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 O HS + OH ) 2 (l ) ( aq ) ( 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 qumico enargita (elementos ms relevantes)
Feed ppm % As 117000 11.70 Cu 378000 37.80 Sb 4610 0.461

Anlisis mineralgico de la muestra de enargita

Mineral Enargite Tennantite Covellite Pyrite Quartz Ideal Formula Cu3AsS4 (Cu,Ag,Fe,Zn)12As4S13 CuS FeS2 SiO2 Enargite Head Sample (%) 60.4 4.9 3.0 25.7 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 Na2S, 10 g of sample on 200 ml of solution, P80 of 30 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 Na2S, 10 g of sample on 200 ml of solution, P80 of 30 um and 95oC

Effect of temperature on Sb extraction at 3.5 M NaOH, 1.0 M Na2S, 10 g of sample on 200 ml of solution, P80 of 30 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) 3.5 3.0 2.0 1.1 1.5 [Na2S] (M) 1.0 0.5 1.0 1.0 0.5 As Average 0.067 0.257 0.324 Sb Average 0.004 0.008

0.009 0.052

1.232

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 Head 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 Cu (%) 40.00 48.48 48.49 42.39 49.17 45.65 Fe (%) 12.00 12.70 15.66 12.45 15.87 14.64 Zn (%) 0.316 0.362 0.346 0.330 0.384 0.342 Ag (%) 0.0193 0.0243 0.0239 0.0241 0.0246 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 500 RPM agitation speed

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 500 RPM agitation speed

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
Mineral Enargite Quartz Pyrite Tennantite Bornite Digenite Covellite Tenorite Chalconatronite Sodium Copper Sulphide Ideal Formula Cu3AsS4 SiO2 FeS2 (Cu,Ag,Fe,Zn)12As4S13 Cu5FeS4 Cu9S5 CuS CuO Na2Cu(CO3)23(H2O) NaCu5S3 3.00 Enargite head sample 60.4 5.90 25.7 4.90 Enargite leach residue after 6 hours 1.80 6.00 34.4 1.20 34.2 4.20 4.60 1.70 5.80 6.10 53.4 6.40 7.10 33.1 Enargite 2 leach residue after 24 hours

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

4 5

100.0 99.82

99.98 99.97

99.27 98.99

33.29 26.65

Resultados
Precipitacin sulfuro de arsnico
Main Elements As (%) 29.53 Sb (%) 1.311

Main Phases Orpiment Claudetite Hydrogen Sodium Sulfate Sodium sulfur oxide hydrate As2S3 As2O3 H5Na(SO4)3 Na2(S2O3)*5H2O

Resultados
Cristalizacin tioarsenato de sodio Presencia de arsnico(V)
Main Phases Sodium sulphide Arsenate Hydrate Sodium Sulphide Arsenate Hydrate Sodium Sulphide Arsenate Hydrate Na3AsO2S211H2O Na3AsO2S27H2O Na3AsS48H2O

Precipitation parameters Highest concentration seen (M) Concentration after precipitation (M) Content in solid precipitate (%) Average removal from solution (%)

As 1.30 0.70 11.8 42.0

Sb 0.032 0.030 0.320 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