431307 Chemical Metallurgy Laboratory ก !

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%&ก 'ก()*+ 3/2551 !$)/#0/1)&"2"#/*3 2 *

ก
 
 7
Pyrometallurgical Extraction of Lead from Battery Scrap
)*+
,-./ก
 
145+67$820ก'ก(9:8):#6;)<ก =#3;"#$>?>ก0+@กAB?1?6 *+1กC)*+15+6!%4A#8

01
<$ 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)*+$!:6/3ก 78;2A#8!)<ก *
9R1&#
(Battery Recycling) 145+62<"#$>?>ก0+9D78^#?)<1DW2AB?1?6 *+#Vก7$!C :0;A:;72%4)*+ 1.

23
 1. Battery Recycling

789
:ก;)<= 
1
431307 Chemical Metallurgy Laboratory ก !"#$ก
%&ก 'ก()*+ 3/2551 !$)/#0/1)&"2"#/*3 2 *
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+)*+1&#56B$38!:8/1#: (IV) 66ก9R:L (PbO2) C2"& ;6;A^C20F9KKS72
AB?1?6 *+ (Grid) )<@ก"#$>^!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)
ก8G,-1.H< :I-/-,-JKLLMN,ก)
2
431307 Chemical Metallurgy Laboratory ก !"#$ก
%&ก 'ก()*+ 3/2551 !$)/#0/1)&"2"#/*3 2 *
1. 1R#L>!9KKSABB?>ก0+ X>60:9K1DW21R#L61#Zก") 9#?L A#>@C/9K@>1DW21R#Lก0#2ก
2. ก 60:9K& 0F;A ก1ก:DEก /A?ก?C;@กก 60:9K& 0F;65+2o
3. ก 60:9K& 0F;)*+ 2, 3, .... 1ก:DEก /1$!562ก02 A?CDEก /1ก:/862ก#0B ก0BDEก /ก @C/9K
4. DEก /ก @C/9K)3ก& 0F;1ก:1$!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

7. #>#/ก : H2SO4 !*&!18!82 40 % ":/!# &!=C;@<14> 1.3 =8789K9D22o @>4BC

 #>#/ก : H2SO4 !*&!=C;@<14>#:#;1$#56 1.1 ?86;2<9D60:9K7$!C
8. 1& 5+6;!56)*+780:&!=C;@<14>6;ก : H2SO4 &56 9r": !1?6 L
DEก /6;ก @C/ก >A9KA#>ก  L@9K)0+9D :0;2*F
ก @C/ก >A9K
Pb (s) + PbO2 (s) + 4H+ (aq) + 2SO42 - (aq) ⇌ 2PbSO4 (s) + 2H2O (l)
ก  L@9K

=';A!8C1R#L>!9KKSABB?>ก0+@>60:9K7$!C9:8 A?CกZ!*ก 15+6!%414 > PbSO4 )*+1ก:'F2)*+0F)0F;

6; B;C2$#3:#C;6/VC)*+ก82%2> )<7$80F)0F;6;'กก C62 A#>)<7$815+6!%472)*+3: D\u$2*F/0;9!C6@Aก89
9:8
Table 1. Compares an old type of battery in hard rubber casing with a modern type of battery .
The lead-bearing components of a battery are:

Grid metal, poles, bridges 44 %

Pb 96 i 98 %, Sb 2 i 4 %, (Ca) < 0.5 %
Paste 56 %
PbSO4 60 %, PbO (PbO2) 19 % , Pb 21 %
Total 100 %
(Dr. Ing. Heino Vest (2002) , Fundamentals of the Recycling of Lead-Acid Batteries , p 3)

-JJ+)P =8กก6;1*/63?$ก ! Battery scrap )0F;$!:6/VC72 VD6; D >ก6B6; PbSO4 100 %

3
431307 Chemical Metallurgy Laboratory ก !"#$ก
%&ก 'ก()*+ 3/2551 !$)/#0/1)&"2"#/*3 2 *
1 @>$CD >ก6B:8/[?3 Pb , S A#> O 6/C;#>ก*+1D6 L1RZ2?L":/2F<$20ก

)Z. )<ก $!#1DW2 86/#>@กV? "!1#ก3#6;

86/#>":/!#6;[?372 D >ก6B
= (!#6>?6!6;[?3 x @<226>?6!6;[?372V? x 100) / !#"!1#ก3#6; D >ก6B
Atomic weight : Pb = 207.20 , S = 32.07 ; O = 16.00
Molecular weight PbSO4 = 207.20 + 32.07 + (4 x 16.00) = 303.27
Pb = 100 x (207.20 x 1) / 303.27 = 68.32 %
S = 100 x (32.07 x 1) / 303.27 = 10.57 %
O = 100 x (16.00 x 4) / 303.27 = 21.10 %

=872ก ):#6;ก<$2:7$878 Battery scrap 50 g.

:0;20F2 Battery scrap 50 g. @>D >ก6B:8/
Pb = 0.6832 x 50 g = 34.16 g. S = 0.1057 x 50 g. = 5.29 g. A#> O = 0.2110 x 50 g. = 10.55
g.

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:$#6!?06; FeS #; ":/78 Fluxing materials 1C2 Na2CO3 A#> CaCO3
Soda ash (Na2CO3) 1DW2 1&!*)*+! =@0Bก0BกR4(&56 Sulfur dioxide )*+6/VC72C26;A#ก
Na2CO3 → Na2O + CO2
S + Na2CO3 + 2 C = Na2S + 3 CO (g)
4
431307 Chemical Metallurgy Laboratory ก !"#$ก
%&ก 'ก()*+ 3/2551 !$)/#0/1)&"2"#/*3 2 *
@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
3 1;5+629 &56

1. =89!C78& LB62 DEก /)*+@>1ก:'F2)*+63X$%V! 950 °C &56

PbSO4 + Na2CO3 = PbO + Na2SO4 + CO2 ∆G0 = - 1.4 kJ/mol
PbO2 + Fe = PbO + FeO ∆G0 = - 247.8 kJ/mol

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

C 1DW2 reducing agent C @>A/C;16 O )*+6/VC72 PbSO4 A#8ก#/1DW2กR CO (g) $ 56 CO2(g)

@';C/7$81ก:ก A/ก166>?6!6; O 66ก@ก PbSO4 145+67$89:81DW2 Pb

5
431307 Chemical Metallurgy Laboratory ก !"#$ก
%&ก 'ก()*+ 3/2551 !$)/#0/1)&"2"#/*3 2 *
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)

Some lead oxide is reduced by carbon or carbon monoxide , as shown

2 PbO + C → 2 Pb + CO2
PbO + CO (g) → Pb (l) + CO2
2 Pb (s) + O2(g) → 2 PbO (s)
PbO (s) + CO2(g) → PbCO3(s)
26ก@ก2*F/0;!*DEก /65+2 o 6*ก
2 FeS (s) + 3 O2 (g) → 2 FeO (s) + 2 SO2 (g)
3 FeS + 5 O2 → Fe3O4 + 3 SO2 (g)
2 FeS2 → 2 FeS + S2 (g)
S2(g) + 2 O2(g) → 2 SO2(g) , S8(s) + 8 O2(g) → 8 SO2(g)
S + O2 → SO2 , 2 SO2 + O2 → 2 SO3 , S + 2 SO3 + 3 SO2
Roast reaction processes
PbO + SO3 → PbSO4
PbS + 2 PbO → 3 Pb + SO2
PbS + PbSO4 → 2 Pb + 2 SO2
2 PbS (s) + 3 O2 (g) → 2 PbO (s) + 2 SO2 (g)
<G,
: 
1ก *+cd,,ก)O,:ก:
e0< :d) 3 ;P
1. "#$>?>ก0+$#6!1$#)*+1 */กC Lead bullion (1-3 wt% Sb)
2. 1!)$#6!1$# (Matte) 1DW2 D >ก6B6; Metal sulfide 1C2 FeS, Na2S, PbS, A#> Sb2S3
3. A#ก$#6!1$# (Slag) 6@@>1DW2 Metal oxide , Carbonate A#> Sulfate
26ก@ก2*F Gas phase กZ6/VC72 VD6;กR CO2, CO, O2 , S2 , SO2, SO3, A#> PbO (g) ก0B PbS (g) 6*ก@<22
1#Zก286/

6
431307 Chemical Metallurgy Laboratory ก !"#$ก
%&ก 'ก()*+ 3/2551 !$)/#0/1)&"2"#/*3 2 *

Slag (l)

Matte (l)

Lead (l)

23
 7. ก8G,< ก N;กfg0<  Slag, Matte N, Lead <G,
1ก *+N Pyrometallurgy

,-Nกh0ก ,)0ก *+cd,,ก)

1. ,-Nก
KJP
 2;P -N)= J
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)

7
431307 Chemical Metallurgy Laboratory ก !"#$ก
%&ก 'ก()*+ 3/2551 !$)/#0/1)&"2"#/*3 2 *
=8!*"#$>?>ก0+$#;1$#566/VC6*ก@<22$2'+;72 Slag $ 56 Matte 2*FA#82<16 Slag A#> Matte 9D=!)*+:2 =8$ก=Vก
2F<…2 $ 562F<7?8:2>#>#/"#$>?>ก0+กZ!*"6ก#>#/#;9DD21D†‡626/VCก0B2F<D>D $ 56A$#C;2F<7?8:29:8 @';
1 */ก >BBA#ก)*+!*C2D >ก6B6; soda ash C1DW2 >BBA#ก)*+9!CD#6:%0/?C6+;A:#86!

cd,cI:;J (Na) :
e0Z+dJjP IA (cd,N .K0/)

!B0?)*+<&0uB;D >ก 6;[?3$!VC IA &561DW2[?3)*+!*&!C6;9);1&!*V;!ก 1C2
- [?3$!VC IA )<DEก /ก0BกR66กR1@2726ก9:81 Z 9:81DW2 D >ก6B66ก9R:L
2 Na (s) + O2 (g) → Na2O2 (s)
- [?3$!VC IA )<DEก /ก0B2F< 32A ; A#>&/4#0;;2 1ก: #>#/1B A#>กR9r": 1@2 :0;2*F
2 Na (s) + 2 H2O (l) → 2 Na+ (aq) + 2 OH- (aq) + H2 (g)
- [?372$!VC IA !*&!C6;972ก 1ก:DEก /ก0B2F<!กกC[?3$!VC IIA A#>$!VC IIIA ?!#<:0B
[?3$!VC IA #>#/2F<9:8:* 1C2 2Na + 2H2O → 2NaOH + H2

!B0?)*+<&0uB;D >ก 6; D >ก6B6;[?3$!VC IA 1C2 1DW2 D >ก6B96662ก !*@3:$#6!1$#

A#>@3:1:56:V; 1C2 Na2+CO32- (mp 854 °C)
-  D >ก6B66ก9R:L6;[?3$!VC IA #>#/2F<@>1ก:DEก /ก0B2F< 9:8 #>#/1B
1C2 Na2O (s) + H2O (l) → 2 Na+ (aq) + 2 OH- (aq)
-  D >ก6B66ก9R:L 9r: 6ก9R:L R0#9K:L A#>9r9: L 6;[?3$!VC IA 1C2 Na2O, NaOH, Na2S, A#> NaH
ˆ#ˆ 1!5+6#>#/2F< #>#/)*+9:8!*!B0?1DW21B C2 D >ก6B&#69 :L!*!B0?1DW2ก#;

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
431307 Chemical Metallurgy Laboratory ก !"#$ก
%&ก 'ก()*+ 3/2551 !$)/#0/1)&"2"#/*3 2 *
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

Production of sodium sulfide

Na2SO4 + 2 C → Na2S + 2 CO2
Na2SO4 + CH4 → Na2S + CO2+ 2 H2O

Production of sodium silicate (water glass)

2 Na2SO4 + 2 SiO2+ C → 2 Na2SiO3 + 2 SO2 + CO2
SO2 + Na2SO4 + H2O → 2 NaHSO3

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
431307 Chemical Metallurgy Laboratory ก !"#$ก
%&ก 'ก()*+ 3/2551 !$)/#0/1)&"2"#/*3 2 *

23
 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. ,-Nก

 2;P -N)= J
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
431307 Chemical Metallurgy Laboratory ก !"#$ก
%&ก 'ก()*+ 3/2551 !$)/#0/1)&"2"#/*3 2 *

23
 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
431307 Chemical Metallurgy Laboratory ก !"#$ก
%&ก 'ก()*+ 3/2551 !$)/#0/1)&"2"#/*3 2 *

23
 15. CaO-FeO-SiO2 equilibrium phase diagram showing the extent of the completely liquid region
at 1150 °C , 1200 °C N, 1250 °C

Z+dJjP IIA (cd,N .K0/: /

) :fP0 Z+N.I;J (Calcium) Ca
-J
-1.H
,ก < Z+dJjP IIA &56 @3:1:56:A#>@3:$#6!1$# V;กC[?3$!VC IA 72&B1:*/ก02
14 >[?3$!VC IIA !*&!A ;6;402[>"#$>!กกC
!B0?);1&!*6;[?3$!VC IIA )*+<&0uB;D >ก 1C2
- [?3$!VC IIA )<DEก /ก0B66กR1@21ก:66ก9R:L 1C2 Ca (s) + O2 (g) → 2 CaO (s)
- [?3$!VC IIA (/ก182 Be) )<DEก /ก0B2F< 8กC[?3$!VC IA A#>DEก / 32A ;286/กC 1ก: #>#/
1B A#>กR9r": 1@2 :0;2*F Ca (s) + 2 H2O (l) → Ca2+ (aq) + 2 OH-(aq) + H2 (g)

-J
-1.H
,ก < -
,ก < Z+dJjP IIA
- 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$8กR CO2 1C2
CaCO3 (s) → CaO (s) + CO2 (g)
- 66ก9R:L6;[?3$!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
431307 Chemical Metallurgy Laboratory ก !"#$ก
%&ก 'ก()*+ 3/2551 !$)/#0/1)&"2"#/*3 2 *
- ก #>#/2F<6; D >ก6B6;[?3$!VC IIA  D >ก6B921? ?A#> D >ก6B&#69 :L6;[?3$!VC IIA
#>#/2F<9:8:* C2 D >ก6B& LB612? (CO32-) 9r": 1@2K61K? (HPO42-) R0#1K? (SO42-) "& 1!? (CrO42-)
A#>9r: 6ก9R:L (OH-) #>#/2F<9:8286/$ 56=56C9!C#>#/ /ก182 MgSO4 #>#/2F<9:8:*

-
,ก  -23ก ,;K=< -

(cJ / 0g1 100 g)
CaCrO4 870 x 10 - 4
CaSO4 11 x 10 - 4
CaCO3 0.13 x 10 - 4
Ca(OH)2 16 x 10 - 4
Ca(NO3)2 7.7 x 10 - 1

Lime and limestone

The solubility of calcite in distilled water free of carbon dioxide has been reported as ca. 15 mg/L
at 20 °C
The solubility in distilled water in equilibrium with atmospheric carbon dioxide is approximately double the
above value.
Flue Gas Desulfurization. A growing use of limestone is in the treatment of flue gas to remove
sulfur dioxide. The limestone is finely ground to 90 % less than 45 micrometer and reacted with flue gases
in a scrubber . The resulting calcium sulfate may be converted to salable gypsum, in which case the
MgCO3 content should not exceed 1 % . (From: Industrial Inorganic Chemistry and Products, Volume 4.
p 2854 and 2858 )

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

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CaSO4 + 2 C → CaS + 2 CO2

CaS + 3 CaSO4 → 4 CaO + 4 SO2
4 CaSO4 + 2 C → 4CaO + 4 SO2 + 2 CO2
2.s0)ก

23
 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).

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23
 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)

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Wt% FeS →
23
 19. Phase diagram for Na2S b FeS system

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23
 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 )

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1 / T x 104
23
 22. Vapor pressures of Sb, As, Pb and their oxidic and sulfidic compounds.
Standard free energy btemperature diagrams : Application to metal extraction

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23
 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

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23
 24. ∆G0 b T diagram for sulphide formation.

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23
 25. ∆G0 b T diagram for oxide formation.

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38< ,ก)
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125+6;@ก?>ก0+!*#0ก(X>&#8/ก0B Ca2+ 1!5+618VC C;ก/@';!0ก@> !6/VCก0B Ca2+ =8 C;ก/!*ก )< Ca2+
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ก 1ก:" &"#$?@;125+6;@ก?>ก0+@>0:;ก  8; hemoglobin 6;1!Z:1#56:A:; R'+;D >ก6B:8/
globulin A#> heme ?>ก0+@>1ก*+/86;ก0Bก  8; hemoglobin 72 2 >/>&56 >/>)*+ 1 0:;ก )<;26;
ALA ()*+@>)<7$81ก: prophyrin R'+;@> !ก0B1$#Zก1ก:1DW2 heme) >/>)*+ 2 &560:;ก !?06; heme A#>
globulin )<7$81ก:1DW2 gemoglobin :0;A:;72 VD)*+

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 26. N-ก <<)ก - = hemoglobin :0x Oก,ก)
(^.: .ก3#/ "6?ก>, CH 485 1&!*+;A:#86! , <20ก4!4L!$)/#0/ !&<A$;, 4!4L& 0F;)*+ 2 2541, $28
203)
>:0B&!1DW24(6;?>ก0+&56 72^V87$uC!*&C 80 9!"& ก 0!?C61#56: 100 cm3 721:Zก!*&C 40 9!"& ก 0!
?C61#56: 100 cm3 6ก )*+1ก:@ก4(6;?>ก0+&56)<7$81629R!L)*+1 C;ก  8;1!Z:1#56:A:;!*D >)[%4#:#; @';
!*^#)<7$8ก  8;1!Z:1#56:A:;#:#; ก 2<66กR1@29D/0;C2?C; o 6; C;ก/721!Z:1#56:A:;@';#:#;:8/
1!5+6#:#;@2='; >:0B$2'+;@>1DW2602? /=';*? 26ก@ก20F2?>ก0+/0;! =)<#/1R#L!6;$#/2: )<7$8
1821#56:72!6;15+6! @';1DW21$?37$8D:* (>6/C; 32A ; =81DW2!ก o @>)<7$8?B6:1DW260!4?A#>=';?/72
)*+3: A#>/0;!*602? /?C6ก 1@ u1?B"?6;) ก72& %L6*ก:8/ 26ก@ก20F2/0;1DW24(ก0B45 &56 9D)<#/
ก >B2ก 1!?B6#R'!?C; o 6;45

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(G. Gottstein , physical Foundations of materials science, Springer, 2004, p 114)

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