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Pyrometallurgical Extraction of Lead from Battery Scrap
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<$ 0B72DEB0?ก 2*F20ก'ก(@>9:8'ก(ก =#3;"#$>?>ก0+@กกก6;1*/63?$ก ! Battery- scrap
!)0F;'ก(ก K6 LA!) (Forming of Matte) A#>ก K6 L!A#ก (Forming of slag)
1R#L>!9KKSABB?>ก0+ (Lead Storage Battery) 1!5+6=Vก78;29D1DW21#D >!X 2 DY @>1ก:ก
15+6!%4@29!C! =78;2?C69D9:86*ก)<7$8?86;R5F6AB?1?6 *+#Vก7$!C!1D#*+/2 AB?1?6 *+1กCกZก#/1DW2กก
6;1*/63?$ก ! Battery scrap )*+ @>?86;78[*ก ก<@0:)*+1$!>!14 >"#$>?>ก0+!*&!1DW24(V ;
%>ก XL72D\@@3B022*FA$#C;A C?>ก0+B21D#56ก"#ก!*1$#566/VC286/#; Battery scrap @';9:8ก#/1DW20?=3:BA$#C;
7$!C6;"#$>?>ก0+ R'+;[*)*+DEB0?ก02":/)0+9DกZ&56 ก 2<16AB?1?6 *+1กC)*+$!:6/3ก 78;2A#8!)<ก *
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23
1. Battery Recycling
789
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1R#L>!9KKSABB?>ก0+ (Lead storage battery) @0:1DW21R#L)3?/%V! 14 >1!5+6^#?'F2A#8?86;2<16
9D)<ก L@9KกC62@';@>@C/ก >A9KKS9:8 A#>1!5+6@C/9K$!:A#8! =2<9D)<ก L@9K7$!C9:86*ก
"#$>?>ก0+1DW2[?3)*+!*&!$2A2C2V; @';1DW2^#)<7$81R#L>!9KKS2:2*F7$84#0;;2?C6$2'+;$2C/!#?+<
(0.022 Kwh/kg) 1R#L>!9KKSABB?>ก0+1!5+6)<ก ?C615+6!0F9KKSABB623ก !@<22 6 1R#L @';)<7$8!*
0ก/L9KKS6;1R#LD >!X 12 "#?L A?C#>1R#LD >ก6B:8/0F9KKSA6"2:1DW2?>ก0+60:45F2^ 3 >1DW2
V4 32 0F9KKSA&"):1DW2A^C2?>ก0+)*+18B$38!:8/1#: (IV) 66ก9R:L (PbO2) C2"& ;6;A^C20F9KKS72
AB?1?6 *+ (Grid) )<@ก"#$>^!6;?>ก0+A#>4#; (1 i 3 wt% antimony-lead alloys) (:V%4)*+ 2. A#> 3. )
":/)*+0F9KKS)0F;6;0F@3C!72 #>#/ก :ก<!>=0218!82 40% ":/!# (D >!X 5.3 mol / dm3) !*&!
=C;@<14> 1.3 A#>=8&!=C;@<14>?+<กC 1.1 @>?86;2<9D L@9K
23
2. The six galvanic cells in a 12-volt automobile battery.
(H.Stephen Stoker, Introduction to Chemical Principles, Fourth Edition, 1993, p 618)
23
3. A single lead storage battery cell
(H.Stephen Stoker, Introduction to Chemical Principles, Fourth Edition, 1993, p 619)
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4. DEก /ก @C/9K)3ก& 0F;1ก:1$!562ก02
5. 1R#L>!9KKSAB?>ก0+ E0Cell = 2.04 V 1!5+62<!?C6ก02 6 1R#LABB623ก ! !*&!?C;0ก/L 12 V
6. 1R#L>!9KKSABB?>ก0+ X>@C/9KA#>60:9K )*+78A#>1ก:'F27$!C1DW29D?!? ;2*F
ก OP;KL ก
KL
)*+78 Pb, PbO2 A#> PbSO4 PbSO4 A#> H2O
)*+1ก: PbSO4 A#> H2O Pb, PbO2 A#> PbSO4
O} Connell 9:8)<ก $#6! (Smelting) Battery scrap )*+63X$%V! 1000 i 1100 º C ^#ก $#6!4BC
D >ก6B:8/ 6 wt%Pb, 54.22 wt% PbSO4 , 10.9 wt% PbO, 19.0 wt% PbO2 A#>C2D >ก6B65+2 o )*+1$#561DW2
plastic A#> acid component D >!X 9.88 wt%
Battery scrap C27$uC1DW2 D >ก6B)*+6/VC72 VDK6 L!6; PbSO4 :0;20F272ก 2<16 Battery scrap
!)<ก =#3;145+67$89:81DW2"#$>?>ก0+1 @>$ Reducing agent !@0B$ 56A/C;16[?3 S A#> O 66ก!@ก
PbSO4 Reducing agents ?0<&0u)*+1 @>2<!78กZ &56 Fe A#> C
@กก 'ก() BC Fe 1DW2[?3)*+9!C#>#/72 Pb )0F;72%41DW26;1$#A#>6;AZ; 1 ! =78
Fe 1DW2 Reducing agent 145+6A/C;16 S @ก PbSO4 14 >1!5+6:V@ก ∆G0 i T diagram for sulphide
formation. 4BC)*+63X$%V! 0- 1420 ºC 182ก K6; FeS ?+<กC PbS :0;20F2 FeS stable !กกC PbS @';
B6ก9:8C Fe ! = *:RL16 S @ก PbS A#8@>ก#/1DW2 D >ก6B FeS (S + Fe = S 2- + Fe 2+ ; Fe )<
?01DW2 Reducing agent)
:0;!ก PbS + Fe → FeS + Pb ∆G01273 K = -25 kJ
A?C125+6;@ก FeS D >ก6BR0#9K:L)*+!*@3:$#6!?0V;D >!X 1190 ºC (%4)*+ 5. ) @';?86;$ C/
=#3;145+6#:@3:$#6!?06; FeS #; ":/78 Fluxing materials 1C2 Na2CO3 A#> CaCO3
Soda ash (Na2CO3) 1DW2 1&!*)*+! =@0Bก0BกR4(&56 Sulfur dioxide )*+6/VC72C26;A#ก
Na2CO3 → Na2O + CO2
S + Na2CO3 + 2 C = Na2S + 3 CO (g)
4
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@ก Phase diagram Na2S i FeS 4BC1 ! =@0:C2^!7$8!*@3:$#6!1$#?+< o 9:8$#/&C 1C2
640 ºC , 650 ºC, 695 ºC :0;A:;72%4)*+ 6.
23
5. Fe-S system (ASM, Metals Handbook). 23
6. Phase diagram for Na2S b FeS
system
(R. Schuhmann, JR, Metallurgical Engineering, Volume 1 Engineering Principles, 1952, P 301)
9:8!* /;2ก @0/1 5+6; Thermodynamic Analysis of the Soda ash smelting of Lead acid battery
residue in a rotary furnace. ^V81*/2&56 A. Guerrero, A. Romero, R.D. Morales and F. Chavez 7$886!V#
1ก*+/ก0BDEก /1&!*98
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2. =860? C26; C/PbTot !*&C6/VC >$C; 0 A#> 0.004 DEก /)*+@>1ก: &56
3 Na2SO4 + 2 Pb + FeO + 5C = 2PbS + FeS + 3Na2CO3 + 2CO2 ∆G0 = - 564.93 kJ/mol
3. =860? C26; C/PbTot V;กC 0.01 PbS =Vก *:L6*ก& 0F;":/DEก /
Na2SO4 + PbS + FeO + 2C = Pb + FeS + Na2S + Na2CO3 + CO2 ∆G0 = - 464.72 kJ/mol
5
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Coke (85% fixed C) $ 56 Anthracite (80% fixed C) A#> 1(*Fก#';1$#Zก$#C6 Iron chip (!*C2D >ก6B6;
Fe
A#> Fe2O3) $ 56 Mill scale )<$28)*+1DW2?0)<7$81ก:DEก / Carbothermic reduction 6; Lead sulfate A#>
Lead oxide
2 C + O2 → 2 CO , 2 CO + O2 → 2 CO2 , CO2 + C → 2 CO
CS2(l) + 3 O2(g) → CO2(g) + 2 SO2(g)
6
431307 Chemical Metallurgy Laboratory ก !"#$ก
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Slag (l)
Matte (l)
Lead (l)
23
7. ก8G,<
ก N;กfg0<
Slag, Matte N, Lead <G,
1ก *+N Pyrometallurgy
1. ,-Nก
KJP
2;P
-N)=
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Slag system Na2O-FeO-SiO2
23
5. The Na2O-FeO-SiO2 system
125+6;@กก 78 Na2CO3 1DW2 Fluxing material 145+6C/7$8! =K6 L! Slag A#> Matte @>1ก:ก
$#6!9:8)*+63X$%V!?+<กCก 78 CaCO3 1DW2 Fluxing material A?Cก 78 Na2CO3 กZ!*861*/6/VC)*+C 125+6@ก
Na2CO3 1DW2 D >ก6B& LB612?6;[?3$!VC IA @';!*&!! =72ก #>#/722F<9:8:* (:0;A:;72%4)*+
8 - 11)
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=8!*"#$>?>ก0+$#;1$#566/VC6*ก@<22$2'+;72 Slag $ 56 Matte 2*FA#82<16 Slag A#> Matte 9D=!)*+:2 =8$ก=Vก
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1 */ก >BBA#ก)*+!*C2D >ก6B6; soda ash C1DW2 >BBA#ก)*+9!CD#6:%0/?C6+;A:#86!
Soda ash
Soda ash can be used in aqueous solution to remove sulfur dioxide from process gas or off-
gases, forming sodium sulfate and sodium bicarbonate :
Na2CO3 + SO2 → Na2SO3 + CO2
CO2 + Na2CO3 + H2O → 2 NaHCO3
2 Na2CO3 + SO2 + H2O → Na2SO3 + 2 NaHCO3
Calcination of Bicarbonate.
Thermal deposition of curde bicarbonate to carbonate liberates carbon dioxide, ammonia, and
water vapor . The product is technical-grade soda ash, which contains sodium chloride . The main
reaction is
2 NaHCO3 → CO2 + H2O + Na2CO3
And side reactions are
NH4HCO3 → NH3 + CO2 + H2O
8
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NaHCO3 + NH4Cl → NH3 + CO2 + H2O + NaCl
Leblance Process.
Na2SO4 + 2 C → Na2S + 2 CO2
Na2S + CaCO3 → Na2CO3 + CaS
Na2SO4 + 2 C + CaCO3 → Na2CO3 + CaS + 2 CO2
23
8. Solubility in the system Na2CO3- H2O 23
9. Solubility in the system H2O-NaHCO3-
Na2CO3
Temperature and concentrations of at 24.9 °C , 30 °C and 50 °C
the two-salt points and the cryohydric point.
9
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10. Solubility of sodium sulfate 23
11. pH values of aqueous solutions of
Na2CO3 at 25 °C
(From: Industrial Inorganic Chemistry and Products, Volume 5. p 4392 , Volume 6. p 4477 )
2. ,-Nก
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Slag system CaO-FeO-SiO2 72 >BB2*F78 CaCO3 1DW2 Fluxing material A)2ก 78 Na2CO3 1!5+6
1D */B1)*/B4BC Slag system 6; CaO-FeO-SiO2 @>$#6!9:8)*+63X$%V!?+<3:&56 1105 °C (%4)*+ 13 A#> 14)
$ 56 1150 °C (%4)*+ 12 , 14 ,A#> 15) 72X>)*+ Slag system Na2O-FeO-SiO2 @>$#6!9:8)*+63X$%V!?+<3: &56
800 °C (%4)*+ 5.)
23
12. Liquidus isotherms of
CaO-SiO2-FeO system
10
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13. Liquidus surfaces and immiscibility region in the ternary system CaO b FeO b SiO2 (from
Bowen et al.) (J.J. Moore, Chemical Metallurgy, Second edition, 1990, p. 164)
23
14. The FeO-SiO2-CaO ternary system , showing compositions of several lead blast furnace
slags.
(Fathi habashi , Handbook of Extractive Metallurgy, Volume 2, 1997, p595)
11
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15. CaO-FeO-SiO2 equilibrium phase diagram showing the extent of the completely liquid region
at 1150 °C , 1200 °C N, 1250 °C
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- ,ก
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- 1DW2 D >ก6B96662ก /ก182 D >ก6B Be B;2:1DW2"&11#2?L 1C2 BeCl2
- @3:$#6!1$#A#>@3:1:56:V;
- & LB612?6;[?3$!VC IIA 1^A#81ก:DEก /7$8กR CO2 1C2
CaCO3 (s) → CaO (s) + CO2 (g)
- 66ก9R:L6;[?3$!VC IIA )<DEก /ก0B2F<1ก: D >ก6B9r: 6ก9R:L)*+1DW26;AZ; R'+;#>#/2F<9:89!C:*
#>#/)*+!*!B0?1DW21B 1C2 CaO (s) + H2O (l) → Ca(OH)2 (s)
12
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- ก #>#/2F<6; D >ก6B6;[?3$!VC IIA D >ก6B921? ?A#> D >ก6BE :L6;[?3$!VC IIA
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A#>9r: 6ก9R:L (OH-) #>#/2F<9:8286/$ 56=56C9!C#>#/ /ก182 MgSO4 #>#/2F<9:8:*
Quicklime
Ground quicklime is also used for the desulfurization of iron in the ladle before charging into the
steelmaking furnace.
Quicklime has the advantage over hydrated lime of drying out the soil. It does this by absorbing
30 % of its own weight of moisture and also by generating heat which accelerates evaporation.
Calcium sulfate
Part of the Calcium sulfate is reduced to calcium sulfide, which reacts above 900 ° C with the
remaining
calcium sulfate to from calcium oxide and sulfur dioxide
13
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16. Phase diagram for the system SiO2 b 2Na2O.SiO2 .
From F.C. Kracek, J. Phys. Chem., 34, 1588 (1930), and J. Am. Chem. Soc., 61, 2869 (1939).
14
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17. The liquidus plot for the SiO2- CaO b Na2O phase diagram.
(Donale R. Askeland, The Science and Engineering of Materials, third S.I Edition, CHAPMAN & HALL, P
468)
23
18. Fe-S system (ASM, Metals Handbook).
(R. Schuhmann, JR, Metallurgical Engineering, Volume 1 Engineering Principles, 1952, P 301)
15
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Wt% FeS →
23
19. Phase diagram for Na2S b FeS system
16
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20. Phase diagram of the Na-S system between the compositions Na2S2 and 100 % S
(From: Industrial Inorganic Chemistry and Products, Volume 6. p 4509 )
23
21 . Phase diagram of the system Na2SO4 b Na2S
(From: Industrial Inorganic Chemistry and Products, Volume 6. p 4518 )
17
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1 / T x 104
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22. Vapor pressures of Sb, As, Pb and their oxidic and sulfidic compounds.
Standard free energy btemperature diagrams : Application to metal extraction
18
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23. ∆G0 b T diagram for sulphide formation.
For calculation of equilibrium p S2 and equilibrium p H2 / p H2S use points S and H respectively on the
∆G0 axis at o K
19
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24. ∆G0 b T diagram for sulphide formation.
20
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25. ∆G0 b T diagram for oxide formation.
21
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