Aluminum Recycling and Processing for Energy Conservation and Sustainability John A.S.

Green, editor, p 245-249 DOI: 10.1361/arpe2007p245

Copyright 2007 ASM International All rights reserved. www.asminternational.org

APPENDIX F

Theoretical Energy Data and Calculations

THE THEORETICAL MINIMUM energy requirement for producing any chemical is determined based on the net chemical reaction used to produce the product. It is dened as the energy required to synthesize a substance in its standard state from substances also in their standard states. It can be calculated by summing the reaction energies of the products minus the energies of the reactants. This report calculates the theoretical minimum energy by assuming the reactants enter and the by-products leave the system at room temperature and that molten aluminum leaves the system at 960C (1760 F). This report has chosen 960C (1233 K) as the molten metal temperature. This value is an approximation of the average operating cell temperatures of industrial cells. Some studies assume that the gases evolved during reduction leave the system at the molten metal temperature. In these studies, the theoretical minimum is 2.5 to 3% higher than the numbers calculated here. The additional energy for heating of the emissions is shown in the individual tables. Theoretically, it is possible to capture all the energy associated with these gaseous emissions. However, there is currently no available economic means of recovering this energy. In practice, the emission gas stream is diluted with air in the cells to lower the temperature that the cell hoods and ducts are exposed to. The emission gas is collected from hundreds of hooded pots and treated before release to the atmosphere. Only a very small portion of the heat is actually absorbed and returned to the system. The minimum theoretical energy requirement for aluminum production requires the evaluation of three energy factors: the energy required to drive the reduction reaction forward, the energy required to maintain the system at constant pressure and temperature, and the energy required to change the temperature of the reactant and/or product. The thermodynamics and chemical equilibrium of reactions are described by the equation G = HTS, and the numeric values are given in Table F.6. The energy required to drive the reaction forward is the Gibbs free energy value (G). The energy required to maintain system equilibrium is the difference between the heat of reaction (H) and the Gibbs free energy value (G), which equals the entropy term (TS). Because the Gibbs free energy requirement is less than the heat of reaction for alumina reduction, additional energy must be added to the system to maintain the system temperature. Otherwise, the system would cool as the reaction proceeds. (Reduction cells operate at atmospheric conditions, and no pressure change results during reduction.) The numeric values for G, H, and S are given in Table F.6. A detailed discussion of the theoretical requirements is made in Current and Energy Efciency of Hall-Hroult CellsPast, Present and Future, by Warren Haupin and William Frank, published in Light Metal Age, June 2002.

246 / Aluminum Recycling and Processing for Energy Conservation and Sustainability

Table F.1
Reactants temp.

Theoretical minimum energy for Hall-Heroult carbon anode system

Products temp. Reaction thermodynamics at 298 K (Productsreactants) cal/g mole Al

(2 Al2O3 + 3 C) to (4 Al + 3 CO2) = Net 2 Al2O3 25 C Carbon 3C 25 C anode cell 3CO2 25 C 4 Al 960 C G H S 756,358 801,000 24.3 0 0 4.1 0 0 27.1 282,779 282,155 153.2 118,395 129,711 11,311 kWh/kg 5.11 0.49 0.39 5.99 0.17

Process theoretical minimum energy requirements Electrolytic work requirement (G) Thermal energy for temperature maintenance (HG) Thermal energy for Al at 960 C Theoretical minimum Thermal energy for CO2 at 960 C

Note: Thermodynamic values for G, H, and S are from Table F.6. Heat capacity data are from Table F.9 and Appendix G.

Table F.2
Reactants temp.

Theoretical minimum energy for Hall-Heroult inert anode system

Products temp. Reaction thermodynamics at 298 K (productsreactants) cal/g mole Al

2 Al 960 C Inert Al2O3 25 C

G H S

(Al2O3) to (2 Al + 1.5 O2) = Net 378,179 0 400,500 0 12 14

0 0 74

189,089 200,250 11,155 kWh/kg

Process theoretical minimum energy requirements anode cell 1.5O2 25 C Electrolytic work requirement (G) 8.16 Thermal energy for temperature maintenance (H G) Thermal energy for Al at 960 C Theoretical minimum Thermal energy for O2 at 960 C

0.48 0.39 9.03 0.27

Note: Thermodynamic values for G, H, and S are from Table F.6. Heat capacity data are from Table F.9 and Appendix G.

Table F.3
Reactants temp.

Theoretical minimum energy for carbothermic reduction

Products temp. Reaction thermodynamics at 298 K (Productsreactants) cal/g mole Al

Al2O3 25 C Carbothermic reactor 3C 25 C

2 Al 960 C

(Al2O3 + 3 C) to (2 Al + 3 CO) = Net G 378,179 0 H 400,500 0 S 12.2 4.1

0 0 13.5

98,424 79,247 141.9

139,878 160,626 21,347 kWh/kg 6.03 0.90 0.39 7.32 0.19

Process theoretical minimum energy requirements Work requirement (G) 3CO Thermal energy for temperature maintenance (HG) 25 C Thermal energy for Al at 960C Theoretical minimum Thermal energy for CO at 960C

Note: Thermodynamic values for G, H, and S are from Table F.6. Heat capacity data are from Table F.9 and Appendix G.

Appendix F: Theoretical Energy Data and Calculations / 247

Table F.4
Reactants temp.

Theoretical minimum energy for reduction of aluminum chloride

Products temp. Reaction thermodynamics at 298 K (productsreactants) cal/g mole Al

Inert 2 AlCl3 25 C anode cell

2 Al 960 C

(2 AlCl3) to (2 Al + 3 Cl2)= Net G 300,574 H 336,616 S 48.1

0 0 13.5

0 0 159.9

150,287 168,308 18,664 kWh/kg 6.48 0.78 0.39 7.65 0.19

Process theoretical minimum energy requirements Electrolytic work requirement (G) Thermal energy for temperature maintenance (H G) Thermal energy for Al at 960 C Theoretical minimum Thermal energy for Cl2 at 960 C

3Cl2 25 C

Note: Thermodynamic values for G, H, and S are from Table F.6. Heat capacity data are from Table F.9 and Appendix G.

Table F.5
Reactants temp.

Theoretical minimum energy for kaolinite/aluminum chloride reduction

Products temp. Net aluminum reaction Carbochlorination (960 C) (Productsreactants) cal/g mole Al

(3 Al2O3.2SiO2 + 14 C + 21 Cl2) to (6 AlCl3 + 6 SiCl4 + 7 CO + 7 CO2) = Net G H S 2,374,053 2,531,520 0 0 19 0 0 1119 901,721 1,009,847 144 884,799 942,161 474 229,655 184,910 331 659,819 658,363 357 50,323 43,960

14 Al 7Al2O3.2SiO2 25 C Kaolinite 960 C to aluminium 14SiO2 chloride 25 C

Chloride reduction (700 C) (2 AlCl3) to (2 Al + 3 Cl2) = Net G H S 300,574 336,616 48 0 0 14 0 0 160 150,287 168,308 18,664 kWh/kg 1.90 6.48 0.78 0.39 5.76 0.11 0.25

Process theoretical minimum energy requirements to reduction system 14 C 25 C 7CO 25 C 7CO2 25 C Thermal work for AlCl3 production Electrolytic work requirement (G) Thermal energy for temperature maintenance (HG Thermal energy for Al at 960 C Theoretical minimum Thermal energy for CO2 at 960 C Thermal energy for CO at 960 C

Note: Thermodynamic values for G, H, and S are from Table F.6. Heat capacity data are from Table F.9 and Appendix G.

Table F.6 Thermochemistry data for elements and compounds associated with aluminum production
Chemical formula J/mol cal/mol J/mol cal/mol J/mol K cal/mol K J/mol K cal/mol K H(s) G(s) S(s) Cp (s)

Chemical Abstracts Service Registration No. (CAS RN)

Molecular weight

Aluminum Aluminum chloride Corundum Gibbsite(a) Kaolinite(a) Kaolinite, meta Graphite Chlorine Carbon monoxide Carbon dioxide Oxygen Water Silica dioxide Silicon tetrachloride 21.6

7429-90-5 7446-70-0 1334-28-1 ... 1332-58-7 ... 7440-44-0 ... 630-08-0 124-38-9 7782-44-7 ... 14808-60-7 10026-04-7

26.98 133.34 101.96 155.96 ... 162.04 12.01 70.91 28.01 44.01 32.00 18.00 60.08 169.90

Al 0 704,200 AlCl3 1,675,700 Al2O3 1,293,100 Al2O3.3H2O . . Al2O3 SiO2 2H2O 4,119,000 . ... Al2O3 SiO2 C 0 0 Cl2 (g) CO (g) 110,523 393,513 CO2 (g) 0 O2 (g) 241,826 H2O (g) 910,700 SiO2 657,000 SiCl4 (g)

0 168,308 400,500 309,058 984,465 843,840 0 0 26,416 94,052 0 57,798 217,663 157,027

0 628,800 1,582,300 1,154,900 3,793,900 ... 0 0 137,268 394,383 0 228,582 ... 617,000

0 150,287 378,179 276,028 906,764 791,351 0 0 32,808 94,260 0 54,632 220,615 147,467

28.3 100.7 50.9 ... ... ... 5.7 222.9 197.9 213.6 205.0 188.8 41.46 330.70

6.764 24.061 12.165 ... ... ... 1.361 53.286 47.301 51.061 49.003 45.132 9.909 79.039

24.35 91.84 79 ... ... ... ... ... ... ... ... 33.598 ... 90.3

5.82 21.95 18.88 ... ... ... ... ... ... ... ... ...

Source: D.R. Lide, Ed., Handbook of Chemistry and Physics, 80th ed., CRC. (a) Source: S. K. Saxena, Ed., Advances in Physical Geochemistry, data courtesy of Mr. B. Hemingway at U.S.G.S.

Table F.7
Al2O3(a) C(a) Heats of formation in calories per gram mole Al(a) CO2(a) CO(a)

Changes in heat of formation values as a function of temperature

O2

Temperature

248 / Aluminum Recycling and Processing for Energy Conservation and Sustainability

25 727 827 927 960 1027 1127

298 1000 1100 1200 1233 1300 1400

400,300 404,400 404,000 403,600 403,500 403,200 402,800

0 2310 3320 3850 4030 4390 4930

0 18,710 21,710 24,740 25,750 27,790 30,850

94,050 94,400 94,250 94,300 94,300 94,300 94,300

26,400 26,750 26,900 27,000 27,100 27,300 27,350

0 9249 10,515 11,843 12,295 13,233 14,685

(a) Source: Values from Technical Working Group on Inert Anode Technologies, Appendix A.9, p 11

Appendix F: Theoretical Energy Data and Calculations / 249

Table F.8
Reactants temp.

Theoretical minimum energy for gibbsite dehydration

Products temp.

Gibbsite dehydration reaction (Al2O3.3H2O) to (Al2O3 + 3H2O) = Net

(Productsreactants) cal/g mole Al2O3

Al2O3 Al2O3.3H2O 25 C 3 H2O 25 C 25 C Kiln

618,117

400,500

173,393

44,223

Process theoretical minimum energy requirements kWh/kg alumina 0.50

Note: Thermodynamic values for G, H, and S are from Table F.6. Heat capacity data are from Table F.9 and Appendix G.

Table F.9 Heat of capacity equations for gases associated with aluminium production
Standard molar heat capacity, C=a + bT + cT2

cal/mol K O2 CO CO2 Cl2

a 6.148 6.420 6.214 7.576

b103 3.102 1.665 10.396 2.424

c107 9.23 1.96 35.45 0.65

Source: W.F. L udar, A Different Approach to Thermodynamics, 1967 T in degrees K

Table F.10
Reactants temp.

Theoretical minimum energy for kaolinite dehydration

Products temp. Reaction (productsreactants)

Al2O3.2SiO2 25 Al2Si2O5 (OH)4 25 Kiln

Al2Si2O5 (OH)4 G H 906,764 984,465 S

to (Al2O3.2SiO2 + 2 H2O) = Net 791,351 843,840

cal/g mole Al2O3.2SiO2

115,596

25,029 kWh/kg 0.18

2 H2O 25

Theoretical minimum