1. Lecture Topic 3: Industrial Organic Chemistry Ref: “Organic Building Blocks of the Chemical Industry”, by H.H. Szmant “Industrial Organic Chemistry”, by K. Weissermel and H.-J. Arpe Premise :Classification of organic chemicals by: COST PRODUCTION VOLUME STARTING MATERIAL Goal :Ability to 1. identify bulk, fine and specialty chemicals 2. give examples of primary building blocks and of C 1, C 2, C 3, C 4 and higher acyclic and cyclic organic building blocks 3. the manufacture of a common chemical from souces to final products

2. Medicinals and other specialties Dyes Fine Chemicals Flavours, fragrances Specialties Organic intermediates Common plastics Commodities Resins, Elastomers Primary organic building blocks 10 5 10 6 10 7 10 8 10 910 10 11 10 12 Pseudo-commodities Inorganic heavy chemicals Demand (lb/y) Unit cost ($/lb) 0.01 0.1 1 10 >100 Cost - Volume

3. Source: C&E News Jan 8 2007 US Chemical production 2003-2006 (Import-Export)

4. Special position of inorganics: Metal and energy prices rose Why should we care ? => inflation => Fed hike => filters down to mortgages, credit cards …

5. Canada produces anything: Metals Coal Gas Oil Why the deficit ? Many reasons. Not enough value addition (manpower, R&D) Economy of scales (~size of population + others)

6. Take home message: Inorganics Dominate, PE top organic The Top Ten

7. KEY SUCCESS FACTORS cost technical service links with customer INDUSTRY CHARACTERISTICSBULK CHEMICALSFINE CHEMICALSSPECIALTY CHEMICALS LongModerateShort/moderate > 100>1,000>50,000 >10,000t/y<10,000t/yhighly variable <5 $/kg>5 $/kg>10 $/kg nonevery lowhigh lowhigh moderatemoderate/low process application Product life cycle # of products Product volumes Product prices Product differentiation Value added Capital intensity R&D focus   – – Cost/Volume: Implications

8. 1850+Coal Tar (side product of “coal gasification”) 1920+ Acetylene (from CaC 2, Reppe Chemistry) 1950+ Ethylene (from oil) 1973+ CH 4, CO/H 2 (syngas) Future: CO/H 2 from Coal (exothermic) CO 2 fixation via: Plants, Animals (endothermic) CO 2 fixation (endothermic) 1850-Plants, Animals The History of Industrial Chemistry is linked to Building Blocks

9. A building block is any (organic) chemical that can be used to synthesize other (organic) chemicals. There are very few truly primary, large-volume organic building blocks. These are all currently obtained from: petroleum refining natural gas coal ammonia carbon dioxide renewable resources What is a Building Block

10. Walter Julius Reppe BASF Ludwigshafen Reppe Chemistry: Make everything from acetylene. Examples The first Building Block: The Age of Acetylene Tricky technology, acetylene explodes under pressure (~ 5 atm). Acetylene forms explosive salts with heavy metals (no copper tubes & valves !). Largely replaced by ethylene & C 1 Chemistry. “Inorganic” entry (CaC 2 ) into organic chemistry. Still very valuable for fine chemicals Could make a comeback with cheap energy.

11. Building Blocks: Primary, Secondary… 1º BB 2º BBs 3º BB Ethyleneethylene dichloridevinyl chloride ethylene oxideethylene glycol ethyl benzenevinyl acetate Propylenepropylene oxide acrylonitrile isopropyl alcohol cumeneacetone n-butyl alcohol Benzeneethyl benzenestyrene cumenephenol acetone bisphenol A Methanolacetic acidvinyl acetate formaldehyde MTBE Toluene Xylenesterephthalic acidPolyester

12. C 1 -Chemistry C 1 Chemistry in a nutshell:

14. C 1 -Chemistry and the Power of Syngas

15. Advanced C 1 -Chemistry: Natural Products

17. C 1 -Chemistry Database http://www.aist.go.jp/RIODB/c1db/index.html

18. (+)From:Natural Gas (CH 4 ) Crude Oil Coal1976 3 % 198212 % 200016 %50 % of it SASOL, South Africa (–)Energy intensive (+++)More than 500 years of coal reserves (+++)Anything can be made from Syngas (as long as it contains carbon or hydrogen) NH 3 (Haber-Bosch process) Oxo-products (Hydroformylation Gas, Diesel, Lubricants, waxes….. (Fischer-Tropsch process) (–)Syngas is dirty (CO, CO 2, H 2, H 2 S, COS) but easy to clean (+)Very clean Diesel (low sulfur) fuel from syngas (SASOL) Syngas: A Second Look

19. A Brief History of Syngas (H 2 /CO) Haber Bosch Process Hydrogen for ammonia synthesis obtained as syngas, CO removed Fischer-Tropsch: Hydrocarbons from Syngas “Synthetic fuel” crucial for German war machine Leuna plant alone 900,000 t/year, bombed in June 1944 Technology of the future if oil runs out, center of SASOL company Hydroformylation: Aldehydes, Alcohols, Amine … from Syngas Largest homogeneously catalyzed process Origin of modern transition metal catalysis

20. Production of Organometallics Verbindungen -Silicones900.000 t/a -Al-Alkyles 90.000 t/a -Sn-Alkyles 35.000 t/a Products obtained with organometallic catalysts - Polypropylene17.000.000 t/a - Polyethylene36.000.000 t/a -„Oxo“-Products 5.000.000 t/a - Acetaldehyd 2.200.000 t/a - Acetic Acid 1.000.000 t/a Organometallics in Industry

21. History of Catalytic Industrial Processes Very small number of crucial discoveries Very small number of players + Minute amount of “right” catalyst = Massive production (and $), = High number of processes & products The golden path: 1. Understand the first processes 2. Understand which are expanding and why

22. Petrochemistry & Catalysis: Wacker, Monsanto etc.

24. The Start of C 1 Chemistry: Hydroformylation (Oxo Process) O. Roelen, Ger. Pat., 949 548, 1938. Discovered by Otto Roelen who tried to find out the cobalt catalyzed FT process produces alcohols Largest homogenously catalyzed process in the world (~ 10 billion Kg of aldehydes) 1968: Introduction of phosphines to stabilize cat. Use of watersoluble Rh-phosphine complexes 1970: Rh (better n/iso ratio, but EXPENSIVE) 2004: 75 % use Rh; Major process propene to butanol

25. Max Planck is so impressed that he drops his breakfast sandwich permanently (-> sandwich complexes) and Quantum Mechanics temporarily… … to rush to the scene of the accident and inspect a good bottle of n-butanol. Good for Otto, because Max controls funding. Hydroformylation (Oxo Process): Instant Recognition

26. Mechanism of the Hydroformylation: From Hieber to Heck Walter Hieber (right) the pioneer or metal carbonyl chemistry (left:Behrens, his lecture assistant). Heck-Breslow meachnism (1960/61)

27. For ratio of H 2 /CO = 1:1 reaction rate is pressure independent due to the opposing orders of H 2 and CO. Increasing the H 2 /CO ratio is of limited use for increasing the overall reaction rate because HCo(CO) 4 is only stable under certain minimum CO partial pressures at a given temperature. Nothing is more practical than a good theory (L. Boltzmann) Mechanism MUST be comply with rate law Sounds boring, but…

28. Stability of HCo(CO) 4 /Co 2 (CO) 8 species with respect to precipitation of cobalt metal (cobalt concentration is 0.4 wt. %). Catalysts are Survivors

29. Industrial Catalyst Design (Cheat sheet) Catalyst: Optimized combination of: mechanical properties catalytic properties physical properties Three Types of Catalysts: Heterogeneous (insoluble)used for high p, high T Homogeneous (soluble) used for low T, high/low p Enzymes low T, low p Selectivity increase Heterogen. < homogen. < Enzyme

30. Heterogeneous Catalyst Design

31. Alkenes (C 2 -C 4 ) are water soluble enough that migration into the aqueous catalyst phase occurs. Remigration of the aldehyde product back into the more soluble organic phase allows easy separation of product from catalyst. n/iso 18:1 (propene) via water soluble catalyst. Rates are slower than with conventional Rh/PPh 3 catalysts due to lower alkene concentrations in the water phase and higher amounts of the inactive tris-phosphine Rh complex. The process is limited to the shorter chain alkenes that have some appreciable water solubility. Alkenes higher than pentene are not soluble enough in water. Using TPPTS instead of PPh3 gives a highly water soluble catalyst: HRh(CO)[TPPTS Na 3 ] 3. In aqueous solution the catalyst essentially has a  9 charge, making it totally insoluble in all but the most polar solvents Emile Kuntz (Rhone-Poulenc) has a very good idea

32. Franz Joseph Emil Fischer Kaiser-Wilhelm Institut Mülheim 1913 Director of the newly founded Kaiser-Wilhelm- Institute for Coal Research (Mülheim / Ruhr 1925 Discovers formation of hydrocarbons from Syngas with Hans Tropsch Fischer Tropsch Chemistry: 1925 +

33. 1.Carbide-methylene 2.Hydroxycarbene 3.CO insertion

36. Oil Producing Countries Mio t

37. USChinaJPRussiaGermany IndiaBrasil Comsumption Production Mio t Oil Production/Consumption by Countries

38. Reality Check I: Are We Becoming More Oil Dependent ? Tons of Crude / Million Euro of GDP (Germany) Importance of oil for GDP of G7 countries is dropping

39. Plus:500+ years of proven reserves at current consumption levels Can substitute Oil & Gas: directly (generation of electricity) indirectly (Coal gasification - > Syngas -> Chemicals) Large reserves in countries that do not have oil & gas: USE China Minus:Can’t be pumpe (no pipeline) transport expensive unless close to water High in sulfur Coal - Oil - Coal ?

40. Use of Coal

41. Electricity From Coal

42. Energy and the CO 2 Footprint

43. Types of Coal

44. Geology and Origin of Coal

45. Coal Players: Peabody, BHP, Teck-Cominco

46. Major Coal Producers: USA, China

47. Major Coal Reserves: Australia

50. Xylenes 600,000 tons NaphtalenePhtalic Anhydride 100,000 tons Coumarone Thermoplastic resins Inks Rubber Anthraquinone Anthracen e 40,000 tons Dyes H 2 O 2 Indene

51. Building Block Analysis: Aspirin ®

52. CuMined as an ore and refined PdMined and refined (Sudbury, Ontario: “anode slime”) H 2 SO 4 H 2 O + 0.5 O 2 + SO 2 pyrometallurgical byproduct O 2 Fractional distillation of liquid air Acetic acidMethanol + CO (Monsanto process) NaOHElectrolysis of brine (NaCl + H 2 O) “chloralkali cell” Origin of other Reagents

53. Science is naming….

54. 1. Natural gas:C1 2. Propane:C 3 3. Gasoline: C 7 - C 9 4. NaphtaC 6 -C 11 5. Kerosene (Paraffin):C 11 -C 18 5. Diesel oilC 13 -C 15 6. Lubricating Oil C 18 -C 25 7. Fuel oil C 20 -C 27 1. Gases 2. Petrol 3. Naphta 4. Kerosene 5. Diesel oil 6. Lubricating Oil 7. Fuel oil 8. Greases & Waxes 9. Bitumen Oil: From Crude Oil to Distillates Classified by b.p.Classified by Use Good source of information: http://tonto.eia.doe.gov/dnav/pet/pet_pnp_top.asp

55. Distillates - A second look Higher boiling fractions distilled under vacuum

56. Petrol and Diesel engines operate differently A high tendency to autoignite is undesirable in a gasoline engine but desirable in a diesel engine. We need two rating systems Fuel: Gasoline vs. Diesel

57. Developed by the chemist Russel Marker  Isooctane (2,2,4-trimethylpentane) = 100  n-heptanee =0.  87-octane equivalent to a mixture of 87 vol-% isooctane and 13 vol-% n-heptane.  n-Heptane ? high purity n-heptane originally obtained by distillation of pine resin. Heptane from crude oil is a mixture of isomers and would not give a precise zero point. Different Octane numbers, depending on test protocol: RON = Research Octane Number (used in Europe) MON = Motor Octane Number PON = Pump Octane Number = (RON + MON)/2 (US, CAN) Isooctane is not the most knock-resistant substance available. Ethanol has RON of 129 Liquified petroleum gass (LPG) > 110. Octane Number

58. Peak Deficits of high octane fuels: 1940 + WW II (aircrafts) 1960 + Polyesters (Terephatic acid) deplete aromatics Quick Fix (Kettering & Midgley, GM, Dupont, 1924+) Tetraethyllead PbEt 4 (“Leaded gasoline”) as octane booster (1:1200) Easily decomposed to its component radicals, scavenges radicals that would start the combustion prematurely, thereby delaying ignition. Production (EtCl + Na-Pb alloy) peaks at 600.000 t/a (insae, MKD) Phased out (except for Yemen, Afghanistan, North Korea and some African countries) Highly toxic (“Chernobyl of the ‘20ies) Incompatible with car catalysts (1975 California) which contain Pt, Pd New chemistry allows upgrading of fuel at refinery But:Still used in aviation fuels ! Octane Boosters

59. This photo, taken in April 1933, shows a Lincoln Nebraska gas station of the Earl Coryell Co. selling "Corn Alcohol Gasoline." The test marketing of ethanol blends was common in the Midwest at this time, but it did not succeed due to the market dominance of the major oil companies. Coryell was subsequently among complainants to the Justice Dept. in the US v. Ethyl antitrust lawsuit of 1936, which Ethyl lost in a Supreme Court decision in 1940. (Nebraska Historical Society) PbEt 4 ’s early competitor: Ethanol

60. colourless to yellow liquid Melting point: -136 C Boiling point: 84 C at 15 mm Hg, (decomposes near 200 C) Toxicology Highly toxic - may be fatal if inhaled or ingested. Possible mutagen. Experimental carcinogen. Accumulative poison. Danger of reproductive effects. Note low LD50s below. Irritant. Toxicity data RL-RAT LD50 12.3 mg kg -1

61. C 1 building blockSourceUse CH 4 (methane) Natural gasenergy, H 2, CO, CH (4-x) Cl x CO (carbon monoxide) Coal (as Syngas)CH 3 OH, HCOOH, esters, amides, Oxo acids, etc. CH 3 OH (methanol)CO + 2H 2 H 2 CO, MTBE, CH (4-x) Cl x, Cracking of C 3 H 8, C 4 H 10 CH 3 COOH H 2 CO (formaldehyde)CH 3 OH, Cracking of LPGPolymers (UF, PF, POM) HCOOH (formic acid)CO + H 2 O Fine chemicals CO 2 (carbon dioxide)Water-gas-shift rxn.Supercritical fluids (SCFs) CS 2 (carbon disulfide)S 8 + Coke or CH 4 Cellulosics, M + SCN –, thiourea Cl 2 CO (phosgene)CO + Cl2R-C=N=O polyurethanes (H 2 N) 2 CO (urea)NH 3 + CO 2 Fertilizer, Resins (UF) HCN (hydrogen cyanide)HCONH 2 - H 2 OMethacrylonitrile, ClCN byproduct (acrylonitrile) C 1 Chemistry

62. The Monsanto Process First large scale process based on methanol = milestone in the history of building blocks. Long development due to corrosion problems 60 atm 250 o C corrosion problems Has largely replaced the two step Wacker process: Acetic acid is one of the most important secondary C 2 -building blocks and used to make vinylacetetate (foils), cellulose acetate…

63. C 2 building blockSourceUse CH 2 =CH 2 (ethylene)thermal cracking of naturalFeedstock for ~30% of all gas, refinery gas, crude oilpetrochemicals!! Polymers (Polyethylenes etc.) Alphaolefins (LDPE), PVC Polystyrene, Polyvinyl acetate Polyethylene oxide CH 3 CH 2 OH (ethanol)fermentation,Gasoline additive (USA), hydration of ethyleneEthylene by dehydration (Brazil, India, Peru, Pakistan), Solvent, Esters (ethyl chloride, ethyl acetate) CH 3 CH=O (acetaldehyde)Wacker-Hoechst (ethylene)CH 3 COOH, Acetic anhydride, Monsanto process (MeOH)Peracetic acid CH 3 C(=O)OOH, Aldol condensation products CH 3 COOH (acetic acid)&Monsanto process (MeOH)Vinyl acetate (PVA), Cellulose CH 3 COOCOCH 3 (aceticOxidation of C 4 -C 8 hydro-acetate, Solvent, Acetate salts, anhydride)carbons or acetaldehydeChloroacetic acids HCCH (acetylene)Coal via CaC2 or 1,4-Butanediol, vinyl acetate from hydrocarbons C 2 Chemistry

64. C 3 building blockSourceUse CH 3 CH 2 CH 3 (propane)LPGPropylene, energy CH 3 CHCH 2 (propene)Thermal cracking of LPG,Polypropylene, Acrylonitrile, natural and refinery gasOxo products (butyraldehyde, butanol, etc.),Propylene oxide Isopropanol, Cumene, Oligomers (nonene, dodecene, heptene) CH 3 COCH 3 Hock process (coproduct)Methyl methacrylate, Methyl (acetone)Isopropanol (dehydrogen’n)isobutyl ketone, Bisphenol A, Wacker-Hoechst (propene)Aldol condensation products, Solvent CH 3 CH 2 COOHCH 2 CH 2 (hydroformylation)Food preservative, Amyl and (propionic acid)Vinyl propionate, Herbicides C 3 Chemistry

65. C 4 building blockSourceUse C 4 H 10 (butanes)LPG1-Butene, Maleic anhydride, MTBE, thiophene C 4 H 8 (butenes, isobutene) Cracking of C n  4 Polymer/alkylate gasoline, Polymers/copolymers, alcohols C 4 H 9 OH (butyl alcohols)Propene, acetaldehydeMEK, Solvent, Fuel additive CH 3 (CH 2 ) 2 CHO Propene, acetaldehyde2-Ethylhexanol, Trimethylol- (butyraldehydes) propane Maleic anhydrideOxidation of C 4 -feedstocksUnsaturated polyester resins, Benzene (V 2 O 5 catalyst)Fumaric acid, Pesticides HO(CH 2 ) 4 OH Acetylenepoly(1,4-butylene terphthalate) (1,4-butanediol)1,3-butadieneTHF, H 2 N(C 4 H 8 )NH 2 H 2 C=CH-CH=CH 2 Cracking of C n  4 Elastomers (i.e., synthetic (1,3-butadiene)rubbers), Chloroprene, THF C 4 Chemistry

69. C 4 Chemistry: Rubber

70. Primary Building BlocksSource(s)Use Petroleum: C n H n+2 (n  5)Fossil fuelsSolvent, Fuel, Lubricant, (pentanes, hexanes, heptanes, etc.,Alkylbenzenes, Alcohols, and other n-paraffins)Chlorinated paraffins, Lower m.w. alkanes/olefins Mineral waxes: Ozocerite,Fossil fuelsCoatings Montan wax(lignite) Fatty Acids: Lard, Tallow, PalmRenewablePVC stabilizer, Surfactant, oil, Corn oil, Castor oil, etc.(animal/plant)Glycerine, Methyl laurate, Fatty amines (antistatic agents) Tall-Oil Fatty Acids (TOFA)RenewableFuel in pulping operations, (pulp byproduct)Dimer/trimer acids for coatings TerpenesRenewableFragrance/flavour “essential” (plant)oils, Turpentine Fermentation Products:RenewableH 2 S removal from refinery gas, Amyl alcohols (plant) Carboxylic acids,Food industry, Pharmaceuticals, Monosodium glutamate (MSG)Laundry products, etc. C 5 And higher (acyclic)

71. Building blocksSourceUse BenzeneCoal, Oil, PetroleumEthylbenzene (for styrene), C 6 H 6 (thermal/catalytic process)Cumene (for phenol/acetone), Cyclohexane, Nitroenzene Toluene Coal, Oil, PetroleumSolvent, Benzoic acid, Phenol, C 6 H 5 CH 3 (thermal/catalytic process)Nitrotoluenes, aminotoluenes Xylenes Coal, Oil, PetroleumPhthalic acids and anhydrides C 6 H 4 (CH 3 ) 2 (thermal/catalytic process) (plasticizers, synthetic fibers) Cumene C 6 H 5 CH(CH 3 ) 2 BenzeneHock process (phenol/acetone) Phenol C 6 H 5 OHCumene (Hock process)Phenol resins, Bisphenol A, Benzene, Toluene, ε-Caprolactam CyclopentadieneC 5 cracking fractions,Polymers (for resins, contact Coal taradhesives, printing ink resin) CyclohexaneCrude gasoline,Cyclohexanone (feedstock for Benzene (hydrogenation)nylon precursors) Cyclic Building Block & Aromatics

72. EpichlorohydrinEpoxy resin Structural adhesives Structural sealants Primer paints Electrical insulation Fiber reinforced plastic composites Bisphenol A or Brominated Bisphenol A Tires Rubber hoses Foam for seats Caulks & sealants Bumpers & fenders Vinyl Dashboards Electrical insulation Vinyl tops Floor mats Body side moldings Molded armrests Exterior & interior trim Upholstery Modular window frame units Polyurethanes Polyisocyanates Cl 2 Vinyl chloride monomer Ethylene Cl 2 CO 2 Phosgene Cl 2 Allyl chloride Propylene BTX