You are on page 1of 5
Powder Technology 103 Ž 1999 . 260–264 Arsenic removal through the decrepitation of colemanite ores

Powder Technology 103 Ž1999. 260–264

Powder Technology 103 Ž 1999 . 260–264 Arsenic removal through the decrepitation of colemanite ores Fatma

Arsenic removal through the decrepitation of colemanite ores

Fatma Arslan a,) , Cuneyt Arslan b , Mehmet S. C¸elik a

¨

a Istanbul Technical UniÕersity, Mining Faculty, Mining Engineering Department, Mineral and Coal Processing DiÕision, 80626 Maslak, Istanbul, Turkey b Istanbul Technical UniÕersity, Chemistry and Metallurgy Faculty, Metallurgical Engineering Department, ExtractiÕe Metallurgy DiÕision, 80626 Maslak, Istanbul, Turkey

Received 17 August 1998; received in revised form 10 December 1998; accepted 11 January 1999

in revised form 10 December 1998; accepted 11 January 1999 Abstract Despite their high boron contents,

Abstract

Despite their high boron contents, some boron deposits in Turkiye¨ contain considerable amountS of arsenic. Arsenic in boron minerals receives penalty in marketing and thus its removal is necessary. Since colemanite undergoes decrepitation at temperatures near its decomposition, the objective of this study was to determine the extent of arsenic removal through the decrepitation of colemanite ores with high As content. The effect of temperature, retention time, and particle size range was investigated and the degree of arsenic removal and the quality of colemanite concentrate were quantified. The results reveal that arsenic removals of 95–98% with As levels as low as 0.02% in the colemanite concentrate are achieved. q 1999 Elsevier Science S.A. All rights reserved.

Keywords: Decrepitation; Boron minerals; Colemanite; Arsenic; Calcination; Beneficiation

minerals; Colemanite; Arsenic; Calcination; Beneficiation 1. Introduction Hydrated boron minerals undergo reduction in

1. Introduction

Hydrated boron minerals undergo reduction in their original weight after the heat treatment, due to loss of water molecules. Thermal treatment of boron minerals also results in some structural modifications, due to formation of micropores and the resultant expansion of the crystal matrix upon development of uneven distribution of stresses. Such internal stresses subsequently induce fractures and in turn, fragmentation of the crystals. When they are heated to the decomposition temperature, some minerals, such as colemanite, break to a fine powder. A similar phenomenon may also occur upon cooling. This phenomenon is called decrepitation. Clearly, one should distinguish the differ- ence between decrepitation and calcination of volatile min-

erals, e.g., barite or calcite, where the original mineral is

converted to the oxide form w 3,4 x . Decrepitation followed by air tabling is utilized at the American Borate plant near Lathrop Wells, NV, for up- grading of colemanite w5x. The possibility of decrepitation followed by wet tabling has been recently suggested as an alternative to air tabling w6x. Enhancement of boric-acid production upon decrepitation of colemanite at tempera- tures higher than 6008C has been reported w7x. Decrepita- tion properties of colemanite ore have also been studied to some extent w3,8x. These studies indicated that although most boron minerals exhibit various degrees of hydration, only colemanite appears to undergo decrepitation. Cole-

Turkiye¨ has the largest boron reserves in the world. Boron deposits are located in four regions, namely; Eskise- hir-Kirka, Kutahya-Emet,¨ Balikesir-Bigadic, and Kestelek- Bursa. Some of these deposits contain considerable amount of arsenic in spite of their high boron contents. Boron ores are generally upgraded by concentration techniques includ- ing physical, chemical, and physicochemical processes. Among these processes, flotation and heat treatment are potential techniques for the removal of arsenic from the boron ores.

P 5H O. by flotation has been studied w1,2x. One of these studies claims that 80% of the arsenic minerals was con- centrated by flotation using potassium amyl xanthate as collector at a natural pH of 9.3. In another study, a colemanite concentrate with 44.4% B O content was recovered with 85.1% efficiency from a colemanite ore assaying 22.9% B O and 0.27% As. An arsenic concen- trate of 15.72% As was obtained with 85.5% recovery, leaving the final colemanite concentrate with 0.05% As.

The removal of arsenic from colemanite ŽCa

2

267

B

O

2

3

2

3

removal of arsenic from colemanite Ž Ca 2 267 B O 2 3 2 3 )

) Corresponding author. Tel.: q90-212-285-6357; Fax: q90-212-285- 6863; E-mail: arslan@sariyer.cc.itu.edu.tr

0032-5910r99r$ - see front matter q 1999 Elsevier Science S.A. All rights reserved.

PII: S0032- 5910 Ž 99 . 00020-0

r 99 r $ - see front matter q 1999 Elsevier Science S.A. All rights reserved.

F. Arslan et al.r Powder Technology 103 (1999) 260–264

Table 1 Particle size distribution and corresponding chemical analysis of colemanite sample

261

Particle size range Žmm.

Amount by wt.%

% B

2

O

3

% As

 

Content

 

Distribution

Content

Distribution

y 4.76 q 3.36 y3.36 q 2.36 y2.36 q 1.68 y1.68 q 1.00 y1.00 q 0.841 y0.841 q 0.600

17.2

31.7

17.7

0.46

18.4

16.4

30.9

16.5

0.36

13.8

15.6

30.8

15.7

0.38

13.8

13.9

30.7

13.9

0.40

12.9

4.1

21.8

4.0

0.40

3.8

7.4

29.0

7.0

0.69

11.9

y0.600

25.4

30.4

25.0

0.43

25.4

Total

100.0

30.7

100.0

0.43

100.0

25.4 Total 100.0 30.7 100.0 0.43 100.0 manite produces a fragmentation pattern similar to that of

manite produces a fragmentation pattern similar to that of minerals ground in ball mills. Earlier studies on decrepitation of colemanite were performed with either pure colemanite mineral or coleman- ite ores. Therefore, in the light of these studies, arsenic removal during the decrepitation of colemanite ores consti- tuted the main objective of this study. The effects of several parameters on the arsenic removal and the quality of colemanite concentrate were investigated. Results were compared with those obtained with the decrepitation of pure colemanite ores in terms of the decrepitation proper- ties and the B O content.

2

3

2. Experimental

2.1. Materials

Representative colemanite samples were taken from the lump-size tailings Žy150 mm. stockpiled out of the hand-

sorting operation to the Emet Concentrator in Turkiye.¨ The sample size was reduced to below 4.76 mm through a series of crushers and then screened to several size groups as shown in Table 1. The percent B O and As contents in corresponding size ranges are also given. The analysis shows no definitive trend between the As content and particle size ranges. As seen from the table, the original samples contained 30.7% B O and 0.43% As. The ar-

S . and

realgar ŽAs

be noted that pure hydrated colemanite and calcined anhy-

drous colemanite, respectively, assay 50.81% and 65.17% BO. 2 3

senic minerals were mainly those of orpiment ŽAs

S . by mineralogical examinations. It should

2

3

2

3

2

3

2

2

2.2. Methods

Experiments were conducted in a Heraeus muffle fur- nace. Tests were carried out in a 600-cm Ž10 =15 =4 cm. steel box with a lid. The sample box was first brought to the desired temperature; 50 g of sample was immedi- ately placed into the box and then returned to the furnace to start the experiment. At the end of each experiment, the

3

start the experiment. At the end of each experiment, the 3 sample box was removed and

sample box was removed and weighed immediately to determine the weight loss. Screen analysis was then per- formed on some samples, followed by chemical analysis. The B O content of colemanite samples was determined by volumetric titration using mannitol, whereas As was analyzed spectrophotometrically and by the Gutzeit method Žby Etibank Emet Colemanite Works. for accuracy check. Both methods gave almost the same results.

2

3

3. Results and discussions

The effects of temperature, time, and particle size range on the removal of arsenic from colemanite ores along with environmental aspects are delineated below.

3.1. Effect of temperature

Samples in the size range of y4.76 q 3.36 mm were subjected to the heat treatment at temperatures varying

were subjected to the heat treatment at temperatures varying Fig. 1. Weight loss change with temperature

Fig. 1. Weight loss change with temperature during the decrepi-

tation of pure colemanite and colemanite ore containing high arsenic

Ž

y4.76q3.36 mm particle size range, 15 min heating time . .

262

F. Arslan et al.r Powder Technology 103 (1999) 260–264

F. Arslan et al. r Powder Technology 103 (1999) 260–264 Fig. 2. Variation of percent passing

Fig. 2. Variation of percent passing 0.2 mm with time for pure and colemanite ore with high arsenic content Žy4.76q3.36 mm particle size range

from 3008 to 5508C, for 15 min. Similar to the earlier studies conducted on decrepitation of pure colemanite from the same region w3x, weight loss and the amount of sample passing through a 0.2-mm screen were determined upon heat treatment. The results are shown together in Figs. 1 and 2. The percent weight loss increased with increasing temperature up to 5008C and leveled off above that. Studies conducted earlier indicated that the onset of dehydration of colemanite occurred at 2628C and that of decomposition at 4128C w4x. As seen from Fig. 1, the percent weight loss upon decrepitation of pure colemanite mineral showed similar trend to that obtained with the arsenical colemanite ore. However, higher percent weight losses were observed with arsenical colemanite ores as compared to the pure colemanite. This is probably due to the presence of clay minerals in the colemanite ore which experience a different weight loss pattern on heating. As shown in Fig. 2, marginal differences are observed on the fragmentation behavior of pure and arsenical colemanite upon decrepitation, as measured by the percentage passing through a 0.2-mm screen. This shows that arsenical cole- manite ore displays similar fragmentation pattern with that of pure colemanite. Percent weight loss, and % B O and

2

3

Table 2 Decrepitation of arsenical colemanite ore at different temperatures

Temperature

Weight

B

2

O

3

As

As removal

Ž

8C

.

loss Ž. %

Ž. %

Ž. %

Ž. %

300

 

6.2

33.8

 

0.39

20.0

350

14.6

37.1

0.25

48.2

400

16.5

38.0

0.20

55.3

450

21.2

40.2

0.17

71.0

500

30.2

45.4

0.026

96.1

550

30.0

45.3

0.024

96.4

0.026 96.1 550 30.0 45.3 0.024 96.4 Fig. 3. Arsenic removal from colemanite ore upon heat
0.026 96.1 550 30.0 45.3 0.024 96.4 Fig. 3. Arsenic removal from colemanite ore upon heat
0.026 96.1 550 30.0 45.3 0.024 96.4 Fig. 3. Arsenic removal from colemanite ore upon heat

Fig. 3. Arsenic removal from colemanite ore upon heat treatment vs. temperature Ž15 min heating time, y4.76q3.36 mm particle size range

As contents together with % As removals at different temperatures are presented in Table 2. While percent weight loss and % B O contents increased with increasing tem- perature, % As content decreased with increasing tempera- ture. Fig. 3 shows % As removal vs. temperature. Increasing the temperature from 3008 to 5508C resulted in an increase in the % As removal up to 5008C and remained almost

constant above that. This is the temperature range where arsenical ores are roasted w9x. Arsenic, sulfur and many of their compounds have significant vapor pressures at the roasting temperatures of arsenical concentrates Ži.e., 4508

to 6508C

Table 3 lists vapor pressures of some arsenical

compounds of interest w9–12x. The equilibrium vapor pres-

sures of arsenic and sulfur increase with increasing temper- ature and become significant under the conditions of 0.01 and 0.1 atm and 5008 and 6008C, usually employed for

and

S . are not stable above 3078C as evident in

roasting. Arsenic sulfides, such as realgar

orpiment ŽAs

Table 3. The arsenic sulfides present in the concentrates or

in the vapor phase decompose at higher temperatures to yield elemental arsenic and sulfur vapors which easily

2

3

Ž

As

2

S

2

.

2

3

Table 3 Vapor pressure of certain species during roasting of arsenical sulfide concentrates w7–10x

Species in

Species in

Equilibrium vapor pressure

vapor phase

condensed phase

Ž

mm Hg

.

 

3078C

 

4078C

5078C

Sulfur

a

Sulfur

5

14

bp 5258C

Arsenic

a

Arsenic

0.0002

 

5.6

sp 6038C

Arsenic

Arsenopyrite

0.0002

1.3

158

As

4

S

4

Realgar

0.62

77.3

b

Orpiment

10.7

248.5

a Includes all polymers.

b Includes arsenic, sulfur and combined sulfides.

F. Arslan et al.r Powder Technology 103 (1999) 260–264

263

Arslan et al. r Powder Technology 103 (1999) 260–264 263 Fig. 4. Phase-stability diagram for As–S–O

Fig. 4. Phase-stability diagram for As–S–O system at 3078C w9.x

oxidize by air w9x. Two oxidation products, As O and SO , leave the roaster as off-gases along with nitrogen and any unused oxygen. Fig. 4, which shows the As–S–O phase stability dia- gram at 3078C, has been drawn based on the thermody- namic data compiled from various sources w12–14x. This is

a typical temperature for the early stages of roasting. There

is

to

a strong driving force to oxidize both sulfur and arsenic

SO and As O , as evident in Fig. 4. A similar phe-

2

3

2

2

23

nomenon occurs during the decrepitation of colemanite ores with high arsenic content. Complete fragmentation of

pure colemanite is only observed above 5008C and this is

in agreement with the optimum arsenic removal tempera-

ture found both theoretically and experimentally.

3.2. Effect of retention time

Decrepitation experiments using samples in the particle

size range of y4.76 q 3.36 were performed at 4508C for 5

to 30 min. Experimental results are shown in Table 4.

Increasing the time of heat treatment resulted in an in-

crease in % As removal, as presented in Fig. 5. The %

B

increased with increasing the time of decrepitation. It is to

be noted that at 4508C, even 20 min of heating time is not

sufficient to reach As removals of 90% and thus, 5008C

O content of the colemanite concentrates were also

2

3

Table 4 Results of the decrepitation experiments run at 4508C for different periods

Time

 

Weight

B

2

O

3

As

As removal

Ž

min

.

loss Ž. %

Ž. %

Ž. %

Ž. %

 

5

1

32.0

 

0.45

3.0

15

 

23

41.2

0.12

80.0

20

25

42.3

0.083

86.5

30

26

42.8

0.043

93.0

42.3 0.083 86.5 30 26 42.8 0.043 93.0 Fig. 5. Arsenic removal vs. retention time at
42.3 0.083 86.5 30 26 42.8 0.043 93.0 Fig. 5. Arsenic removal vs. retention time at
42.3 0.083 86.5 30 26 42.8 0.043 93.0 Fig. 5. Arsenic removal vs. retention time at

Fig. 5. Arsenic removal vs. retention time at 4508C Žy4.76q3.36 mm particle size range

appears to be necessary for reaching As removals of over 90% at 15 min decrepitation time.

3.3. Effect of particle size

Experiments performed in different particle size ranges are shown in Table 1. The results obtained under optimum conditions of 5008C and 15 min are tabulated in Table 5 and Fig. 6. As seen in Table 5, decreasing the particle size marginally affected the % As removal and % B O con- tent of the colemanite concentrates. The amount of mate- rial passing through a 0.2-mm screen upon heat treatment is almost the same. This is in line with our earlier results on pure colemanite, where no dependence of particle size on fragmentation of decrepitated colemanite upon decrepi- tation was found w3x.

2

3

3.4. EnÕironmental aspects

Since arsenic and most of its compounds are toxic, environmental pollution caused by arsenic emissions which leave the roasters should carefully be controlled and mini-

Table 5 Results of decrepitation tests run with samples of different size ranges Ž5008C and 15 min heating time.

Particle size

Wt.% less than 0.2 mm

Weight

B

2

O

3

As

As removal

range Ž mm

.

loss %

Ž.Ž.

%

Ž. %

Ž. %

y4.76 to q3.36 y3.36 to q2.36 y2.36 to q1.68 y1.68 to q1.00 y1.00 to q0.841

85.7

30.2

45.4

0.026

96.1

82.9

28.6

43.3

0.017

96.6

82.2

27.0

42.2

0.018

96.5

83.2

27.6

42.2

0.018

96.7

83.7

26.0

40.3

0.022

95.9

y0.841 to q0.600 83.6

25.8

39.1

0.018

98.1

y0.600

83.8

25.8

41.0

0.025

95.7

95.9 y 0.841 to q 0.600 83.6 25.8 39.1 0.018 98.1 y 0.600 83.8 25.8 41.0

264

F. Arslan et al.r Powder Technology 103 (1999) 260–264

F. Arslan et al. r Powder Technology 103 (1999) 260–264 Fig. 6. Arsenic removal vs. particle

Fig. 6. Arsenic removal vs. particle size at 5008C for 15 min.

mized. The atmospheric emission of arsenic consists of As O , both as a particulate matter or as vapor present in equilibrium with air w9x. Therefore, it is important to install not only an efficient condensation system operating at low temperature, about 1008C, but also a particulate collection system. The particulate emissions could be managed by using a hot electrostatic precipitator, an air quench in a mixer-cooler and a cold baghouse either by themselves or in combination w15x. As for the solids, arsenic oxide could be purified and sold to the alloy manufacturing industry and the agricultural chemical industry w16x. Otherwise, the arsenic compounds should be stored in a sealed space.

2

3

4. Conclusions

Ž1. Decrepitation tests were conducted on colemanite samples assaying 30.7% B O and 0.43% As. Effects of temperature, retention time, and particle size on the arsenic removal and the B O content of the concentrates were investigated. Arsenic removal was found to be independent of the particle size. Increasing the temperature resulted in an increase in the percent arsenic removal. Decrepitated colemanite concentrate contained 0.026% As which corre- sponded to the As removal of 96.1% at 5008C and 15 min of heating time. The corresponding B O grade of the concentrate varied in the range of 40–45% B O .

2

3

2

3

2

3

2

3

Ž2. This experimental study reveals that most of the arsenic present in the arsenical colemanite ores could be removed during decrepitation. While the decrepitated cole- manite concentrate with very low arsenic content is suit- able for use in the production of boric acid, the arsenic- containing minerals leave the furnace as As O and SO . Air pollution emitted by this process could be eliminated by the sublimation of the off-gases yielding technical grade As O , sublimation of which is repeated until the desired purity is reached.

2

3

23

2

References

w1x D. Boztepe, Beneficiation of B O by decreasing arsenic content of y3 mm ponds tailing of Emet colemanite concentrator, MS thesis, ITU Mining Faculty, 1988 Žin Turkish

w

M. Kose,¨ S. Ertekin, M. Gunduz,¨¨ M. Oztoprak, Selective recovery of colemanite and arsenic minerals from boron tailings, Proceedings of XIth Turkish Mining Congress of Turkey, 1989, pp. 407–415 Žin Turkish with English abstract w3x M.S. Celik, A. Uzunoglu, F. Arslan, Powder Technol. 79 Ž21994.

2

3

¨

2

x

167–172.

w

M.S. Celik, T. Batar, Y. Akin, F. Arslan, Upgrading schemes for boron minerals through calcination, Miner. Metall. Processing J. 15 Ž11998. 5356. w5x P.R. Smith, R.A. Walters, Mining Eng., Feb. 1980, p. 199. w6x O.F. Emrullahoglu,˘ M. Kara, R. Tolun, M.S. C¸elik, Powder Tech- nol. 77 Ž1993. 215. w7x T.W. Davies, S. C ¸olak, R.M. Hooper, Powder Technol. 65 1991

.

4

x

Ž

433.

w8x S. Sener, G. Ozbayoglu, Separation of ulexite from colemanite by calcination, Min. Eng. Ž6June 1995. 697–704.

w9x M.C. Jha, M.J. Kramer, Recovery of gold from arsenical ores, in: V.

, ing, Extraction, and Processing, TMS of AIME, 1984, pp. 337–265. w10x B.A. Strathdel, L.M. Pidgeon, Thermal decomposition of vapor

Precious Metals: Min-

Kudryk, D.A. Corrigan, W.W. Liang ŽEds

pressure measurements on arsenopyrite and on arsenical ores, Cana- dian Mining and Metallurgical Bulletin, December 1961, pp. 883–

887.

w11x R. Hultgren, P.D. Desai, D.T. Hawkins, M. Gleisser, K. Kelly, D.D. Wagman, Selected Values of the Thermodynamic Properties of the Elements, American Society for Metals, Metals Park, OH, 1973.

w

K.C. Mills, Thermodynamic Data for Inorganic Sulfides, Selenides and Tellurides, Butterworth, London, 1974.

w13x A.D. Mah, Thermodynamic data for arsenic sulfide reactions, US Bureau of Mines Report of Investigations 8671, 1982. w14x D.R. Stull, H. Prophet, JANAF Thermochemical Tables, 2nd edn., NSRDS-NBS37, National Bureau of Standards, Washington, DC,

12

x

1971.

w

x

15 J.O. Burckle, G.H. March, R.L. Meek, Arsenic emissions and

control-gold roasting operations, Environmental J. 6 Ž 1981 . 443–451.

w

x

16 W.H. Lederer, R.J. Fenstenheim inhold, New York, 1983.

Ž

Eds. . , Arsenic, Van Nostrand-Re-

w x 16 W.H. Lederer, R.J. Fenstenheim inhold, New York, 1983. Ž Eds. . , Arsenic,