PHENOL/ACETONE/CUMENE February 2012 Report Contents Phenol/Acetone/Cumene Table of Contents A Report by Nexant’s CHEMSYSTEMS Process Evaluation/Research Planning (PERP) Program PERP09/10-4 - Published February 2012 www.chemsystems.com Section Page 1 Summary ................................................................................................................... 1 1.1 COMMERCIAL PRODUCTION TECHNOLOGIES .................................. 1 1.1.1 Cumene Consumption ........................................................................ 2 1.1.2 Selection of Phenol Technologies by Customers for Grassroots and Retrofitting Projects .................................................................... 4 1.2 ALTERNATIVE AND “DEVELOPING” TECHNOLOGIES ..................... 5 1.2.1 SBB to Phenol Process....................................................................... 5 1.2.2 Benzene Oxidation (with Nitrous Oxide) to Phenol Process ............. 5 1.3 PROCESS ECONOMICS .............................................................................. 6 1.3.1 Sensitivity Analyses ........................................................................... 8 1.3.2 Concluding Remarks .......................................................................... 8 1.4 COMMERCIAL MARKET ANALYSIS ...................................................... 11 1.4.1 Global Cumene Supply, Demand, and Trade .................................... 11 1.4.2 Global Phenol Supply, Demand, and Trade....................................... 11 2 Introduction .............................................................................................................. 13 2.1 CUMENE ....................................................................................................... 13 2.1.1 Brief History of Cumene Production ................................................. 14 2.2 PHENOL ........................................................................................................ 15 2.2.1 Brief History of Phenol Production ................................................... 15 2.3 ACETONE ..................................................................................................... 16 2.3.1 Brief History of Acetone Production ................................................. 17 3 Commercial Cumene Processes .............................................................................. 18 3.1 PROCESS CHEMISTRY .............................................................................. 18 3.2 CATALYST COMPARISON ....................................................................... 20 3.3 COMMERCIAL ZEOLITE CATALYZED PROCESSES ........................... 23 CHEMSYSTEMS PERP PROGRAM 1 www.chemsystems.com PERP09/10-4, Phenol/Acetone/Cumene A00101.0010.4105 PHENOL/ACETONE/CUMENE February 2012 Report Contents 3.3.1 Badger Licensing ............................................................................... 23 3.3.2 Polimeri Europa/Lummus Technology .............................................. 25 3.3.3 UOP.................................................................................................... 32 4 Cumene to Phenol Process Chemistry ................................................................... 35 4.1 CUMENE OXIDATION TO CUMENE HYDROPEROXIDE .................... 35 4.2 CUMENE HYDROPEROXIDE CLEAVAGE TO PHENOL AND ACETONE ..................................................................................................... 39 5 Phenol Production - A Generic Description .......................................................... 42 5.1 OXIDATION ................................................................................................. 42 5.2 CHP CONCENTRATION (CUMENE STRIPPING) ................................... 44 5.3 CHP CLEAVAGE ......................................................................................... 44 5.4 NEUTRALIZATION ..................................................................................... 45 5.5 PRODUCT RECOVERY AND AMS HYDROGENATION ....................... 47 5.6 ECONOMIC BENEFIT ................................................................................. 49 5.6.1 Cumene Consumption ........................................................................ 49 5.6.2 Selection of Phenol Technologies by Customers for Grassroots and Retrofitting Projects .................................................................... 50 6 Commercial Phenol and Acetone Technologies .................................................... 52 6.1 ILLA INTERNATIONAL ............................................................................. 52 6.1.1 Process Features ................................................................................. 53 6.1.2 Process Description ............................................................................ 53 6.2 KBR ............................................................................................................... 78 6.2.1 Process Features ................................................................................. 78 6.2.2 Process Description ............................................................................ 79 6.3 MITSUI CHEMICALS (ACETONE RECYCLE PROCESS) ...................... 84 6.3.1 Process Chemistry .............................................................................. 84 6.3.2 Process Description ............................................................................ 85 6.4 POLIMERI EUROPA AND LUMMUS TECHNOLOGY ........................... 88 6.4.1 Process Features ................................................................................. 88 6.4.2 Process Description ............................................................................ 89 6.5 SUNOCO/UOP .............................................................................................. 94 6.5.1 Process Features ................................................................................. 94 6.5.2 Process Description ............................................................................ 94 7 Alternative and “Developing” Technologies ......................................................... 98 CHEMSYSTEMS PERP PROGRAM 2 www.chemsystems.com PERP09/10-4, Phenol/Acetone/Cumene A00101.0010.4105 PHENOL/ACETONE/CUMENE February 2012 Report Contents 7.1 CUMENE ....................................................................................................... 98 7.1.1 Cumene via Alkylation of Benzene with Isopropanol ....................... 98 7.2 SEC-BUTYLBENZENE (SBB) .................................................................... 99 7.2.1 Alkylation of Benzene to sec-Butylbenzene ...................................... 99 7.2.2 Shell Process for Alkylation of Benzene to sec-Butylbenzene (SBB) using trans-2-Butene .............................................................. 101 7.2.3 ExxonMobil Process for Alkylation of Benzene to sec- Butylbenzene (SBB) using Ethylene ................................................. 101 7.3 PHENOL WITH METHYL ETHYL KETONE (MEK) AND ACETONE CO-PRODUCTS ........................................................................ 103 7.3.1 sec-Butylbenzene Oxidation to sec-Butylbenzene Hydroperoxide ................................................................................... 103 7.3.2 sec-Butylbenzene Hydroperoxide Cleavage ...................................... 104 7.3.3 Shell Process for SBB/Cumene to Phenol (with MEK/Acetone Co-Products) ...................................................................................... 105 7.3.4 ExxonMobil Process for SBB/Cumene to Phenol (with MEK and Acetone Co-Products) ................................................................. 110 7.4 PHENOL VIA BENZENE OXIDATION WITH NITROUS OXIDE (SOLUTIA/BIC PROCESS) .......................................................................... 111 7.4.1 On-Purpose Nitrous Oxide from Ammonia ....................................... 111 7.4.2 Benzene Oxidation to Phenol with Nitrous Oxide ............................. 115 7.5 PHENOL VIA OXIDATION OF BENZENE WITH HYDROGEN PEROXIDE OR HYDROGEN/OXYGEN .................................................... 121 7.5.1 Polimeri Europa ................................................................................. 121 7.5.2 General Electric ................................................................................. 122 7.6 PHENOL VIA HYDROLYSIS OF BROMOBENZENE ............................. 122 7.6.1 Microvast Power Systems .................................................................. 123 8 Process Economics ................................................................................................... 124 8.1 COSTING BASIS .......................................................................................... 124 8.1.1 Investment Basis ................................................................................ 124 8.1.2 Pricing Basis ...................................................................................... 124 8.1.3 Cost of Production Basis .................................................................... 126 8.2 COST OF PRODUCING CUMENE VIA PROPYLENE ALKYLATION OF BENZENE .................................................................... 127 8.3 COST OF PRODUCING PHENOL VIA CONVENTIONAL CUMENE BASED PROCESS ...................................................................... 131 CHEMSYSTEMS PERP PROGRAM 3 www.chemsystems.com PERP09/10-4, Phenol/Acetone/Cumene A00101.0010.4105 PHENOL/ACETONE/CUMENE February 2012