Canadian Metallurgical Quarterly, Vol. 26, No.2, pp.91-101, 1987 Printed in Great Britain.

0008-4433/87 $3.00 + .00 1987 Canadian Institute of Mining and Metallurgy Pergamon Journals Ltd.

THE BEHAVIOUR OF ARSENIC DURING JAROSITE PRECIPITATION: ARSENIC PRECIPITATION AT 97C FROM SULPHATE OR CHLORIDE MEDIA
J. E. DUTRIZAC and J. L. JAMBOR
Mineral Sciences Laboratories, CANMET, Energy, Mines and Resources Ottawa, Ontario KIA OGl, Canada Canada, 555 Booth Street,

Published by Maney Publishing (c) Canadian Institute of Mining, Metallurgy and Petroleum

(Received 5 November 1986)

AbstractThe behaviour of arsenic during the precipitation of alkali jarosite compounds at 97C has been investigated as a function of the arsenic and alkali concentrations, solution pH and dissolved iron concentration. Arsenite is not precipitated, but arsenate phases are extensively eliminated with the jarosites formed from either sulphate or chloride media. Up to 90% of the initial arsenate can be precipitated, mostly as a separate phase but also as a limited solid solution in the jarosite. Although well crystallized scorodite is formed in chloride media, an amorphous phase, chemically similar to scorodite, usually precipitates in sulphate media at this temperature. The results obtained at 97C suggest a limited solid solubility of As04 ('" 2%) in the alkali jarosites, but this point requires confirmation.

INTRODUCTION The precipitation of jarosite-type compounds (M Fe3(S04h (OH)6 where M = Na, K, Rb, NH4, Ag, -!-Pb, H30, etc.) is widely used in the metallurgical industry as a means of controlling iron, sulphate or alkalis in processing solutions. The principal application is for iron control in sulphate-based hydrometallurgical zinc circuits[lJ although the technology also is being employed in copper and cobalt operations [2]. In cupric chloride/ferric chloride leaching processes, jarosite precipitation can be used for both sulphate and iron control [3]. The precipitation ofjarosite-type compounds from chloride solutions is relatively straightforward provided that a separate source of sulphate is available and the pH of the solution is not too low [4]. Although alkalis are normally added to initiate jarosite precipitation for iron or sulphate control, it is also possible to add excess ferric ion to a sulphate solution with the aim of precipitating unwanted alkalis. The latter technique has been employed for alkali removal from manganese sulphate solutions [5J, and seems to be particularly effective for potassium control, with K levels < 10ppm being achieved readily. The advantages of jarosite precipitation include: the effective elimination of iron, sulphate or alkalis, low losses of soughtafter divalent metals such as Zn, Cu or Mn, and the excellent settling and filtration properties of the precipitates. The jarosite formula can be represented schematically as MB3X2 Y6' where M is nominally monovalent, and B is trivalent. A number of substitutions have been demonstrated for the monovalent M-site [6J and for the trivalent B-site [7]. In addition, the coupled substitution of two divalent ions for a monovalent plus trivalent ion can occur under certain circumstances [7J, and this effect has been illustrated most extensively for Pb2+ + Cu2+ = M+ + Fe3+ [8J. Complete substitution for the SO~- in the X -site has been reported for SeOi - and CrOi - [7J, but many of the common anions such

substitutions for OH- in the monovalent }:site, but it seems possible to replace at least one of the OH- ions with F-. Arsenic is a common impurity in metallurgical ores and concentrates. Arsenic is present as arsenides, e.g. arsenopyrite FeAsS or cobaltite CoAsS, as sulphosalts, e.g. tetrahedritetennantite CU12(Sb,AS)4S13,and as a substitutional element in some sulphides. During oxidative hydrometallurgical processing, at least part of the arsenic is oxidized either to arsenate (AsO~-) or to arsenite (As02 or AsO~-), with the extent of reaction being notably high in 02-pressure leaching systems [9J and in ferric chloride leaching media [10]. Although thermodynamic considerations indicate that arsenate is the stable species, arsenite is extensively metastable in many leaching systems [10, 11]. Despite the fact that arsenic is a common impurity in many hydrometallurgical processing solutions, little has been reported on the behaviour of arsenic species during jarosite precipitation. Yaroslavtsev et al. [12J investigated the precipitation of both arsenate and arsenite with potassium jarosite formed at 90 DC and pH = 1.5. They observed that arsenate was extensively precipitated with the jarosite, but that arsenite tended to remain in solution. Details of the testwork were not provided and it was not demonstrated whether the arsenic species were structurally incorporated by substitution for sulphate in jarosite, or whether they were present as separate phases. Arsenic is often detected in commercial or pilot plant jarosite precipitates [9J, but the form of the arsenic is ill-defined and the range of precipitation conditions reported is generally restricted. Dutrizac and Jambor [13J recently presented some preliminary findings on arsenic incorporation in jarosites formed over a broad range of conditions, and it was concluded that the arsenic mostly was present as a separate phase. Because of the importance of arsenic impurities in hydrometallurgical processing and the general lack of systematic data concerning the behaviour of this element during jarosite precipi-

as MnOi - or TeOi - do not enter the structure

to any
91

tation, the behaviour

of arsenate and arsenite during the

significant extent. Very little work has been reported on

precipitation of various alkali jarosites has been investigated.

92

J. E. DUTRIZAC

and J. L. JAMBOR:

JAROSITE
45

PRECIPITATION

Work was done in both sulphate and chloride media, and over the range of variables likely to be encountered in hydrometallurgical processing. A temperature of 97 DC was selected for the test work as many hydrometallurgical processes ~re conducted at ....., 100 DC. The objectives were to illustrate the general behaviour of arsenic during jarosite precipitation and to offer some commentary on the mechanism of arsenic precipitation.

0.2M 40

Fe3+,O.3

M Na2S04,97C h

"'-

"'-8

pH= 1.6,24

"'"

"'"

35

0
<t..
III

EXPERIMENTAL
Reagent grade chemicals were used for all syntheses. Arsenate was added as Na2HAs04' 7H20, KH2As04 or As20s; arsenite was added as NaAs02 or AS2 3, The form of arsenic used was dependent on the cation under investigation, the need to maintain constant alkali concentration, etc. The jarosites were formed simply by dissolving in water the appropriate sulphate or chloride reagents together with the arsenic, adjusting the pH with H2S04 or MgC03, and then heating the charge to the reaction temperature. Unless stated otherwise, a 24-h retention time was used as this is known to give nearequilibrium conditions at the 97 DC temperature studied [14]. Solid MgC03 was used to raise the pH since magnesium does not form an end-member jarosite-type compound, and also because the solid carbonate reacts slowly enough to prevent local over-neutralization and attendant iron hydroxide precipitation. The experiments were done in a 2-1 reaction kettle fitted with titanium baffles. At the end of the reaction period, the slurries were filtered, and any material adhering to the vessel was removed and also was filtered. The precipitates were washed with 41 of hot water and were subsequently dried at 110 DC. The solution compositions and test conditions generally bracketed the optimum range for jarosite precipitation as identified in previous work [14]. All the precipitates were analyzed chemically, and all were -examined by Guinier-deWolff X-ray diffraction analysis to confirm the presence of a jarosite-type compound and to identify possible impurity phases. Guinier precision focussing cameras are particularly sensitive to impurity phases and, for example, it has been demonstrated that as little as 0.25 wt % scorodite in sodium jarosite can be detected by this technique. Additional X-ray powder patterns of many of the precipitates were obtained using a Debye-Scherrer camera of 114.6 mm diameter, CoKcx1 radiation (). = 1.7889 A), and MgO as an internal standard. Refinements of the data were done using reported procedures [8J and assuming a hexagonal cell with a ~ 7 and c ~ 17A.

30 0 en

----,--,~

"0

0.........

'" '"

~
C z
25

Published by Maney Publishing (c) Canadian Institute of Mining, Metallurgy and Petroleum

.z
:I:
(!)

w u 20 a: w a..

.w

15

.x~ ,
"'8
tV

o/oio.

~OASO'
10

/1
7;---g---g- --g---[j-"loNe
2 DISSOLVED 3 4 5+ As (g / L ) 5

Fig. 1. Effect of dissolved AsS + concentration on the composition the sodium jarosite precipitate made at 97C.

of

RESULTS AND DISCUSSION Effect of arsenate concentration

Figure 1 illustrates the effect of the initial concentration of dissolved Ass+ (added as Na2HAs04' 7H20) on the composition of the sodium jarosite precipitate formed by heating to 97 DC for 24h a 0.2 M Fe(S04)l.s-0.3 M Na2S04 solution of initial pH = 1.6. Previous work [14J has shown that such conditions are near-optimum for the precipitation of alkali jarosites. In the absence of dissolved AsS +, a sodium jarosite is formed that contains ~3.8% Na, ~33% Fe and ~400/0

S04; the calculated formula is Nao.80Fe2.7s(S04h.00(OH)6.00. The difference between the measured sodium content and the theoretical value of 4.7% Na is thought to be due to H3 + substitution for Na + in the sodium jarosite structure [15]. Hence, the formula of the sodium jarosite is (Nao.80H300.20)1.00Fe2.78(S04h(OH)6' The slight deficiency of iron seems to be characteristic of jarosite-type compounds, and the necessary charge neutrality is likely effected by the conversion of some OH- to H20. That is, the true formula is likely (NaO.80 H3 00.20)1.00 Fe2. 78(S04h (OH)S.34(H20 )0.66' As the initial concentration of AsS + in solution increases, the arsenate content of the bulk precipitate also increases and in a nearly linear fashion. The presence of 5 gjI AsS + in the synthesis solution generates a product containing more than 25% As04, and this represents > 90% precipitation of the initially dissolved arsenic values. As the As04 content of the precipitate increases, the S04 content decreases in an inversely proportional manner. The decline in Na follows the trend of sulphate although S04 decreases more rapidly than Na. For example, on increasing the AsS + concentration from 0 to 5 gil, the S04 content of the precipitate decreases to 51 % of its initial value and the Na content declines to 570/0 of its initial concentration. The iron concentration is little affected, and decreases only slightly. Virtually identical results were obtained when the experiments were repeated at pH = 1.4. Figure 2 illustrates the relative partitioning of sulphate and arsenate between the solution and the precipitates made at pH = 1.6 and 97 DC. These particular experiments were done using a ferric ion concentration of 0.3 M and constant concentrations of 0.05 M As04 and 0.6 M Na. The sulphate to arsenate

1. E. DUTRIZAC and 1. L. JAMBOR: JAROSITE PRECIPITATION

0. 8 r------,,......-----,----,----r-----, 0.3 0.7
M Fe 3+
I

93

0.05

As04 ,97C
M

pH=I.6,

l: No =

0.6

40

0.6
o'tlf'

35

e ..J
~ Published by Maney Publishing (c) Canadian Institute of Mining, Metallurgy and Petroleum
en <to

0.5
M= 4.6

cr

III

J30

A_

A_ A

A-

A ---A

o en

.0.4

o~+
0.3

(I)

~ A --

...
Z
l&J l&J

.---A / /

%Fe

en <t L--..J

/
/ 0/ //0

~20 a..
/

0.2
/ /

~/

%As04

0.1
/

/ //0

0.0

0.1

0.2

0.3

0.4
SOLUTION

0.5

[ AS~:~04]

Fig. 2. Relative partitioning of arsenate and sulphate between the solution and the sodium jarosite precipitate made at 97C. Fig. 3. Effect of dissolved As5 + concentration on the composition of the potassium jarosite precipitate made at 97C.

ratios were varied by using different concentrations ofNa2S04 and NaN03, but with a total 0.6 M Na concentration. Nitrate ion has little effect on jarosite formation. As the molar ratio of As04/(As04 + S04) in the synthesis solution increases, the corresponding ratio in the precipitate increases systematically and nearly linearly. The dashed line on the figure represents the ideal precipitation behaviour, and from this it is evident that arsenic is significantly and selectively (m = 4.6) concentrated in the precipitate. In fact, as noted above, more than 90% of the initial dissolved arsenic was precipitated from the more concentrated solutions under these synthesis conditions. Potassium jarosite is the most stable member of the jarosite family [2], and the effect of the initial concentration of As5+ (added as KH2As04) on the formation of potassium jarosite at 97C is illustrated in Fig. 3. The solutions used for these experiments contained 0.2 M Fe(S04)1.5-0.3 M K2S04 at pH = 1.4; the total reaction period was 24 h. The results obtained are similar to those realized for sodium jarosite precipitation (Fig. 1). In the absence of dissolved arsenic, a normal potassium jarosite showing minor hydronium substitution for K + , and a deficiency of iron, is formed. The calculated formula for the end-member jarosite is (KO.87H300.13)l.ooFe2.45(S04h.oo(OH)6.00' Increasing concentrations of dissolved As5 + result in a systematic increase in the As04 content of the product, and an inversely proportional decrease in S04' The K content drops steadily although not as rapidly as S04, and the percentage of iron remains relatively constant. Figure 4 illustrates the relative partitioning of sulphate and arsenate between the solution and the precipitates made from

0.8...----------oy------------,

0.6

~ (5
en
r-""""1

/-m
/

s6.0

c!
en <t

~ en

0.4

0 en
<l

L...--J

0.2

.- .---- .---,I
at 97C.

rl

f/

OJ.Oi:::::---------L.--------~

0.1 As04 ] [ AsO. +504 Solution

0.2

the K-bearing solutions at pH

1.4 and 97 e. Although these

Fig. 4. Relative partitioning of arsenate and 'sulphate between the

solution and the potassium jarosite precipitate made in sulphate media

precipitates were made from solutions having a constant 0.2 M

94

J. E. DUTRIZAC

and J. L. JAMBOR:

JAROSITE

PRECIPITATION
17.0r----~---..------,---__.____-_____,

Published by Maney Publishing (c) Canadian Institute of Mining, Metallurgy and Petroleum

Fe3 + concentration, the K concentration varied slightly as small amounts of KH2As04 were added to the 0.3 M K2S04 solution. As was the case for the synthesis of sodium jarosite (Fig. 2), arsenate is preferentially precipitated from the potassium-bearing solutions. In this instance, however, the molar partitioning coefficient is slightly higher at 6.0 (cf. m = 4.6 for sodium jarosite precipitation, Fig. 2). The behaviour of ammonium jarosite, which like sodium jarosite also is widely used in the metallurgical industry, is more similar to that of sodium jarosite than that of the potassium member. When ammonium jarosite was precipitated in the presence of Ass +, a composition curve similar to Fig. 1 was realized. The precipitates made in the presence of sodium sulphate (Figs 1 and 2) had the characteristic yellow colour of jarositetype compounds, and all the precipitates filtered readily. X-ray powder diffraction analysis indicated only well crystallized sodium jarosite. The high As04 contents of the precipitates, the linear As04/(As04 + S04) molar distribution curve, and the powder diffraction data could be interpreted as indicating As04 substitution for S04 in the sodium jarosite structure: NaFe3(S04h(OH)6

0.2 M Fe3+, 0.3M N02 54,97 16.8 pH = 1.6

e-e-----e-e---

16.4

5 - 0 (504)

1.47

As-O (As04)-1.67

A A

04

-7.3

-e-e-e-e-e--

~
7.1 L...--_------'- __ 0.2
---'- __ --'-- __

...l..-_-----l

0.4

0.6

0.8

1.0

[ AS~~;04

+ AsOl- + H+
--+

Fig. 5. Variation of the unit cell parameters of the sodium jarosite made at 97C with increasing As04/(As04 + S04) mole ratio in the original solution.

NaFe3(S04)(As04)(OH)s

. H20 (1) be viewed with some caution. The arsenate ion is larger than the sulphate (As-O bond length in As04 is 1.686 A whereas the corresponding S-O bond length in S04 is 1.473 A [17J), but this substitution does not always result in significantly larger unit cell parameters. For example, beudantite PbFe3 (As04)(S04)(OH)6 has cell parameters of a = 7.32, c = 17.02 A (PDFI9-689); these parameters are only slightly greater than those of plumbojarosite Pbo.s Fe3(S04h(OH)6: a = 7.32, c = 16.90 A [6,8]. Although there is also a difference in the extent of Pb-site occupancy in beudantite and plumbojarosite, the significantly greater cell parameters expected for beudantite are not observed. There does not seem to be any change in Msite occupancy in the alkali jarosite-arsenate systems under current study. X-ray diffraction analysis of the precipitates made from Kbearing solutions (Fig. 3) indicated some differences relative to the analogous sodium system. Although the precipitates made from solutions containing < 3 gil Ass + (Fig. 3) showed only K-jarosite, those made from solutions initially having 3, 4 or 5 gil Ass + indicated additional minor amounts of well crystallized scorodite FeAs04' 2H20. Presumably scorodite is present in all of the precipitates, but in some, the amount and/or crystallinity of the scorodite is too low to be detected. The unit cell parameters of the potassium jarosite remained relatively constant as the arsenate content of the precipitate increased from 0 to ~ 250/0. The a parameter was constant at 7.31 A, but the c value increased systematically from 17.06 to 17.15 A. This may indicate a slight substitution of AsOl- for soI - in K-jarosite. The results suggest that nearly all of the arsenate is precipitated as scorodite, and that arsenate is not structurally incorporated to a significant extent in the potassium jarosite. Effect of reaction time Figure 6 illustrates the effect of reaction time on the composition of the precipitates made at 97 DC from solutions containing

+ SOI-.

The tetrahedrally co-ordinated AsOl- ion would be isostructural with SO~ - , and charge neutrality would be maintained by conversion of one of the structural OH- ions to H20 as occurs, for example, in the svanbergite (SrAI3(P04) (S04)(OH)6)-goyazite (SrAI3(P04h(OH)s' H20) mineral series. Although this type of reaction may occur to a limited extent, it is thought for the reasons given below that the arsenate is present mostly as a discrete amorphous phase. Firstly, the decrease in the Na content of the arsenatebearing sodium jarosite (Fig. 1) is considerably greater than expected for the hypothetical compound NaFe3(S04)(As04)(OH)s . H20; nevertheless, the possibility of enhanced hydronium substitution for sodium as the arsenate content increases cannot be ruled out. Secondly, Mossbauer spectroscopy indicated the presence of two phases, each containing ferric ions. Although the room temperature spectrum indicated only one species for the precipitate containing ~ 27% As04 (Fig. 1), the more accurate and informative spectrum at 10 K revealed the presence of approximately equal amounts of two similar Fe3 +-bearing compounds. Only one of the spectra was characteristic of jarosite-type compounds [16]. Thirdly, detailed examination of the X-ray powder diffraction patterns provided no evidence of the substitution of As04 for S04' Powder diffraction patterns of the various precipitates of Fig. 1 were indexed assuming a hexagonal cell, and the calculated a and c parameters are illustrated in Fig. 5. The unit cell parameters of the sodium jarosite, the only phase detectable, are plotted as a function of the molar ratio of As04/(As04 + S04) in the precipitate. There is no significant variation of either a or c with increasing arsenate content, even for AsO 4/(AsO 4 + SO 4) molar ratios as high as ~ 0.5. The lack of a significant and systematic variation of a and/or c with increasing arsenate content strongly suggests that the sodium jarosite is largely arsenate-free although this conclusion must

1. E. DUTRIZAC

and J. L. JAMBOR:

JAROSITE 40

PRECIPITATION 80

95

45.-------,-------,r----,----,----.-----,
0.3 M F.e!+,0.3 M NaeS04' 3g/L 97C, pH-I.G AS8+

r------r----,----r---.----,------,

40

A
--A i-A A A

35

70

o
o en
or
;25

en ,h--~---e--o---o-o---o---"""""et..30

% Fe

60
at
C

35

50~
-0--0-_ 0 '0, '0

z
~

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>= .0

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~ 20

cr
25

<t

Published by Maney Publishing (c) Canadian Institute of Mining, Metallurgy and Petroleum

en If tS z
w 0 a::: w Q.
C>

0'"

.z

20

/~
0

',PRODUCT

YIELD

405 0 a: Q. 30

~ .5
Co:)

~
\

\ ; 10 I=--_._--

.:I:

15

0
10

.~
3
(h)

.... --,,..-.....

--O-~---.;----% AsO 20
\0

\
\ 5
\ 10

\
\
0

%Na

-%Na ---...,--

1.8

1.6
pH

1.4

1.2

1.0

0 0.8

Fig. 7. Effect of initial solution pH on the composition of sodium jarosite precipitated at 97 DC from 3 gjl AsS + solutions.

0~-.w~...L----L----L.--~--~:__-~

2
TIME

6 of the

the initial acidity. In this region, the acid produced by hydrolysis of the 0.3 M Fe3 + outweighs the acid initially present in solution. The acid generating equation is: Na2S04

Fig. 6. Effect of reaction time at 97C on the compositi?n sodium jarosite precipitate made from sulphate medIa.

+ 3Fe2 (S04h +

12'H20 ~2NaFe3(S04h(OH)6 + 6H2S04

(2)

OJ M Fe(S04)1.S-0.3 M Na2S04-3 gil Ass+ (as Na2HAs04) at pH = 1.6. The data clearly suggest the precipitation of two compositionally different phases. The initial material to form (t ..... 3 g) is rich in Fe and As04 (",40 % As04) but is deficient in S04 and especially in Na. As the reaction continues, the As04 content drops from ",40 % to about 11 %, the S04 content rises from'" 9 % to 32 0/0, and the Na content increases from a near zero level to about 3 %. About 13 g of precipitate were formed after 5 h of reaction. The chemical data suggest the initial and rapid formation of a ferric arsenate-type compound followed by the progressive, and somewhat slower, precipitation of sodium jarosite. Nevertheless, sodium jarosite was the only phase detected by X-ray diffraction.

As the pH is lowered, the initial acidity becomes more important relative to the hydrolysis acid, and less jarosite is formed. At some point, the initial acidity becomes so high that the iron hydrolysis reaction (equation (2)) is entirely suppressed and no precipitate is formed. Regardless of the initial solution pH, however, the composition of the product remains surprisingly constant. This consistency indicates that precipitation of the amorphous arsenate is affected by pH approximately to the same extent as that of sodium jarosite. Consequently, the fraction of the total arsenic precipitated drops systematically with decreasing pH as shown in Table 1. X-ray diffraction analysis of all the precipitates of Fig. 7 indicated only sodium jarosite. Furthermore, there was no

Effect of initial solution pH

Jarosite-type compounds are formed in acid media, and generally over a restricted pH range. If the pH is too low ( < 1), reduced amounts of jarosite are formed; if the pH is too high (> 2), then other iron compounds with poorer filtration properties precipitate with the jarosite. Figure 7 illustrates the effect of the initial solution pH on the mass and composition of the precipitates made from 0.3 M Fe(S04)1.S-0.3 M Na2S043 gil AsS + solutions at 97C. The product-yield curve is typical of jarosite synthesis at ~ 100C when the pH is not controlled
Table 1. Effect of the initial solution pH on the fraction of :~senate precipitated from 0.3 M Fe(S04)l.S-0.3 M NazS04-5 gil As solutions at 97C pH 1.8 1.7 1.6 1.5 1.4 1.3 1.2 Percentage

AsS

Precipitated

during the course of reaction. There is a region at higher pH

where the amount of precipitate is relatively independent of

91 77 74 68 54 39 30

1.1

10

96

J. E. DUTRIZAC

and J. L. JAMBOR:

JAROSITE

PRECIPITATION

5O,.......-----~----_r_----_.----......,
55
0.2 M
N02

S04

3g/L

As5+

50

pH=I.5,97C

45

0.3 M Fe3+, 4 g/ L As~+ pH-I.5,97C,24h

(As20e)

45

40

~
40
0
III

35 30

~
o
en

i
Published by Maney Publishing (c) Canadian Institute of Mining, Metallurgy and Petroleum
0 z
w

t= 1
%F.

~35

o
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--J.--=A=-----=A----A--Ir--A_ 0

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C)

w a..

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I~.: .".-.-.'-_.------.--'\$
1-__.--.--.--.--.0.1 [Na25~] 0.2 (moI/L)

'--)""10---=0---=0-0/054

% As04

.
0.4

10

10

%Na

0.1

0.2 [Fe!+]

0.3 (moI/L)

0.4

0.5

0.3

Fig.

8. Effect

of Fe3 + concentration on the composItIOn precipitates formed at 97C.

of the Fig. 9. Composition of the sodium jarosite precipitates from solutions containing various concentrations formed at 97C of Na2S04

significant or systematic variation of the unit cell parameters as the pH of the synthesis medium varied; at pH = 2.0, a = 7.35, c = 16.66A, and at pH = 1.2, a = 7.33, c = 16.66A. The X-ray diffraction results suggest that the arsenate is precipitated as an amorphous compound, and that the crystallinity of the arsenate compound at 97 DC is not affected by pH variations in the range 1- 2. The effect oj the Jerric ion and alkali concentrations The effect of the Fe3 + concentration on the composition of the precipitates formed at 97 DC from solutions containing 0.2 M Na2S04-3 gjl Ass+ at pH = 1.5 is illustrated in Fig. 8. It is clear that ferric ion concentration exercises a major influence on the relative precipitation of jarosite and the suspected arsenate phase. In the absence of dissolved Fe3 +, no precipitate is formed. As the iron concentration increases, the total weight of the precipitate also increases linearly. This behaviour is expected because there is a stoichiometric excess of sodium to form sodium jarosite for all of the iron concentrations investigated [14]. In dilute (0.03 M Fe3 +) iron solutions, the product is greenish yellow and contains 24.3 % Fe and 64.3 0/0 As04, but negligible amounts of sodium or sulphate. Although amorphous to X-rays, the product is near scorodite in composition (FeAs04 2H20: Fe 24.4 %, As04 60.7 %, H20 14.8 %), and is probably best considered as "amorphous scorodite". As the iron concentration of the solution increases, there is a dramatic decline in the As04 content of the precipitate, and a corresponding increase in the S04 and Na contents. This indicates that the amount of amorphous "scorodite" is decreasing relative to sodium jarosite.

Figure 9 shows the vanatlon in the composItIon of the precipitates made from solutions having various initial concentrations of Na2 S04. All tests were done at 97 DC for 24 hand utilized solutions containing 0.3 M Fe(S04)l.s-4 gil Ass+ (as As20S) at pH = 1.5. In the absence ofNa2S04 an iron arsenate containing '" 38 10 As04, 10 % S04 and 28 % Fe is formed. As expected, no sodium was detected in this precipitate. X-ray diffraction showed this compound to be amorphous, and this observation is consistent with the data reported above. As the Na2 S04 concentration of the solution increases, the Na content of the precipitates rises rapidly to a value of '" 3 % Na at 0.05 M Na2S04. A sodium sulphate concentration of 0.05 M is approximately the stoichiometric concentration needed to form sodium jarosite from all the 0.3 M Fe3 + present. Higher sodium concentrations have little effect on the composition of the product. The increase in Na is paralleled by an increase in S04 and a decline in As04. The composition of the precipitates is nearly constant for Na2S04 concentrations >0.05 M. X-ray diffraction study of the precipitates made in the presence of Na2 S04 indicated only sodium jarosite. Similar experiments were carried out whereby the (NH4h S04 concentration of 0.3 M Fe(S04)l.s-4 gjl AsS + (as As20S) solutions was varied from 0 to 0.3 M. The compositions of the precipitates made from the ammonium-bearing solutions paralleled those shown in Fig. 9. In the absence of(NH4hS04' the precipitate contained'" 31 % Fe, 42 % As04 and 8 % S04. As the (NH4hS04 concentration increased, the ammonium content of the product increased to about 0.05 M (NH4h S04, but thereafter remained nearly constant. Although the Fe

J. E. DUTRIZAC and 1. L. JAMBOR: JAROSITE PRECIPITATION

50 ..---~----r----,;---.---.-----r--.-----"'" 0.5 M FeCI3, 3 M NaCl, 0.2 M Na2S04

97

Table 2. X-ray diffraction data and chemical analyses for precipitates made from chloride solutions containing As5 + As5 + concentration of solution (gil) 0.00 0.10 0.25 0.50 0.75 1.0 1.0
% As04 in

45

97C,pH=1.0

precipitate 0.00 0.37 0.74 1.43 1.85 2.60 2.88 7.47

X-ray data Na-jarosite Na-jarosite Na-jarosite Na-jarosite Na-jarosite Na-jarosite Na-jarosite + trace scorodite Na-jarosite + minor scorodite

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0: W

1.0 (?)

Published by Maney Publishing (c) Canadian Institute of Mining, Metallurgy and Petroleum

~ 20 :I:
C)

15

10

34 DISSOLVED

5 AS6+( 9 / L )

Fig. 10. Effect of the As5 + concentration on the composition of the sodium jarosite precipitates formed from chloride media at 97C.

content remained nearly constant, the S04 content increased sharply and the As04 content decreased in an inverse manner. For synthesis solutions containing 0.2 M (NH4h S04, the precipitate contained ~ 2.5 0/0 NH4, 32 0/0 Fe, 34010 S04 and 10010 As04
Behaviour of arsenate (Ass
+)

in chloride solutions

It is well established that jarosite-type compounds can be precipitated from chloride solutions, provided that a separate source of sulphate is available and that the pH is closely regulated [3,4]. The effect of arsenate concentration (as Na2HAs04) on the composition and properties of the precipitates formed at 97C from 0.5M FeCI3-3M NaCI-0.2M Na2S04 solutions at pH = 1.0 was studied, and the chemical data are presented in Fig. 10. In the absence of dissolved arsenic, a sodium jarosite was formed that analysed 4.04 0/0 Na, 32.8 0/0 Fe and 39.8 % S04' Its calculated formula is (Nao.8SH3 0o.ls)1.00Fe2.84(S04h.oo(OH)6.00 although this representation ignores the minor conversion of OH to H2 to maintain charge neutrality resulting from the slight deficiency of Fe. As the concentration of As04 increased in the solution, the products obtained became progressively richer in As04 and deficient in S04; the Fe content decreased slightly and the Na content dropped appreciably. For example, in the presence of 4 gil Ass + in the chloride medium, the product contained 2.47 % Na, 27.3010 Fe, 22.1 0/0 S04 and 26.4 0/0 As04. Comparison with Fig. 1 indicates that, chemically, Ass + behaves similarly in either sulphate or chloride media. A major difference between the two systems, however, is in the crystallinity of the iron arsenate precipitate. In the presence of sodium ion at 97C in sulphate media, the iron arsenate precipitate is amorphous. In the corresponding chloride system,

the arsenate-bearing precipitate is readily identifiable as scorodite (FeAs04' 2H2 0) by X-ray diffraction. Furthermore, the intensity of the scorodite lines increased systematically with increasing amounts of As04 in the precipitate. Table 2 presents some of the Guinier X-ray diffraction data obtained from these precipitates. Precipitates containing up to 2.60 wt 0/0 As04 consist only of sodium jarosite having a = 7.32 and c = 16.61A. A trace of scorodite was present in the precipitate containing 2.88 0/0 As04 and a minor amount of scorodite was detected in the product having 7.47 % As04. There was no variation in either a or c of the sodium jarosites formed in this series of tests. Separate tests were done whereby synthetic scorodite was mixed with sodium jarosite and subsequently analysed by Guinier X-ray diffraction. In those experiments the equivalent of 0.60 wt % As04 was detected on the Guinier pattern as a distinct trace, and 1.81 0/0 As04 gave strong scorodite lines. The scorodite formed in chloride media (Fig. 10 and Table 2) is well crystallized as is evident from the sharpness of the powder diffraction lines. Scorodite in the precipitates having lower As04 contents presumably also is well crystallized, and thus the lack of detection of scorodite may be indicative of a limited solid solution of As04 in sodium jarosite. Assuming a detection limit of ~0.60 0/0 As04, the data of Table 2 suggests a solubility limit of ~ 2 0/0 As04. That the substitution of this quantity of As04 does not affect the cell parameters of the sodium jarosite is unexpected, and this aspect will be discussed in greater detail in a subsequent paper. Although the reasons for the crystallization of scorodite in chloride solutions and the formation of amorphous iron arsenate in sulphate solutions under similar conditions are not known, the similarities in precipitation behaviour in the two systems strongly suggest that the amorphous arsenate perceived in sulphate media at 97C is chemically similar to scorodite.
Behaviour of arsenite ( As3
+)

in sulphate and chloride media

Figure 11 illustrates the effect of the concentration of As3 + on the composition of the precipitates made at 97C from 0.3 Fe(S04)l.s-0.3 M Na2S04 solutions at pH = 1.5. The experiments were run for 24 h under a nitrogen atmosphere to prevent air oxidation of the arsenic. The As3 + was added to the solution as NaAs02. It is evident that the composition of the precipitate is independent of the As3 + concentration of the starting solution, and that the measured composition corresponds closely to that of sodium jarosite. The arsenic content of the precipitate, arbitrarily expressed as As03,

98
45

J. E. DUTRIZAC

and J. L. JAMBOR:

JAROSITE

PRECIPITATION

55 r----,----.---.-------r----,---~--y__-____,
%504 50 0.3M Fe(504)1.5 ,O.2MK2S04, 97C,24 h pH: 1.5

40

H=--....-ot:j------'tt--------u---o-

ex..

0 en

..,

35

45
%504

%Fe

--0--0--0

--0--0--0--0-

.i
z ~ z

0 en

C 25
O.3M Fe3+,O.3 M Na~S04

%~

Published by Maney Publishing (c) Canadian Institute of Mining, Metallurgy and Petroleum

w u 20 a: w Q.

pH=I.5,97C

i.:.o --e--e--e--e--e--e--e~ ...

ffi

~ ~ w ~

25

15

a:

~ 20
C)

10

15

5
10 %K

0 0 Fig. 11. Behaviour 2 3 4

As5+(g/L)

--0----="---.0--0--0--0--05 6 at
5 DISSOLVED

of As3 + during sodium jarosite 97C in sulphate media.

precipitation

0..... ---=.J===--'==w===4J===-L==:.e===.t--==---l o 2 3 4 5 6 7 8 DISSOLVED As3+ (gIL) Fig. 12. The effect of As3+ on the composition of the potassium jarosite precipitate made at 97C from sulphate media.

increases steadily with increasing amounts of As + in solution, but the maximum "As03" content of the solid is always < 0.60/0. Clearly, negligible amounts of As3 + are precipitated; even the limited amount of As precipitation observed probably arises either from a minor amount of As5 + in the arsenite reagent, or from the gradual oxidation of As3 + by ferric sulphate [18]. That is, the minor amounts of arsenic are precipitated as arsenate and not as arsenite. To investigate the effect of possible air oxidation of As3 +, the above experiments were repeated, but with the vessels open to the air. Virtually identical results were realized, and the "As03" contents of the products were < 0.60/0, thereby indicating that air oxidation of As3 + was not a significant factor under the conditions used for these tests. Potassium jarosite is the most stable of the jarosite compounds, and under a given set of conditions it usually will incorporate more of a given impurity than sodium jarosite [7]. Accordingly, a systematic series of experiments was done whereby potassium jarosite was precipitated at 97C from pH = 1.5 solutions; these solutions contained 0.3 M Fe(S04)1.5-0.2 M K2S04 and As3+ concentrations (added as AS203 in a small amount of KOH solution) ranging from 0 to 7 gjl. The results (Fig. 12) are similar to those realized for sodium jarosite under similar conditions (Fig. 11). The nearly constant quantity of precipitate obtained was found by X-ray diffraction to consist only of (potassium) jarosite in which the a or c parameters remained constant despite increased concentrations of arsenic. Chemically, a "normal" potassium jarosite is formed that contains'" 7.5 % K, 30 % Fe and 41 % S04' The "As03" contents of the precipitates are consistently less than 0.3 wt %. These data, together with those of Fig. 11,

indicate that As3 + is not precipitated significantly during jarosite formation, and this conclusion is in agreement with the observations of Yaroslavtsev et al. [12]. The charge and co-ordination of the As02 or AsO~ - ions make them unlikely replacements for SO~ - in the structure of jarosites. Precipitation of sodium jarosite in the presence of As3 + in chloride media gave significantly different results (Fig. 13). These precipitates were made by heating 0.5 M FeC13-3 M NaCI-0.2 M Na2S04 solutions at pH = 1.0 for 24 h at 97 in a vessel open to air. As the As3 + concentration of the solution increases, arsenic in the precipitate (reported as As04 for reasons noted below) increases significantly, and the sulphate content decreases in an inverse manner. The iron content decreases slightly and there is an important reduction in the Na content. The mass of the precipitate increases gradually as the As3 + concentration of the solution increases. The data are somewhat similar to those realized using As5 + in the chloride synthesis solution (Fig. 10) except that the results, especially those for S04 and As04, are more scattered when the arsenic is added as As3 +. X-ray diffraction analysis indicated minor to major quantities of scorodite in the precipitates made from solutions initially containing > 0.5 gjl As3 +. Because a chloride system was used, the scorodite was well crystallized. The precipitate made from 0.5 gil As3 + solution contained 0.57 % As04 and consisted of sodium jarosite only. The precipitate made from 1.0 gil As3 + solution contained 2.88 wt % As04 and contained a trace of

cc

1. E. DUTRIZAC

and 1. 1. JAMBOR:

JAROSITE

PRECIPITATION

99

50,....-- ---r-------r----,...---..,..----,-------r---r--......, 45
O.5M FeC13,3.0M NoCI,O.2M No2S04

97C,pH=1.0

\.1..

.; ;3

b.

% AS04 % Fe

.Z

1LI U

z
a::
IJJ lL.

Published by Maney Publishing (c) Canadian Institute of Mining, Metallurgy and Petroleum

.C) IJJ

0 0

---

% 504

:I:

15

10
0

3 4 56 DISSOLVED As3+(g/U

Fig. 13. The influence of As3 + on the composition of the sodium jarosite precipitates made at 97C from chloride media.

scorodite. As noted above, 2.88 % AsO 4 if present as well crystallized scorodite, would give strong lines on the Guinier X-ray pattern. The conclusion is that part of the As04 may be present in solid solution in the jarosite structure. The presence ofscorodite (FeAs04' 2Hz 0) in the precipitates made from solutions initially containing only As3 + suggests the rapid oxidation of As3 + to Ass + in chloride media. In fact, ion chromatographic analysis [11,18] of the precipitates dissolved in hydrochloric acid indicated only Ass + and the absence of As3 +. Unlike sulphate solutions where As3 + is very slowly oxidized by ferric sulphate, chloride solutions provide a suitable medium for the relatively rapid oxidation of As3 + [11]. As3
+

series of experiments was done at 97C using pH = 1.5 solutions containing 0.3 M Fe(S04)1.S-0.3 M Naz S04 and various concentrations of Ass +. The initial and final solution volumes and ,AsS + concentrations were determined together with the mass and As04 content of the dried precipitates; in most cases the total arsenic accountability was better than 900/0 . Figure 14 illustrates the effect of the Ass + concentration of the initial solution on the relative distribution of Ass + between the precipitate and the final solution. Although there is considerable scatter, the results indicate that in dilute arsenic solutions (AsS + < 0.4 gil), about one-quarter of the arsenic is precipitated with the sodium jarosite during the 24-h reaction periods employed. As the concentration of Ass + in the initial solution increases, the fraction of arsenic co-precipitated with the sodium jarosite also increases. For dissolved arsenic concentrations > 5 gil, about 90 % of the arsenate is precipitated with the jarosite. Although jarosite precipitation could be useful in arsenic control in a hydrometallurgical circuit, it does not yield really low arsenic concentrations in the final solution. For example, in many of the tests involving even modest (-- 1 gil As04) arsenic concentrations, the final arsenic concentration was commonly several hundred mg/l; these concentrations arise, at least in part, from the higher terminal acidities ( -- 0.3 M) caused by hydrolysis acid generated during the reaction. High acidities are known to increase the solubility of scorodite [19] and, of course, the amorphous iron arsenate phase will have a higher solubility than well crystallized scorodite.

CONCLUSIONS
The behaviour of As3 + and Ass + during alkali jarosite precipitation has been investigated over a wide range of synthesis conditions. Although arsenate is readily precipitated with the alkali jarosites, it seems to be present mostly as a separate phase. There is no indication of extensive AsO~substitution for S04 in the jarosite structure although a limited degree (--20/0) of As04 substitution is suggested. During sodium or ammonium jarosite precipitation in sulphate media at 97C, an amorphous arsenate phase, chemically similar to scorodite FeAs04' 2Hz 0, is formed. In such systems, arsenate is selectively precipitated relative to sulphate. During potassium jarosite precipitation from sulphate media at 97C, crystallized scorodite is formed from arsenic-rich solutions but an amorphous arsenate is produced from dilute media. Again, arsenate is selectively precipitated relative to sulphate. X-ray diffraction study of the jarosites showed little variation of either the a or c parameters with increasing arsenate concentrations in the precipitate, and this suggests that the extent of arsenate substitution in these species is minimal. It is shown that the amorphous arsenate phase or scorodite precipitates more rapidly than jarosite-type compounds; initial precipitates are therefore enriched in AsO 4 and are deficient in alkalis and S04' Solution acidity seems to affect the precipitation of the jarosite and arsenate phases equally at 97C; consequently, the composition of the precipitates does not vary significantly for initial pH variations in the range 1-2. The total mass of

+ 2FeCl3

Ass

+ 2FeClz + 2CI-.

(3)

Presumably, the arsenite added to the synthesis solution is rapidly oxidized to arsenate which then precipitates as FeAs04' 2Hz 0 (scorodite) with the sodium jarosite. Variations in the oxidation rates are likely responsible for the considerable scatter of the As04 contents of the precipitates, and the resulting variations in sulphate. Although the arsenic is readily precipitated in chloride media, there is no indication that As3 + (arsenite) itself is precipitated with or in the jarosite. Arsenate distribution during jarosite precipitation

The above data indicate that extensive co-precipitation of arsenate (as crystalline scorodite or amorphous iron arsenate chemically similar to scorodite) occurs during jarosite formation. The extent of arsenate precipitation has been shown to be highly dependent on the Ass + concentration, the alkali and ferric ion' concentrations, the solution pH, etc. To give

some indication of the general deportment of arsenate under

near-optimum conditions for jarosite formation, however, a

precipitate formed, however, decreases with increasing acid

concentrations, and hence, less As04 is precipitated from the

100
140

J. E. DUTRIZAC

and J. L. JAMBOR:

JAROSITE

PRECIPITATION

120

0.3

M Fe{S04)

us'

0.3

M NQ2S04,

pH = 1.5

~ 100 w
Cf)

<t -J <t

a:::
80

z (5
0 60
t-

~oo
0

a:
z

~ ~~8

Published by Maney Publishing (c) Canadian Institute of Mining, Metallurgy and Petroleum

w u 0:: 40 w a..

y.

,
I
2

I o"j g,,@'-..
0 0
......

.~

PRECIPITATE

20

O~AL 0

SOLUTION

0 3 4 5 DiSSOLVED
+

7 6 As!S+ ( g/ L )

10

II

Fig. 14. Relative

partitioning

of As5

between the solutions and the precipitates sulphate solutions.

formed at 97C from

more acidic environment. Both ferric ion and alkali concentrations affect the relative extent of precipitation of the arsenate phase, whose precipitation is favoured by low concentrations of either ferric ion or alkali sulphate. The crystallinity of the arsenate phase, however, is not influenced by such concentration variations. Arsenite is not precipitated during jarosite formation in sulphate media at 97C, and there is no indication of arsenite incorporation in the jarosite structure. Partial oxidation of the arsenite to arsenate, however, leads to arsenic co-precipitation with jarosite-type compounds. Arsenate is readily precipitated with alkali jarosites made from chloride media at 97C and the degree of precipitation is similar to that observed in the corresponding sulphate systems. A notable difference, however, is that scorodite is well crystallized in chloride media. Guinier X-ray results obtained from the jarosite-scorodite precipitates formed in chloride media indicate that '" 2 wt % As04 substitution occurs in sodium jarosite, but this observation requires confirmation. Arsenite compounds are not precipitated during jarosite formation in chloride media, but because As3+ is rapidly oxidized to Ass + by FeCl3 media, extensive arsenic precipitation does occur. During alkali jarosite formation at 97C, As04 precipitation increases from '" 25 % in dilute solutions to ",90 % for solutions containing > 5 gjl Ass +. The extent of arsenate precipitation depends on many factors, however, and considerable variation in the amount of arsenic precipitated can be expected. Because most of the arsenate precipitated occurs as crystalline or amorphous FeAs04 . 2Hz 0, the behaviour of this element in jarosite storage ponds might differ significantly from that of the jarosite itself. In particular, the oxidizing acidic conditions necessary to stabilize the jarosite could well result in the progressive dissolution of the arsenic.

REFERENCES
1. V. Arregui, A. R. Gordon and G. Steintveit, The jarosite processpast, present and future, in Lead-ZincTin 'SO (edited by J. M. Cigan, T. S. Mackey and T. J. O'Keefe) pp. 97-123. TMS-AIME, Warrendale, PA (1979). 2. J. E. Dutrizac, Jarosite-type compounds and their application in the metallurgical industry, in Hydrometallurgy Research. Development and Plant Practice (edited by K. Osseo-Asare and J. D. Miller) pp. 531-551. TMS-AIME, \Varrendale, PA (1982). 3. G. E. Atwood and R. W. Livingston, The CLEAR process-a Duval Corporation development, paper presented at the Annual Conference of Gesellschaft Deutscher Metallhutten und Bergleute, Berlin, September 26-29, 1979. 4. J. E. Dutrizac, Jarosite formation in chloride media, Proc. Australas. Inst. Min. Metall. 278,23 (1981). 5. P. D. Bowerman, T. W. Clapper and W. G. Laughlin, Manufacture of manganous sulphate solutions, U.S. Patent 4,489,043, Dec. 18, 1984. 6. J. E. Dutrizac and S. Kaiman, Synthesis and properties of jarositetype compounds, Can. Mineral. 14, 151 (1976). 7. J. E. Dutrizac, The behaviour of impurities during jarosite precipitation, in Hydrometallurgical Process Fundamentals, (edited by R. G. Bautista), pp. 125-169. Plenum, New York (1984). 8. J. L. Jambor and J. E. Dutrizac, The synthesis of beaverite, Can. Mineral. 23, 47 (1985). 9. G. B. Harris, S. Monette and R. W. Stanley, Hydrometallurgical treatment of Blackbird cobalt concentrate, in Hydrometallurgy Research, Development and Plant Practice, (edited by K. OsseoAsare and J. D. Miller), pp. 139-150. TMS-AIME, Warrendale, PA (1982). 10. J. E. Dutrizac and R. M. Morrison, The leaching of some arsenide and antimonide minerals in ferric chloride media, in Hydrometallurgical Process Fundamentals, (edited by R. G. Bautista), pp. 77112. Plenum, New York (1984). 11. L. K. Tan and J. E. Dutrizac, Determination of As(III) and As(V) in ferric chloride-hydrochloric acid leaching media by ion chromatography, Analyt. Chem. 57, 1027 (1985). 12. A. S. Yaroslavtsev, L. S. Getskin, A. U. Usenov and E. V. Margulis, Behaviour of impurities when precipitating iron from sulphate zinc solutions, Tsvet. Metally 16(4),41 (1975). 13. J. E. Dutrizac and J. L. Jambor, Impurity control during jarosite precipitation, in Proc. 15th Ann. Hydrometal. Meeting, Impurity Control and Disposal, (edited by A. J. Oliver), paper 23. CIM, Montreal (1985). 14. J. E. Dutrizac, Factors affecting alkali jarosite formation, Metall.

AcknowledgementsThe authors recognize the assistance of O. Dinardo and D. J. Hardy with the precipitation studies and the help of E. J. Murray and P. Carriere with the X-ray determinations.

J. E. DUTRIZAC and J. L. JAMBOR: JAROSITE PRECIPITATION

Trans. 148, 531 (1983). 15. J. A. Ripmeester, C. I. Ratcliffe, J. E. Dutrizac and J. L. Jambor, Hydronium ion in the alunite-jarosite group, Can. Mineral. 24,435 (1986). 16. A. Leclerc, Room temperature Mossbauer analysis of jarosite-type compounds, Phys. Chern. Minerals 6, 327 (1980). 17. M. Boubia, M. T. Averbuch-Pouchot and A. Durif, Ordered As04

101

and S04 tetrahedra in diammonium trihydrogen arsenate sulfate, Acta Cryst. C41, 1562 (1985). 18. L. K. Tan and J. E. Dutrizac, Determination of arsenic (III) and arsenic (V) in ferric sulphate-sulphuric acid leaching media by ion chromatography, Analyt. Chern. 57, 2615 (1985). 19. P. M. Dove and J. D. Rimstidt, The solubility and stability of scorodite, FeAs04' 2H20, Am. Mineral. 70, 838 (1985).

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