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 Ability to 1. identify bulk, fine and specialty chemicals 2. give examples of primary building blocks and of C1, C2, C3, C4 and higher acyclic and cyclic organic building blocks 3. the manufacture of a common chemical from sources to final products
1

Goal:

Cost - Volume
100 >100

Medicinals and other specialties Flavours, fragrances

10 10

Unit cost ($/lb) Unit cost ($/lb)

Specialties Fine Chemicals

Dyes

Common plastics Resins, Elastomers Organic intermediates Commodities

1 1

Pseudo-commodities

0.1 0.1

Primary organic building blocks Inorganic heavy chemicals

0.01 0.01

105

106

10 7

Demand (lb/y)

Demand (lb/yr)

108

109

1010

101 1

1012
2

Cost/Volume: Implications

INDUSTRY CHARACTERISTICS BULK CHEMICALS

FINE CHEMICALS

SPECIALTY CHEMICALS

Product life cycle # of products Product volumes Product prices Product differentiation Value added Capital intensity R&D focus
KEY SUCCESS FACTORS

Long > 100 >10,000t/y <5 $/kg none low high process

Moderate >1,000 <10,000t/y >5 $/kg very low high moderate process

Short/moderate >50,000 highly variable >10 $/kg high high moderate/low application

cost technical service links with customer

History of Organic Materials in Building Blocks

18501850+ 1920+ 1950+ 1973+ Future I Future II (+50 y) Plants (example Dyes), Animals (example soap) Coal Tar (side product of coke production) Acetylene (from CaC2, Reppe Chemistry) Ethylene (from oil) CH4, CO/H2 (syngas) - oil, gas, coal CO/H2 from Coal CO2 fixation via: Plants, Animals catalysts (exothermic)

(endothermic) (endothermic)
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What is a Building Block

Building block Any (organic) chemical that used to synthesize other (organic) chemicals. 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

The first Building Block: The Age of Acetylene

Walter Julius Reppe
BASF Ludwigshafen

Reppe Chemistry: Make everything from acetylene. Examples

Co(I)
R C N N R

Ni(CN)2 PPh3 Ni(CN)2

HC CH O

CH2O

HO CH2 C

CH2 OH

Tricky technology, acetylene explodes under pressure (~ 5 atm). Acetylene forms explosive salts with heavy metals (no copper tubes & valves !). Largely replaced by ethylene & C1 Chemistry. Interesting: Inorganic entry (CaC2) into organic chemistry. Still very useful for high value fine chemicals Could make a comeback with cheap energy.

The Age of Acetylene: THF

Building Blocks: Primary, Secondary

1 BB
Ethylene

2 BBs
ethylene dichloride ethylene oxide ethyl benzene propylene oxide acrylonitrile isopropyl alcohol cumene n-butyl alcohol ethyl benzene cumene

3 BB
vinyl chloride ethylene glycol vinyl acetate

Propylene

acetone

Benzene

styrene phenol acetone bisphenol A vinyl acetate

Methanol CH4, syngas Toluene Xylenes

acetic acid formaldehyde MTBE (Me-O-tBu)

terephthalic acid

Polyester
8

The C1-Highway
C1 Chemistry in a nutshell:

C1-Chemistry and the Power of Syngas

10

Syngas: A Second Look

(+) From: Natural Gas (CH4) Crude Oil Coal 1976 1982 2000

3% 12 % 16 %

50 % of it SASOL, South Africa

() (+++) (+++)

Energy intensive More than 500 years of coal reserves (-> China, US) Anything can be made from Syngas (as long as it contains carbon or hydrogen) NH3 (Haber-Bosch process) Oxo-products (Hydroformylation Gas, Diesel, Lubricants, waxes.. (Fischer-Tropsch process)

() (+)

Syngas is dirty (CO, CO2, H2, H2S, COS) but easy to clean Very clean Diesel (1 ppm sulfur) from syngas (SASOL, Oryx process)
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A Brief History of Syngas (H2/CO)

Haber Bosch Process First industrial production of syngas to obtain H2 for ammonia synthesis CO CO is washed out with Cu(I) -amine solutions. Fischer-Tropsch: Hydrocarbons from Syngas Synthetic fuel crucial for German war machine Leuna plant alone produced 900,000 t/year, bombed in June 1944 Technology of the future if oil runs out. Expert: SASOL, South Africa

Hydroformylation: Aldehydes, Alcohols, Amines from Syngas Largest homogeneously catalyzed process Origin of modern transition metal catalysis
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Intermezzo: Organometallics in Industry

Production of Organometallics
Silicones Al-Alkyles Sn-Alkyles 900.000 t/a 90.000 t/a 35.000 t/a

Products obtained with organometallic catalysts

Polypropylene Polyethylene Oxo-Products Acetaldehyd Acetic Acid 17.000.000 t/a 36.000.000 t/a 5.000.000 t/a 2.200.000 t/a 1.000.000 t/a
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Organometallic Catalysis: Processes

14

Organometallic Catalysis: Value

15

The Start of C1 Chemistry: Hydroformylation (Oxo Process)

O. Roelen, Ger. Pat., 949 548, 1938. Otto Roelen tries to find out why the Co catalyzed Fischer Tropsch process gives alcohols as side products Largest homogenously catalyzed process in the world (~ 10 billion Kg of aldehydes) 1968: Introduction of phosphines to stabilize catalyst 1970: Rh (better n/iso ratio, but VERY EXPENSIVE) 1980 Use of watersoluble Rh-phosphine complexes 2004: 75 % use Rh; Major process propene to butanol (C3 -> C4)
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Hydroformylation (Oxo Process): Instant Recognition

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.
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Mechanism of the Hydroformylation: From Hieber to Heck

Walter Hieber (right) the pioneer or metal carbonyl chemistry (left:Behrens, his lecture assistant and later notable carbonyl complex researcher).

Heck-Breslow meachnism (1960/61)

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Rate Laws and Industrial Processes

Rate laws obtained from Measurements A mechanistic hypothesis
[H2] [CO]

d (Aldehyde) dt

k [Alkene] [Cat]

Sounds boring, but 1. Nothing is more practical than a good theory (Ludwig Boltzmann) 2. For H2/CO = 1:1 the reaction rate is pressure independent (!) due to the opposing orders of H2 and CO. 3. Increasing the H2/CO ratio seems a good idea, but it turns out that the catalyst HCo(CO)4 requires a minimum CO partial pressures to prevent decomposition
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Catalyst Stability: Example Hydrolformylation

Stability of HCo(CO)4/Co2(CO)8 species vs. metal deposition

20

Types of Industrial Catalysts

Three Types of Catalysts: Heterogeneous (insoluble, high p, high T) Homogeneous (soluble, low T, any p) Enzymes (expensive, low T, low p, bound to water) Pt Co2(CO)8 yeast

Selectivity: Activity:

Heterogeneous < Homogeneous < Enzyme Heterogeneous < Homogeneous < Enzyme

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Heterogeneous Catalyst Design

Mechanical Stability Catalyst Design

Surface area porosity acidity density composition

Activity Selectivity Stability

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Emile Kuntz (Rhone-Poulenc) has a very good idea

Using TPPTS instead of PPh3 gives a highly water soluble catalyst:
Na

TPPTS P
O3 S

SO 3 Na

HRh(CO)[TPPTS Na3]3. In aqueous solution the catalyst essentially has a 9 charge, making it totally insoluble in all but the most polar solvents (E.G. Kuntz, Fr 2,314,910 (1975))

Na

O3S

Alkenes (C2-C4) 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/PPh3 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.
23

Fischer Tropsch Chemistry: 1925 +

Franz Joseph Emil Fischer
Kaiser-Wilhelm Institut Mlheim

1913 Director of the newly founded Kaiser-WilhelmInstitute for Coal Research (Mlheim / Ruhr 1925 Discovers formation of hydrocarbons from Syngas with Hans Tropsch

CO

+ H2

Ni/Co

(CH2)n
24

Fischer Tropsch Chemistry: Mechanisms

1. 2. 3. Carbide-methylene Hydroxycarbene CO insertion/M-Me

25

Sasol Plant, South Africa

26

Sasol Plant, South Africa

27

The C1-Chemistry Database

http://www.aist.go.jp/RIODB/c1db/index.html

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C1 Chemistry
C 1 building block
CH4 (methane) CO (carbon monoxide) CH3OH (methanol) H2CO (formaldehyde) HCOOH (formic acid) CO2 (carbon dioxide) CS2 (carbon disulfide) Cl2CO (phosgene) (H2N)2CO (urea)

Source
Natural gas Coal (as Syngas) CO + 2H2 Cracking of C3H8, C4H10 CH3OH, Cracking of LPG CO + H2O Water-gas-shift rxn. S8 + Coke or CH4 CO + Cl2 NH3 + CO2

Use
energy, H2, CO, CH(4-x)Clx CH3OH, HCOOH, esters, amides, Oxo acids, etc. H2CO, MTBE, CH(4-x)Clx, CH3COOH Polymers (UF, PF, POM) Fine chemicals Supercritical fluids (SCFs) Cellulosics, M+SCN, thiourea R-C=N=O polyurethanes Fertilizer, Resins (UF)
29

HCN (hydrogen cyanide) HCONH2 - H2O Methacrylonitrile, ClCN byproduct (acrylonitrile)

C2 Chemistry
C 2 building block CH2=CH2 (ethylene) Source thermal cracking of natural gas, refinery gas, crude oil Use Feedstock for ~30% of all petrochemicals!! Polymers (Polyethylenes etc.) Alphaolefins (LDPE), PVC Polystyrene, Polyvinyl acetate Polyethylene oxide CH3CH2OH (ethanol) fermentation, hydration of ethylene Gasoline additive (USA), Ethylene by dehydration (Brazil, India, Peru, Pakistan), Solvent, Esters (ethyl chloride, ethyl acetate) CH3COOH, Acetic anhydride, Peracetic acid CH3C(=O)OOH, Aldol condensation products Vinyl acetate (PVA), Cellulose acetate, Solvent, Acetate salts, Chloroacetic acids 1,4-Butanediol, vinyl acetate

CH3CH=O (acetaldehyde)

Wacker-Hoechst (ethylene) Monsanto process (MeOH) Monsanto process (MeOH) Oxidation of C4-C8 hydrocarbons or acetaldehyde Coal via CaC2 or from hydrocarbons

CH3COOH (acetic acid)& CH3COOCOCH3 (acetic anhydride) HCCH (acetylene)

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C3 Chemistry

C3 building block
CH3CH2CH3 (propane) CH3CHCH2 (propene)

Source
LPG Thermal cracking of LPG, natural and refinery gas

Use
Propylene, energy Polypropylene, Acrylonitrile, Oxo products (butyraldehyde, butanol, etc.),Propylene oxide Isopropanol, Cumene, Oligomers (nonene, dodecene, heptene) Methyl methacrylate, Methyl isobutyl ketone, Bisphenol A, Aldol condensation products, Solvent Food preservative, Amyl and Vinyl propionate, Herbicides

CH3COCH3 (acetone)

Hock process (coproduct) Isopropanol (dehydrogenn) Wacker-Hoechst (propene) CH2CH2 (hydroformylation)

CH3CH2COOH (propionic acid)

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C4 Chemistry

C4 building block
C4H10 (butanes) C 4H8 (butenes, isobutene) C 4H9 OH (butyl alcohols) CH3(CH2)2CHO (butyraldehydes) Maleic anhydride
O O O

Source
LPG Cracking of Cn4 Propene, acetaldehyde Propene, acetaldehyde

Use
1-Butene, Maleic anhydride, MTBE, thiophene Polymer/alkylate gasoline, Polymers/copolymers, alcohols MEK, Solvent, Fuel additive 2-Ethylhexanol, Trimethylolpropane Unsaturated polyester resins, Fumaric acid, Pesticides

Oxidation of C4-feedstocks Benzene (V2O5 catalyst)

HO(CH2) 4OH (1,4-butanediol) H2C=CH-CH=CH2 (1,3-butadiene)

(Acetylene, obsolete) 1,3-butadiene Cracking of Cn4

poly(1,4-butylene terphthalate) THF, H2N(C4H8)NH2 Elastomers (i.e., synthetic rubbers), Chloroprene, THF
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The Monsanto Process

First large scale process based on methanol = milestone in the history of building blocks. Development delayed for many years due to corrosion problems
[Rh, I-] CH3OH + CO H3C C OH O

60 atm 250 oC corrosion problems

Has largely replaced the two step Wacker process:

O H2C CH2 + H2O [PdCl2] H3C C H O2 H3C C OH

Acetic acid is one of the most important secondary C2-building blocks and used to make vinylacetetate (foils), cellulose acetate
33

C5 And higher (acyclic)

Primary Building Blocks Petroleum: CnHn+2 (n5) (pentanes, hexanes, heptanes, etc., and other n-paraffins) Mineral waxes: Ozocerite, Montan wax Source(s) Fossil fuels Use Solvent, Fuel, Lubricant, Alkylbenzenes, Alcohols, Chlorinated paraffins, Lower m.w. alkanes/olefins Coatings

Fossil fuels (lignite)

Fatty Acids: Lard, Tallow, Palm oil, Corn oil, Castor oil, etc. Tall-Oil Fatty Acids (TOFA) Terpenes Fermentation Products: Amyl alcohols Carboxylic acids, Monosodium glutamate (MSG)

Renewable (animal/plant) Renewable (pulp byproduct) Renewable (plant) Renewable (plant)

PVC stabilizer, Surfactant, Glycerine, Methyl laurate, Fatty amines (antistatic agents) Fuel in pulping operations, Dimer/trimer acids for coatings Fragrance/flavour essential oils, Turpentine H2S removal from refinery gas, Food industry, Pharmaceuticals, Laundry products, etc.
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Cyclic Building Block & Aromatics

Building blocks
Benzene C6H6 Toluene C6H5CH3 Xylenes C6H4(CH3)2 Cumene C6H5CH(CH3)2 Phenol C6H5OH Cyclopentadiene Cyclohexane

Source
Coal, Oil, Petroleum (thermal/catalytic process) Coal, Oil, Petroleum (thermal/catalytic process) Coal, Oil, Petroleum (thermal/catalytic process) Benzene Cumene (Hock process) Benzene, Toluene, C5 cracking fractions, Coal tar Crude gasoline, Benzene (hydrogenation)

Use
Ethylbenzene (for styrene), Cumene (for phenol/acetone), Cyclohexane, Nitroenzene Solvent, Benzoic acid, Phenol, Nitrotoluenes, aminotoluenes Phthalic acids and anhydrides (plasticizers, synthetic fibers) Hock process (phenol/acetone) Phenol resins, Bisphenol A, _-Caprolactam Polymers (for resins, contact adhesives, printing ink resin) Cyclohexanone (feedstock for nylon precursors)

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Mio t

Saudi-Arabia Russia USA Iran Mexico China Venezuela Canada Norway

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Oil, Gas & Coal: Oil Producing Countries

UA Emirates

Coal - Oil - Coal ?

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: US China Minus: Cant be pumped (no pipeline) Transport expensive unless close to water High in sulfur
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CHM 4010

Building Blocks from Coal

Coal
Only 11 % of Benzene Aromatics 95 % of Condensed Aromatics Carbon Black, Graphite

"Long Term, Coal is the only plausible alternative to Oil as raw material for the chemical industry"
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CHM 4010
O NH3 (6%) CH4, H2S, CO, H2 (14%) Cl

The Coal Tree

MeOH, AcOH, Ac2O Cl CS2 CO H2 SiC CCl4 S Rayon R2N S

Oxo chemicals Coal Coke CaC2

calcium cyanamide CaN C NH acetylene HC CH

Fuel & exports Road Tar Coal Tar

Metallurgy

Water gas: H2 (51%), CO (42%), CO2 (6%), N2 (1%) Producer gas: N2 (75%), CO2 (14%), CO (10%), Ar (1%) Tar O

Electrodes and C fibers

Pitch Naphtha BTX Indene Coumarone Anthracene Phenanthrene

(benzene, toluene, xylenes)

Tar bases CH3 N N N CH3 CH3

Light Oil H2C Tar acids OH CH3 CH3 CH3 C 39 H2 Fluorene Acenaphthene CH2 N H Carbazole

Cresols Xylenols

Creosote Phenol

CHM 4010 Top Four Condensed Aromatics

O

600,000 tons
O

Xylenes

Naphtalene

Phtalic Anhydride

100,000 tons

Indene

Thermoplastic resins Inks Rubber

O

Coumarone

40,000 tons
O

Dyes H 2O 2 Anthracene Anthraquinone 40

Building Block Analysis: Aspirin

O OH O O CH3 T < 90EC O OH OH O O O CH3

H3C

Acetyl Salicylic Acid A.S.A. 90% yield

Hock process 1. O2 2. H2SO4

Salicylic Acid

Acetic anhydride
liquid phase 50EC, 3-4 bar Shawinigan (Canada)

Kolbe-Schmitt reaction

1. CO2 2. H2SO4 ONa H3C O

Cu(acetate)2

OH NaOH

O2

Acetaldehyde Phenol FOSSIL FUELS: LPG, Coal, Petroleum, etc.

thermal cracking PdCl2 / CuCl2 Wacker-Hoechst Process

Cumene

Kellogg/Monsanto H2SO4 liquid phase T & P > STP

+
Benzene
catalytic processes

H2C CH2

0.5 O2

Ethylene Propylene
thermal cracking

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Aspirin: Origin of other Reagents

Cu Pd H2SO4 O2 Acetic acid NaOH

Mined as an ore and refined Mined and refined (Sudbury, Ontario: anode slime) H2O + 0.5 O2 + SO2 pyrometallurgical byproduct

Fractional distillation of liquid air Methanol + CO (Monsanto process) Electrolysis of brine (NaCl + H2O) chloralkali cell

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Oil: From Crude Oil to Distillates

Classified by b.p.
1. 2. 3. 4. 5. 6. 7. 8. 9. Gases Petrol Naphta Kerosene Diesel oil Lubricating Oil Fuel oil Greases & Waxes Bitumen

Classified by Use
1. 2. 3. 4. 5. 5. 6. 7. Natural gas: Propane: Gasoline: Naphta C1 C3 C7 - C9 C6-C11

Kerosene (Paraffin): C11-C18 Diesel oil Lubricating Oil Fuel oil C13-C15 C18-C25 C20-C27

Good source of information: http://tonto.eia.doe.gov/dnav/pet/pet_pnp_top.asp 43

Distillates - A second look

Name Refinery Gas Petrol Naphtha Kerosene (paraffin) Diesel Oil Number of Carbon Atoms 3 or 4 7 to 9 6 to 11 11 to 18 11 to 18 Boiling Point (C) below 30 100 to 150 70 to 200 200 to 300 200 to 300 Uses Bottled Gas (propane or butane). Fuel for car engines. Solvents and used in petrol. Fuel for aircraft and stoves. Fuel for road vehicles and trains. Lubricant for engines and machines. Fuel for ships and heating. Lubricants and candles. Road surface and roofing.

Lubricating Oil Fuel Oil Greases and Wax Bitumen

18 to 25 20 to 27 25 to 30 above 35

300 to 400 350 to 450 400 to 500 above 500

Higher boiling fractions distilled under vacuum

44

Fuel: Gasoline vs. Diesel

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

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Octane Number
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.
46

Octane Boosters: Et4Pb

Peak Deficits of high octane fuels: 1940 + WW II (aircrafts) 1960 + Polyesters (Terephatic acid) deplete aromatics

Quick Fix (Kettering & Midgley, GM, Dupont, 1924+) Tetraethyllead PbEt4 (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 catalysts allows upgrading of fuel at refinery
47

But:

Still used in aviation fuels !

PbEt4and its early competitor: Ethanol

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 48 Court decision in 1940. (Nebraska Historical Society)