Sulfuro de Sodio

LIXIVIACION DE ENARGITA
USANDO SULFURO DE SODIO
Temario
Revisin literaria
Objetivos
Resultados
Conclusiones
REVISION LITERARIA
Revisin literaria
Enargita Cu3AsS4
Sulfosal de cobre
Fuente de metales
preciosos
Alto contenido de
arsnico
Arsnico
Cancergeno
Alta movilidad en
efluentes
Revisin Literaria
Alternativas para tratar minerales que contienen
arsnico
Pirometalurgia (Tostacin, Fundicin)
Lixiviacin a presin
Lixiviacin atmosfrica (cida/bio)
Lixiviacin alcalina (amoniaco, hipoclorito, sulfuro)
Revisin Literaria
Lixiviacin con sulfuro de sodio
(Curreli 2009, Anderson 2008)
Reaccin propuesta:
3Na2 S + 2Cu3 AsS 4 3Cu2 S + 2 Na3 AsS 4
Condiciones:
80 a 107oC
Altas concentraciones de NaOH
necesarias para evitar la hidrlisis
del sulfuro acuoso:
S (2aq ) + H 2O(l ) HS(aq ) + OH (aq )
Revisin Literaria
Segunda constante de disociacin del sulfuro de
hidrgeno (Giggenbach, 1971; Licht, 1988 )
H 2 S = HS + H +
K1 107
HS = H + + S 2
K 2 = 10 17
Na2 S + H 2O = NaHS + NaOH
Revisin Literaria
Reacciones esperadas:
Na2 S ( aq ) + H 2O(l ) NaHS ( aq ) + NaOH ( aq )
2Cu3 AsS 4 ( s ) + 3 NaHS ( aq ) + 3 NaOH ( aq ) 2 Na3 AsS 4( aq ) + 3Cu 2 S ( s ) + 3H 2O( l )
Efecto directo del NaOH
OBJETIVOS
Objetivos
Confirmar posibilidad de lixiviar enargita usando Na2S y NaOH
Estudiar condiciones de lixiviacin ms cercanas a una
operacin real
Analizar posibilidades para remover el arsnico de la solucin
Identificar reas de investigacin relevantes para el proceso
RESULTADOS: LIXIVIACION
Resultados
Anlisis mineralgico de
la muestra de enargita
Anlisis qumico
enargita (elementos
ms relevantes)
Mineral
Feed
As
Cu
Sb
ppm
117000
378000
4610
11.70
37.80
0.461
Ideal Formula
Enargite Head Sample

(%)
Enargite
Cu3AsS4
60.4
Tennantite
(Cu,Ag,Fe,Zn)12As4S13
4.9
Covellite
CuS
3.0
Pyrite
FeS2
25.7
Quartz
SiO2
5.9
Resultados
Variables estudiadas
Temperatura
Agitacin
Tamao de partcula
Concentracin de NaOH y Na2S
Estequiometra en pruebas con alta densidad de pulpa
Resultados
Efecto de la temperatura
Effect of temperature on As extraction at 3.5 M NaOH, 1.0 M
Na2S, 10 g of sample on 200 ml of solution, P80 of 30
um and 500 RPM agitation speed
Effect of temperature on Sb extraction at 3.5 M NaOH, 1.0 M

um and 500 RPM agitation speed
Resultados
Efecto de la agitacin
Effect of agitation on As extraction at 3.5 M NaOH, 1.0 M
um and 95oC
Effect of temperature on Sb extraction at 3.5 M NaOH, 1.0 M

um and 95oC
Resultados
Efecto del tamao de
partcula
Effect of particle size on As extraction at 3.5 M NaOH, 1.0 M
Na2S, 95oC 10 g of sample on 200 ml of solution and 500
RPM agitation speed
Effect of particle size on Sb extraction at 3.5 M NaOH, 1.0 M

Na2S, 95oC 10 g of sample on 200 ml of solution and
500 RPM agitation speed
Resultados
Efecto de la
concentracin
Effect of NaOH and Na2S concentration on As extraction at 95oC 10 g
of sample on 200 ml of solution, P80 of 30 um and 500 RPM
agitation speed
Effect of NaOH and Na2S concentration on Sb extraction at 95oC 10 g

of sample on 200 ml of solution, P80 of 30 um and 500 RPM
agitation speed
Resultados
Efecto de la concentracin
Solid residue Analysis after leaching for 6 hours at 95oC
[NaOH] (M)
[Na2S] (M)
As Average
Sb Average
3.5
1.0
0.067
0.004
3.0
0.5
0.257
2.0
1.0
1.1
1.0
1.5
0.5
0.324
0.008
0.009
1.232
0.052
3.852
0.145
Resultados
Efecto de la concentracin
(selectividad)
Selectivity of the sodium sulphide leach. Cu, Fe, Zn and Ag
remain unleached after 6 hours at 95oC and 500 RPM
Sample
Cu (%)
Fe (%)
Zn (%)
Ag (%)
Head
40.00
12.00
0.316
0.0193
3.5 M NaOH 1.0 M Na2S
48.48
12.70
0.362
0.0243
48.49
15.66
0.346
0.0239
42.39
12.45
0.330
0.0241
3.0 M NaOH - 0.5 M Na2S
49.17
15.87
0.384
0.0246
45.65
14.64
0.342
0.0229
Resultados
Efecto de la estequiometra
Effect of stoichiometry on As during the leach of 200 g of
sample at 95oC on 200 ml of solution, P80 of 30 um and
Effect of stoichiometry on Sb during the leach of 200 g of

sample at 95oC on 200 ml of solution, P80 of 30 um and
Resultados
Prueba en 3 etapas
1st Stage: 200 g of sample in 200 ml of solution
with 200 % Stq. NaOH, 100 % Stq. Na2S at
95oC, P80 of 30 um and 500 RPM
2nd Stage: Residue from stage 1 leached in 200

ml of solution with the same reagent
concentrations of stage 1 at 95oC and 500
RPM
3rd Stage: Residue from stage 2 leached in 200

ml of solution with the same reagent
concentrations of stage 1 at 95oC and 500
RPM
Resultados
Enargite solid residues after leaching 10 grams of enargite in 200 ml of a 3.5 M
NaOH and 1.0 M Na2S solution at 95oC and 500 RPM
Enargite leach
residue after 6
hours
Mineral
Ideal Formula
Enargite head
sample
Enargite
Cu3AsS4
60.4
1.80
Quartz
Pyrite
SiO2
FeS2
5.90
25.7
6.00
34.4
Tennantite
(Cu,Ag,Fe,Zn)12As4S13
4.90
1.20
Bornite
Cu5FeS4
34.2
Digenite
Cu9S5
4.20
Covellite
CuS
Tenorite
CuO
1.70
Chalconatronite
Na2Cu(CO3)23(H2O)
5.80
Sodium Copper Sulphide
NaCu5S3
6.10
3.00
Enargite 2 leach
residue after 24
hours
7.10
33.1
6.40
4.60
53.4
Resultados
Residuo completamente lixiviado (sin pulir)
Resultados
Residuo completamente lixiviado (pulido)
Resultados
Residuo parcialmente lixiviado (pulido)
Resultados
Residuo parcialmente lixiviado (sin pulir)
RESULTADOS: REMOCION DE
ARSENICO DESDE LA SOLUCION
Resultados
Remocin de arsnico desde la solucin
Ferrihidrita
Escorodita
Arsenatos de calcio
Sulfuro de arsnico
Cristalizacin de tioarsenato de sodio
Resultados
Precipitacin sulfuro de arsnico
Final pH
As removal (%)
Sb removal (%)
S(2-) removal (%)
H2SO4/(As+Sb) mass ratio
99.93
99.98
99.49
55.98
99.95
99.96
99.45
45.12
100.0
99.98
99.27
33.29
99.82
99.97
98.99
26.65
Resultados
Precipitacin sulfuro de arsnico
Main Elements
As (%)
Sb (%)
29.53
1.311
Main Phases
Orpiment
As2S3
Claudetite
As2O3
Hydrogen Sodium Sulfate

Sodium sulfur oxide hydrate
H5Na(SO4)3
Na2(S2O3)*5H2O
Resultados
Cristalizacin tioarsenato de
sodio
Presencia de arsnico(V)
Main Phases
Sodium sulphide Arsenate Hydrate
Na3AsO2S211H2O
Sodium Sulphide Arsenate Hydrate
Na3AsO2S27H2O
Sodium Sulphide Arsenate Hydrate
Na3AsS48H2O
Precipitation parameters
As
Sb
Highest concentration seen (M)
1.30
0.032
Concentration after precipitation (M)
0.70
0.030
Content in solid precipitate (%)
11.8
0.320
Average removal from solution (%)
42.0
4.500
CONCLUSIONES
Conclusiones
Arsnico y antimonio pueden ser lixiviados
selectivamente de la enargita usando NaOH
y Na2S (NaHS), dejando el cobre en el
residuo solido.
Arsnico (V) parece ser la forma mas estable
de arsnico en solucin y puede cristalizar
como tioarsenato de sodio
Conclusiones
Los problemas de filtrado parecen
incrementar con la presencia de erdita
(tioferrato de sodio)
Probablemente el mecanismo de control
sea la reaccin qumica
Gracias

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LIXIVIACION DE ENARGITA

USANDO SULFURO DE SODIO

S (2aq ) + H 2O(l ) HS(aq ) + OH (aq )

Na2 S + H 2O = NaHS + NaOH

Efecto directo del NaOH

Enargite Head Sample

Effect of temperature on Sb extraction at 3.5 M NaOH, 1.0 M

Effect of temperature on Sb extraction at 3.5 M NaOH, 1.0 M

Effect of particle size on Sb extraction at 3.5 M NaOH, 1.0 M

Effect of NaOH and Na2S concentration on Sb extraction at 95oC 10 g

3.5 M NaOH 1.0 M Na2S

2.0 M NaOH 1.0 M Na2S

1.1 M NaOH 1.0 M Na2S

3.0 M NaOH - 0.5 M Na2S

1.5 M NaOH 0.5 M Na2S

Effect of stoichiometry on Sb during the leach of 200 g of

2nd Stage: Residue from stage 1 leached in 200

3rd Stage: Residue from stage 2 leached in 200

Sodium Copper Sulphide

S(2-) removal (%)

H2SO4/(As+Sb) mass ratio

Hydrogen Sodium Sulfate

Sodium Sulphide Arsenate Hydrate

Sodium Sulphide Arsenate Hydrate

Highest concentration seen (M)

Concentration after precipitation (M)

Content in solid precipitate (%)

Average removal from solution (%)

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