World Chemicals Sales (2010)

Transcription

1 World Chemicals Sales (2010) billion Ʃ billion China Source: Cefic Chemdata International 128 Asia Europe NAFTA Latin America 45 Others 1

2 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

3 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 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

4 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 ,3 bn 4

5 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

6 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

7 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

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

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

10 Polyurethanes 10

11 Propylene Oxide Product Life Cycle Technologies Propylene oxide capacity [kt/a] Total Chlorohydrin MTBE/PO SM/PO Cumene Year HPPO

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

13 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

14 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

15 HPPO Pilot Plant Ludwigshafen 15

16 HPPO Production Plant Antwerp 16

17 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

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

19 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 19

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

21 Polyacrylates 21

22 Life Cycles of Acrylic Acid Technologies Capacity (Mio. t/a) Cyanhydrin, Acrylonitrile and Propiolactone process Propylene oxidation Reppe process

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

24 Improvement of Acrylic Acid (AA) Catalysts AA Yield [Index] CO 2 Emission / t AA [%] Propene load [Index] % 30 % % % 67 % Electricity City with two persons households

25 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 25

26 Light Duty Engine Production (Million) Others Diesel Gasoline Source: JD Power, Engine & Transmission Forecast, Q4/

27 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

28 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 Light-duty Heavy-duty Motorcycle 28

29 Transition State Motorcycle 29

30 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

31 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

32 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

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

34 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

35 Fluctuation of Precious Metal Prices (Average prices p.a.) Price ($/tr.oz.) Rhodium Platinum Palladium Year

36 Emission Limits and Precious Metal Content of Light Duty Gasoline Catalysts Ford, Engine displacement 2 l g/km g/ft CO Total Hydrocarbons + NOx None Methane Hydrocarbons Pt + Pd + Rh Rh EURO EURO EURO EURO EURO

37 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 v ppm but high conversions and selectivities needed - Rapid oscillations between lean and rich atmospheres - Temperatures from ambient to 1000 C - Space velocities from h -1 to h -1 To cope with other challenges 37

38 Operator of Chemical Catalysts 38

39 Operator of Automotive Catalysts 39

40 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 40

41 Primary Energy Share Traditional Coal Oil Gas Hydro Nuclear New Renewables Biofuels Primary energy share [%] Source: Royal Dutch/Shell Group, Energy Needs, Choices and Possibilities 41

42 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

43 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

44 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 44

45 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

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

47 Electrocatalysts for Fuel Cells 0.05µm Pt /C 47

48 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

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

50 MOF Unique Properties World record values in surface areas typ m²/g 200 µm 50

51 MOF Milestones by Prof. O. Yaghi (Berkeley) Surface World record MOF ,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 Year 51

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

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

55 MOF Hydrogen Storage Capacities (50 bar, 77K) g H 2 / l Tank COOH COOH COOH HOOC COOH COOH COOH HO COOH OH COOH O O OH OH 71 H 2, liq (1 bar, 20K) Zn COOH COOH 23 Zn Cu Al 33 Zn OH 42 Zn O H 2, gas (700 bar, 298K) H 2, gas (350 bar, 298K)

56 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

57 MOF Natural Gas Storage (Mercedes Sprinter, 295 K) Methane [g CH4 / l tank ] Tank + MOF A520 Tank Distance [km] Pressure [bar] Customer value: higher distance or lower pressure 57

58 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

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