Phenol Production by ExxonMobil 3-step Process PEP Review 2020-02 April 2020 IHS Markit | PEP Review 2020-02 Phenol Production by ExxonMobil 3-step Process Review 2020-02 Phenol production by ExxonMobil 3-step Process Rajesh Kumar Verma, Associate Director Abstract In 2017, the world demand for phenol was ~12.8 million tonnes. The three largest contributors to the worldwide capacity in 2017 were Northeast Asia, United States, and Western Europe. The largest end- use for phenol is in the manufacture of bisphenol A (BPA). Although it is under regulatory pressure for health and safety reasons, BPA is the key building block for making polycarbonate and epoxy resins. The next largest use for phenol is in the production of phenol–formaldehyde (PF) resins. PF resins are used primarily in wood adhesives, for example, for bonding the layers of plies in exterior plywood. Since its commercialization in the early 1950s, the cumene hydroperoxide (CHP) process has become the dominant technology for phenol production. Well over 90% of the world phenol production is based on this technology. A drawback of this process is the substantial production of acetone coproduct. While well-established global markets for acetone exist, the demand for this coproduct has not always kept pace with the demand for phenol in certain regions. This has been a factor stimulating interest in new “non-coproduct” phenol technologies, which would produce phenol directly from benzene. More recently, ExxonMobil has developed a 3-step route from benzene to phenol that co-produces cyclohexanone, which has excellent commercial value and market compared to acetone. This PEP review evaluates the ExxonMobil’s 3-step process for the production of phenol, using benzene as feedstock and provide the economics for the process at the US Gulf Coast. The process shows excellent product economics and higher product yield and could be the future phenol production process. There is no commercial reference available yet for this process, our plant design and economics are based on the patent’s information and the author’s engineering judgement. This review also includes the market status assessment of supply and demand trends for phenol and cyclohexanone, with the iPEP Navigator tool attached to the electronic version of this review as well. Confidential. © 2020 IHS Markit. All rights reserved. 1 April 2020 IHS Markit | PEP Review 2020-02 Phenol Production by ExxonMobil 3-step Process Contents 1 Introduction 7 2 Summary 8 Exxon’s 3-step phenol process 8 Exxon 3-step process comparison with other commercialized processes 11 Environmental footprint 12 3 Industry status 14 Phenol 14 Cyclohexanone 19 4 Technology review 22 Natural recovery 22 Recovery from coal tar and petroleum streams 22 Phenol production on Industrial scale 22 Patents review 24 Benzene Hydro-alkylation 26 Poly-cyclohexylbenzenes transalkylation 28 CHB oxidation 29 Hydroperoxide cleavage and separation 30 5 Phenol Production by ExxonMobil 3-step Process 34 Process design basis 34 Process description and discussion 36 Section 100—Benzene Hydro-alkylation and product separation 36 Section 200—Cyclo-hexylbenzene oxidation and cleavage section 37 Section 300—p-Di-cyclohexylbenzene transalkylation 39 Section 400—Cyclo-hexane de-hydrogenation 40 Section 500—Phenol and cyclohexanone product recovery 40 Cost estimates 58 Fixed capital costs 58 Production costs 58 Confidential. © 2020 IHS Markit. All rights reserved. 2 April 2020 IHS Markit | PEP Review 2020-02 Phenol Production by ExxonMobil 3-step Process Tables Table 2.1 Exxon's three-step process for phenol production—Summary 10 Table 2.2 Exxon's three-step process comparison with other processes 12 Table 2.3 Exxon's three-step process for phenol production—Environmental footprint 13 Table 3.1 World top producers of phenol by shareholder—2017 14 Table 3.2 Worldwide phenol plant production capacities in -000s tons/annum for year 2019 15 Table 3.3 World supply/demand for phenol (thousands of metric tons) 18 Table 3.4 World consumption of phenol—2017 (thousands of metric tons) 19 Table 3.5 World top producers of (uncoupled) cyclohexanol/cyclohexanone—2018 (thousands of metric tons) 20 Table 4.1 Benzene hydroalkylation reactor typical product from patent US8329956 27 Table 5.1 Design basis and assumptions for Exxon's three-step process for phenol production 35 Table 5.2 Exxon's three-step process for phenol production—Major stream flows 42 Table 5.3 Exxon's three-step process for phenol production—Major equipment 52 Table 5.4 Exxon's three-step process for phenol production—Utilities summary 57 Table 5.5 Exxon's three-step process for phenol production—Total capital investment 59 Table 5.6 Exxon's three-step process for phenol production—Variable costs 60 Table 5.7 Exxon's three-step process for phenol production—Production cost 61 Figures Figure 4.1 Benzene catalytic hydroalkylation reactors from patent EP2103585 27 Figure 4.2 Process scheme for benzene hydroalkylation to produce phenol from patent EP2189975 28 Figure 4.3 Overall process scheme to produce phenol and cyclohexanone from benzene from US4021490 31 Figure 4.4 Overall process scheme (part 1) to produce phenol and cyclohexanone from cyclohexylbenzene from WO2014/137623 32 Figure 4.5 Overall process scheme (part 2) to produce phenol and cyclohexanone from cyclohexylbenzene from WO2014/137623 32 Figure 5.1 Effect of benzene feed price on phenol product value 62 Figure 5.2 Effect of cyclohexanone by-product price on phenol product value 62 Figure 5.3 Effect of plant capacity on net production cost of phenol 63 Appendix C Figures Figure 5.1 PFD 1 of 4: Benzene hydro de-alkylation and solvent extraction section 75 Figure 5.1 PFD 2 of 4: Cyclohexylbenzene oxidation and cleavage section 76 Figure 5.1 PFD 3 of 4: Poly-cyclohexylbenzene transalkylation section and cyclohexane dehydrogenation sections 77 Figure 5.1 PFD 4 of 4: Phenol and cyclohexanone product recovery section 78 Confidential. © 2020 IHS Markit. 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