401_2007_fuels metals energy

7/29/2019 401_2007_Fuels Metals Energy

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Electricity Consumption and Politics

As shown in the issue of The economist


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Innovation - A Multiplayer Game


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Semiconductor Silicon: The Mount Everest of Purification

Crude Si + HCl -> HSiCl3

Distillation removes many metals as non-volatile chlorides

BCl3, PCl3 AsCl3 are volatile => incomplete removal

Chemical Vapor Deposition of Silanes to gives Si, furtherreduces impurity level.

Czochralski crystal pulling

Zone refining further reduces impurity level

Ingots are cut into wafers backside is scratched,scratches act as getters for impurities.

Si is taylor made for customer: more then 500 different flavors

Demand for Solar Silicon has surpassed demand of computer silicon (CPUs RAM) in 2006 !

Silicon The Mount Everest of Purification


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Annual growth: 25-30 %

$ 7 Billion (2004) up from 4.7 Billion (2003)

2010: Sales $ 40 Billion, Profit $ 3 Billion (without China & India)

Demand for Solar Cells outstrips supply (!)

Bottleneck: Supply of pure Si

Demand for Solar Silicon surpassed electronic Si in 2005

Installation (2004) Germany 300 MW (40 000 jobs)

Japan 280 MW US 90 MW ()

Largest Players: 1. Sharp (Japan)2. BP (UK)3. Solarworld (Germany)4. Q-Cells (Germany

Solar Energy - Some Hard Facts


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Solar Energy - Some Hard Facts

Annual growth: 25-30 % $ 4.7 Billion (2003) $ 7 Billion (2004) Expected 2010: $ 40 Billion Demand for S.Cells outstrips supply (!) Bottleneck: Supply of pure Si

Demand for Solar Si surpassed electronic Si in 2005

Installation (2004) Germany 300 MW Japan 280 MW US 90 MW

Largest Players: 1. Sharp (Japan)2. BP (UK)3. Solarworld (Germany)4. Q-Cells (Germany


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Solar energies daily profile matches demand (!)

Rating of solar installations in kWp (kilpo Watt peak)

mono- or polycrystalline silicon are dominant materials

SC produce direct current

Solar cell silicon easy to recycle

3 years operation to recover prouction energy

Production costs down 8 % every year (past 20y)

Breakeven with current el price predicted for 2015

Solar Energy - Some Facts


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Solar Energy - What the Market Thinks


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World Solar Energy: $4.7 Bn (2003)

US Solar Energy: 40% global market (1997)

13% global market (2003)

Alternative Energies: >$100 Bn (2006)

Solar Energy - The Price of Bad Politics


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Solar electricity currently more expensive than fossil electricity

Breakeven: 2011 (Germany) even earlier in California, Spain (China, India)California, 12 pm: $ 0.8 conventional - $ 0.4 solar

Will depend on political decisions (no incentive = baseline)

Solar Energy - Cost Analysis 2004 to 2050


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Terminal 2 Munich 450 MWh = 400 t CO2 / year

The CO2 Gain


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Silicon

Ferrosilicon (8 - 97 % Si, rest iron),

- Deoxygenation of steel- Acid-resistant material in chemical reactors (cheaper than Ti)

Metallurgical Grade (MG) Silicon, 98.5 -99.7 %

- 30 % used to alloy aluminum

Electronic Silicon

SiO2(g) + 2C(s) + 2Cl2(g) SiCl4(g) + 2CO(s)

SiCl4(distilled) + 2Mg(pure) Si(s) + 2MgCl2

SiO2 (quartz, silica), aluminosilicates (feldspar, etc.)

Energy (lots of it)

10 Mio t

1 Mio t

Fiber optics, ultrapure SiO2 (hydrolysis of SiCl4), GeO2, P4O10

Silicones

40103

t

2 $/kg

2000 $/kg

(wafers)

Energy = 1/3

SiO2 + C

2000 oC

Si + CO


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Silicones (Organopolysiloxanes) Hydrolysis & polycondensation of organochlorosilanes

RnSiCl

4-n

leads to unique organic-inorganic hybrid polymer

Rochow Process

Inclusion of RSiCl3 will Inclusion of R3SiCl willlead to chain branching. cause chain termination.

Can be oils, waxes, elastomers (rubbers)

Thermal stable, resistant to oxidation,good electrical insulators, water repellent, biocompatible,low chemical reactivity => The worlds best special polymers

RCl(g) + Si(s)heat

Cu catalystRnSiCl4-n (n = 1-3)

nR2SiCl2 + nH2O Si O

R

R

Si O

R

R

Si O

R

R

+ 2nHCl

R

Si

R

O Si

R

R

RSi

O

OO

Si

SiSi


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Silicone oils change viscosity only slowly with temperature=> hydraulic fluids used in aircrafts

Silicone rubber elastic over wide temperature range, low Tg (-110oC)

=> O-rings on planes, space crafts etc.

=> soles used for moon boots (lunar night: -180oC; lunar day: +130oC)

NASA 1986 NASA 1969

Silicones: Applications


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Are Commodities becoming Expensive ?


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The Future of Commodities: 2050


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The Future of Commodities: 2050


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Mining Companies 2005


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Mining Companies 2006


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Metal Consumption: Car


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What Resources Matter to the Chemical Industry ?

Coal, Gas, Oil

Electricity (Hydro, nuclear or above)

Water (solvent, coolant)

Metals (Fe .. Rh)

Nonmetals (Chlorine, Bromine . Selenium)

Minerals (CaMgCO3, Phosphates, Potassium)

Human Resources

IP


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Iron (+ V, Cr, Mn, Co, Ni)

Base metals: Al, Cu, Zn, Pb, Ni

Precious Metals: Ag, Au, Pd, Pt,

Specialty Metals: Ca, Zr, Ti, Ga, In

Lanthanides, U

Metals


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Base Metal Prices (US $ / pound)April 2006

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Pb Al Zn Cu Ni U

U: Will go to $ 100-200


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Precious Metal Prices (US $ / ounce)

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Ag Ru Ir Os Pd Au Re Pt Rh

US $ / ounce


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Reduction of Ores

Oxide + Coke Fe, Zn, Variations:Sulfides -> Oxides -> MetalsCarbonates -> Oxides -> Metals

Chloride + Metal TiCl4/Mg = Kroll process 1956+

Fluoride + Mg Lanthanides, Zr & other specialty metals

Electrolysis: Al2O3, MgCl2, NaCl

Unique methods Au(CN)2- + Zn (cementation)


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Specialty Metals - Alloys - Ceramics

Found in any high tech device - Advanced Materials

First use usually in defense / aerospace after WWII

Early research crucial for Renaissance of Inorganic Chemistry

Excellent studies in dedicated journals:

1955: Inorg. Nucl. Chem.1959: J. Less Common Met. -> J. Alloys and Compounds1966: Inorg. Nucl. Chem. Lett.


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Aluminum: KF + ALF3 + Al2O3

Al3O3 - > Al + O2Energy Intensive (2/3 of price)

Na3AlF3 as solvent, Very corrosive

Carbon Electrodes -> CO, CO2 COF2

(600g /1 kg of Al)

Al2O3 from Bauxite (Fe,Al oxide)Purification of Bauxite with NaOH

Al is easy to recycle

Low weight = green(lowers transportation costs)


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Predicts reduction of oxides bycoke (C)

Flat: C + O2 -> CO2Rising: C + 0.5 O

2

-> CO

CO wins at high T

Intersection of C/CO line with MOxline predicts minimum T forreduction

Minimum T may be too high to beuseful

Not deductible from E.Diagram:Carbide formation (Early TM)

Ellingham Diagram(G vs. T)


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Iron & Steel


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Uranium

50 % from Canada, Australia

New Producers: Urasia Energy (Kazakhstan)Paladin Resources (Namibia)SXR Uranium (Canada)

If price hits o $ 200 => seawater extraction

1-2 % of Powerplant cost is Uranium

Cheapest mining option: in situ leaching (if geology collaborates).2005 world production


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In Situ Leaching of Uranium


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Uranium

Flooding of Camecos Cigar Lake Mine October 2006

Destroys 20 % of future world Uranium production

Uranium shortage becomes clear

Massive investments in other Uranium mines (e.g. Urasia Energy /Kazakhstan)


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Idaho, 1951: First reactor to produce electricity (200W = 4 lightbulbs)

Leading country (in % electricity): France, 80 %

Reactor types:a) Heavy water (D2O, CANDU, Can & India) - no U enrichmentb) 235U enriched reactors

c) Breeder reactors (Plutonium based, 2, Japan & France)d) Thorium reactors (experimental stage only)

Under construction or planned : 156 (all type b)

1 pound Uranium = 20,000 pounds of coal

Cost of mining Uranium 3-5 % of electricity cost Cost of enriching Uranium 20 % of electricity cost

Finnish study: Doubling of coal (gas) = 31 % (66 %) rise in el priceDoubling of U = 9 % rise in el. price

Nuclear Power Plants (I)


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Isotope Enrichment: 235Uranium - 2H (=D)

D2O (nat. ~ 1 % D) enriched in all electrolysis processes

Rarely done in dedicated plants (-> Norway 1943)

Distillation of water from el.-chemical plants (5 - 10 %)

Uranium: 238U >> 235U >> 233U

Enrichment of235U through- Gas diffusion- Gas centrifuge- Laser (Israel, see my CHEM 207 comments)

All three processes require UF6 (highly corrosive, low melting solid

Production: U3O8 (yellow cake) + HF -> UF4 ; UF4 + F2 -> UF6


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Nuclear Power Plants (II)

Future reactor designs:

Standardization (simplifies approval process, spare parts, training)Currently done only in France

Reprocessing of spent nuclear fuel unsolved problem

- Most complex industrial separation problem

- more than 100 radiocative elements and isotopes

- Biggest problems:Plutonium (t1/2 = 40,000 years)Volatiles (Xe, I2)

Massive volume increase (x 100 !)Gives highly corrosive & radioactive solutions (HNO3) The future according to MKD:

China & India will build whether we like it or notAlternative energies will take over before nuclear loop is closed,=> nuclear power is a stopgap measure (but an important one).


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Lanthanides: Abundant but tricky to separate

Ion exchange chromatography, stationary phase is sulfonated polystyrene

HO3S

SO3H


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Metals And Minerals: Zinc

Brass (Cu-Zn alloy) known in Assyria & Babylon, up to 1800

exclusively mined in India, current mines in China, Canada, Japan,Australia Korea

Common byproduct of Pb, Cu, Ag mining

50 % for galvanization (corrosion inhibition) 20 % for brass

Essential metal with no substitutes !

Demand > supply, new mines planned in Bolivia, China

Largest producer: Teck-Cominco (Canada)

World production 10.3 Mio tons (2004), up 6% from 2003

Price expected to rise due to lack of new mines &steeply rising demand from India/China


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The Mining Cycle: Example Zinc

Development of a mine takes on average 15 years or more

Long time frame leads to in oversupply - undersupply cycles

BRIC boom likely to translate into a long commodity boom for Fe, Zn, Ni, Cu


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Metals And Minerals: Copper

16.5 Mio t 2005. Largest Producer: Codelco Mine (Chile)

Producing countries US > CAN > Zaire, Sambia, Poland

Indispensable electrical conductor (only Ag, Au are better)

PhD of metals - demand prediction very complex, measure of world economy

No general agreement on price developmentPrice predicted to fall in 2007 but rise again 2009


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Copper as Indicator of Global Economic Growth

MKD: global economic growth is larger than prediction, around 5 % in 2007.See price development in next chart


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Copper Prices:

http://www.kitcometals.com/charts/copper_historical.html


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40 % of Chiles exports, 9 % of GDP

20 % of Chiles copper from Escondida mine (10,000 jobs)

Chile: A Copper Super Power


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Electrolytic refining necessary for electric applications

PGM + Se + Te + Au + Ag as side product

High recycling rate (90 % of used copper)

Purification of Copper


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Metals And Minerals: Nickel

No technical use up to 1850

At present 70 % of Ni used for stainless steel

Largest producers: Norilsk Nickel (former Stalinis concentration camp)Inco (now CVRD of Brasil)

Worldwide demand for stainless steel growing 5% annually

New minesVosey's Bay, Inco planned 2006: 60,000 t

real 2006: 12,000 t

Ravensthorpe (AUS) 50,000 /y 2007

Hot commodity, see next slide


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Nickel Prices

http://www.kitcometals.com/charts/nickel_historical_large.html#5years


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Platinum, Palladium

Pt First described by Italian Humanist Caesar Scaliger

Known to South American Indians even earlier

Usually byproduct of Cu and Ni refining but pure Pt minesexist in South Africa

80 % of Pt from S.A., Russian production decreasing

50 % of Pd from Russia

Largest consumer: Car Catalysts, Ostwald Process Largest producer: Anglo Platinum (Anglo American)


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1

Ag

Ru

Ir

OsPdAuPtRh

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US $ / ounce

Precious Metal Prices


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Silver

Small market (10 % of Gold), strong price fluctuations

Sideproduct of Ni, Pb, Cu, Au mining

Main mines in Mexico, Peru, Australia, China, Poland

Main players: Rio Tinto (GB), BHP Minerals (AUS)

Largest Ag and Pb mine: Cannington (BHP, Australia)

Use 40 % industrial use (mainly electroncis30 % jewlery25 % Photography (will go to zero)

Digital photography led to price drop, but prices are rising since 1998Currently 6 - 7 $ /ounce

Future: Increasing demand (electronics)Declining reserves, no new minesCurrent reserves last 5 years


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Mining of Silver since Inca days (1462, Huaya Ccpac)

45,000 tons of silver = 8 million dead Indians (mercurypoisoning)

UNESCO World Heritage Site

Silver in History: Bolivia - Potos (4050m)


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