CH3130 - Unit5A

Petrochemicals – 3. Product Profiles

Anand Mohan,
Associate Professor, Chemical Engineering
 Overview

• Syngas: Composition, Products, Product Profile

• Syngas Products
 Methanol (CH3-OH); Derivative: Acetic Acid (CH3-COOH)
 Formaldehyde (H-CHO)
• Ethylene Derivatives
 Polyethylene
 Ethylene Oxide (C2H4-O) & Ethylene Glycols (Mono-,Di-, Tri-)
 Vinyl Chloride
 Ethanol (C2H5-OH) & Acetaldehyde (CH3-CHO)
• Propylene Derivatives
 Propylene Oxide (C3H6-O); Derivatives: Propylene Glycol, Polyol, Propylene Carbonate
 IsoPropanol
 Acrylic Acid (CH2=CH-COOH): Propylene Route
• Aromatics: Benzene, Toluene, Xylene, Ethyl Benzene
• Aromatics Derivatives: Phenol, Aniline, Benzoic Acid etc.
 Syngas: Composition, Products

• Syngas (or Synthesis Gas): A Product H2:CO World

capacity
common name for two gas (L-tpa)
mixtures Methanol 2:1 1.6 – 12.75
H2 + CO (used to make CH3OH)
Acetic Acid 0:1 2.75 – 5.45
H2+ N2 (used to make NH3)
Acetic 0:1 0.9
• Different chemicals produced anhydride
based on the ratio (table) Oxo-alcohol 2:1 1.15 – 2.75
Formic acid 0:1 0.45
• Technologies utilizing Syngas+CH4 Methyl 0:1 0.09
Fischer-Tropsch synthesis (for formate
Olefins) Methyl 1:1 0.45
Oxidative coupling of CH4 (for Methacrylate
Ethane, Ethene)
Methanol to Olefin Technology
Syngas Product Profile
 Syngas Product – 1) Methanol (CH3OH)

• History
 First obtained In 1661
 Rectification of crude wood vinegar over milk of lime
 Named as Adiaphorous Spiritusliglorum
• Usage (One of largest volume chemicals produced in the world)
 Chemical feedstock (71% for formaldehyde, acetic acid, methyl methacrylate,
dimethyl terephthalate)
 Methyl fuel
 Miscellaneous
• New Applications (Ref. CHEMCON 2016)
 Internal Combustion Engines
 Direct Methanol Fuel Cells
 Conversion to Olefins, Gasoline
 Dimethyl Ether (CH3-O-CH3): Substitute for diesel
• Global Demand projection from 44.9 mt in 2010 to 122.6 mt in 2020 (Chem
Ind Digest 2012)
 Products from Methanol

Polyethylene • Fiber & Packaging Film

Terephthalate • Containers, Coating of wires

Methyl Methacrylate • Cast Sheet, Surface Coating

(MMA) • Molding resins, Oil additives

MTBE • Oxygenate for Gasoline

• Dimethyl acetamide, Dimethyl formamide

Dimethylamine • 1,1-Dimethyl hydrazine (Rocket Propellant)

Methyl acetate • Paint Remover

• Vinyl acetate, Acetic anhydride, Acetyl chloride

Acetic Acid • Ethyl acetate, Butyl acetate, Isopropyl acetate
Methanol Production in India
Methanol Derivatives– 1A) Acetic Acid (CH3COOH)

• Largest Methanol-based chemical

in Volume
• World installed capacity (2002):
9.56x106 ton
• Consumption (2002): 8.3x106 ton
• Consumption Growth
 2002-2007: 3.4%
 2007-2012: 2.5%
• Announced Δcapacity (2012):
0.99x106 ton
• Ref. Chemical Industry News
(2004)
Installed Capacity of Acetic Acid in India
 Acetic Acid Product Profile

• CMC Manufacture, Drilling Mud Thickeners

Monochloro-Acetic Acid • Food Industry, Pharmaceuticals, Textiles
• Coatings, Adhesives
Ethyl/Isopropyl/Butyl Acetate • Inks and Cosmetics

Vinegar • Food Preservative

Cellulose Acetate • Fibers, Plastic Film

Acetic Anhydride • Pharmaceuticals, Cellulose Acetate

• Polymer fiber, Packaging

Terephthalic Acid • Photographic Films, Magnetic Tape
• Polyvinyl acetate, Polyvinyl chloride (PVC)
Vinyl Acetate • Paints, Adhesives, Coatings
 Syngas Product – 2) Formaldehyde (H-CHO)

• Commercial Availability Product Uses

 Aqueous solution with 30% to Thermosetting
56% wt HCHO Resins: Urea,
 Solid form as paraformaldehyde Formaldehyde Melamine,
Phenols
• Usage (see table for Products)
 Sealant 1,4-Butadiol
 Herbicides / Fertilizers Methylene di-
 Coatings isocyanate
 Pharmaceuticals Fertilizer,
Disinfectant,
• Installed capacity (2003-04): 2.72 Corrosion
Lakh ton Inhibitor, Reducing
Agent
• Production (2003-04): 1.89 Lakh
ton P-Formaldehyde
 Ethylene: Product Profile

• Ethylene is called the King of Product Uses

chemicals Polyethylene, LDPE, Films, Moldings, Pipes, Cable
LLDPE, HDPE Covering, Netting
Highest volume organic chemical
(produced & sold), 150 Mton in Ethylene Oxide & Antifreeze, Polyester,
2016 Ethylene Glycol Solvents, Detergent
Building Block for petrochemicals Styrene Synthetic Rubber, Polystyrene
• Product of Naphtha Cracking
• Extensive Product Profile Vinyl Chloride PVC (piping)
(table)
Ethanol Industrial Solvent
• Large tonnage of ethylene used Chemical Intermediates
to manufacture Acetaldehyde Acetic Acid, Acetic anhydride,
Polyethylene (CH3-CHO) Cellulose Acetate
Ethylene oxide
Ethylene glycols Ethyl Chloride Tetraethyl lead
Styrene Vinyl Acetate PV acetate, PV alcohol
World Ethylene Production & Consumption

Total Production: 117.3x106 tons (2008)

Source: Howard Rappaport of CMAI-Plastics (2009)
World Ethylene Capacity
India Ethylene Capacity & Production
 Propylene: Product Profile

• Propylene is called the “Crown Product Uses

Prince” of chemicals
Polymers Polypropylene, Nylon
Superficially similar to Ethylene 66, Acrylic sheets,
Manuf. of high-usage Thermoplastics,
Synthetic materials Propylene Oxide Surfactant, Manuf of
Isopropyl Amines,

Propylene Glycol Food Additive, Paints &

• Product of Coatings, Plasticizer
Naphtha (Steam) Cracking
Polyols Manuf of Polyurethane
Dehydrogenation of Propane & Polyester
Recovery from FCC Light End
Isopropanol Cosmetic, Solvent,
(CH3-CH(OH)-CH3) Manuf of Acetone &
Isopropyl acetate
• Large Product Profile (table)
• Increase in demand driven by Acrylonitrile Acrylic fiber, Acrylic acid,
(CH2=CH-C≡N) Methyl Methacrylate,
polypropylene demand (Mall 2007)
Propylene Product Profile
 Aromatics: Usage

• Aromatics are feedstock for Aromatic Uses

intermediates used in Benzene Alkyl Benzene, Cumene,
Manuf. of synthetic fibres, Naphthalene,
rubbers, explosives, pesticides Chlorobenzene (for DDT)
Manuf. of Organic Chemicals Toluene Solvent, Benzoic Acid
(for Caprolactum), Nitro
Toluenes,
• Very Valuable but also P-Xylene Terephthalic acid/DMT
carcinogenic
O-Xylene Phthalic anhydride
• Major Aromatics
(B) Benzene Ethyl Benzene Styrene (99%
(T) Toluene consumption)
(X) Xylene (dimethyl-B)
(EB) Ethyl-B
Aromatics Product Profile
 Aromatics: Consumption & Production

• Benzene
 2009: 36.5 Mton, 69.2% capacity
utilized
 2009-14: 4.7% p.y ↑ (SRI Consulting)
 Ethyl Benzene consumes 52.6%
• Toluene
 2009: 18.4 Mton, 64% capacity utilized
 2009-14: 3.6% p.y↑ (SRI Consulting)
• Xylenes
 2009: 41 Mton, 74% capacity utilized
 2009-14: 5.2% p.y↑(SRI Consulting)
 P-Xylene: 5.5% p.y↑ (SRI Consulting)
• Ethyl-Benzene, 2002: see table

Aromatics Consumption,
Chemical Industry News (2004)
 Aromatics Products: Profile

• Following major products are derived from Aromatics

• Ethyl Benzene (C6H5-C2H5)

Styrene (C6H5-CH=CH2)
• Phthalic Anhydride C6H4(-COO-)(-C=O)
• Cumene (Isopropyl Benzene: C6H5-C3H7)

• Phenol (C6H5OH)
Caprolactam (CH2)5-C(O)NH), Aniline also
Bisphenol (42% in 2009) and Resins (28% in 2009)
Acitaminophen = Paracetamol
• Aniline (C6H5-NH2)
• Benzoic Acid (C6H5-COOH)
 Summary

• Syngas: H2 + CO
Methanol: CH3OH (Proj. 122.6 M-tpa in 2020)
Acetic Acid (Largest by volume)
Formaldehyde
• Ethylene (C2H4): Highest vol. organic chemical, Prod. 150 Mton in 2016
Polyethylene
Ethylene Oxide (C2H4-O) & Ethylene Glycols (Mono-,Di-, Tri-)
Vinyl Chloride
Ethanol (C2H5OH) & Acetaldehyde (CH3-CHO)
• Propylene: “Crown prince” of chemicals
Propylene Oxide (C3H6-O) and its derivatives
Isopropanol (aka Isopropyl alcohol)
Acrylic Acid (CH2=CH-COOH): Propylene Route
• Aromatics (Valuable but carcinogenic)
Benzene, Toluene, Xylene, Ethyl Benzene
• Aromatics Derivatives: Phthalic Anhydride, Phenol, Aniline, Benzoic Acid