Efficient Co-production of

Cyclohexanone and Phenol

Dr. C. Morris Smith

Project Chief Scientist

ExxonMobil Chemical Company

 10th China International Polyamide & Intermediates Forum

Efficient Co-production of Cyclohexanone

and Phenol

C Morris Smith, Ph.D.

ExxonMobil Chemical Company

Integrated Global Technology

European Technology Center

Brussels
Clinton, NJ
Baytown, TX Shanghai

Baytown Technology Center Bangalore

Shanghai Technology Center

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 10th China International Polyamide & Intermediates Forum

Focused Strategic Effort

Industry-leading technology creates innovative solutions

Advantaged feeds
• Feed flexibility

Lower-cost manufacturing processes

• Advanced process and catalysts
• Improved energy efficiency and reliability

Premium products
• Higher performance
• Higher value

Advanced Capabilities

Expertise in catalysis and process, products, applications and

manufacturing

State-of-the-art capabilities
• Fast catalyst discovery
• Advanced chemical characterization
• Scale-up

World-class expertise
• Catalyst discovery and scale-up
• Process development and manufacturing
• New products and applications

Globally leveraged
• Application development
• Strong customer support

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 10th China International Polyamide & Intermediates Forum

Hurdles to Cyclohexanone + Phenol Co-production

First identified by Rhone-Poulenc in 1954, EP # 6B712264

Significant work in the patent literature by Texaco, Phillips and Phenolchemie over 50+
years did not lead to a commercial process

Poor selectivity and low yield continued to limit commercial potential

Cyclohexylbenzene (CHB) yield affected by over-alkylation to heavies and

over-hydrogenation to lights

Poor oxidation selectivity due to 10 secondary H’s that are also subject to oxidation,
but don’t yield the desired products

ExxonMobil Advances Enable New Route

Conventional Hock Process
Alkylation Oxidation Cleavage
+ +
Zeolite O2 H2SO4
Cumene Cumylhydroperoxide

New Route
OH

In 1993, ExxonMobil introduced a new zeolite Cumene process that was rapidly
commercialized worldwide

New process greatly improves CHB selectivity using a new Hydroalkylation catalyst

Selective oxidation of benzylic H achieved using N-Hydroxyphthalamide (NHPI)

New EM Process Co-produces Cyclohexanone and Phenol at high yields

Decouples the production of Phenol and Acetone

All in a process with leading-edge energy efficiency

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 10th China International Polyamide & Intermediates Forum

New EM Process Technology Development

Research scoping from 2000 to 2005

Process development began in 2008

More than 100 patents filed

Pilot plant demonstrating integrated

process

Integrated process design and model

Seven reactive steps, multiple separations

VLE data generation for non-ideal

oxygenate species

Detailed CFD modeling / design of critical
mechanical systems
New EM Process – Baytown, TX Pilot Plant Facility

Scoping for commercial design underway

New EM Process: Hydroalkylation

Hydroalkylation Oxidation Cleavage OH

2H2 + +
Zeolite O2 NHPI H2SO4

Highly selective production of Yield ~ 97%

Cyclohexylbenzene (CHB)

No Propylene feed
Transalkylation

Cyclohexene generated in-situ and
undergoes hydroalkylation over
Hydroalkylation
noble metal / zeolite catalyst
2H2 + + +

Cyclohexane recovered using
selective catalytic dehydrogenation Cyclohexylbenzene

Heavies transalkylated to CHB

Dehydrogenation

Minimal yield loss from unrecoverable
alkylation / isomerization products

Enabled by proprietary catalysts

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 10th China International Polyamide & Intermediates Forum

New EM Process: Oxidation

Hydroalkylation Oxidation Cleavage OH

2H2 + +
Zeolite O2 NHPI H2SO4

Thermal oxidation of CHB not Yield ~ 94%

selective to desired PCH-HP

Selectivity improved by NHPI, a
Hydrogenation Dehydration
chain propagating agent

NHPI radical (PINO•) abstracts only
the benzylic H, accelerating
oxidation to desired PCH-HP Oxidation
+
NHPI

Low levels of secondary
hydroperoxides formed; some Phenyl Cyclohexyl Hydroperoxide (PCH-HP)
recoverable to CHB

Minor yield loss also occurs by
Heavy
PCH-HP decomposition Oxygenates

High oxidation yield enabled by

NHPI under optimized conditions
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New EM Process: Cleavage

Hydroalkylation Oxidation Cleavage OH

2H2 + +
Zeolite O2 NHPI H2SO4

PCH-HP cleaved to Phenol and Yield ~ 99%

Cyclohexanone

Rates controlled to eliminate
1-phenylcyclohexanol 1-phenylcyclohexene Cyclohexylbenzene
Cyclohexanone loss reactions

1-Phenylcyclohexene formed but
O
easily recovered Cleavage
+

β-scission can lead to the loss of
Pheno Cyclohexanone
PCH-HP by forming 6-Hydroxy- l
hexaphenone (6HHP)

When optimized, product O
Heavy
selectivity is nearly stoichiometric Oxygenates
6-hydroxyhexaphenone (6HHP)

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 10th China International Polyamide & Intermediates Forum

New EM Process Flow Diagram

Hydrocarbon
Hydrocarbon Loop
Loop Overall Product Yield ~ 90%

Oxygenates
Oxygenates Separation
Separation
Hydrogen Hydrogen Cyclohexane
Purification Dehydrogenation Cyclohexanone

Cleavage Cyclohexanone
Product Phenol
Fractionation Fractionation
Benzene Benzene
Purification Hydroalkylation

Phenol Phenol
Purification

Hydrocarbon
Fractionation

Spent Air to Oxidation

Oxidation
Scrubber
Loop
Loop
Transalkylation
Hydrogenation Oxidation Cleavage

Vent Air
to Flare
WO2009131769

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Efficiency, Co-production Drive Advantage

New EM Process Conversion 25%

H2 50% Phenol
Co-production of Phenol and
Oxidation
Hydroalkyation
Cleavage
Separations Cyclohexanone in one large-scale line
Benzene 50% Cx-one
CHB
• 45% lower equipment count

Higher conversion / yield process

Phenol Conversion 25%
C3= 62% Phenol • Smaller equipment
Cumene Oxidation
Alkylation Separations
Cleavage
Benzene 38% Acetone
• Reduced energy requirements

AMS De-
Hydrogenation phenolization

Avoids Acetone, no Propylene feed

Cyclohexanone Conversion 4%

Cyclohexane Cyclohexanol
Products for highest quality

Recovery Dehydration
applications
H2
Oxidation 100% Cx-one
Hydrogenation Separations
Cleavage
Benzene
Cyclohexane

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 10th China International Polyamide & Intermediates Forum

Summary

New EM Process produces two high value products in the Benzene derivative
chain

Breakthrough catalysis enables efficient co-production of Cyclohexanone and

Phenol eliminating Acetone co-product and Propylene sourcing

Leading-edge process design leads to substantial reduction in equipment count,

increased scale, and improved capital utilization

Significantly improved energy efficiency supports more sustainable production

of petrochemical intermediates

Commercial-scale facilities scoping is underway

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