Ustulao de sulfetos Metlicos

A ustulao de sulfetos metlicos para a obteno de metais de interes visa satisfazer as

necessidades dos mercados, alm disso, tem como objetivo o aproveitamento dos compostos
de enxofre formados nas reaes.

Nos processos de reduo pode ter possibilidade de acontecer desde o ponto de vista
termodinmico quando feito o calculo para a energia livre de Gibbs, alem disso para a reao
acontecer necessrio ter presente os valores da constante de equilbrio.

Na figura um (1) pode-se observar a reduo para a obteno de chumbo Pb, a partir de
sulfato de chumbo PbS, a reao intermdia do Oxido de Chumbo com o sulfeto acontece s
para temperaturas superiores a 18000C, pois por abaixo desta temperatura a constante de
equilbrio para esta reao menor que zero k2<0, pelo que invivel desde o ponto de vista
industrial pelas altas temperaturas requeridas para a obteno de chumbo via ustulao de
sulfeto de Chumbo. Na tabela da figura um (1) tem o resumo dos valores das constantes de
equilibro para as reaes de ustulao de sulfetos.
Na figura dois (2), pode-se observar o comportamento das reaes em a ustulao de sulfeto
de Zinc ZnS para a obteno de Zn. Como pode se observar em a segunda reao, a energia
livre de Gibbs maior a zero G0>0, pelo que esta reao dificilmente acontecer, alm disso,
na tabela da figura dois (2) os valores da constante de equilibro so sempre menores que
zerok2>0
Na figura trs (3) e quatro (4), mostra a formao de Cu a partir de CuS e Cu2S
respectivamente, como pode-se observar, possvel desde temperaturas baixas a obteno de
Cu, contudo pela razo estequiomtrica, e de formao de suas molculas e muito mais
favorvel a obteno de Cu a partir de Cu2S (relao 2:Cu, 1:S) que CuS (relao 1:Cu, 1:S)
Na figura cinco (5), pode-se ver que a formao de Ni, a partir de NiS, praticamente invivel
para a faixa de temperatura estudada (0-20000C). A reao dois, onde vai reagir o oxido de
Niquel e o Sulfuro de Ni 1 3 + 2 3 = + 1 3 2() a constante de equilbrio
vai ser negativa em toda a faixa de temperaturas, pelo que a obteno de Ni, apartir de seu
sulfeto
no

possvel
pela
faixa
de
temperatura
estudada.

K1
1,28E+50
8,10E+35
5,02E+27
2,26E+22
3,93E+18
6,46E+15
4,63E+13
9,20E+11
3,81E+10
2,79E+09
3,48E+08
5,91E+07
1,08E+07
2,40E+06
6,37E+05
1,97E+05
6,88E+04
2,68E+04
1,14E+04
5,28E+03
2,61E+03

K2
3,19E-12
3,76E-08
8,03E-06
2,56E-04
3,17E-03
2,09E-02
8,86E-02
2,76E-01
6,89E-01
1,43E+00
2,31E+00
3,46E+00
4,47E+00
5,46E+00
6,47E+00
7,46E+00
8,42E+00
9,33E+00
1,02E+01
1,10E+01
1,17E+01

KR
4,08E+38
3,05E+28
4,03E+22
5,77E+18
1,25E+16
1,35E+14
4,10E+12
2,54E+11
2,63E+10
3,98E+09
8,05E+08
2,05E+08
4,83E+07
1,31E+07
4,12E+06
1,47E+06
5,79E+05
2,50E+05
1,17E+05
5,80E+04
3,06E+04

PbS + O2(g) = Pb + SO2(g)

40

20

G
(KJ/mol)

T (0C)
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000

-20

-40

-60

-80

-100
200

400

600

800

1000

1200

1400

1600

Temperarura (K)
2/3PbS + O2(g) = 2/3PbO+ 2/3SO2(g)
1/3PbS + 2/3PbO = Pb + 1/3SO2(g)
PbS + O2(g) = Pb + SO2(g)

Figura 1. Ustulao de PbS

K1
K2
KR

1800

2000

K1
1,09E+54
7,06E+38
1,17E+30
2,23E+24
2,11E+20
2,20E+17
1,11E+15
1,65E+13
5,40E+11
3,17E+10
2,90E+09
3,76E+08
6,45E+07
1,39E+07
3,58E+06
1,08E+06
3,69E+05
1,41E+05
5,93E+04
2,59E+04
1,24E+04

K2
1,84E-35
4,30E-25
4,03E-19
3,04E-15
1,60E-12
1,88E-10
7,63E-09
1,44E-07
1,57E-06
1,13E-05
5,98E-05
2,47E-04
8,39E-04
2,43E-03
6,20E-03
1,42E-02
2,96E-02
5,72E-02
1,03E-01
1,73E-01
2,68E-01

KR
1,99E+19
3,03E+14
4,72E+11
6,77E+09
3,38E+08
4,15E+07
8,44E+06
2,38E+06
8,47E+05
3,59E+05
1,73E+05
9,29E+04
5,41E+04
3,37E+04
2,22E+04
1,53E+04
1,09E+04
8,06E+03
6,13E+03
4,50E+03
3,31E+03

ZnS + O2(g) = Zn + SO2(g)

40

20

G
(KJ/mol)

T(0C)
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000

-20

-40

-60

-80

-100
200

400

600

800

1000

1200

1400

1600

Temperarura (K)
2/3ZnS + O2(g) = 2/3ZnO + 2/3SO2(g) K1
1/3ZnS +2/3 ZnO = Zn + 1/3SO2(g)
K2
ZnS + O2(g) = Zn + SO2(g)
KR

Figura 2. Ustulao de ZnS

1800

2000

K1
4,36E+47
1,21E+34
1,75E+26
1,37E+21
3,48E+17
7,52E+14
6,60E+12
1,53E+11
7,10E+09
5,55E+08
6,45E+07
1,02E+07
2,07E+06
5,77E+05
1,96E+05
7,47E+04
3,16E+04
1,45E+04
7,18E+03
3,78E+03
2,10E+03

K2
7,59E-02
1,21E+00
5,67E+00
1,49E+01
2,87E+01
4,55E+01
6,37E+01
8,22E+01
9,98E+01
1,16E+02
1,31E+02
1,45E+02
1,69E+02
1,70E+02
1,62E+02
1,55E+02
1,47E+02
1,39E+02
1,32E+02
1,25E+02
1,18E+02

KR
3,31E+46
1,46E+34
9,95E+26
2,04E+22
9,99E+18
3,42E+16
4,21E+14
1,26E+13
7,09E+11
6,44E+10
8,42E+09
1,48E+09
3,50E+08
9,82E+07
3,18E+07
1,16E+07
4,64E+06
2,02E+06
9,48E+05
4,72E+05
2,48E+05

CuS + O2(g) = Cu + SO2(g)

40

20

G
(KJ/mol)

T(0C)
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000

-20

-40

-60

-80

-100
0

200

400

600

800

1000

1200

1400

1600

Temperarura (K)
2/3CuS + O2(g) = 2/3CuO + 2/3SO2(g) K1
2/3CuO +1/3 CuS = Cu + 1/3SO2(g) K2
CuS + O2(g) = Cu + SO2(g)
KR

1800

2000

K1
2,61E+45
7,21E+31
9,01E+23
6,19E+18
1,44E+15
2,88E+12
2,39E+10
5,35E+08
2,45E+07
1,90E+06
2,22E+05
3,57E+04
7,24E+03
2,15E+03
7,95E+02
3,31E+02
1,52E+02
7,62E+01
4,10E+01
2,34E+01
1,41E+01

K2
3,45E-05
8,72E-03
1,65E-01
1,01E+00
3,38E+00
7,90E+00
1,47E+01
2,37E+01
3,43E+01
4,62E+01
5,88E+01
7,39E+01
1,01E+02
1,08E+02
1,07E+02
1,06E+02
1,04E+02
1,02E+02
9,94E+01
9,69E+01
9,43E+01

KR
9,01E+40
6,29E+29
1,49E+23
6,26E+18
4,86E+15
2,27E+13
3,52E+11
1,27E+10
8,39E+08
8,79E+07
1,31E+07
2,64E+06
7,27E+05
2,33E+05
8,53E+04
3,50E+04
1,58E+04
7,76E+03
4,07E+03
2,27E+03
1,33E+03

Cu2S + O2(g) = 2Cu + SO2(g)

20

G
(KJ/mol)

T(0C)
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000

-20

-40

-60

-80

-100
200

400

600

800

1000

1200

Temperarure (K)

1400

1/2Cu2S + O2(g) = CuO + 1/2SO2(g) K1

CuO + 1/2Cu2S = 2Cu + 1/2SO2(g) K2
Cu2S+ O2(g) = 2Cu + SO2(g)
KR

Figura 4. Ustulao de Cu2S

1600

1800

2000

K1

K2

KR

4,05E+54
1,88E+39
2,59E+30
4,48E+24
3,91E+20
3,54E+17
1,59E+15
2,17E+13
6,57E+11
3,59E+10
2,98E+09
3,16E+08
4,53E+07
8,26E+06
1,84E+06
4,83E+05
1,46E+05
4,95E+04
1,86E+04
7,66E+03
3,52E+03

2,44E-14
1,01E-09
4,45E-07
2,24E-05
3,42E-04
2,47E-03
1,12E-02
3,70E-02
9,68E-02
2,14E-01
4,06E-01
6,63E-01
1,01E+00
1,44E+00
1,97E+00
2,67E+00
3,64E+00
4,79E+00
6,13E+00
7,67E+00
9,08E+00

9,90E+40
1,89E+30
1,15E+24
1,00E+20
1,34E+17
8,74E+14
1,79E+13
8,03E+11
6,36E+10
7,68E+09
1,21E+09
2,10E+08
4,56E+07
1,19E+07
3,62E+06
1,29E+06
5,30E+05
2,37E+05
1,14E+05
5,87E+04
3,19E+04

NiS + O2(g) = Ni + SO2(g)

20

-20

G
(KJ/mol)

T(0C)
0
100
200
300
400
500
600
700
800
900
1000
1100
1200
1300
1400
1500
1600
1700
1800
1900
2000

-40

-60

-80

-100
200

400

600

800

1000

1200

1400

1600

Temperarure (K)
K1
NiS + O2(g) = Ni + SO2(g)
1/3NiS + 2/3NiO = Ni + 1/3SO2(g)
K2
2/3NiS + O2(g) = 2/3NiO + 2/3SO2(g) KR
Figura 5. Ustulao de NiS

1800

2000