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 C1, C2, C3, C4 and higher acyclic and
cyclic organic building blocks
3.
trace the manufacture of a common
chemical from primary sources to final
products
Which ge do we live in ?
(A brief history of organic chemistry)
1850-
Plants, Animals
1850+
1920+
Coal Tar (side product of “coal gasification”)
Acetylene (from CaC2, Reppe Chemistry)
1950+
Ethylene (from oil)
1973+
CH4, CO/H2 (syngas)
Future:
CO/H2 from Coal, exothermic (~400 years)
CO2 fixation via:
• Plants, Animals
• CO2 fixation
(endothermic)
(endothermic)
Cost vs. Demand in the Chemical Industry
>100
Medicinals and other specialties
Flavours, fragrances
Dyes
10
Specialties
Fine
Chemicals
1
Common plastics
Resins, Elastomers
Pseudo-commodities
Organic intermediates
Commodities
Primary organic
building blocks
0.1
Inorganic heavy
chemicals
0.01
105
106
107
108
109
Demand (lb/y)
1010
1011
1012
Organic Chemical Industry Characteristics
INDUSTRY CHARACTERISTICS
Product life cycle
# of products
Product volumes
Product prices
Product differentiation
Value added
Capital intensity
R&D focus
BULK CHEMICALS
FINE CHEMICALS
SPECIALTY CHEMICALS
Long
> 100
Moderate
>1,000
Short/moderate
>50,000
>10,000t/y
<10,000t/y
highly variable
<5 $/kg
>5 $/kg
>10 $/kg
none
very low
high
low
high
high
high
process
moderate
process
moderate/low
application
KEY SUCCESS FACTORS



• technical service
–


• links with customer
–
• cost


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.
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
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 dichloride
ethylene oxide
ethyl benzene
vinyl chloride
ethylene glycol
vinyl acetate
Propylene
propylene oxide
acrylonitrile
isopropyl alcohol
cumene
n-butyl alcohol
acetone
Benzene
ethyl benzene
cumene
styrene
phenol
acetone
bisphenol A
Methanol
acetic acid
formaldehyde
MTBE
vinyl acetate
Toluene
Xylenes
Butadiene
Urea
terephthalic acid
A Closer Look at the Principle Sources of
Primary Organic Building Blocks
Boiling pt.
Natural Gas:
Liquid petroleum
gasses (LPGs)
Crude Petroleum :
methane (85%)
ethane
(9%)
propane (3%)
butanes (1%
nitrogen (1%)
-161.4°C
-88°C
-42°C
-0.5°C
LPGs
light naphtha or straight-run gasoline
heavy naphtha ( C10)
kerosene, jet fuel ( C16)
gas oils, diesel fuel ( C25)
lubricating oils
light fuel oil, heavy fuel oil, bunker oil
residue: asphalt
50-100°C
150-200°C
175-275°C
200-400°C
350+°C
Coal is used as: fuel (electric power plants, etc.)
precursor of coke (crude form of elementary C)
source of syngas (synthesis gas)
S
CCl 4
MeOH, AcOH, Ac2O
Rayon
R2N
S
O
NH3 (6%)
CH4, H2S, CO, H2 (14%)
Cl
CS 2
Cl
SiC
CO H2
calcium
cyanamide CaN C NH
Oxo chemicals
Coal
CaC 2
Coke
acetylene
HC CH
Water gas: H2 (51%), CO (42%), CO2 (6%), N2 (1%)
Metallurgy
Fuel & exports
n
Producer gas: N2 (75%), CO2 (14%), CO (10%), Ar (1%)
Road Tar
Coal Tar
Tar
O
Electrodes
and C fibers
Pitch
Naphtha BTX
Indene
Coumarone
(benzene, toluene, xylenes)
Tar bases
CH 3
Anthracene
Phenanthrene
Light Oil
CH 3
H2C
CH 2
CH 3
N
N
N
Tar acids
OH
Cresols
Creosote
Phenol
Xylenols
CH 3
Acenaphthene
N
H
Carbazole
CH 3
CH 3
C
H2
Fluorene
C1 Chemistry
C1 building block
Source
Use
CH4 (methane)
Natural gas
energy, H2, CO, CH(4-x)Clx
CO (carbon monoxide)
Coal (as Syngas)
CH3OH, HCOOH, esters,
amides, Oxo acids, etc.
CH3OH (methanol)
CO + 2H2
Cracking of C3H8, C4H10
H2CO, MTBE, CH(4-x)Clx,
CH3COOH
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)
thiourea
S8 + Coke or CH4
Cellulosics, M+SCN–,
Cl2CO (phosgene)
polyurethanes
CO + Cl2
R-C=N=O for
(H2N)2CO (urea)
NH3 + CO2
Fertilizer, Resins (UF)
HCN (hydrogen cyanide)
HCONH2 - H2O
byproduct (acrylonitrile)
Methacrylonitrile, ClCN
C2 Chemistry
C2 building block
Source
Use
CH2=CH2 (ethylene)
thermal cracking of natural
gas, refinery gas, crude oil
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)
CH3CH=O (acetaldehyde)
Wacker-Hoechst (ethylene)
Monsanto process (MeOH)
CH3COOH, Acetic anhydride,
Peracetic acid CH3C(=O)OOH,
Aldol condensation products
CH3COOH (acetic acid)&
CH3COOCOCH3 (acetic
anhydride)
Monsanto process (MeOH)
Oxidation of C4-C8 hydrocarbons or acetaldehyde
Vinyl acetate (PVA), Cellulose
acetate, Solvent, Acetate salts,
Chloroacetic acids
HCCH (acetylene)
Coal via CaC2 or
from hydrocarbons
1,4-Butanediol, vinyl acetate
C3 Chemistry
C3 building block
Source
Use
CH3CH2CH3 (propane)
LPG
Propylene, energy
CH3CHCH2 (propene)
Thermal cracking of LPG,
natural and refinery gas
Polypropylene, Acrylonitrile,
Oxo products (butyraldehyde,
butanol, etc.),Propylene oxide
Isopropanol, Cumene,
Oligomers (nonene, dodecene,
heptene)
CH3COCH3
(acetone)
Hock process (coproduct)
Isopropanol (dehydrogen’n)
Wacker-Hoechst (propene)
Methyl methacrylate, Methyl
isobutyl ketone, Bisphenol A,
Aldol condensation products,
Solvent
CH3CH2COOH
(propionic acid)
CH2CH2 (hydroformylation)
Food preservative, Amyl and
Vinyl propionate, Herbicides
C4 Chemistry
C4 building block
Source
Use
C4H10 (butanes)
LPG
1-Butene, Maleic anhydride,
MTBE, thiophene
C4H8 (butenes, isobutene)
Cracking of Cn4
Polymer/alkylate gasoline,
Polymers/copolymers, alcohols
C4H9OH (butyl alcohols)
Propene, acetaldehyde
MEK, Solvent, Fuel additive
CH3(CH2)2CHO
(butyraldehydes)
Propene, acetaldehyde
2-Ethylhexanol, Trimethylolpropane
Maleic anhydride
Oxidation of C4-feedstocks
Benzene (V2O5 catalyst)
Unsaturated polyester resins,
Fumaric acid, Pesticides
HO(CH2)4OH
(1,4-butanediol)
Acetylene
1,3-butadiene
poly(1,4-butylene terphthalate)
THF, H2N(C4H8)NH2
H2C=CHCH=CH2
(1,3-butadiene)
Cracking of Cn4
Elastomers (i.e., synthetic
rubbers), Chloroprene, THF
O
O
O
C5 and Higher Acyclic Building Blocks
Primary Building Blocks
Source(s)
Use
Petroleum: CnHn+2 (n5)
(pentanes, hexanes, heptanes, etc.,
and other n-paraffins)
Fossil fuels
Solvent, Fuel, Lubricant,
Alkylbenzenes, Alcohols,
Chlorinated paraffins,
Lower m.w. alkanes/olefins
Mineral waxes: Ozocerite,
Montan wax
Fossil fuels
(lignite)
Coatings
Fatty Acids: Lard, Tallow, Palm
oil, Corn oil, Castor oil, etc.
Renewable
(animal/plant)
PVC stabilizer, Surfactant,
Glycerine, Methyl laurate,
Fatty amines (antistatic agents)
Tall-Oil Fatty Acids (TOFA)
Renewable
(pulp byproduct)
Fuel in pulping operations,
Dimer/trimer acids for coatings
Terpenes
Renewable
(plant)
Fragrance/flavour “essential”
oils, Turpentine
Fermentation Products:
amyl alcohols, carboxylic acids,
Monosodium glutamate (MSG)
Renewable
(plant)
H2S removal from refinery gas,
Food industry, Pharmaceuticals,
Laundry products, etc.
Cyclic Building Blocks - Aromatics
Building blocks
Source
Use
Benzene
C6H6
Coal, Oil, Petroleum
(thermal/catalytic process)
Ethylbenzene (for styrene),
Cumene (for phenol/acetone),
Cyclohexane, Nitroenzene
Toluene
C6H5CH3
Coal, Oil, Petroleum
(thermal/catalytic process)
Solvent, Benzoic acid, Phenol,
Nitrotoluenes, aminotoluenes
Xylenes
C6H4(CH3)2
Coal, Oil, Petroleum
(thermal/catalytic process)
Phthalic acids and anhydrides
(plasticizers, synthetic fibers)
Cumene C6H5CH(CH3)2
Benzene
Hock process (phenol/acetone)
Phenol C6H5OH
Cumene (Hock process)
Benzene, Toluene,
Phenol resins, Bisphenol A,
ε-Caprolactam
Cyclopentadiene
C5 cracking fractions,
Coal tar
Polymers (for resins, contact
adhesives, printing ink resin)
Cyclohexane
Crude gasoline,
Benzene (hydrogenation)
Cyclohexanone (feedstock for
nylon precursors)
• Structural adhesives
• Structural sealants
Cl2
Allyl chloride
Epichlorohydrin
• Primer paints
Epoxy resin
• Electrical insulation
Propylene
• Dashboards
• Electrical insulation
• Vinyl tops
• Floor mats
• Upholstery
• Modular window
frame units
BTX
• Fiber reinforced plastic
composites
Bisphenol A or
Brominated Bisphenol A
Ethylene
Vinyl
Vinyl chloride
monomer
Cl2
• Body side moldings
• Molded armrests
• Exterior & interior trim
• Tires
• Rubber hoses
• Foam for seats
• Caulks & sealants
• Bumpers & fenders
CO2
Polyurethanes
Polyisocyanates
Phosgene
Cl2
Aspirin
O
OH
O
O
CH 3
OH
OH
O
+
T < 90C
O
Acetyl Salicylic Acid
A.S.A.
90% yield
H3C
liquid phase
50C, 3-4 bar
1. CO2
2. H2SO4
O
OH NaOH
Shawinigan
(Canada)
Cu(acetate) 2
ONa
H3C
+
O2
H
Acetaldehyde
2. H2SO4
Phenol
Kellogg/Monsanto
H2SO4
liquid phase
T & P > STP
+
catalytic
processes
CH 3
Acetic anhydride
Kolbe-Schmitt
reaction
1. O2
Benzene
O
Salicylic Acid
Hock
process
Cumene
O
FOSSIL FUELS:
LPG, Coal, Petroleum, etc.
thermal
cracking
H2C CH 2
Ethylene
Propylene
thermal
cracking
PdCl2 / CuCl2
+
0.5 O2
Wacker-Hoechst
Process
Origin of the Other Reagents
Cu
Mined as an ore and refined
Pd
Mined and refined (Sudbury, Ontario: “anode slime”
H2SO4
H2O + 0.5 O2 + SO2
O2
Fractional distillation of liquid air
Acetate
Acetic acid
NaOH
Electrolysis of brine (NaCl + H2O) “chloralkali cell”
pyrometallurgical byproduct
Methanol + CO (Monsanto process)
Hydroformylation (“Oxo Process”