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 and PRODUCTION VOLUME BUILDING BLOCKS derived from 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.trace the manufacture of a common chemical from primary sources to final products

2. Genetically modified Food Irreversible cross contamination Possibility of new lectins (autoimmune diseases) Financial risk - importbans in EU, Japan

3. Which ge do we live in ? (A brief history of organic chemistry) 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 (~400 years) CO 2 fixation via: Plants, Animals (endothermic) CO 2 fixation (endothermic) 1850-Plants, Animals

4. Cost vs. Demand in the Chemical Industry 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

5. Organic Chemical Industry Characteristics 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   – –

6. Example of a Specialty Chemical E.g., a heat-stabilizer additive for flexible PVC film Could be a mixture of: Zn and Ca stearates triisononyl phosphite epoxidized soybean oil Could be formulated as a liquid concentrate with a minimal amount of di(2-ethylhexyl)phthalate. The producer keeps the exact identities and proportions of the metal soaps, phosphite esters, epoxidized oils, and plasticizers secret, giving the customer only the proportions of additive to be used per 100g of resins.

7. What is meant by a “Building Block”? 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 obtained more or less directly from: petroleum refining natural gas coal ammonia carbon dioxide renewable resources

8. Primary, Secondary, and Tertiary Organic Building Blocks that are in the Top 50 Chemicals in the U.S. Economy Primary Building Blocks Secondary BBs Tertiary BBs Ethylene ethylene dichloridevinyl chloride ethylene oxideethylene glycol ethyl benzenevinyl acetate Propylene propylene oxide acrylonitrile isopropyl alcohol cumeneacetone n-butyl alcohol Benzene ethyl benzenestyrene cumenephenol acetone bisphenol A Methanol acetic acidvinyl acetate formaldehyde MTBE Toluene Xylenes terephthalic acid Butadiene Urea

9. A Closer Look at the Principle Sources of Primary Organic Building Blocks Natural Gas:methane (85%)-161.4°C ethane (9%)-88°C propane (3%)-42°C butanes (1%-0.5°C nitrogen (1%) Liquid petroleum gasses (LPGs) Crude Petroleum :LPGs light naphtha or straight-run gasoline 50-100°C heavy naphtha (  C 10 ) 150-200°C kerosene, jet fuel (  C 16 ) 175-275°C gas oils, diesel fuel (  C 25 ) 200-400°C lubricating oils 350+°C light fuel oil, heavy fuel oil, bunker oil residue: asphalt Boiling pt.

10. Coal is used as:fuel (electric power plants, etc.) precursor of coke (crude form of elementary C) source of syngas (synthesis gas)

11. C 1 Chemistry 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 + Cl 2 R-C=N=O for 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)

12. C 2 Chemistry 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

13. C 3 Chemistry 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

14. C 4 Chemistry 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=CHCH=CH 2 Cracking of C n  4 Elastomers (i.e., synthetic (1,3-butadiene)rubbers), Chloroprene, THF

15. C 5 and Higher Acyclic Building Blocks 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, carboxylic acids,(plant)Food industry, Pharmaceuticals, Monosodium glutamate (MSG)Laundry products, etc.

16. Cyclic Building Blocks - Aromatics 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)

17. 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

18. Aspirin

19. Origin of the Other Reagents 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 AcetateAcetic acidMethanol + CO (Monsanto process) NaOHElectrolysis of brine (NaCl + H 2 O) “chloralkali cell”