Presented by

Jarukit Junjiewchai 57010169

Chaiwat Kositwiwatkun 57010340
Thithawat Techan 57010498
Pattraporn Samaikaew 57010967
Sorasak Madee 57011317
Department of Chemical Engineering, Faculty of Engineering
King Mongkut’s Institute of Technology Ladkrabang, Academic Year 2017
1
Outline

Introduction
Market Study
Production Technology
Conclusion

2
 The History of Cyclohexane

1859 1923
First purpose-drilled oil well Dougherty and Taylor
in Pennsylvania used nickel as a catalyst

1901 1945
Benzene hydrogenation, forming cyclohexane, Du Pont Patented hydrogenation
in the presence of metal catalysts has been of benzene to cyclohexane
investigations by Sabatier and Senderens

Ref: Aftalion F., A History of the International Chemical Industry, 2001 3

 Chemistry of Cyclohexane
Properties
Chemical Formula C6H12
−1
Molar Mass 84.16 g·mol
Appearance Colorless Liquid
Odor Sweet, Gasoline-like
Density 0.7781 g/mL, Liquid
Melting Point 6.47 °C
Found naturally in petroleum Boiling Point 80.74 °C

Solubility in Water Immiscible

Hydrogenation of benzene to
Solubility Soluble
cyclohexane in ether, Alcohol, Acetone
Miscible with Olive Oil
Vapor Pressure 78 mmHg (20 °C)
4
 Applications of Cyclohexane

Adipic Acid Nylon 66 Electrical Parts,

Automotive Parts
Cyclohexane

Caprolactam Nylon 6 Clothing, Carpeting,

Mesh, Trawl

Solvents, Additives

Ref: Cyclohexane Market Analysis By Application, 2017 5

 Global Cyclohexane Demand by Application
The global cyclohexane market size was estimated at 9,192 kilotons in 2016.

Asia Pacific was leading the cyclohexane consumer;

accounted for over 38.3% of the total revenue in 2016.

Other

XX %
Adipid acid and
caprolactum

Increasing consumption of automotive and textile applications are expected

to be a key factor driving growth.
Ref: Cyclohexane (CX): 2018 World Market Outlook and Forecast up to 2027, [online],
available at https://mcgroup.co.uk/researches/cyclohexane-cx
6
 Manufacturers
China is the largest producer and consumer of cyclohexane globally.
Manufacturer Capacity (ton/year) Technology
Chevron Philips Chemical 820,000 IFP
Huntsman 362,500
Mobil Chemical 350,000 IFP
CEPSA 180,000
BASF 130,000 A new process
(developed by BASF)

Aromatics Thailand Co. 150,000 ton/year IFP Technology

7
 Production Technologies
Production Technologies

Historical Modern

Fractional Distillation Isomerization Hydrogenation of Benzene

of Crude Oil

Vapor Phase Liquid Phase

OUP Hydrar Process Bexane Process IFP Process

8
Hydrogenation of Benzene to Cyclohexane

∆H298 = -206 KJ/mol

Catalysts: Pt, Ni, Raney-Nickel Highly Exothermic Reaction

Side Reaction

9
 UOP Hydrar Process
Recycle H2
Purge
H2 3 Packed Bed Reactors Separator
Cyclohexane
Benzene in Series

Recycle Cyclohexane

Operating Condition Advantages Disadvantages

Liquid phase • Catalyst sulfur tolerance • Number of reactor
T = 200-350 oC (up to 300 ppm) • Hot spot formation due to
P = 30 Bar • Long life catalyst stationary catalyst
Catalyst: Pt on Li salt • Good temperature control • Expensive catalyst
• No attrition due to stationary • Downtime due to shut down
catalyst of the reactor for catalyst
replenishment

10
Ref: Mcketta J., Cunningham A., Encyclopedia of Chemical Processing and Design Volume 14, Marcel Dekker, 61-82, 1984
Franck H. G., Stadelhofere J. W., Industrial Aromatic Chemistry, Springer-verlag, 191-193, 1949
 Bexane Process
Recycle H2
Purge
H2 Mixer Multitubular Separator
HX Cyclohexane
Benzene Reactor

Operating Condition Advantages Disadvantages

Vapor phase • Catalyst prevent isomerization • Consume high amount of
T = 370 oC and cracking of cyclohexane electrical energy
P = 30 Bar • No attrition due to stationary • Downtime due to shut down
Catalyst: Proprietary catalyst of the reactor for catalyst
noble metal replenishment
• Preheating of feed required

11
Ref: Mcketta J., Cunningham A., Encyclopedia of Chemical Processing and Design Volume 14, Marcel Dekker, 61-82, 1984
Franck H. G., Stadelhofere J. W., Industrial Aromatic Chemistry, Springer-verlag, 191-193, 1949
 IFP Process
Recycle H2
Fuel Gas
H2 Main Finishing Separator
Cyclohexane
Benzene Reactor Reactor

External HX

Operating Condition Advantages Disadvantages

Liquid phase • No feed preheating required • Attrition of mobile catalyst
T = 200 oC (isothermal) • Good temperature control • Friction wear of equipment
P = 40 Bar (ewer side reactions) due to moving catalyst
Catalyst: Nikcel, • Easier catalyst replacement • Lower catalyst life
Raney-Nickel (without shutting down)
• Cheaper catalyst than Pt
• Lower energy costs

12
Ref: Mcketta J., Cunningham A., Encyclopedia of Chemical Processing and Design Volume 14, Marcel Dekker, 61-82, 1984
Franck H. G., Stadelhofere J. W., Industrial Aromatic Chemistry, Springer-verlag, 191-193, 1949
 Hazardous Chemicals
Hazard Benzene Hydrogen Cyclohexane
Main hazards Potential occupational Flammable Flammable
carcinogen, flammable
Hazard
pictograms

NFPA 704

Flash point −11.63 °C Not applicable −20 °C

Autoignition 497.78 °C 560°C 245 °C
temp.
Explosive 1.2 - 7.8% 4.0 - 75% 1.3% - 8%
limits

13
 Case Study - Flixborough Disaster
Since 1967, Nypro, UK had produced caprolactam from cyclohexane.
Reactor was leaking.

Install a bypass system

The bypass ruptured

Cyclohexane leaked

Vapor cloud

Explosion

14
 Conclusion

• Specified Capacity
• Selected Technology

15
Thank you very much for your attention.

16
Properties Benzene Hydrogen Cyclohexane
Chemical Formula C6H12
−1
Molar Mass 84.16 g·mol
Appearance Colorless Liquid
Odor Sweet, Gasoline-like
Density 0.7781 g/mL, Liquid
Melting Point 6.47 °C

Boiling Point 80.74 °C

Solubility in Water Immiscible

Solubility Soluble
in ether, Alcohol, Ac
etone
Miscible with Olive
Oil
Vapor Pressure 78 mmHg (20 °C)
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Gross Profit

18
 FED – UOP Hydrar Process

Ref: Franck H. G., Stadelhofere J. W., Industrial Aromatic Chemistry, Springer-verlag, 191-193, 1949 19
FED – Bexane Process

20
 FED – IFP Process

Ref: Franck H. G., Stadelhofere J. W., Industrial Aromatic Chemistry, Springer-verlag, 191-193, 1949 21
Catalysts

22
Cyclohexane Sales Specification
(Chevron Phillips Chemical Company )

23
Production Capacity

24
Global Consumption of Cyclohexane

China alone is estimated to account for 40% of total demand.

25
Cyclohexane Market in North America

North America cyclohexane market volume by application, (Kilo Tons)

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Energy Consumption

28
Recommended Reaction Phase

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