~

J. S. Atr. Inst. Min. Metal., vol. 92, no. 1.

Jan. 1992. pp. 17-25.

The removal of cyanide from aqueous solution by the use of

ferrous sulphate
by M. D. Adams*

SYNOPSIS .. .
The treatment of goldi>lant tailings with ferr~u~ ~ulphate to remove the cyanide IS c.urr~tJy In use, on several gold
plants. In some cases there is scope for optimlzln~ the pro~~ss. The present work provides ~ detatle? study of the
reaction between cyanide and ferrous sulphate. Optimal conditions for the remov~1 of total cyan!d~ reQul~e a p~ of 5,.5
to 6,5 and an Fe:CN molar ratio of 0,5. Ferrocyanide ion is shown to be unstable In aqueous acidic sol~!on, with rapid
oxidation to ferricyanide, (Fe(CNIg-I, and formation .of Fe(C~)5H~q3- at pH value~ below 4, The precipitate !rom the
reaction between cyanide and ferrous sulphate consists mainly 01 Insoluble P~usslan blue, Fe4[Fe(CNI&!.3,and IS shown
to be unstable in the presence of alkaline solution, since it decomposes rapidly at pH values above I to form ferro-
cyanide, (Fe(CNltl, in solution and various insoluble iron oxides,

SAMEVATTING ,
Verskeie goudmyne behandel tans goudaanleguitskotte met ferrosulfaat om sianied te verwy~er, Daa~ bestaa,n In som-
mige gevalle 'n behoefte aan prosesoptimering. Die huidige werk behels 'n uitvoerige stud le van die reaksle tussen
sianied en ferrosulfaat. Die optimale toestande vir die verwydering van 9ie totale, si~ni~d, vereis 'n, p~ v~n ?,5 tot ~,5
en 'n motere verhouding van Fe:CN van 0,5. Daar word getoon d~t die f~rroslanledloon onstablel IS In n watenge
suuroplossing, met vinnige oksidasie tot ferrisianied, (Fe(CNIg'). en die vormlng van Fe!CN~5H203- by pH-waardesonder
4. Die presipitaat van die reaksie tussen sianied en ferrosulfaat bestaan hoofsaakhk u~ onoplosb,are berlyn~blo~,
Fe4 [Fe(CNI,J3, en daar word getoon dat dit onstabiel is in die teenwoordi~heid van Onal.kahese oplosslng aange~len dlt
by pHwaaraes bo 7 vinnig ontbind om ferrosianied, (Fe(CNltl, in oplosslng en verskE!le onoplosbare ysterokslede te
vorm.

INTRODUCTION Fe2++ 6 CN- ~ Fe(CN)~-. [2]

The treatment of toxic industrial-waste streams is becom-
ing increasingly important internationally, and much atten- 2 Fe2++ Fe(CN)t- -7 FeFelI(CN)6J... [3]
tion is being focused on the disposal of cyanide wastes from
gold plants. The insoluble white ferrous ferrocyanide product rapidly
absorbs oxygen from the air and turns deep blue, with the
At present, the main area of concern is the detoxification formation of ferric ferrocyanide8. The vivid blue colour of
of gold-plant tailings prior to their use as backfilling in
these compounds is due to a charge-transfer transition
mined-out stopes. Most mines currently using the backfill between the FeIT(CN)%-and the Fern ions9. The following
procedure are treating the gold-plant tailings with ferrous
redox couple could account for the reaction:
sulphate. The ferrous ions in solution react with free
cyanide to form the ferrocyanide complex in solution:
3 FeFell(CN)6 ~Fef[Fen(CN)6h<J..) +
Fe2++ 6 CN- ~ Fe(CN)1;-. , [1] 2 Fe2++ 4e - , [4]

O2 + 4 H+ + 4e - ~. 2 H2O, [5]
A drawback of the process depicted in equation [l) is that
ferrocyanide is known to be unstable under conditions of
However, the reaction is not likely to be simple since
high temperature, low pH, and ultraviolet lighti-3. In a back-
there is a range of Prussian blue products depending on the
filling operation, the solution is drained and re-used, result-
solution conditions. One such compound is the so-called
ing in a build-up of ferrocyanide. Moreover, it is possible
that some of the solution may escape and contaminate the
'soluble Prussian blue', MFeIIT[FeU(CN)6I (M = K or Na),
which forms a colloidal solution with water!. Moreover, the
natural ground water.
precipitation and oxidation of ferrous hydroxides are reac-
When an excess of ferrous sulphate is added to a cyanide- tions that are also likely to play a role.
containing solution, the cyanide can be immobilized as an
The aim of the present work is to elucidate the optimum
insoluble precipitate, Fe4[Fe(CN6)h, known as Prussian
conditions for the removal of cyanide from solution by the
blue. Various patents have been taken out that relate to this
use of ferrous sulphate, and to demonstrate the regimes of
procesg4-7, including the addition of insoluble ferrous sul-
stability of the soluble and insoluble complexes that are
phides and the co-addition of iron and copper7. The reaction
formed during the reaction.
proceeds as follows:
. Mintek,
PrivateBagX3015, Randburg, 2125 Transvaal. EXPERIMENTAL PROCEDURE
<C> The South African Institute of Mining and Metallurgy, 1992. SA
ISSN 0038-223JV3.00 + 0.00. Paper received 5th November, All the chemicals used were of A.R. grade, and the solu-
1990.

Journal of the South African Institute of Mining and MetaHurgy JANUARY 1992 17
 tions were made up with deionized water. RESUL 1S AND DISCUSSION
In the precipitation experiments, 500 ml of solution con-
taining 0,5 g of NaCN (0,02 M) was placed in a magnetic- Reaction of FeSO4 with CN-
ally stirred beaker, and the pH value was adjusted by the
In the only previous comprehensive studylO of the reac-
use of H2SO4 or NaOH. To this was added 500 ml of a
tion between FeSO4 and CN-, oxygen was excluded from
freshly made-up solution containing 1,419 g of
the reaction vessel, which meant that the reactions of rele-
FeSO4.7H2O (0,01 M). The Fe:CN ratio was changed by
varying the mass of ferrous sulphate used. The Fe:CN vance were those shown in equations [2] and [3]. In the
presence of oxygen, as was the case in the present experi-
molar ratios vary by approximately 0,1 around the nominal
ments, the white ferrous ferrocyanide precipitate turned blue
value 0,5. As these values are still in excess of the stoichio-
almost instantaneously via reactions [4] and [5],
metric value of 0,17 for complexation as Fe(CN)~-, the
overall trends still hold. The pH value of the ferrous sul- Effect of Fe:CN- Ratio
phate solution was not adjusted. The stoichiometry of reactions [2] to [5] demands an
Before and during the experiments carried out on the Fe:CN- molar ratio of 0,39. The effect of variations in the
effect of oxygen, both solutions were. purged with either Fe:CN- ratio on the resultant solution species is shown in
oxygen or nitrogen gas for 10 minutes before being mixed. Fig. 1. Theoretically, complete conversion to Fe(CN)%- is
Prior to the experiments with pulp tailings, 0,5 g of achieved at an Fe:CN- molar ratio of 0,17, and this is borne
NaCN was added to 1 litre of the tailings. FeSO4,7H2O out in Fig. 1. At an Fe:CN- molar ratio of 0,10, there is
(1,419 g) was dissolved in the minimum amount (10 ml) of insufficient Fe2+ to complex with all the CN- and, at
water. This was added to the tailings at the start of the Fe:CN- ratios of 0,5 and higher, blue precipitates were
experiment. obtained, and no cyanide-containing species were detected
Samples of solution were filtered and contacted with in solution after 6 hours.
Dowex 50-S8 cation-exchange resin so that excess Fe2+ Detailed results are shown in Table I, where the pH value
could be removed and further reaction prevented. The pH at t = o refers to the 500 ml NaCN solution before it was
value of the sample was then adjusted to about 11 with mixed with the FeSO4 solution. The value of F~ at t =o
NaOH, to stabilize both the Fe(CN)%- and the CN- in solu- refers to the total iron concentration in the 500 ml of FeSO4
tion. The samples were immediately analysed for solution before it was mixed with the NaCN solution, but
Fe(CN)%-, Fe(CN)t, and CN- by use of ion chromatogra- corrected to a total volume of 1 litre. It is interesting to note
phy3. Aluminium foil was used to protect the experimental that the pH value of the FeSO4 solution prior to the mixing
apparatus and sample containers from light at all times. varied between 3,6 and 5,0, depending on the FeSO4 con-
During the experiments designed to demonstrate the sta- centration. These low pH values are a result of the hydroly-
bility of the Prussian blue precipitate, the pH value was sis of Fe2+ in aqueous solution. The steady decrease in pH
adjusted to the required value after 2 hours. Samples were after the two solutions had been mixed is probably due to
taken periodically, and were pretreated and analysed as the slow oxidation of Fe(n) to hydrated Fe(m) oxides, a pro-
described above. The pH value of the solution was main- cess that involves further hydrolysis and the liberation of
tained at the required level. protons. At Fe:CN- molar ratios of 0,5 and higher, no
To characterize the precipitate, a large batch was made
up as follows: the masses and volumes were quadrupled,
and the precipitate was filtered after 2 hours at the required 250
pH value. The precipitate was washed with deionized water Fe~N)~ F~~~)~..~f.:
prior to being dried in a vacuum desiccator for 24 hours.
Volume of solution (after mixing) : 1 litre
For the experiments carried out to demonstrate the stabil- 200 Mass of NaCN : 0,5 g
ity of ferrocyanide ion, 250 ml solutions of ~Fe(CN)6 Oxygen in solution : 6,5 mg/1
(0,001 M) were made up and placed in round-bottomed ~
flasks with reflux condensers. One solution was exposed to C
sunlight, and one was kept covered. Ultraviolet-visible .2 150 ~
spectra were recorded with a Beckman Acta MIV spec-
trophotometer, and the Fe(CN)i- concentration was moni-
tored by measurement of the absorbance at 420 nm, where 1,00 \
~
Fe(CN)~- does not absorb. Free cyanide was measured
periodically by ion chromatography. X-ray diffractograms ~()G> ,
:
c :
of Prussian blue precipitates were obtained by use of Cu Ka
radiation with a Philips PW1O50125 X-ray diffractometer. <3 50 \
Vacuum-dried samples of precipitate for infrared spec-
trophotometry were pulverized for 5 minutes in a Spex
5100 mixer/mill, and 6 mg were then shaken manually with 0
0 1 2 3 4 5
200 mg of dry KBr. Spectra were obtained with a Perkin-
Fe:CN Ratio
Elmer 1725X Fourier Transform Infrared Spectro-
photometer used in conjunction with a diffuse reflectance Fig. 1-Effect of Fe:CN ratio on solution species after 6 hours
(DRIFT) accessory. of reaction

18 JANUARY 1992 Journal of the South African Institute of Mining and Metallurgy
 TABLE I sary excess, resulting in a high consumption of reagent.
Effect of Fe:C~ molar ratio on the reaction of cyanide with
For the remainder of the present testwork, an Fe:CN-
ferroullulphate .

ratio of 0,5 was used.

Conditions: Volume of solution (after mixing) llitre Effect of pH
Mass ofNaCN 0,5 g In this set of experiments, the pH of the cyanide solution
Oxygen in solution 6,5 mg/1
was varied between 4 and 13, while that of the ferrous sul-
Fe:ar- Tune pH Precipitate Concentration in solution phate solution remained unadjusted. The concentration of
solution species was measured as a function of equilibrium
mg/1 mg/1 (expressed as eN)
pH, and is shown in Fig. 2. Details of the results, including
min Fer Fe(CN)1;- Fe(~- ar- the initial pH values of the solutions, are listed in Table 11.
0,1 10,5 None 48 NA NA
It should be noted that no precipitates were formed when
0 265-
5 10,4 None 134 ND 113 the FeSO4 solution was added to cyanide solutions that had
30 10,4 None 134 ND 109 initial pH values of 4 or 7, and that only a small amount of
360 10,4 None 51 133 ND 95 precipitaie was obtained from the cyanide solution with an
initial pH value of 8,5. Analysis of these solutions yielded a
0,25 0 10,5 None 162 NA NA 265 value of about 50 mg/l (as CN) for both Fe(CN)%- and free
5 6,4 None 211 ND 15,4 CN-, and the concentrations of these species dropped over
30 6,4 None 225 ND 10,4
360 6,4 None ll8 215 ND 3,4 the 6-hour period (Table 11).
Fig. 2 also indicates that a significant amount of ferro-
0,5 0 10,5 None 218 NA NA 265 cyanide forms in solution at final pH values of greater than
5 6,3 Brown! ND ND 1,58 approximately 6,5. This is due to the decomposition of
turquoise
6,1 0,76
Prussian blue under alkaline conditions, and is discussed in
30 Blue ND ND
360 5,2 Blue 0 ND ND ND more detail later in this paper.
The optimum equilibrium pH range for the precipitation
4 0 10,5 Brown! ll16 NA NA 265 of Prussian blue is between 5,5 and 6,5 and, under these
turquoise conditions, it is possible to achieve very low levels of
5 5,0 Turquoise ND ND 1,49
4,7 Turquoise
cyanide species in solution after 5 minutes. Lower pH val-
30 ND ND ND
360 3,3 Blue 822 ND ND ND ues result in incomplete precipitation, whereas higher pH
values result in the decomposition of the Prussian blue
ND Not detected NA Not analysed product. In the present work, the optimum pH value was
attained by the mixing of the FeSO4 and CN- solutions
Fe(CN)i- or Fe(CNH- species were detected in solution without any prior adjustment of the pH value of the cyanide
even after only 5 minutes of reaction, at which time about solution (natural pH value of 10,5). The presence of lime
1,5 mg/l of free cyanide was detected. The cyanide level and other soluble species in tailings may necessitate some
may be reduced to below the detection limit (0,02 mg/l) by adjustment of the pH value when this method is applied to
an increase in either the reaction time or the Fe:CN- ratio. plant tailings.
In each case where a precipitate formed, an instantaneous
colour change (brown, followed by blue-green) was noted, 250
followed by the familiar bright blue of Prussian blue. These .. 3--CN
Fe(CN)e Fe(CN)e
'.8.".,...4-...
colours suggest that a portion of the Fe2+ precipitates as --
Fe(OH)2 on contact with the alkaline cyanide solution, fol- Volume of solution (after mixing) : 1 litre
lowed by rapid oxidation to F~O3.n H2O. Reactions such as :2 200 Mass of NaCN : 0,5 g
0 Mass of FeSO4.7H20 : 1,419 g
the following may also occur to some extent: Cl
:0,5
E Ratio of Fe:CN
C Oxygen in solution :6,5mgll
Fe2+ ~ Fe3 + e - [6]
"""""""""""""""""""""""""'" ~ 150
"0
11)
Fe3+ + 6 CN- ~ Fe(CN)~- [7]
.5
"""""""""""""""""'" c
.2 100
4 Fe2+ + 3 Fe(CN)~- ~ Fe4[Fe(CN)6h (J.) . [8] ~
'E
CD
u
Exact identification of the form in which the iron initially c
precipitates is difficult, owing to the short time-span during 8 50
which the precipitate exists before being converted to
Prussian blue. Moreover, the chemistry of the iron (m)
oxides is complex, with the existence of a range of possible 0
hydrated F~O3.n H2O species of varying colour. 2 4 6 8 10 12 14
pH after 5 miD
Beckennll suggests that an Fe:CN- ratio of 16 should be
used for the effective removal of cyanide, but the results Fig. 2-Effect of pH on solution species after 5 minutes of
illustrated in Fig. 1 indicate that this would be an unneces- reaction

Journal of the South African Institute of Mining and Metallurgy JANUARY 1992 19
 TABLE 11 that under these conditions Fe2+ and/or Fe(0H)2 are oxi-
Effect of pH on the reaction of cyanide with ferrous sulphate dized to form hydrated ferric oxides prior to reaction with
Conditions: Volwne of solution (after mixing) I litre CN-, thus reducing the Fe2+:CN- ratio. This is borne out by
Mass of NaCN 0,5 g the observed colour changes.
Mass of FeSO4.7HzO 1,419 g
Ratio of Fe:CN 0,5
The presence of nitrogen resulted in a lower oxygen con-
Oxygen in solution 6,5 mg/l centration in the solution, and no ferricyanide was detected.
However, these results highlight another effect: the slower
pH Time Precipitate Concentration in solution rate of oxidation leads to the presence of a substantial
mg/l mg/l (expressed as CN) amount of Fe(CN)%- in the solution after 6 hours, which
may possibly be attributed to the higher solubility of
min Fe.r Fe(CN)t- Fe(CN)t CW
FeI!FeII(CN)6 compared with that of FeIII4[FeII(CN)6h-
4,0 0 None 225 NA NA 194 Even in this case, however, there was also some pre-oxida-
3,9 5 None 42,S ND 40 tion of divalent iron prior to the reaction with the CN-, as
3,9 30 None 25,0 ND 60 evidenced by the colour changes (Table IlI).
3,9 360 None 237 23,0 ND ND
Effect of Pulp
7,0 0 None 229 NA NA 288
In an effort to determine the effect of pulp solids on the
4,8 5 None (pale blue 41,4 ND 38
4,7 30 soIns) 72,S ND 9
reaction, the ferrous sulphate method was applied to a sam-
4,1 360 242 17 ND 5,2 ple of pulp tailings from a mine. Two tests were carried
.
out, the fIrst with no pH adjustment and the second with
8,5 0 None 236 NA NA 323 the pH value adjusted to 6 immediately after the addition of
4,8 5 Brown/turquoise 32 ND 51 the FeS4. The samples of plant solution produced chro-
4,2 30 Blue 33,8 ND 24
3,6 4,5
matograms that contained many additional peaks, and it
360 Blue 193 24 ND
could not be established whether these were due to
9,5 0 None 243 NA NA 267 cyanide-containing species. The results are shown in Table
5,2 5 Brown/turquoise 2,3 ND 49 IV.
4,2 30 Blue 5,8 ND 40
3,4 360 Blue 1,7 ND ND
In both cases, satisfactory levels of total cyanide were
attained. It should be noted that the initial level of free
10,5 0 None 218 NA NA 315 cyanide was artificially high because the samples had been
6,3 5 Brown/turquoise ND ND 1,58 spiked with NaCN. The low concentrations of Fe(CN)~- at
6,1 30 Blue ND ND 0,76 pH values of 7,2 and 8,5 are somewhat surprising (Fig. 2).
5,2 360 Blue 0 ND ND ND
This effect could possibly be due to the presence of very
11,5 0 None 230 NA NA 249
insoluble complex precipitates of Fe(CN)~- with various
7,5 5 Brown/green 30,3 ND ND base metals. Since copper was the only base metal detected
6,8 30 Turquoise 7,0 ND ND in the tailings apart from iron, and since the concentration
6,7 360 Turquoise 30 20,4 ND ND of the Cu(CNH- was found to drop steadily (Table IV),
these results are consistent with the formation of the highly
13,0 0 None 232 NA NA 250
13,0
insoluble Cu2Fe(CN)6 in addition to the precipitation of
5 Green/brown 98 ND ND
13,0 30 Blue/brown 88 ND ND Prussian blue.
12,9 360 Brown 85 63 ND ND
Nature and Stability of the Soluble Complexes
ND Not detected NA Not analysed The results in the previous section show that ferricyanide
is not formed to any signifIcant extent under the conditions
pertinent to the precipitation of Prussian blue, and that fer-
Effect of Oxygen rocyanide is the main soluble complex that is formed.
The precipitation reaction, equations [2] to [5], involves The potential-pH diagram for the Fe-CN-H2O system is
the oxidation of Fell to Fern, and it is therefore useful to shown in Fig. 3. The Fe(CN)~- species is thermodynami-
determine the effect of oxygen on the precipitation cally unstable with respect to oxidation within the region of
reaction. Much discrepancy exists12 in the literature regard- stability of water, which is shown bounded by the broken
ing the mechanism involved in the oxidation of ferrous ion lines in Fig. 3. The ion is clearly also unstable with respect
by oxygen; however, the kinetics are both pH and [2]
to changes in pH. This is exemplified by the results of a
dependent12.
species-distribution calculation, obtained by means of the
In the present work, the cyanide solution was saturated Haltafal114computer program. The results are illustrated in
by the bubbling of either oxygen or nitrogen for 15 minutes Fig. 4, together with the relevant chemical equilibria and
prior to contact with the FeS04 solution. Bubbling was stability constants used. The ferrocyanide ion is thermody-
continued throughout the reaction. The results are shown in namically unstable in acidic solutions, with the following
Table Ill. reactions illustrating acid attack:
The presence of excess oxygen resulted in the occurrence
of both Fe(CN)%- and Fe(CN)i- in solution, and suggests Fe(CN)~- + Hp+ ~ Fe(CN)5H2O~ + HCN [9]

20 JANUARY 1992 Journal of the South African Institute of Mining and Metallurgy
 TABLE III
Effect of oxygen on the reaction of cyanide with ferrous sulphate
Conditions: Volume of solution (after mixing) I litre
Mass ofNaCN 0,5 g
Mass of FeS4.7HzO 1,419 g
Ratio of Fe;CN 0,5

Gas [z} Time pH Precipitate Concentration ID solution

bubbling mg/l min mg/l mg/l (expressed as CN)

Fe,- Fe(CN)1,- Fe(CN)t- CN"

>20 0 10,5 None 232 NA NA NA

z 4,8 Brown/green 10,0 6,3
5 ND
30 4,2 Brown/green 20,0 0,7 ND
360 3,9 Blue 0 22,2 8,8 ND

None 6,5 0 10,5 None 218 NA NA 315

5 6,3 Brown/turquoise ND ND 1,58
30 6,1 Blue ND ND 0,76
360 5,2 Blue 0 ND ND ND

Nz 2,0 0 10,5 None 236 NA NA NA

5 6,1 Brown/turquoise 7,5 ND 5,8
30 5,2 Blue 1,0 ND 5,1
360 4,6 Blue 0 31,7 ND ND

ND Not detected NA Not analysed

however, preliminary work18 suggests that reactions [9] and

Fe(CN)i- + 6 H+ ~ FeZ++ 6 HCN . [10] [10] also occur to some extent.
"""""""""
Williams8 reports that these reactions, as well as the oxi- Nature and Stability of the Precipitates
dation of ferrocyanide to ferricyanide, occur relatively To fully understand and optimize the reaction between
rapidly in acidic solutions, particularly after exposure to FeSO4 and CN-, it is necessary to characterize the precipi-
light or heat. In alkaline solutions, ferrocyanide also tates formed. Moreover, it is essential to establish the stabil-
becomes unstable8, owing to the decomposition of the com- ity of the precipitates under various conditions pertinent to
plex and the precipitation of FezO3.nH2O. It is also evident backfill operations.
from Fig. 4 that the region of stability of ferrocyanide
Characterization of Precipitates
diminishes in size with a decrease in the ferrocyanide con-
There are several types of Prussian blue that are formed
centration.
under various conditions, and the colloidal variations would
The stability of ferrocyanide under the conditions of
interest was investigated with the use of quantitative visible
2
spectrophotometry for the determination of Fe(CNn- in
Fe(CN)"-
solution, and ion chromatography for the determination of 6
Fe3+
CN-.
FeOOH FcOOH
Fig. 5 shows that a significant amount of the Fe(CN)i- in ---
-----------
K4Fe(CN)6 solution is oxidized to Fe(CN)~-, particularly in --------
solutions with a pH value of 4. A complicating factor is the ----
precipitation of Prussian blue from these solutions. The pH -----------------
4 solutions appeared somewhat green in colour; the pH 1 Fe2+ ~
solutions contained a fine blue precipitate; the pH 7 solu-
Eh 0 ----
tions remained yellow in colour. The maximum in ----- - Fe(CNt Fep.
Fe(CN)1- concentration at a pH value of 4 can thus be ~-------------
explained by the observation that an increasing amount of
Prussian blue was formed in more acidic solutions, thus -1
2-
Fe(OH).
removing the Fe(CN)~- ion from solution, probably in the Fe
form of soluble Prussian blue, KFeIII[FeII(CN)6]' which [Fe] 0,0001 M
=
forms a colloidal blue solution. The effect of sunlight is [CN)
=
0,001 M

somewhat variable, and further experiments would be -2

0 4 8 12 16
required to quantify and characterize the chemistry pH
involved.
Fig. 3-Potential-pH diagram for the Fe-CN-H20 system at
No free cyanide could be detected in these solutions; 25C (after Ciminelli13)

Journal of the South African InsUtute of Mining and Metallurgy JANUARY f992 ,- 21
 1 100
Initial (K.Fe(CN)6J : [,0 mmolt1 PH7glght
Volume of solution: 250 rnl
p~~!lrk
GI
'tJ
'c 0,8 80 pH4;lIght
~
~ ~
.; p~~d_ark
e 'tJ
.! C pH1llght
:0,6- ~
u
60

U
UI
GI "E
.S! ..-------------- p"!!id.ark
GI ~
I

C-
UI
z0,4
(,)
~ 40
i'tJ
'0 1(
c: [F8(CN):"J, (CN], 0
.SI
20
0,2 1581,0
~ 0,1
LL b.OOI 158,1 .A t.
,ooXI1 15,8
,-,/ --
0,00001 1,8
0
0 0 10 20 30 40 50 60
0 2 4 6 8 10 12 14
pH Tlme,h
Fig. 5-Effect of pH on the rate of oxidation of ferrocyanlde In
Equilibrium Stability Solubility Ref. aqueous solution
constant product
B"
KfiJ
not be acceptable as an immobilized form of cyanide.
Fe2+ + 6 CN- (:) Fe(CN)t 1,000 x 1038 15 Elemental analyses of the precipitate obtained under opti-
Fe2+ + 5 CN-+H20 (:)Fe(CN)sH23- 5,000 x 1027 16 mal conditions (Fe:CN 0,5; pH value 5,5 to 6,5) are shown
Fe(CN)t+ H+(:)HFe(CN)t 1,995 x 104 17 in Table V, together with the theoretical elemental ratios of
Fe(CN)t + 2 H+(:) H~e(CN)t 7,943 x 1()6 17
possible products.
Fe2+ + OH- (:) FeOH+ 1,995 x 10-10 15 The exact identification of the precipitate is not possible
Fe2+ + 2 OH- (:) Fe(OH)2 1,585 x 10-21 15
on the basis of the elemental analyses alone; however, the
Fe2+ + 3 OH- (:) Fe(OH)i 1,000 x 10-31 15
Fe2+ + 4 OH- (:)Fe(OH)~- 1,000 x 104 15
low concentration of sodium in the precipitate suggests that
it is more compatible with Fe4[Fe(CN)6h than with
H+ + OH- (:) H2O 9,886 X 10-IS 17 NaFe[Fe(CN)~. The presence of 4,4 per cent oxygen over
H+ + CN- (:) HCN 1,622 x 10g 17 and above that associated with water is probably due to a
Fe(OH)2 (5) (:) Fe2+ + 2 OH- 1,112 X1013 15
small amount of iron oxide. The lack of a mass balance
probably arises from the nitrogen analyses, which were car-
Fig. 4-Effect of pH on the stability of ferrocyanlde In aqueous
ried out with an instrument designed for the analysis of
solution alloys.
The characteristic bandsJ9 common to both insoluble and
soluble Prussian blue were evident in the infrared spectrum
of the precipitate, and in particular in the very strong u(CN)

TABLE IV
Removal of cyanide from pulp tailings by Prussian blue precipitation using FeSO4

CondiJions: Volume of sluny I litre

Mass ofNaCN O,5g
Mass ofFeSO..7Hp 1,419 g

pH of pulp Time Concentration, mg/l (expressed as CN)

min CN- Fe(C~- Fe(CN}t Cu(CN)1- SCN- CNO-

10,5 0 741 9,4 ND 14,6 ND ND

-
8,5
5 2,7
2,0
4,7
2,7
1,2
1,2
8,6
6,0
ND ND
30 ND ND
7;1. 360 0,4 ND ND ND ND ND

10,5 0 741 9,4 ND 14,6 ND ND

6 5 2,0 5,2 2,2 12,7 ND ND
6 30 0,5 4,2 ND ND ND ND
6 360 2,5 ND ND ND ND ND

ND N at detected

22 JANUARY 1992 Journal of /he South African Institute of Mining and Metallurgy
band at 2084 cm-I. The X-ray-diffraction peaks of the pre- disappearance of Prussian blue and the appearance of iron
cipitate were close to those reported20 for pure oxides. The results listed in Table VI also suggest that, in
Fe4[Fe(CN)6h. the presence of alkaline solutions, a small amount of the
precipitate may contain co-precipitated soluble Prussian
Chemical Stability of Prussian Blue blue, as evidenced by the somewhat higher sodium contents
It has been reported8 that Prussian blue decomposes of the precipitates under these conditions.
when contacted with alkaline- solution, and this should be
taken into account in any process that places large amounts Infrared spectra of some of the precipitates after 2 hours
of Prussian blue underground. of contact with the various solutions are shown in Fig. 7.
The precipitates in contact with solutions having a pH
A detailed investigation of this reaction is reported here. value of 6 and less are not changed to any great extent. The
The precipitate obtained under optimal conditions was precipitates in contact with solutions having pH values of 6
exposed to solutions of various pH values for several
to 9 retain a very strong C == N stretch at 2084
weeks, and both solid and solution phases were character- cm-!; however, the three characteristic bands at 1140 1056
ized by a variety of techniques. The solution compositions and 996 cm-! begin to disappear. Between pH value~ of 10
are shown in Fig. 6. Significant quantities of ferrocyanide and 13, the 2084 cm-! band begins to disappear, and the
were found in the solution at pH values of 7 and above, and Prussian blue starts to decompose. The other bands intro-
the Fe(CN)t- concentration increased with time. Free duced at high pH values can all possibly be attributed to
cyanide was analysed for but not detected in any of the
various forms of Fe203.n Hp.
solutions. In the case of the pH 13 solution, almost com-
plete decomposition to Fe(CN)~- occurred after 28 days. X-ray diffractograms for the precipitates under different
The presence of some Fe(CN)t- in certain samples is incon- pH conditions are compared in Fig. 8. The precipitates in
sistent, and could be due to oxidation in the sample bottle contact with solutions of pH 1 to 8 display only the X-ray-
itself. (There is no logical explanation for the large concen-
tration of Fe(CN)t- that formed after 7 days at a pH value
of 7, most of which disappeared after 28 days.)
EJ
The precipitate itself appeared progressively more brown
and less blue in colour as the pH value of the contacting
OD 1'(\
solution was raised, which suggests thatF~O3.n HP is the
other product of the reaction:
I

\ ~~v'\

~
\
Fe4[Fe(CN)6h + (2n - 6) H2O + 12 OH- ~
2 F~O3-'nH2O+ 3 Fe(CN)~-. ..., [11]
~
Elemental analyses of the precipitates after 2 hours of
contact with the various solutions are shown in Table VI. I

The steady drop in carbon and nitrogen contents and the

increase in iron and oxygen contents are consistent with the
EJ"'
(\ '

300
I
. Fe(CNLr8JFe(CNr IZJCN- I
{~~ i

,11
250 Volume of solution (alter mixing) : 1 litre \,
-.:.
Mass of NaCN : 0,5 g \ Iq
Z
0 Mass of FeSO4.7H20 : 1,419 g V
CII Ratio of Fe:CN : 0,5
E 200 Oxygen in solution : 6,5 mg/I
C M.
0
:s
'0III 150
.5
c
.2
CV
~GI 100
C>
C
0
0
50

Tlme,days
0
0 , 728 0 1 728 0 1 728 0 1 728 0 1 728 .... ... ...
"" """.t
,.. ,...
""
lOO ..,

pH 10 13 Wavenumbers, OH
4 7

Fig. 7-lnfrared spectra of Prussian blue precipitate after 2

Fig. 6-Decomposltlon of Prussian blue with pH and time hours of contact with solutions of varying pH value

Journal of the South African Institute of Mining and Metallurgy JANUARY 1992 23
 TABLE V
Elemental analyses of Prussian blue precipitate

Compound Elemental analysis, %

Na Fe C N 0 H2O

Precipitate as analysed 0,016 34,6 14,5 6,0 4,4 24,1

Precipitate col'leCled 0,021 45,6 19,1 7,9 5,8
to the anhydrous state

Fe.[Fe(CN)6]J 0 45,5 25,2 29,3 0

NaFe[Fe(CN)6I 7,9 38,4 24,8 28,9 0
FezOJ 0 69,9 0 0 43,0
Fe(OH}z 0 62,1 0 0 35,6
FeO'OH 0 62,9 0 0 18,0

TABLE VI
Elemental analyses of Prussian blue precipitate after 2 hours of contact with solutions of varying pH value

Compound pH of Elemental analysis, %

solution Na Fe 'C N 0 H2O
Precipitate 1 0,003 30,7 16,5 8,8 2,4
4 0,006 33,3 14,5 9,3 3,2
6* 0,016 34,6 14,5 6,0 4,4 24,1
7 0,63 42,5 9,4 7,2 6,1
8 0,68 49,3 8,9 3,6 lI,7 22,2
9 0,47 53,5 4,1 2,8 17,3
II 0,52 53,1 4,9 3,3 17,9
12 0,30 56,1 5,8 2,8 18,4
13 0,18 62,8 1,0 0,3 26,6 lI,8

Fe.Fe(CN)6]] 0 45,5 25,2 29,3 0

NaFe[Fe(CN)6] 7,9 38,4 24,8 28,9 0
Fe20] 0 69,9 0 0 43,0
Fe(OH}z 0 62,1 0 0 35,6
FeO.OH 0 62,1 0 0 18,0

Natural pH of the solution after precipitation

*

diffraction (XRD) peaks characteristic of Fe4[Fe(CN)6h- At cyanide in solution as a result of oxidation; nitrogen bub-
higher pH values, these peaks drop in intensity, whereas bling results in the formation of ferrocyanide in solution.
peaks due to 'Y-F~O3 increase in intensity, The XRD tech- The ferrocyanide ion is unstable in acidic solution, and
nique is sensitive only to crystalline compounds, which forms either the pentacyanide ferrous complex,
means that the various forms of F~O3.n H2O detected in Fe(CNh.H2O3-, or undergoes rapid oxidation to ferri-
the infrared spectra are probably amorphous. cyanide, Fe(CN)t-. These reactions occur at pH values of
less than 4.
CONCLUSIONS The precipitate that forms in the reaction between excess
Environmental regulations require that total cyanide in FeSO4 and CN- was identified as comprising mainly insol-
solution should be reduced to a specified level, and do not uble Prussian blue, Fe4[Fe(CN)6h- The Prussian blue pre-
refer to cyanide in solids. Therefore, the ferrous sulphate cipitate is stable over a pH range of 1 to 7, but is unstable
method must be optimized for the formation of the Prussian in alkaline solution, decomposing rapidly to form Fe(CN)%-
blue precipitate, and not the soluble ferrocyanide complex. in solution. It forms various insoluble iron oxides,
The optimal conditions for the removal of cyanide by reac- Fe203.n H2O (n = 1-3), at pH values above 7.
tion with FeSO4 and the formation of Prussian blue are as
follows: ACKNOWLEDGEMENT
pH 5,5 to 6,5 The work described here was carried out in collaboration
with the Chamber of Mines as part of its research pro-
Fe:CN 0,5.
gramme, and is published by permission of the Chamber of
The bubbling of either oxygen or nitrogen was found to Mines. The contribution to this work by O.L. Wellington,
be detrimental to the removal of cyanide: oxygen bubbling MJ. Hemmings, E.A. Jones, and KT. Win tie is greatly
results in the formation of both ferrocyanide and ferri- appreciated.

24 JANUARY 1992 Journal of the South African Institute of Mining and Metallurgy
 Fc.[Fe(CN)6h

Fc.[Fc(CN)JJ
Fc.[Fc(CN),h
Fc.[Fc(CNMJ

~'-~IT
B
=B
~-
-
~
~ A A- A-A -B
EJ

-"- --.J'I.. B
a
6
8
.,-FcZOJ
.,-FcZOJ .,-FcZOJ .,-FeZOJ
8
63 575451 434035 30 25 18 29

Fig. S-X-ray dlffractograms of Prussian blue precipitate after 2 hours of contact with solutions of varying pH value
cyanides with ferrous sulphate. Chem. Stosow., vol. 16, no. 1. 1972.
REFERENCES pp. 79-100.
1. CHADWICK. B.M., and SHARPB, A.G. Transition metal cyanides and 11. BECKENN,W.E. Treatment of cyanide waste. Electroplating and Metal
their complexes. Advances in inorganic chemistry and radiochemistry. Finishing, Dec. 1972, pp. 20-21.
Erneleus, H.J., and Sharpe, A.G. (eds.). New York, Academic Press, 12. VERBAAN,B., and CRUNDWELL,F.K. An electrochemical model for the
1966. pp. 83-176. leaching of a sphalerite concentrate. Hydrometall., vol. 16. 1986. pp.
2. ZAIDI, S.A., and CARRY, J. Ultraviolet irradiation for removing iron 345-359.
cyanide from gold mill effluents. Conference on cyaniik and the envi- 13. CIMINELLI,V.S.T. Oxidation of pyrite in alkaline solutions and hetero-
ronment. Van Zyl. D. (cd.). Fort Collins, Colorado State University, geneous equilibria of sulphur- and arsenic-containing minerals in
1984. pp. 363-377. cyaniik solutions. Ph.D. Thesis, Pennsylvania State University, 1987.
3 POHLANDT,C. Chromatographic separation and determination of stable p.170.
metal cyanide complexes in gold processing solutions. S. Afr. J. 14. lNOR!, N., KAKOLOWlcz, W., SILU!N, LG., and WARNQVIST,B. High-
Chem., vo138, no. 3. 1985. pp. 110-114. speed computers as a supplement to graphical methods. V. Haltafall, a
4. WBSTBROOK, C.W., PARCFLL, T., CLAYTON, G.L., and KLOCK, B.V. general program for calculating the composition of equilibrium mix-
Waste water process. V.S. Patent 4211 646. 8th Jul. 1980. tures. Talanta, vol. 14. 1967. pp. 1261-1286.
IS. KRAGTEN, l Atlas of metal-ligand equilibria in aqueous solution.
5. KENT, WJ., and BABCOCK,A.R. Process for the removal of cyanides
Chichester, Ellis Horwood, 1978.
from effluent. V.s. Patent 4 250 030. 10th Feb., 1981.
16. BECK, M.T. Critical survey of stability constants of cyano complexes.
6 NEVILU!, RG. Method for the removal of free and complex cyanides
Pure & Appl. Chem.,vol. 59,no. 12. 1987. pp. 1703-1720.
from water. V.S. Patent 4 312 760. 26th Jan., 1982.
17. SMITI~, R.M., and MARTELL, A.E. Critical stability constants. Vo14:
7. GOODWIN,E. Process for the removal of cyanide and other impurities Inorganic Complexes. New York, Plenum, 1976.
from solution. S. Afr. Patent 8813302. 10th May, 1988. 18. HEMMINOS, M.l Mintek, Randburg, pcrsonal communication, Feb.
8. WILLIAMS, H.E. Cyanogen compounds. 2nd edn. London, Edward 1990.
Amold, 1948. pp. 170-200. 19. WILDE, RE.,. GHOSH, S.N., and MARSHALL, B.J. The Prussian blues.
9. ROBIN. M.B. The colour and electronic configurations of Prussian Inorg. Chem., vol. 9, no. 11. 1970. pp. 2512-2516.
blue.lnorg. Chem., vol. I. no. 21962. pp. 337-342. 20. SMITH, J.V. (cd.). X-ray powder diffraction file. Philadelphia,
10. SZARAWARA.J., and POCIECHA, Z. Equilibria of the complexing of American Society for Testing Materials, 1960. p. 1-0239.

Journal of the South African Institute of Mining and Metallurgy JANUARY 1992 25
~.'

GR Bozzoli Awards *
The Anglo American Corporation, Murray & Roberts, MR GEORGE BROWN
and Mr George Brown were recipients of the GR Bozzoli
Awards for 1991. Mr George Brown, former Electrical Service Manager in
These Awards, named after Professor G. R. Bozzoli, a the Engineering Department of AECI, who retired from
highly respected past head of Electrical Engineering, Dean AECI recently, was nominated by the Department of
of the Engineering Faculty, and Vice-Chancellor of Wits Electrical Engineering for consistently promoting and influ-
University, are presented annually by the Faculty of encing the cause of education at South African universities.
Engineering at Wits to individuals and organizations for Since the 1960's, Mr Brown has played a leading role in
their outstanding contribution to enginering education. strengthening the staff and computing facilities in the
Department of Electrical Engineering at Wits, helping to
ANGLO AMERICAN establish an FRD programme in the field of process control,
Anglo American was nominated for its foresight in estab- and serving on advisory committees investigating the
lishing the Cadet Scheme ten years ago. The Scheme was structure and teaching of undergraduate programmes.
aimed at developing technologically trained black PROGRESS IN ENGINEERING
engineers and managers. The Scheme is now administered
by the Engineering Faculty and sponsored by eleven engi- Professor Alan Kemp, Dean of the Engineering Faculty,
neering companies. It provides a pre-university year of told guests at the Awards ceremony that, in the past year,
academic upgrading and attention to problem-solving, the Faculty had made good progress in its strategic priori-
language, and study skills, as well as practical experience in ties of improving the quality of education in terms of both
the work environment. students and staff, developing closer associations for
Anglo American's selfless concern for the future of eng- mutual benefit with industry, and addressing the needs of
ineering education in South Africa is also illustrated by the educationally disadvantaged students.
recent decision of the Chairman's Fund to finance an He said: 'The average matriculation mark in higher-grade
engineering stream of the College of Science at Wits mathematics, science, and home language of
University over the next five years at a cost of more than 2 admitted first-year students is now more than 70 per cent,
million rands. probably the highest in any engineering faculty in South
This will enable 60 students from disadvantaged educa- Africa.' It was important that pass rates reflected this
tional backgrounds to spend two years of intensive improved quality of student, and attention was being given
preparation in gaining credit for first year. to the teaching process to counterbalance the negative
effects of massive cuts in university subsidies by the State.
MURRAY & ROBERTS A first priority for private-sector funding is the establish-
Murray & Roberts was nominated for the Bozzoli Award ment of scholarships, fellowships, and named chairs that
by the School of Mechanical Engineering and the can support full-time post-graduate students to act as part-
Department of Civil Engineering in recognition of substan- time teaching assistants while undertaking their research
tial support, including a new CAD facility for first-year and coursework. In addition, the Engineering Faculty at
mechanical-engineering students, an annual grant to Wits had a proud record of developing, together with the
support a member of the civil-engineering staff on overseas private sector, more academic support schemes addressing
research study, and the provision of teaching equipment. the needs of more disadvantaged students than most facul-
ties in South African universities.
. Released by Lynne Hancock Communications, P.O. Box 3712, Mr Paul Kruger, Manging Director of Sasol, was guest
Honeydew, 2040 Transvaal. speaker at the presentation.

26 JANUARY 1992 Journal of the South African Institute of Mining and A allurgy