DEVELOPMENT MEMORANDUM TO: S$.L. Lerner DATE: July 31, 1990 WRITTEN BY: T.J. Bergman FILE CODE: 12-0:25 SUBJECT: Cumene Oxidation COPIES TO: ne! wi: D.A. Haid, F. ye. . Kings1e icella, L.M. Li W we = ers, K.A. The Bound Brook cumene oxidation literature and a computer simulation of the Georgia-Gulf cumene oxidizers were studied to determine the projected effect of oxygen on reaction rate and cumyl hydroderoxide yield. It was shown that the use of oxygen will increase neither of these if the reactors operate with air at the mass transfer/kinetic limiting boundary. Altering the operating temperature so that oxygen is required does not improve the observed yield for a given reaction rate. It is unlikely that any improvement in rate or yield will be observed in the direct injection tests proposed for Georgia-Gulf because they operate at the mass transfer/kinetic limiting boundary. If they should want to increase the capacity of the reactors in the future, they should raise the temperature in their oxidizers (sustaining some small yield loss) and raise the air flow rate (they currently have excess blower capacity) simultaneously. It was also discovered that the yield to CHP obtained in the oxidizers was higher than expected (95%). Since there is little room for yield improvement, and since there is no advantage for oxygen over air in cumene oxidations, there is little incentive for an LOR program with this chemical. For such a program to be successful, the LOR would have to alter the reaction mechanism such that the yield is improved to greater than approximately 97%. BACKGROUND In phenol production, cumene is first oxidized to cumyl hydroperoxide (CHP) then Cleaved in sulfuric acid to form phenol and acetone. These reactions are performed in two different process steps; only the oxidation step is a potential oxygen user. . BUSINESS CONFIDENTIALPage 2 Development Memorandum T.J. Bergman cumene oxidation reactors are either mass transfer or kinetic limited. In the mass transfer limited regime, the reaction rate is limited by the oxygen dissolution rate. In the kinetic limited regime, the reaction rate is limited by the reaction kinetics. The cumene oxidation reaction is zeroth order with respect to oxygen (1). Therefore, if the reaction is kinetic limited, increasing the amount of oxygen available will not increase the reaction rate. Also, the headspace oxygen level varies depending on whether the reactor is operating in the mass transfer or kinetic limited regime. In the mass transfer limited regime, the headspace oxygen level is typically 2-3%. In the kinetic control regime, it is typically greater than 7%. ‘The cumene oxidation reaction produces two by-products in significant quantities: dimethylphenylcarbinol (DMPC) and aceto- phenone (AP). The formation of these by-products is zeroth order {n oxygen. Therefore, if both the CHP and by-product formation reactions are not mass transfer limited, the CHP yield should not be effected by oxygen level, unless a significant amount of cumene is combusted to CO and CO, at high oxygen levels. The oxidation rate and yield are strong functions of temper— ature. As the temperature increases, the CHP and by-product formation rates increase and the yield decreases. To maintain the reactor temperature precisely, the reactor contents are circulated at a relatively high rate through the heat exchanger. OPTIMIZATION Table 1 summarizes the effects of temperature and injected oxygen level on rate, yield and headspace oxygen content. typically, the temperature is specified at a level where the desired overall conversion (approximately 30%) is achieved within the given reactor volume. The total reactor volume is typically large so that the long residence times necessary at low tempera- tures can be accommodated. The air supply rate then is set at a level that minimizes the headspace oxygen level but satisfies the oxygen demand of the reaction. This occurs at the transition between the mass transfer and kinetic control regimes. Figure 1 shows the location of this transition point as a function of temperature, air flow rate and CHP concentration. =~ BUSINESS CONFIDENTIAL(H/oaSW) SLWE YTY oor ozt (ungowea tuoram) [ang] oot 0 roy o-0€ oz ; IOULNOD USASNVUL SSYW ---- (2) & IOULNOD TZaNIN —— 4 oo cid o! GWIOd! 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