached from the flue dust and 3 13.9 95.4 20.9 (iron
about 4% of the arsenic values remain in the solution. inadvertently
With reduced concentration of acid, the arsenic in solu depleted)
4. 20.1 94.6 -5.1 (iron replenished)
tion is only slightly decreased. If the concentration of 40 5 22.0 91.2 2.7
acid is increased above 44 grams per liter, the copper
extracted increases to some extent and the arsenic val
ues remaining in solution go up very rapidly. For exam For none of these cycles was there any evolution of
ple, at an H2SO4 concentration of 130 grams per liter, arsine gas during the copper cementation step per
about 35% of the arsenic values remain in the solution 45 formed on the leach solution therefrom.
rather than being precipitated. Whereas this invention is here illustrated and de
The temperature in the autoclave is not critical, since scribed with specific reference to an embodiment
arsenic precipitation during the leaching of the copper thereof presently contemplated as the best mode of
depends upon both temperature and time. The presently carrying out such invention in actual practice, it is to be
preferred temperature is 140 C. over a time period of 50 understood that various changes may be made in adapt
one hour. With the one hour leach time, as the tempera ing the invention to different embodiments without
ture is reduced copper extraction is reduced only departing from the broader inventive concepts dis
slightly, but the arsenic remaining in solution increases closed herein and comprehended by the claims that
rapidly to about 20% at 100° C. Above 140 C., copper follow.
extraction is increased slightly but the arsenic in solu 55 We claim:
tion remains about constant. Therefore, the upper limit 1. In a process for the recovery of copper values from
for temperature is a matter of economics, the consider highly toxic, smelter flue dusts and/or refinery sludges
ation being cost of energy required to increase the tem containing arsenic values as at least part of the toxic
perature against the minor increases in copper extrac constituents, which process includes the leaching of
tion. 60 such a flue dust and/or sludge with sulfuric acid at
As previously indicated, temperature is related to elevated temperature and under a pressurized oxygen
time, so lower temperatures for longer times may be atmosphere for solubilizing copper values and render
used. The preferred temperatures will depend upon the ing insoluble the highly toxic values, the improvement
time available for each leaching cycle. Generally the comprising conducting the leaching step under such
leach time required for similar results will double for 65 conditions of sulfuric acid concentration, temperature,
each 10° C. decrease in temperature. Therefore, approx and pressure as will precipitate toxic constituents while
imately the same results are obtained with a four hour leaving a relatively small but significant amount of ar
each at 120° C., a two hour leach at 130 C., and the senic solubilized in the resulting copper-pregnant leach
 4,149,880
5 6
solution; separating the liquid and solid phases from the ues from the group consisting of bismuth, lead, anti
leaching step; recovering copper values from the preg mony, and cadmium.
nant leach solution by cementation on metallic iron, 6. The improvement of claim 1, wherein the rela
there being substantially no evolution of arsine gas dur tively small but significant amount of arsenic left in the
ing the cementation step of the process; separating the copper-pregnant leach solution is within the range of
solid and liquid phases of the copper cementation step; about 0.5 to 2.0 grams per liter.
and recycling the barren leach solution from the cemen 7. The improvement of claim 6, wherein the feed
tation step to the aforesaid leaching step to supply solu material contains about 13.5% copper and about 13.5%
bilized iron values during leaching. arsenic, and the sulfuric acid concentration is about 44
2. The improvement of claim 1, wherein the solids are 10
grams per liter.
recycled to the smelter; and a major portion of the 8. The improvement of claim 1, wherein the rela
barren leach solution is used to slurry the feed materials tively small but significant amount of arsenic left in the
prior to the leaching step.
3. The improvement of claim 2, wherein the leached copper-pregnant leach solution is within the range of
material also contains zinc values and a minor portion of 15 about 1.0 gram per liter.
the barren leach solution is treated for the recovery of 9. The improvement of claim 1, wherein the feed
the zinc values, the residual liquid not being returned to material contains about 13.5% copper and about 13.5%
the processing circuit. arsenic, the relatively small but significant amount of
4. The improvement of claim 1, wherein the leached arsenic left in the copper-pregnant leach solution is
material also contains molybdenum values and the preg 20 about 1.0 gram per liter, the sulfuric acid concentration
nant leach solution is treated for the recovery of molyb is about 44 grams per liter, the temperature is about 140
denum values prior to the copper cementation step. Centigrade, the pressure is about 50 psi, and the leach
5. The improvement of claim 1, wherein the leached ing time is about one hour.
material also contains one or more additional toxic val
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