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Efficient Co-Production of Cyclohexanone and Phenol

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Efficient Co-Production of Cyclohexanone and Phenol 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 1 Integrated Global Technology European Technology Center Brussels Clinton, NJ Baytown, TX Shanghai Baytown Technology Center Bangalore Shanghai Technology Center 2 47 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 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 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 5 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 6 49 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 7 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 noble metal / zeolite catalyst Hydroalkylation 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 8 50 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 + Low levels of secondary NHPI 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 9 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 Cyclohexanone loss reactions 1-phenylcyclohexanol 1-phenylcyclohexene Cyclohexylbenzene 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) 10 51 10th China International Polyamide & Intermediates Forum New EM Process Flow Diagram Hydrocarbon Loop Overall Product Yield ~ 90% Oxygenates Separation Hydrogen Hydrogen Cyclohexane Purification Dehydrogenation Cyclohexanone Cleavage Cyclohexanone Product Phenol Fractionation Fractionation Benzene Benzene Hydroalkylation Purification Phenol Phenol Purification Hydrocarbon Fractionation Spent Air to Oxidation Scrubber Loop Transalkylation Hydrogenation Oxidation Cleavage Vent Air to Flare WO2009131769 11 Efficiency, Co-production Drive Advantage New EM Process Conversion 25% H2 50% Phenol Co-production of Phenol and Oxidation Hydroalkyation Separations Cleavage 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 • Reduced energy requirements Benzene 38% Acetone 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 12 52 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 13 53 .
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