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 commonchemical from primary sources to finalproducts

Genetically modified Food

Irreversible cross contaminationPossibility of new lectins (autoimmune diseases)

Financial risk - importbans in EU, Japan

Which ge do we live in ?(A brief history of organic chemistry)

1850+ Coal Tar (side product of “coal gasification”)

1920+ 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 (endothermic) • CO2 fixation (endothermic)

1850- Plants, Animals

Cost vs. Demand in the Chemical Industry

Medicinals and other specialties

Dyes

FineChemicals

Flavours, fragrances

Specialties

Organic intermediates

Common plastics

Commodities

Resins, Elastomers

Primary organicbuilding blocks

105 106 107 108 109 1010 101

1 1012

Pseudo-commodities

Inorganic heavy chemicals

Demand (lb/y)

Uni

t cos

t ($/

lb)

0.01

0.1

1

10

>100

Organic Chemical Industry Characteristics

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 <10,000t/y highly variable

<5 $/kg >5 $/kg >10 $/kg

none very low high

low 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

–

–

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 minimalamount 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 BBsEthylene ethylene dichloride vinyl chloride

ethylene oxide ethylene glycolethyl benzene vinyl acetate

Propylene propylene oxideacrylonitrile isopropyl alcoholcumene acetonen-butyl alcohol

Benzene ethyl benzene styrenecumene phenol

acetonebisphenol A

Methanol acetic acid vinyl acetateformaldehydeMTBE

TolueneXylenes terephthalic acid

ButadieneUrea

A Closer Look at the Principle Sources of Primary Organic Building Blocks

Natural Gas: methane (85%) -161.4°Cethane (9%) -88°Cpropane (3%) -42°Cbutanes (1% -0.5°Cnitrogen (1%)

Liquid petroleum gasses (LPGs)

Crude Petroleum : LPGslight naphtha or straight-run gasoline 50-100°Cheavy naphtha ( C10) 150-200°Ckerosene, jet fuel ( C16) 175-275°Cgas oils, diesel fuel ( C25) 200-400°Clubricating oils 350+°Clight fuel oil, heavy fuel oil, bunker oilresidue: asphalt

Boiling pt.

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

Coal Coke

Coal TarRoad Tar

Pitch

Light OilTar bases

Tar acidsN N N

CH3

CH3

O

NH

MetallurgyFuel & exports

Electrodes and 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

R2NS

S

n

acetylene HC CH

C NHCaNcalciumcyanamide

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 H2CO, MTBE, CH(4-x)Clx,Cracking of C3H8, C4H10 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) S8 + Coke or CH4 Cellulosics, M+SCN–, thiourea

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

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

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

C2 ChemistryC2 building block Source Use

CH2=CH2 (ethylene) thermal cracking of natural Feedstock for ~30% of allgas, refinery gas, crude oil petrochemicals!!

Polymers (Polyethylenes etc.)Alphaolefins (LDPE), PVC Polystyrene, Polyvinyl acetate Polyethylene 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), Cellulose CH3COOCOCH3 (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

C3 Chemistry

C3 building block Source Use

CH3CH2CH3 (propane) LPG Propylene, energy

CH3CHCH2 (propene) Thermal cracking of LPG, Polypropylene, Acrylonitrile,natural and refinery gas Oxo products (butyraldehyde,

butanol, etc.),Propylene oxideIsopropanol, Cumene, Oligomers (nonene, dodecene,heptene)

CH3COCH3 Hock process (coproduct) Methyl methacrylate, Methyl(acetone) Isopropanol (dehydrogen’n) isobutyl ketone, Bisphenol A,

Wacker-Hoechst (propene) Aldol condensation products,Solvent

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

C4 Chemistry

C4 building block Source Use

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

C4H8 (butenes, isobutene) Cracking of Cn4 Polymer/alkylate gasoline,Polymers/copolymers, alcohols

C4H9OH (butyl alcohols) Propene, acetaldehyde MEK, Solvent, Fuel additive

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

Maleic anhydride Oxidation of C4-feedstocks Unsaturated polyester resins,

Benzene (V2O5 catalyst) Fumaric acid, Pesticides

HO(CH2)4OH Acetylene poly(1,4-butylene terphthalate) (1,4-butanediol) 1,3-butadiene THF, H2N(C4H8)NH2

H2C=CHCH=CH2 Cracking of Cn4 Elastomers (i.e., synthetic (1,3-butadiene) rubbers), Chloroprene, THF

O OO

C5 and Higher Acyclic Building Blocks

Primary Building Blocks Source(s) Use

Petroleum: 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

Mineral waxes: Ozocerite, Fossil fuels CoatingsMontan wax (lignite)

Fatty Acids: 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, carboxylic acids, (plant) Food industry, Pharmaceuticals, Monosodium glutamate (MSG) Laundry products, etc.

Cyclic Building Blocks - Aromatics

Building blocks Source Use

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

Cyclohexane, Nitroenzene

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

Xylenes Coal, Oil, Petroleum Phthalic acids and anhydrides C6H4(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, ε-Caprolactam

Cyclopentadiene C5 cracking fractions, Polymers (for resins, contact Coal tar adhesives, printing ink resin)

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

Epichlorohydrin Epoxy 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

Cl2Vinyl chloride monomer

Ethylene

Cl2

CO2

Phosgene

Cl2 Allyl chloride

Propylene BTX

Aspirin

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 / CuCl2 Wacker-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

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 pyrometallurgical byproduct

O2 Fractional distillation of liquid air

Acetate Acetic acid Methanol + CO (Monsanto process)

NaOH Electrolysis of brine (NaCl + H2O) “chloralkali cell”