Efficient Co-production of Cyclohexanone and Phenol

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1 Efficient Co-production of Cyclohexanone and Phenol Dr. C. Morris Smith Project Chief Scientist ExxonMobil Chemical Company

2 Efficient Co-production of Cyclohexanone and Phenol C Morris Smith, Ph.D. ExxonMobil Chemical Company 1 Integrated Global Technology European Technology Center Brussels Clinton, NJ Baytown, TX Shanghai Baytown Technology Center Bangalore Shanghai Technology Center 2 47

3 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 3 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 4 48

4 Hurdles to Cyclohexanone Phenol Co-production First identified by Rhone-Poulenc in 1954, EP # 6B 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 5 ExxonMobil Advances Enable New Route Conventional Hock Process Alkylation Zeolite O 2 SO 4 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 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 6 49

5 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 New EM Process Baytown, TX Pilot Plant Facility Detailed CFD modeling / design of critical mechanical systems Scoping for commercial design underway 7 New EM Process: 2 Zeolite O 2 NHPI OH SO 4 Highly selective production of Cyclohexylbenzene (CHB) No Propylene feed Cyclohexene generated in-situ and undergoes hydroalkylation over noble metal / zeolite catalyst Cyclohexane recovered using selective catalytic dehydrogenation Heavies transalkylated to CHB Minimal yield loss from unrecoverable alkylation / isomerization products Enabled by proprietary catalysts Yield ~ 97% Cyclohexylbenzene Dehydrogenation Transalkylation

6 New EM Process: 2 Zeolite O 2 NHPI OH SO 4 Thermal oxidation of CHB not selective to desired PCH-HP Selectivity improved by NHPI, a chain propagating agent Yield ~ 94% Hydrogenation Dehydration NHPI radical (PINO ) abstracts only the benzylic H, accelerating oxidation to desired PCH-HP Low levels of secondary hydroperoxides formed; some recoverable to CHB Minor yield loss also occurs by PCH-HP decomposition High oxidation yield enabled by NHPI under optimized conditions 9 NHPI Phenyl Cyclohexyl Hydroperoxide (PCH-HP) Heavy Oxygenates New EM Process: 2 Zeolite O 2 NHPI OH SO 4 PCH-HP cleaved to Phenol and Cyclohexanone Yield ~ 99% Rates controlled to eliminate Cyclohexanone loss reactions 1-phenylcyclohexanol 1-phenylcyclohexene Cyclohexylbenzene 1-Phenylcyclohexene formed but easily recovered β-scission can lead to the loss of PCH-HP by forming 6-Hydroxyhexaphenone (6HHP) Pheno l Cyclohexanone O When optimized, product selectivity is nearly stoichiometric O Heavy Oxygenates 6-hydroxyhexaphenone (6HHP) 10 51

7 New EM Process Flow Diagram Hydrocarbon Loop Overall Product Yield ~ 90% Hydrogen Hydrogen Purification Cyclohexane Dehydrogenation Oxygenates Separation Cyclohexanone Purification Product Fractionation Cyclohexanone Phenol Fractionation Phenol Purification Phenol Hydrocarbon Fractionation Spent Air to Scrubber Loop Transalkylation Hydrogenation WO Vent to Flare Air 11 Efficiency, Co-production Drive Advantage New EM Process Conversion 25% Hydroalkyation CHB Separations 50% Phenol 50% Cx-one Co-production of Phenol and Cyclohexanone in one large-scale line 45% lower equipment count Phenol Conversion 25% C 3= Alkylation Cumene Separations 62% Phenol 38% Acetone Higher conversion / yield process Smaller equipment Reduced energy requirements AMS Hydrogenation Dephenolization Avoids Acetone, no Propylene feed Cyclohexanone Conversion 4% Cyclohexane Recovery Cyclohexanol Dehydration Products for highest quality applications Hydrogenation Cyclohexane Separations 100% Cx-one 12 52

8 Summary New EM Process produces two high value products in the 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 13 53