World Chemicals Sales (2010) - PDF Free Download

World Chemicals Sales (2010) billion 1200 1000 1147 Ʃ 2 353 billion 800 600 400 578 455 200 0 China Source: Cefic Chemdata International 128 Asia Europe NAFTA Latin America 45 Others 1

Chemical Industry Sales (2010) Sectoral Breakdown (Europe) Consumer chemicals 12,8 % Basic inorganics 13,6 % Specialties 25,6 % Petrochemicals 24,0 % Source: Cefic Chemdata International Polymers 24,0 % 2

Large-Scale Catalytic Processes 1888 Sulfuric acid production by the contact process 1913 Ammonia synthesis (Haber-Bosch process) 1922 High pressure process for production of methanol 1926 1945 Coal liquefaction process for fuel production 1930 Production of synthesis gas for ammonia and methanol 1977 Acrylic acid process 1988 Low pressure production of methanol on the basis of lean gas 1997 Process for decomposition of N 2 O (greenhouse gas) 2003 High-load process for production of phthalic anhydride 2008 Propylene oxide from propylene and hydrogen peroxide 3

Heterogeneous Catalysts Global Market 2010 Chemicals 3,0 bn Chemical Industry 4,0 bn 35,4 % Environment 4,2 bn 37,2 % Mobile Emissions 3,7 bn Polyolefins 1,0 bn Refinery 3,1 bn 27,4 % Stationary Emissions 0,5 bn Source: BASF estimates SRI Consulting 2011 11,3 bn 4

Process Research and Chemical Engineering (GC) Research Organization Heterogeneous Catalysis (GCC) New Technologies (GCN) GCC/C GCC/E GCC/P GCC/S Chemical and Process Engineering (GCP) Organic Synthesis and Homogeneous Catalysis (GCS) 5

Major Research Sites for Heterogeneous Catalysis (BASF Group) Beachwood, OH Iselin, NJ Union, NJ Huntsville, AL Savannah, GA Pasadena, TX Attapulgus, GA Vidalia, LA DeMeern, Netherlands Nienburg, Germany Hannover, Germany Ludwigshafen, Germany Heidelberg, Germany (hte) Shihwa, Korea (HCC) Numazu, Japan Shanghai, China (NECC) Guilin, China Iselin Ludwigshafen Shanghai 6

Process Research and Chemical Engineering (GC) Research Focus Product innovation Process innovation Process optimization Process Research and Chemical Engineering Extension of the value chains Development of new technologies Raw material change 7

Process Research and Chemical Engineering Chemical Synthesis Catalysis Chem. Reaction Engineering Unit Operations Technical Process 8

Propylene Oxide HPPO Process + H 2 O 2 - H 2 O O 9

Polyurethanes 10

Propylene Oxide Product Life Cycle Technologies Propylene oxide capacity [kt/a] 8 000 6 000 Total 4 000 Chlorohydrin 2 000 MTBE/PO SM/PO Cumene 0 1965 1975 1985 1995 2005 Year HPPO 2010 11

Propylene Oxide State-of-the-Art Technologies at BASF Chlorohydrin 1930 + Cl 2 + H 2 O Cl OH + Ca(OH) 2 - CaCl 2 O 2.2 t salt/t PO OOH + O 2 SM/PO 1975 - H 2 O OH O 2.3 t SM/t PO BASF-HPPO JDA with DOW 2008 + H 2 O 2 - H 2 O O water only 12

Propylene Oxide (HPPO Process) BASF Catalyst Microscopic catalytic site + H 2 O 2 + CH 3 OH Macroscopic catalyst CH 3 O SiO SiO H Ti H O O OSi Proprietary Ti-zeolite System O + H 2 O 13

Propylene Oxide (HPPO Process) Simplified Process Flowsheet Epoxidation using fixed-bed catalyst arrangement off-gas low boilers pure PO Propylene H 2 O, glycols H 2 O 2 methanol methanol recycle reactor off-gas crude PO water glycols separation methanol purification pure PO Full H 2 O 2 conversion and solvent methanol recycle, PO distillation for final purification 14

HPPO Pilot Plant Ludwigshafen 15

HPPO Production Plant Antwerp 16

HPPO Economic and ecological advantages 300 kt/a Plant in Antwerp 75% reduction of waste water 35% lower energy consumption 25% lower capital investment Only water as co-product 17

Recognition of HPPO Technology IChemE Award 2009 York, GB, Nov. 2009 40 th Kirkpatrick Honor Award 2009 New York, Nov. 2009 US Presidential Green Chemistry Award Washington, June 2010 18

Acrylic Acid CH 2 CH C O O H Acrylic acid, stabilized 839 2218 corrosive flammable Colourless liquid with perceptible odour (T m = 13 C, T b = 141 C) corrosive flammable (flash point ~ 49 C) 20

Polyacrylates 21

Life Cycles of Acrylic Acid Technologies Capacity (Mio. t/a) 5.4 4.8 4.2 3.6 3.0 2.4 1.8 1.2 0.6 0 Cyanhydrin, Acrylonitrile and Propiolactone process Propylene oxidation Reppe process 1950 1960 1970 1980 1990 2000 2010 22

Acrylic Acid from Propene Step 1: CH 2 CH CH 3 + O 2 Propene Bi-Fe-Mo-O 300-350 C CH 2 CH C O H Acrolein H = - 341 kj/mol + H 2 O Step 2: O CH 2 CH C + 0.5 O 2 H Acrolein Mo-V-O 250-300 C CH 2 CH C O OH Acrylic Acid H = - 254 kj/mol Process developed by SOHIO and Nippon Shokubai Since 1977 at BASF 23

Improvement of Acrylic Acid (AA) Catalysts AA Yield [Index] CO 2 Emission / t AA [%] Propene load [Index] 120 33 % 30 % 200 50 % 110 150 100 90 100 % 67 % Electricity City with 275 000 two persons households 100 50 1976 1981 1986 1991 1996 2001 2006 2011 24

Light Duty Engine Production (Million) 66 15 51 57 12 45 72 16 56 74 17 57 77 17 60 85 1 18 66 92 1 20 71 98 1 22 75 102 1 23 78 Others Diesel Gasoline 2008 2009 2010 2011 2012 2013 2014 2015 2016 Source: JD Power, Engine & Transmission Forecast, Q4/2011 26

Engine out emissions Passenger Cars Gasoline (Audi / 2,0 l) NEDC g/km Diesel (BMW / 2,0 l) g/km Trucks WHTC Diesel (MAN / 12,4 l) g/kwh CO 5,15 0,95 2,79 1,40 Hydrocarbons 1,05 0,16 0,20 0,10 NO x 1,35 0,13 6,78 3,50 Soot Insign. 0,05 0,06 0,03 27

Worldwide Emission Regulations Current regulations Future regulations USA Europe US Tier 2, CA LEV II US 2007 Euro 3 Euro 5 US 2010 Euro 5 Global, 4a Global, 4a Euro 4 Euro 6 Phase in Global, 4b Euro 6 Global, 4b CA LEV III Brazil Euro 3 Euro 4 Euro 4 Euro 5 Euro 5 Russia India China Euro 3 Euro 3 Euro 3 Euro 4 Euro 4 Euro 3 Euro 4 Euro 4 Euro 3 Euro 4 Euro 4 Euro 5 Euro 5 Euro 5 Euro 4 South Korea Euro 5 Japan Euro 6 Global, 4a Global, 4b Euro 3 Vietnam Thailand 2007 Euro 7 -to be decided in 2016 Euro 3 2008 2009 2010 2011 2012 2013 2014 2015 2016 Light-duty Heavy-duty Motorcycle 28

Transition State Motorcycle 29

Main Reactions in Vehicle Exhaust Gas Treatment Gasoline engines: (1) (2) (3) Diesel engines: (4) Pt / Pd CO + O 2 CO 2 Pt / Pd Hydrocarbons + O 2 CO 2 + H 2 O Rh (Pd) NOx + CO CO 2 + N 2 (1), (2) NO + O 2 Pt NO 2 TWC DOC (1), (2), (4) (5) (6) C + NO 2 CO + NO CSF C + O 2 CO 2 (7) NO + NO 2 + O 2 + NH 3 Cu/Fe/V N 2 + H 2 O SCR (8) NH 3 + O 2 Pt N 2 + H 2 O AMOX 30

Vehicles and Catalyst Families Gasoline Engine LDG Catalysts TWC Applications Diesel Engines LDD DOC DOC + CSF DOC + CSF + SCR HDD DOC + CSF + SCR + AMOX Motorcycles TWC 31

Emission Control in Trucks (Euro VI) Diesel (for soot burn off) Urea DOC CSF SCR AMOX Diesel Oxidation Catalyst (DOC) Oxidation of - carbon monoxide - hydrocarbons Oxidation of NO to NO 2 Catalyzed Soot Filter (CSF) Soot filtration Soot burn off Oxidation of CO and hydrocarbons Selective Catalytic Reduction (SCR) Reduction of NOx to nitrogen Hydrolysis of urea Ammonia Oxidation Catalyst (AMOX) Oxidation of NO to NO 2 Oxidation of ammonia to nitrogen 32

General Structure of Automotive Catalysts Coatings on honeycomb Catalyst Exhaustgas from engine Top coat Middle coat Bottom coat Honeycomb 33

General Structure of Catalytic Soot Filters (CSF) Inlet channel Soot layer Outlet channel Porous Filter Wall Soot-laden gas Catalyst Plug Gas must filter through wall Soot-free gas 34

Fluctuation of Precious Metal Prices (Average prices p.a.) Price ($/tr.oz.) Rhodium Platinum Palladium 6 000 4 000 2 000 0 1985 1990 1995 2000 Year 2005 2010 35

Emission Limits and Precious Metal Content of Light Duty Gasoline Catalysts Ford, Engine displacement 2 l g/km g/ft 3 3.5 3.0 CO Total Hydrocarbons + NOx None Methane Hydrocarbons Pt + Pd + Rh Rh 120 100 2.5 80 2.0 1.5 60 1.0 40 0.5 20 0 EURO 1 1992 EURO 2 1996 EURO 3 2000 EURO 4 2005 EURO 5 2009 0 36

Key Features of Automotive Catalysts Automotive catalysts have: To manage different chemical reactions at the same time (oxidation and reduction) To work under varying reaction conditions - Low feed concentrations from 100 to 3 500 v ppm but high conversions and selectivities needed - Rapid oscillations between lean and rich atmospheres - Temperatures from ambient to 1000 C - Space velocities from 10 000 h -1 to 200 000 h -1 To cope with other challenges 37

Operator of Chemical Catalysts 38

Operator of Automotive Catalysts 39

Primary Energy Share Traditional Coal Oil Gas Hydro Nuclear New Renewables Biofuels Primary energy share [%] 80 60 40 20 0 1850 1900 1950 2000 2050 Source: Royal Dutch/Shell Group, Energy Needs, Choices and Possibilities 41

Syngas to Olefins Reaktion: CO + 2 H 2 Katalysator Kohlenwasserstoffe + H 2 O CO CO C 2 H 4 CO C 3 H 6 CO C 100 H 200 C* C 2 * C 3 * C 100 * Mechanismus: Katalysator C 2 H 6 C 3 H 8 CO CH 4 CO + H 2 O H 2 + CO 2 C* Katalysator Methanisierung Fe* Katalysator Wassergas Shift Produkte: Breite Produktverteilung: C1 (Methan) C100 (Wachse) 42

Benzene from Methane 5,5 A CH 4 CH x C 2 H y C 2+ H z HZSM-5 Mo 2 C Zeolite (HZSM-5) 43

PEM Fuel Cell Proton Exchange Membrane Air Hydrogen Electrons Protons Cathode Electrolyte (Cell division) Anode Water 1 2 O 2 + 2H + + 2e - H 2 O H 2 2H + + 2e - 45

Cost Target for Fuel Cell Systems mobile portable stationary Submarine - PEM Laptop - DMFC BHPP - MCFC < 1.500 /kw < 750 /kw < 500 /kw < 50 /kw Bus - PEM APU - PEM Home Car - PEM PEM SOFC 46

Electrocatalysts for Fuel Cells 0.05µm Pt /C 47

PEM Fuel Cell Proton Exchange Membrane Air Hydrogen Electrons Protons Cathode Electrolyte (Cell division) Anode Water 1 2 O 2 + 2H + + 2e - H 2 O H 2 2H + + 2e - 48

Metal Organic Framework (MOF) COOH MOF-5 ZnO + COOH 49

MOF Unique Properties World record values in surface areas typ. 1 500-3 000 m²/g 200 µm 50

MOF Milestones by Prof. O. Yaghi (Berkeley) Surface World record MOF-210 10,000 m²/g MOF-200 8,000 m²/g MOF-5 3,000 m²/g MOF-177 5,000 m²/g Zeolite 13X 600 m²/g 1950 1999 2004 2009 2010 Year 51

MOF Unique Properties World record values in surface areas typ. 1 500-3 000 m²/g Dead-volume-free structures in contrast to zeolites and activated carbons Low solid densities 300-500 g/l 200 µm 52

MOF Unique Properties World record values in surface areas typ. 1 500-3 000 m²/g Dead-volume-free structures in contrast to zeolites and activated carbons Low solid densities 300-500 g/l High thermal stability decomposition only at 350-500 C Variable design more than 2 000 structures annually 200 µm 54

MOF Hydrogen Storage Capacities (50 bar, 77K) g H 2 / l Tank 80 70 60 50 COOH COOH COOH HOOC COOH COOH COOH HO COOH OH COOH O O OH OH 71 H 2, liq (1 bar, 20K) 40 30 20 10 0 14 Zn COOH 17 19 COOH 23 Zn Cu Al 33 Zn OH 42 Zn O 23 37 H 2, gas (700 bar, 298K) H 2, gas (350 bar, 298K) 2002 2002 2002 2005 2007 2009 55

MOF Natural Gas Storage Basolite TM A520 Metal: Aluminum Linker: Fumaric acid CO 2 H HO 2 C 20 µm Properties: water-stable, thermally stable up to 350 C 56

MOF Natural Gas Storage (Mercedes Sprinter, 295 K) Methane [g CH4 / l tank ] 70 60 50 40 30 20 10 Tank + MOF A520 Tank Distance [km] 400 300 200 100 0 0 0 10 20 30 40 50 Pressure [bar] Customer value: higher distance or lower pressure 57

MOF Natural Gas Storage Cooperation with Agility: US manufacturer of alternative fuel systems 1 Truck equipped with MOF A520 pellets to store natural gas Successful operation since summer 2010 58