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Lecture Topic 3: Industrial Organic ChemistryRef: 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 andof C1, C2, C3, C4 and higher acyclic andcyclic organic building blocks

3. the manufacture of a common chemical fromsources to final products

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0.01

0.1

1

10

100

Demand (lb/yr)

Unitcost($/lb)

Demand (lb/y)

Un

itc o

st ( $

/ lb

)

0.01

0.1

1

10

>100

Cost - Volume

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KEY SUCCESS FACTORS

cost

technical service

links with customer

INDUSTRY CHARACTERISTICS BULK CHEMICALS FINE CHEMICALS SPECIALTY CHEMICALS

Long Moderate Short/moderate

> 100 >1,000 >50,000

>10,000t/y 10 $/kg

none very low highlow high high

high moderate moderate/low

process process application

Product life cycle

# of products

Product volumes

Product prices

Product differentiation

Value added

Capital intensity

R&D focus

Cost/Volume: Implications

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1850+ Coal Tar (side product of coke production)

1920+ Acetylene (from CaC2, Reppe Chemistry)

1950+ Ethylene (from oil)

1973+ CH4, CO/H2(syngas)- oil, gas, coal

Future I CO/H2 from Coal (exothermic)

Future II CO2 fixation via:

(+50 y) Plants, Animals (endothermic)

catalysts (endothermic)

1850- Plants (example Dyes), Animals (example soap)

History of Organic Materials in Building Blocks

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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

What is a Building Block

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Walter Julius Reppe

BASF Ludwigshafen

HC CH

Ni(CN)2

C C CH2

CH2

HO

OH

Ni(CN)2

PPh3

O

CH2O

Co(I)

N

R

C NR

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 & C1 Chemistry.

Interesting: Inorganicentry (CaC2) into organic chemistry.

Still very useful for high value fine chemicals

Could make a comeback with cheap energy.

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The Age of Acetylene: THF

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Building Blocks: Primary, Secondary

Ethylene ethylene dichloride vinyl chloride

ethylene oxide ethylene glycol

ethyl benzene vinyl acetate

Propylene propylene oxide

acrylonitrile

isopropyl alcohol

cumene acetone

n-butyl alcohol

Benzene ethyl benzene styrene

cumene phenol

acetone

bisphenol A

Methanol acetic acid vinyl acetateCH4, syngas formaldehyde

MTBE (Me-O-tBu)

Toluene

Xylenes terephthalic acid Polyester

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The C1-Highway

C1

Chemistry in a nutshell:

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C1-Chemistry and the Power of Syngas

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(+) From: Natural Gas (CH4

)

Crude Oil

Coal 1976 3%

1982 12%

2000 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)

Syngas: A Second Look

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A Brief History of Syngas (H2/CO)

First industrial production of syngas to obtain H2 for ammonia synthesis CO

CO is washed out with Cu(I)-amine solutions.

Synthetic fuelcrucial 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

Largest homogeneously catalyzed process

Origin of modern transition metal catalysis

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Production of Organometallics

- Silicones 900.000 t/a

- Al-Alkyles 90.000 t/a

- Sn-Alkyles 35.000 t/a

Products obtained with organometallic catalysts

- Polypropylene 17.000.000 t/a

- Polyethylene 36.000.000 t/a- Oxo-Products 5.000.000 t/a

- Acetaldehyd 2.200.000 t/a

- Acetic Acid 1.000.000 t/a

Intermezzo: Organometallics in Industry

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Organometallic Catalysis: Processes

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Organometallic Catalysis: Value

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The Start of C1 Chemistry: Hydroformylation (Oxo Process)

tries to find out why the Co catalyzedFischer 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 )

1980 Use of watersoluble Rh-phosphine complexes

2004: 75% use Rh;

Major process to

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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

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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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Nothing is more practical than a good

theory (Ludwig Boltzmann)

For H2/CO =1:1 the reaction rate is

pressure independent (!) due to theopposing orders of H2 and CO.

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

Rate Laws and Industrial Processes

Rate laws obtained from Measurements

A mechanistic hypothesis

d (Aldehyde)

dt= k [Alkene] [Cat]

[CO]

[H2]

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Catalyst Stability: Example Hydrolformylation

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

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Types of Industrial Catalysts

Heterogeneous (insoluble, high p, high T) Pt

Homogeneous (soluble, low T, any p) Co2(CO)8

Enzymes (expensive, low T, low p, bound to water) yeast

Heterogeneous < Homogeneous < Enzyme

Heterogeneous < Homogeneous < Enzyme

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Heterogeneous Catalyst Design

Surface areaporosityaciditydensitycomposition

ActivitySelectivityStability

MechanicalStability

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P

O3S

O3S

SO3 Na

Na

Na

TPPTS

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.

Using TPPTS instead of PPh3 gives a highly water soluble

catalyst:

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))

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

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Franz Joseph Emil

Fischer

Kaiser-Wilhelm Institut

Mlheim

1913 Director of the newly founded Kaiser-Wilhelm-Institute for Coal Research (Mlheim / Ruhr

1925 Discovers formation of hydrocarbons from

Syngas with Hans Tropsch

Fischer Tropsch Chemistry: 1925 +

CO (CH2)nH2+Ni/Co

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1. Carbide-methylene

2. Hydroxycarbene

3. CO insertion/M-Me

Fischer Tropsch Chemistry: Mechanisms

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26Sasol Plant, South Africa

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Sasol Plant, South Africa

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The C1-Chemistry Databasehttp://www.aist.go.jp/RIODB/c1db/index.html

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Natural gas energy, H2, CO, CH(4-x)Clx

Coal (as Syngas) CH3OH, HCOOH, esters,amides, Oxo acids, etc.

CO +2H2 H2CO, MTBE, CH(4-x)Clx,Cracking of C

3

H8

, C4

H10

CH3

COOH

H2CO (formaldehyde) CH3OH, Cracking of LPG Polymers (UF, PF, POM)

HCOOH (formic acid) CO + H2O Fine chemicals

CO2(carbon dioxide) Water-gas-shift rxn. Supercritical fluids (SCFs)

CS2

(carbon disulfide) S8

+ Coke or CH4

Cellulosics, M+SCN, thiourea

Cl2CO (phosgene) CO + Cl2 R-C=N=O polyurethanes

(H2N)2CO (urea) NH3+ CO2 Fertilizer, Resins (UF)

HCN (hydrogen cyanide) HCONH2- H2O Methacrylonitrile, ClCNbyproduct (acrylonitrile)

C1 Chemistry

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thermal cracking of naturalgas, refinery gas, crude oil

Polymers (Polyethylenes etc.)Alphaolefins (LDPE), PVCPolystyrene, Polyvinyl acetatePolyethylene oxide

CH3CH2OH (ethanol) fermentation, Gasoline additive (USA),

hydration of ethylene Ethylene by dehydration(Brazil, India, Peru, Pakistan),Solvent, Esters (ethyl chloride,ethyl acetate)

CH3CH=O (acetaldehyde) Wacker-Hoechst (ethylene) CH3COOH, Acetic anhydride,Monsanto process (MeOH) Peracetic acid CH3C(=O)OOH,

Aldol condensation products

CH3COOH (acetic acid)& Monsanto process (MeOH) Vinyl acetate (PVA), CelluloseCH3COOCOCH3(acetic Oxidation of C4-C8 hydro- acetate, Solvent, Acetate salts,anhydride) carbons or acetaldehyde Chloroacetic acids

HCCH (acetylene) Coal via CaC2 or 1,4-Butanediol, vinyl acetatefrom hydrocarbons

C2 Chemistry

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CH3CH2CH3(propane) LPG Propylene, energy

, , ,(butyraldehyde,

butanol, etc.),Propylene oxide

Isopropanol, Cumene,Oligomers (nonene, dodecene,heptene)

Hock process (coproduct) , Methyl(acetone) Isopropanol (dehydrogenn) isobutyl ketone, Bisphenol A,

Wacker-Hoechst (propene) Aldol condensation products,Solvent

CH3CH2COOH CH2CH2(hydroformylation) Food preservative, Amyl and(propionic acid) Vinyl propionate, Herbicides

C3 Chemistry

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C4H10(butanes) LPG 1-Butene, Maleic anhydride,MTBE, thiophene

(butenes, ) Cracking of Cn4 Polymer/alkylate gasoline,Polymers/copolymers, alcohols

, acetaldehyde MEK, Solvent, Fuel additive

CH3(CH2)2CHO , acetaldehyde 2-Ethylhexanol, Trimethylol-(butyraldehydes) propane

Maleic anhydride Oxidation of C4-feedstocks Unsaturated polyester resins,Benzene (V2O5 catalyst) Fumaric acid, Pesticides

(Acetylene, obsolete) poly(1,4-butylene terphthalate)THF, H2N(C4H8)NH2

OOO

C4 Chemistry

Cracking of Cn4(1,3-butadiene)

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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

CH3OH + CO H3C C

O

OH

[Rh, I-] 60 atm

250 oC

corrosion problems

Has largely replaced the two step Wacker process:

H3C C

O

OH

H3C C

O

H

H2C CH2 + H2O

[PdCl2] O2

Acetic acid is one of the most important secondary C2-building blocks and used

to make vinylacetetate (foils), cellulose acetate

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CnHn+2(n5) Fossil fuels Solvent, Fuel, Lubricant,(pentanes, hexanes, heptanes, etc., Alkylbenzenes, Alcohols,and other n-paraffins) Chlorinated paraffins,

Lower m.w. alkanes/olefins

Ozocerite, Fossil fuels CoatingsMontan wax (lignite)

Lard, Tallow, Palm Renewable PVC stabilizer, Surfactant,oil, Corn oil, Castor oil, etc. (animal/plant) Glycerine, Methyl laurate,

Fatty amines (antistatic agents)

Tall-Oil Fatty Acids (TOFA) Renewable Fuel in pulping operations,(pulp byproduct) Dimer/trimer acids for coatings

Terpenes Renewable Fragrance/flavour essential(plant) oils, Turpentine

Fermentation Products: Renewable H2S removal from refinery gas,Amyl alcohols (plant) Carboxylic acids, Food industry, Pharmaceuticals, Monosodium glutamate (MSG) Laundry products, etc.

C5 And higher (acyclic)

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Coal, Oil, Petroleum Ethylbenzene (for styrene),C6H6 (thermal/catalytic process) Cumene (for phenol/acetone),

Cyclohexane, Nitroenzene

Coal, Oil, Petroleum Solvent, Benzoic acid, Phenol,C6H5CH3 (thermal/catalytic process) Nitrotoluenes, aminotoluenes

Coal, Oil, Petroleum Phthalic acids and anhydridesC6H4(CH3)2 (thermal/catalytic process) (plasticizers, synthetic fibers)

Cumene C6H5CH(CH3)2 Benzene Hock process (phenol/acetone)

Phenol C6H5OH Cumene (Hock process) Phenol resins, Bisphenol A,Benzene, Toluene, _-Caprolactam

Cyclopentadiene C5 cracking fractions, Polymers (for resins, contact

Coal tar adhesives, printing ink resin)

Cyclohexane Crude gasoline, Cyclohexanone (feedstock forBenzene (hydrogenation) nylon precursors)

Cyclic Building Block & Aromatics

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Oil, Gas & Coal: Oil Producing Countries

Mio t

Venezue

la

Sau

di-Ara

bia

Russ

ia

Iran

USA

Mex

ico

Cana

da

China

Norway

UAEm

ira

tes

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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

Coal - Oil - Coal ?

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CHM 4010CHM 4010CHM 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 toOil as raw material for the chemical industry"

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Coal Coke

Coal TarRoad Tar

Pitch

Light OilTar bases

Tar acidsN N N

CH3

CH3

O

NH

MetallurgyFuel & exports

Electrodesand C fibers

Producer gas: N2 (75%), CO2 (14%), CO (10%), Ar (1%)

Water gas: H2 (51%), CO (42%), CO2 (6%), N2 (1%)

CH3

CH2

Carbazole

Fluorene

PhenanthreneAnthracene

H2C CH2

Acenaphthene

Indene Coumarone

CH3

CH3

CH3

Tar

OH

Phenol

CreosoteCresols

Xylenols

Naphtha BTX(benzene, toluene, xylenes)

NH3 (6%)CH4, H2S, CO, H2 (14%) CO H2

Oxo chemicals

O

Cl Cl

MeOH, AcOH, Ac2O

CS2

CCl4

SiC

Rayon

CaC2

R2N

S

S

n

acetylene HC CH

C NHCaN

calciumcyanamide

CHM 4010CHM 4010CHM 4010 The Coal Tree

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CHM 4010CHM 4010CHM 4010 Top Four Condensed Aromatics

O

O

O

O

O

O

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O

O OH

CH3

O

Acetyl Salicylic AcidA.S.A.

90% yield

OH

O OH

Salicylic Acid

+ H3C O

O

CH3

O

Acetic anhydride

H3C H

O

Acetaldehyde

Cu(acetate)2

liquid phase50EC, 3-4 bar

O2+

Shawinigan(Canada)

PdCl2 / CuCl2Wacker-HoechstProcess

H2C CH2 O2+ 0.5

Ethylene

ONaNaOHOH

Phenol

2. H2SO4

Kolbe-Schmittreaction

2. H2SO4

1. O2

Hockprocess

Cumene

+

Benzene Propylene

FOSSIL FUELS:LPG, Coal, Petroleum, etc.

catalyticprocesses

thermalcracking

1. CO2

thermalcracking

liquid phaseT & P > STP

H2SO4

Kellogg/Monsanto

T < 90EC

Building Block Analysis: Aspirin

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Cu Mined as an ore and refined

Pd Mined and refined (Sudbury, Ontario: anode slime)

H2SO4 H2O +0.5 O2+ SO2 pyrometallurgical byproduct

O2 Fractional distillation of liquid air

Acetic acid Methanol + CO (Monsanto process)

NaOH Electrolysis of brine (NaCl + H2

O)chloralkali cell

Aspirin: Origin of other Reagents

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1. Natural gas: C1

2. Propane: C3

3. Gasoline: C7- C9

4. Naphta C6-C11

5. Kerosene (Paraffin): C11-C18

5. Diesel oil C13-C15

6. Lubricating Oil C18-C25

7. Fuel oil C20-C27

1. Gases

2. Petrol

3. Naphta

4. Kerosene

5. Diesel oil

6. Lubricating Oil7. 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

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NameNumberof

Carbon Atoms

Boiling Point

(C)

Uses

Refinery Gas 3 or4 below30Bottled Gas(propane or

butane).

Petrol 7 to 9 100 to150Fuel forcar

engines.

Naphtha 6 to 11 70 to200Solvents

and used in

petrol.Kerosene(paraffin)

11 to 18 200 to300Fuel foraircraft

and stoves.

Diesel Oil 11 to 18 200 to300Fuel forroad

vehiclesand trains.

Lubricating Oil 18 to 25 300 to400Lubricant for

enginesand machines.

Fuel Oil 20 to 27 350 to450Fuel forshipsand heating.

GreasesandWax

25 to 30 400 to500Lubricants

and candles.

Bitumen above 35 above 500Road surfaceand roofing.

Distillates - A second look

Higher boiling fractions

distilled under vacuum

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Petrol and Diesel engines operate differently

A high tendency to autoignite is undesirable in a gasoline engine butdesirable in a diesel engine.

We need two rating systems

Fuel: Gasoline vs. Diesel

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Developed by the chemist Russel Marker

Isooctane (2,2,4-trimethylpentane)=100

n-heptanee =0.

87-octane equivalent to a mixture of87 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 of129

Liquified petroleum gass (LPG)>110.

Octane Number

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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

But: Still used in aviation fuels !

Octane Boosters: Et4Pb

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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)

PbEt4and its early competitor: Ethanol