Materials Production. T. G. Gutowski. with significant contributions by A. Thiriez 2.83/

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1 Materials Production T. G. Gutowski with significant contributions by A. Thiriez 2.83/

2 Reading a) Masini and Ayres, An Application of Exergy Accounting to Five Basic Metal Industries, 2001 (click here for PDF).

3 Materials Production Mining Primary Mfg Distribution Use Disposition m& m& 0 8 m& m& 0 8 m& m& 0 8 m& m& 0 8 m& m& 0 8 m& m& 0 8 m& pi k m& po k m& pi k m& po k m& pi k m& po k m& pi k m& po k m& pi k m& po k m& pi k m& po k Recycle, Remanufacture, Reuse

4 Mat l Production and Mfg Carbon Dioxide and Toxic Materials per Value of Shipments CO2 (metric ton/$10,000) Toxic Mat'ls (lb/$1000) Chemicals Petroleum and Coal Plastics and Rubber Primary Metal Fabricated Metal Machinery Electronic Transportation Manufacturing industries Weight/Dollars

5 Outline 1. Extraction, Mining 2. Refining, Smelting 3. Mass and Exergy for US industry Copper, Iron, Aluminum, Zinc, Polymers

6 Crustal Abundance

7 Reserves Vs Crustal Abundance Chapman

8 McKelvey Box Increased Economic Feasibility KNOWN Reserves marginally economical Resource Base UNKNOWN Undiscovered Decreasing Geologic Assurance of Existence Adapted from C. F. Murphy, and McKelvey, 1972

9 Known Resources of Uranium Chapman

10 Definitions Reserves- the amount of a commodity that has been located and which can be economically extracted with current technology and prices Resources- reserves plus an estimate of the amount the commodity that is as yet undiscovered but would be profitable to extract plus an estimate of located deposits that are expected to be profitable in the near future due to emerging technologies (cost reductions) or moderate price increases Resource Base- all of a commodity contained in the earth s crust C. F. Murphy

11 Probability of Discovery Function of size of target area and number of attempts to locate a field Early in discovery process, low number of hits Late in discovery process, low probability of undetected field C. F. Murphy

12 Chapman

13 Open-Pit Copper Mine, Utah Source:

14 Copper Ore Grades in the US

15 Chuquicamata, Chile

16 drilling rig in underground mine in the Głogow area of Poland Copper concentrations in this area are about 2%

17 energy requirements for mining and milling, possible future trends underground ~ 1000/g (MJ/t metal) open pit ~ 400/g (MJ/t metal) Chapman and Roberts p 113 & 116

18 Sherwood Plot Chapman & Roberts 1983 Grubler 1998

19 Main Ore Types for Copper globally 90% sulfides, 10% oxides Cu 2 S: Chalcocite Cu 2 0: Cuprite CuFeS 2 : Chalcopyrite (50% of Copper Production) Cu 2 CO 3 (OH) 2 : Malachite Sources:

20 Acid mine drainage 4FeS O 2 +14H 2 O 4Fe(OH) 3 + 8H 2 SO 4

21 Outline 1. Extraction, Mining 2. Refining, Smelting 3. Mass and Exergy for US industry Copper, Iron, Aluminum, Zinc, Polymers

22 Głogow* Copper Smelter *pronounced Gwogov

Copper Smelting Process Source: http://encarta.msn.

23 Copper Smelting Process Source:

24 Copper Smelting Process 1) Copper Ore (~ 1%) Concentrate (~20 to 35%) milling, flotation, separation 2) Roasting and Smelting CuFeS 2 Cu 2 S (matte) 2FeOSiO 2 (slag) % Cu Cu (blister) ~98% Cu

25 Copper Smelting Process 3) Roasting and Smelting 2FeS+3O 2! 2FeO+2SO 2 xfeo + ysio 2!(FeO) x (Si0 2 ) y - slag 2Cu 2 S + 3O 2! 2Cu 2 O + 2SO 2 Cu 2 S + 2Cu 2 O! 6Cu + SO 2 (blister copper ~98%) 4) Electrolytic Refining (99.99%) sulfuric acid electrolyte anode mud (1:100) contains (Cu, Ag, As, Se, Bi,..Au, Te )

26 Source:

electro-refining of copper Cu Ag Au Se Te As Sb Bi Fe Ni 20 5 0.

27 electro-refining of copper Cu Ag Au Se Te As Sb Bi Fe Ni Anode slime analysis (%) see Greadel et al (2002)

28 The Metal Wheel

29 Outline 1. Extraction, Mining 2. Refining, Smelting 3. Mass and Exergy for US industry Copper, Iron, Aluminum, Zinc, Polymers

30 Copper Mass Flows (US)

31 Copper Exergy (US)

32 Copper Summary (US)

33 Tailings pond at Głogow, Poland

34 .02X.9 to smelt,.02x.1 to tailings these tailings will be mined in the future

35 Summary from Masini & Ayres Exergy Analysis for U.S. Industries Metal B o (MJ/kg) B in (MJ/kg) B o / B in Ore grade (percent) Steel 6.7(Fe) % Ore 53% + scrap 93% Aluminum % 26% Alu (bauxite) Copper % 0.6% Zinc % 9%

36 & B Q R*, TR* H& S& fuel + air 1 fuel+ air 1 Energy Conversion for Manufacturing (B) & fuel air H + 0* S& fuel + air 0* & C Q R*, TR* B W & S A W & S materials H& 1 materials S& 1 Materials Processing (C) & materials H 2 materials S& 2 Manufacturing Process (A) product H& 3 product S& 3 H& S& fuel 1 + air fuel+ air 1 D W & S C W & S Energy Conversion for Materials Processing (D) & fuel air H + 0* S& fuel + air 0* & A Q R*, TR* & D Q R*, TR*

37 the fuel requirements of smelting

38 possible future trends in energy use trends reflect lower ore grades

39 bio-toxicity of copper Copper in drinking water (USEPA, WHO) Copper in fresh water ( 5 pbb) bioavailability and the biotic ligand model BLM gastrointestinal effects (NOAEL 2mg/L) Wilson s disease and 5% of population aggressive water

40 Check out these websites for copper mining and smelting

41 Iron: Important oxide ores Hematite: Fe 2 O 3 Magnetite: Fe 3 O 4 Taconite Sources: &

42 Taco night (not to be confused with Taconite) This slide brought to you by Tacoo Bell

Iron Blast Furnace Materials required: 1. Iron Ore 2. Carbon (coke is used both as fuel and reducing agent). 3. Hot air (hot enough to ensure combustion of the fuel). 4.

43 Iron Blast Furnace Materials required: 1. Iron Ore 2. Carbon (coke is used both as fuel and reducing agent). 3. Hot air (hot enough to ensure combustion of the fuel). 4. Flux (removes earthy matter turns into slag) 5. Slag (combination of calcium carbonate, silica, alumina and other impurities). Source:

44 Reactions taking place in the furnace: 2 C + O 2! 2 CO (1300 C) CaO + SiO 2! CaSiO 3 (1200 C) FeO + CO! Fe + CO 2 (800 C C) CaCO 3! CaO + CO 2 (800 C C) CO 2 + C! 2 CO (800 C) Fe 3 O 4 + CO! 3 FeO + CO 2 (600 C) 3 Fe 2 O 3 + CO! 2 Fe 3 O 4 + CO 2 (450 C)

Blast Furnace Source: http://www.ssabox.

45 Blast Furnace Source:

46 Steel Exergy (US)

47 Steel Summary (US)

2 0 Cryolite: Na 3 AlF 6 + many silicates such as clay: H 2 Al 2 (SiO 4 ) 2 H

48 Aluminum It is the most abundant metal (7% of the earth s crust) but one of the most difficult metals to refine Aluminum occurance: Bauxite : Al 2 O 3 2H 2 0 Cryolite: Na 3 AlF 6 + many silicates such as clay: H 2 Al 2 (SiO 4 ) 2 H 2 0 Sources: &

49 Aluminum Production: 1. Bayer Process: obtain Alumina (Al 2 O 3 ) from Bauxite. A. Extraction: dissolve oxides with hot solution of NaOH. Al(OH) 3 + Na + + OH - -! Al(OH) 4 + Na + B. Precipitation: reverse of above, but controlling crystal formation. Al(OH) Na +! Al(OH) 3 + Na + + OH - C. Calcination: water is driven off Al(OH) 3 to form alumina (aluminum oxide). Al(OH) 3 ---> Al 2 O H 2 O Source:

50 2. Hall-Heroult Process (Electrolytic Reaction). Prebake Anode A. Al 2 O 3 is dissolved in molten cryolite (Na 3 AlF 6 ) B. As the current passes through this mixture, (4-5 volts, 50, ,000 amperes) aluminum ions reduce to molten aluminum at the cathode, and oxygen is produce at the anode reacting with carbon to produce CO 2. 2 Al 2 O C! 4 Al + 3 CO 2 Prebake Cell Source:

51 Aluminum Exergy (US)

52 Aluminum Summary (US)

53 Zinc Main Ore Types: Smithsonite: ZnCO 3 Sphalerite: (Zn, Fe)S Hemimorphite: Zn 4 Si 2 O 7 (OH)2 H 2 O Franklinite: (Fe,Mn,Zn)(Fe,Mn) 2 O 4 Sources: &

54 Zinc Production 1. Concentrating Zinc 3-11% as by- product of other metal flotation to 52-60% 2. Roasting reduce/distillation Sulfide to oxide (ZnO) leaching and electrowinning

55 Zinc Production Roasting reactions 2 ZnS + 3 O 2! 2 ZnO + 2 SO 2 ZnS + 2 O 2! 2 ZnSO 4 One can either obtain a mixture of ZnO and ZnSO 4 (for the leaching process) or ZnO (for the distillation process). The product of the above reactions is imbedded in mixtures with other impurities. Leaching & Distillation.

Leaching: I. ZnO and ZnSO 4 are leached with dilute H 2 SO 4 to produce a zinc sulfide solution. ZnO+ + H 2 SO 4! ZnSO 4 + H 2 O II. The solution is purified to precipitate any metal impurities. III.

56 Leaching: I. ZnO and ZnSO 4 are leached with dilute H 2 SO 4 to produce a zinc sulfide solution. ZnO+ + H 2 SO 4! ZnSO 4 + H 2 O II. The solution is purified to precipitate any metal impurities. III. An electrolytic cell is used to deposit the Zinc and sulfuric acid is produced as a by- product (can be used in step I.) The Electrolytic Plant, which is the size of four football fields, consumes the same amount of power as a city of 250,000 people. Source: altour/processes/zinclead/electrolytic.asp

57 Zinc Distillation Furnaces Old School Batch Retort Process (Distillation): I. ZnO in the calcine mixture is mixed with anthracite coal and place in a fire- clay retort. II. It is heated to 1250 C. III. Zinc vapor distills into an attached condenser. Source:

61 Polymer Production

62 energy requirements for materials production (per cm 3 )

63 Materials Production, Homework 1. Estimate the efficiency for the Roasting and Smelting of copper sulfide ore in US Industry. 2. Estimate the efficiency for the final refining step for copper in US Industry. 3. Estimate the energy required to process recycled copper if you can skip the roasting and smelting process. 4. Using the CMU I/O model compare primary and secondary production of 1) aluminum and 2) copper in terms of energy use per dollar of output. Can you also do energy use per kg of output? How do these results compare with Masini and Ayres? 5. Please do an exergy analysis for 2Cu 2 S + 3O 2! 2Cu 2 O + 2SO 2 (An important reaction in copper smelting) Determine B in, B out and B lost How much energy is needed to drive this reaction?

Materials Production. T. G. Gutowski & A. Thiriez 2.83/ March 2, 2006

Materials Production. T. G. Gutowski & A. Thiriez 2.83/ March 2, 2006 Materials Production T. G. Gutowski & A. Thiriez 2.83/2.813 March 2, 2006 Readings #6 3/2 Materials Production a) Masini and Ayres, An Application of Exergy Accounting to Five Basic Metal Industries, 2001