SSSLINDE concsponvence lent | HOB _ryr Gm excel det by. a cc BH Torn Bergman! Strom Dep (OLD SAW MILL FIVER ROAD, TARRYTOWN, WY 10591 mob. M. Lite ose November 1, 1989 oreweira deer Industrial Gases Development coy D.C. decastro Swe! Cumene Literature D. A. Haid F. S. Iacopelli 3. P. Kingsley K. A. Kuberka F. D. Lauricella I have surveyed the literature on the production of phenol from cumene that we have in our files and have prepared the following summary: THE PRODUCTION OF PHENOL FROM CUMENE 1. WHAT PROCESSES AND REACTIONS OCCUR IN THE PRODUCTION OF PHENOL FROM CUMENE? The only industrially signiticant method ror producing phenol is currently via the oxidation of cumene (isopropyl benzene) (1). In this process, cumene is first oxidized to cunyl hydroperoxide (CHP). The CHP is then concentrated (and the unreacted cumene recycled to the oxidation reactors) and cleaved to form phenol and acetone in the presence of sulfuric acid (2). Several by-products are also produced (the major by-products are acetophenone and dimethylphenyl carbinol). at the end of the process, the acid is neutralized with caustic and the resulting salts are removed. The phenol is then separated from the acetone by distillation. The mechanism of the cumene to phenol reaction has been determined (3); the production of CHP from cumene occurs via a free radical mechanism while the production of phenol from CHP occurs via a cationic reaction (hence requiring the presence of an acid). It is clearly the oxidation step that is of interest to Linde. The oxidation reaction is zero order with respect to BUSINESS CONFIDENTIAL2 oxygen. This is demonstrated by the rate expression for the reaction rate==k,_ [Cul] (2k; [cHp]) 7? () On where k, is the rate constant for the propagation reaction, k, is the rat® constant for the termination reaction and k, is the rate constant for the initiation reaction (this expression has been rigorously derived (13)). Therefore, as long as the reactor is not oxygen transfer limited, the reaction will always be op- erating at its optimal rate with respect to the amount of oxygen available. However, if the rate at which oxygen dissolves is lower than the rate at which the oxygen reacts, the reactor is mass transfer limited and the rate can be improved by dissolving more oxygen. Most cumene reactors operate in this regime. If the reactor is oxygen transfer controlled, the appropriate rate expression is: Rate = a k,°[0,), + ar (2) 2 where a is the mass transfer area per unit volume of liquid, k,° is the liquid phase physical absorption coefficient, (0,], is the oxygen concentration at the gas/liquid interface, r is the intrinsic rate (from equation 1) and D, is the diffusivity of oxygen in cumene. The over all production rate may then be calculated for any given reactor by multiplying the reaction rate by the liquid volume. It is also interesting to note the rate expressions for the formation of the most prevalent by products, acetophenone and dimethylphenyl carbinol. These expressions are as follows: Ratey, = Kyp [CuH] [CHP] Q) Ratepyrc = Koype [CHP] where Ky = 0.54389 x 10° % exp(-11395.4/T) — (1/gmole-min) (4) and Kiyec = 0529905 x 10’ x exp(-91284.41/T) (1/min) (Note that the rate, constant for the production of CHP is Koy = 0+276633 x 10° x exp(-7599.29/T) (1/gmole) #(1/min)) An expression for the reaction efficiency has also been derived and ie ac follows: 1 - (k,(2k,[cHPy) V2 Efficiency = Kk, [Cuz (5) 1 + 20k, fax, (CHP) K, [Cai] BUSINESS CONFIDENTIAL3 values for the constants in Equations 1 through 2 obtained from the literature and from Bound Brook reports are listed in Table 1. The oxidation reaction is heat initiated, autocatalytic and has a heat of reaction of -328 BTU/pound of CHP (exothermic). Both the reactants and product, CHP, are insoluble in water but readily soluble in most organic solvents. ‘The reaction is inhibited by phenol and sulfur dioxide as well as several corrosion inhibitors (16). Certain alkyl heterocycles, in conjunction with hydrochloric acid, are very active promoters tor the oxidation reaction. It was also discovered that a wide variety of ‘onium halides ranging from amine hydrochlorides to quaternary ammonium and phosphonium salts have catalytic activity at low concentrations. For example, as little as 50 ppm of lauryltrimethylammonium chloride leads to a rate increase of from 50-75% over uncatalyzed oxidation. The only penalty is a slight (0.5-1%) drop in reaction efficiency. These catalysts act by causing a large amount of the CHP to degrade to the cumyl hydro- peroxide radical, which causes the oxidation reaction to pro- pagate. 2. HOW IS THE REACTION CARRIED OUT? A. HISTORY OF CHP PRODUCTION The first commercially feasible technique for oxidizing cumene to CHP was invented in 1953 (12). This technique made use of heavy metal oxide or carbonate catalysts (which can be ex- pensive) and gave reaction efficiencies that were better than those observed in previous processes, although they were much lower than those observed today. If these catalysts were not used, very long reaction times (on the order of 20 days) were required. Another early technique involved the oxidation of cumene in an organic in water emulsion, which required the use of an emulsifying agent, such as sodium stearate (11). Here, the reaction times involved were reduced over previous processes. B. PRESENT DAY PROCESS Today, the oxidation step is typically carried out in a reactor containing only cumene, cumyl hydroperoxide and a small concentration of reaction by products. No catalysts are re- quired and an aqueous media is not used. Formerly, a sodium salt of cumyl hydroperoxide was used as an accelerator in the oxi- dation reaction. However, this salt has been eliminated due to process improvements. A Schematic diagram ot this process (as it BUSINESS CONFIDENTIAL4 was used at Union Carbide's Bound Brook plant) is shown in Figure 1. In the process used commercially today, the oxidation reaction is carried out ina series of reactors in which the temperature is lowered from one reactor to the next (4). The temperatures used in this step are relatively low (on the order of 100°C) to minimize the production of by-products by de- composition of CHP. The temperature is maintained at a very constant level by circulating the reactor contents through a heat exchanger al 4 high rate. This process is used in the former Bound Brook plant that has been moved to Texas as part of Georgia Gulf (Note: Union Carbide also has (or had) a plant to produce cumene from phenol at Ponce, Puerto Rico). The plant has been producing phenol from cumene at a rate of 180 MM 1b/year by a process licensed fron Allied Chemical (5) (note that Allied also uses approximately the same process). The reaction is carried out in a series of five reactors at a temperature of 99-112°C (the temperature being highest in the first reactor in the series and lowest in the last) and a pressure slightly above 1 atmosphere. Air is added to these reactors through a simple sparger with slot-like holes. In the original process design, the rate at which air was sparged decreased from one reactor to the next. The purpose of doing this was to minimize the amount of oxygen in the headspace. It was thought that since the cumene concen- tration decreases from one reactor to the next, the amount of oxygen required in each consecutive reactor decreases. There- fore, the amount sparged was decreased to maintain the same headSpace oxygen concentration in every reactor. The sparger slot size also decreases from one reactor to the next to main- tain a constant gas injection velocity in all reactors. More recently, the reactor is run with the same air flow rate in each reactor, which has been shown to increase the rate of CHP pro- duction without resulting in headspace oxygen levels above the explosive limits. The reactors are not mechanically agitated; the only source of agitation is a pump-around-loop that turns over each reactor every 35 minutes (the loops also circulates the reactor contents through an external heat exchanger as mentioned above). This process produces 70.1 1b of phenol for each 100 ibs of cumene with a reaction efficiency of 89.5%. The conversion realized in the oxidation process is typically 25-30% (8), although the Georgia Gulf plant has been able to approach 40%. It is not desireable to achieve high conversions in these reactors because BUSINESS CONFIDENTIAL5 high levels of CHP in an oxidation can cause a potentially explosive situation. WHAT ARE THE HYDRODYNAMICS OBSERVED IN BUBBLES COLUMNS, SUCH AS THOSE USED IN CUMENE REACTORS? ‘The two phase flow observed in bubble column reactors is usually divided into three regimes. At the lowest gas flow rates, the separate bubbling regime is observed. Here, the gas flow rate is so low that individual bubbles form at the inlet orifice and a nearly straight path is tollowed to the to top of the liquid phase (13). Very little mixing of the liquid occurs in this regime. The second regime is termed the quiescent regime and has been defined in terms of superficial gas velocities below 0.15 and 0.2 ft/second. In this regime, the gas provides considerable mixing of the liguid but still retains its ordered bubble charac- ter. Thus, the system is approximated by assuming a plug flow gas phase and a well-mixed liquid phase. The last regime is called the turbulent regime. It exists for gas superficial velocities greater than 0.25 ft/s. Here, both the gas and liquid phases can be approximated as well- mixed. The superficial gas velocity observed at Bound Brook was 0.1 ft/s. Therefore, the observed flow regime is quiescent. Gas enters the reactor and rises as individual bubbles. However, the liguid phase is well mixed. Some of the work done at Bound Brook described the effects of fluid properties on bubble formation and size. It was shown, for example, that surface tension has its greatest influence on bubble size for low gas flow rates, large orifice diameters and with liquids of low viscosity. Under these conditions, the bubble size is determined by a balance between buoyancy and surface tension forces. However, as gas flow rates increase, the effects of surface tension decrease. In fact, at the gas flow rates used in most industrial bubble columns, surface tension has an insignificant effect on bubble diameter. With higher gas flow rates, low surface tension and small orifice diameters, the liquid viscous forces become the primary resistance to bubble formation compared to the surface tension force. The size of the orifice used in the sparger also has an effect on the bubble diameter. Figure 2 shows the bubble dia~ BUSINESS CONFIDENTIAL6 meter resulting from various orifice Reynolds numbers for quies- cent flow. Bubble size increases significantly with both orifice diameter and gas velocity in the laminar region. However, for Reynolds numbers greater than 10,000, orifice diameter and velocity have a negligible effect on bubble size. It was indicated that no study had been completed to compare the effect of orifice hole geometry on bubble size. Bound Brook used long, thin slots instead of round hole spargers. Models for predicting fractional gas holdup using the terminal bubble velocity and superficial gas velocity. Both bubble diameter and fractional gas holdup are important in determining the available interfacial area between the gas and the liguid and the amount of oxygen that is transferred. It has also been demonstrated that the average air bubble diameter at Bound Brook was 0.625 cm (19). 4. WHAT EXPERIMENTAL WORK HAS BEEN DONE TO DATE TO STUDY THIS REACTION? A study was conducted at Bound Brook (6) in which the conventional reactor configuration described above was compared with a mechanically agitated reactor on the bench scale level to determine the effect of reactor type on rate and efficiency. A comparison was also made between air and oxygen enrichment. It was found that both agitation and the use of oxygen-enriched streams increased the reaction rate without decreasing the reaction efficiency. With agitation and enrichment, it is possible to obtain rates almost double those presently achieved in the plant. In this study, a 3 liter, bench scale, stirred tank reactor was used. A detailed description of this reactor and the pro- cedures used was given in Reference 6. A titration technique for measuring CHP was also given. Data on reaction rate was given as a function of percent oxygen injected (see Figure 3). A later letter (7) also showed the distribution of products over time in the laboratory reactor and showed very little by product forma- tion with both air and oxygen. It was shown that the best method for analyzing samples of the reactor contents for cumene and cumene oxidation products is liquid chromatography (LC). Analysis by gas chromatography is not reliable because the unstable hydroperoxides tend to form other products not seen in the reactor (10). Liguid chromato- graphy offers advantages over gas chromatography in that it can be used to analyze for nonvolatile and thermally unstable con- pounds. BUSINESS CONFIDENTIAL7 Another study was conducted at Bound Brook in which Equa- tions 1 through 3 and Bound Brook's operating data were used to model the cumene reactor. The purpose of this study was to determine (qualitatively) the effects of percentage of oxygen injected, temperature, bubble size and CHP concentration on the point at which the reaction undergoes the transition from ki- netically controlled to mass transfer controlled. The results of this study are summarized in Figures 4 through 6. Remember that these graphs were made from theoretical equations and, therefore, should be used solely for qualitative observations. Note that the predicted rates are much lower than those observed in Figure 2. This is, once again, a result of the lack of experinental Gata at a variety of operating conditions to back up the data. Note that in the kinetically controlled regime, the bubble size and mole fraction oxygen do not effect the rate. This is because the reaction is zeroth order in oxygen. Note also that in the mass transfer controlled regime, the temperature has little effect on the rate. Increasing the concentration of CHP causes a decrease in the transition temperature from the mass transfer to kinetically controlled regime. The effect of temperature and cumene concentration on reaction efficiency has also been studied. The reaction ef- ficiency is a function of both the temperature of the reaction and the concentration of CHP in the oxidizer. The efficiency decreases as both the temperature and CHP concentration increase. Thus, when operating the oxidizers in the kinetic regime, in- creasing the temperature will increase CHP production, but will dcerease the reaction efficiency; operations in the mass transfer regime will only decrease reaction efficiency as temperature is increased and have no corresponding increase in CHP production (as). Data was also collected at Bound Brook and at Ponce to determine the best parameters to use in Bound Brook optimization computer program, called OXOPT, of which the author is in posses- sion. Using the program, the productivity of the plant was increased from 150 MM pounds of phenol per year to 180 MM pounds of phenol per year. Other experiments showed that it is desireable to keep the liguid level in the oxidizers as high as possible to get the best efficiency. The higher the liguid level, the longer the res- idence time of cumene in the reactor and the lower the temper- ature needed to obtain a given conversion. BUSINESS CONFIDENTIAL8 5. WHY IS PURE OXYGEN OR ENRICHMENT NOT USED TODAY? Despite these results shown in part 4, Bound Brook did not convert their reactors to agitated, oxygenated reactors. One reason for maintaining the reactors as mass transfer limiting devices was to insure that most of the oxygen would dissolve within the reactor, which would insure that the headspace oxygen concentration would remain below the flammability limit of cumene. In addition, they did not want to increase their gas flow rate (which they believed was necessary in order to use enrichment) because they were afraid that more cumene would be lost with the larger air stream (at 109°C, the vapor pressure of cunene is 0.27 atm). It was mentioned that the use of a more ef- ficient sparger than the current slotted version should be beneficial in terms of increased transfer efficiency. However, the spargers were not replaced. In 1973, an economic analysis was conducted to determine the best way to increase the productivity of the oxidizers (14). At that time, the productivity of the plant was 150 MM pounds of phenol per year. The first option was to increase their blower speed to capacity, increase the oxidizer pressure and increase the CHP concentration. With this option, the plant could have boost its capacity to 180 MM pounds of phenol per year for a capital investment cost of $130,000. ‘The second case involved either buying a second blower or using oxygen enrichment. The option of buying a second blower was ruled out because it was unattractive economically and in terms of ease of installation. It was calculated that with oxygen enrichment, the plant's capacity could have been boosted to 200 MM pounds of phenol per year for a capital investment of $185,000 per year. The third option involved a combination of both options 1 and 2 for produc- tivity greater than 220 MM pounds per year and required a capital investment of approximately $2.67 MM. The study considered the impact of increased oxidizer productivity on all oxidizer and downstream equipment and includes a rather complete list of all of the major equipment in the phenol production plant. As a result of this economic analysis, Linde was approached in 1974 about the possibility of conducting tests with oxygen enrichment (15). Supply options and oxygen pricing were dis- cussed. Unfortunately, to this author's knowledge, these tests were never conducted. ‘It should be noted that the study did mention that increases in productivity would probably be ac- companied by decreases in reaction efficiency. Bound Brook was approached (by Linde) about the idea of using oxygen enrichment in the production of CHP in 1979 (9). At that time, it was felt that oxygen enrichment could not be BUSINESS CONFIDENTIAL9 justified based on the anticipated improvement in yield. They expected the yield to actually decrease with enrichment (although the stated reasoning is highly suspect). They stated that the use of oxygen could only be justified if an improvement in capacity were realized (if such an improvement was needed). Since they were operating under capacity at that time, oxygen enrichment was only of academic interest to then. 6. ARE THERE OTHER PRODUCTS MADE FROM THE OXIDATION OF CUMENE (BESIDES PHENOL)? Another product made from cumene is acetophenone. It is a by- product of the phenol process and is formed from the cunyloxy radical. Acetophenone production is likely to be favored in the cumene oxidation process when the temperature and hydroperoxide concentrations are increased over those used in phenol production (17). Acetophenone production is also enhanced through the use of various metallic catalysts. The rate of acetophenone production also increases slightly with high dissolved oxygen levels. Therefore, the efficiency of the phenol process decreases slightly (actually, negligibly) with increased oxygen, as is stated above. Acetophenone may also be made from CHP by thermal cleavage of 80% cumyl hydroperoxide at a temperature of 165°C (18). 7. REFERENCES 1. Pujado, P.R., Salazar, J.R. and Berger, C.V., "Cheapest Route to Phenol", Hydrocarbon Processing, March 1976, pp. 91-96. 2. International Petroleum Encyclopedia, pp. 425-426. 3. Streitwieser and Heathock, Introduction to organic Chemistry, 1976, pp. 1001-1002. 4, Kirk-othmer Encyclopedia of Chemical Technology, v. 17, 1983, pp. 374-377. 5. Shertok, J.T., Baez, E.E. and Chin, H.W., "Cumene oxidizer Optimization: Results of optimization Plant Trials", Bound Brook, NJ, 8/12/77. 6. Stueben, K.C., "Cumene Phenol Process Improvement Program I. The Effect of Mass Transfer on Oxidation Rate", Bound Brook, NJ, 1/20/71. BUSINESS AL10. ui. 12. 13. 14. 15. 16. ng. 18. 19. 10 Letter, K.C. Stueben-C. Ho, 9/19/74. U.S. Patent #3,523,977, "Process for Preparing Cumene Hydro- peroxide", C. Reni and L. Lugo, 8/11/70. trip Report, K. Kiyonaga, UCC, Bound Brook, NY, 7/19/79. Brydia, L.E., "Analysis of Mixtures Containing Cumene and Cunene oxidation Products by Liquid Chromatography", 2/71. U.S. Patent #2,547,938, "Manufacture of Alkyl Benzene Per- oxides", 1951. U.S. Patent #2,632,772, "Manufacture of Peroxidic Compounds", 1953. Gregory, R.A., "The Design of Bubble Reactors with Applica- tion to Cumene Oxidation", Bound Brook, NJ, 8/10/71. Gregory, R.A., "Capacity Study of Bound Brook Phenol unit", Bound Brook, NJ, 9/5/73- Letter, K.C. Stueben-R.J. Cotter, 8/29/74. stueben, K.C., "Ponce Phenol Plant Support Cumene oxidation Program", Bound Brook, NJ, 10/30/73. stueben, K.C., "Approaches to Increased Acetophenone Pro~ duction I: Cumene Oxidation Route", Bound Brook, NJ, 1/3/75. Stueben, K.C., "Approaches to Increased Acetophenone Pro- duction II: Controlled Decomposition of Cumene Hydroperoxide", Bound Brook, NJ, 1/17/75. shertok, J.T., "Cumene oxidizer Optimization: A status Report", Bound Brook, NJ, 6/3/76. ecgun!) yh awe Jie emo TJ. Bergnan ig USINESS Ci TAL1. TABLE 1 KINETIC CONSTANTS USED IN EQUATIONS 1-3 TEMPERATURE = 35°C ‘TEMPERATURE = 105°C i 0.2 1/(mol-sec) 4.3 1/(mol-sec) x, 2.0 x 10‘ 1/(mol-sec) 12.2 x 10° 1/(mol-sec) x . 0.224 x 10° sec’! PARAMETERS USED TO MODEL BOUND BROOK CUMENE OXIDATION REACTORS Dy = 0.4-1.27 em Dy 1s ft H = 1,13 x 10° mm Hg 1/mole k° = 3.06 x 10% - 3.51 x 107 cm/sec Liquid Volume = 1.7 x 10° liters D, = 9.3 x 10% cn*/sec Gas Holdup = 0.1 BUSINESS CONFIDENTIALBovND BRooK ENOL PLANT ESTIMBTED ‘OPERATING CONDITIONS Str ain ro AIM, HBX Oy, fae F308 és $0, /20ppm SRO pECOMPOSER, Varn R, ra v3035, f rorcHr s-30azat DFHYDRATORS Fron gph Onenr _FRM T-Bloz ovo . W30RR vero y- Zou Cumens scAveaERE CRUDE Tow aFRE erat . 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