‘Turton App® Parti.gud 5/11/12 22:22 aM Page 119 ‘Appendix 8 Tnformation for the Preliminary Design of Fifteen Chemical Processes 119 ACRYLIC ACID PRODUCTION VIA THE CATALYTIC PARTIAL OXIDATION OF PROPYLENE [1, 2, 3, 4, 5], UNIT 1000 Acrylic acid (AA) is used as a precursor for a wide variety of chemicals in the polymer and textile industries. There are several chemical pathways to produce AA, but the most common one is via the partial oxidation of propylene. The usual mechanism for produc- ing AA utilizes a two-step process in which propylene is first oxidized to acrolein and then further oxidized to AA. Each reaction step usually takes place over a separate cata lyst and at different operating conditions. The reaction stoichiometry is given below: GH, + 0; 9 CHO + H,0 sere eH +40, +6710. Several side reactions may occur, most resulting in the oxidation of reactants and prod- ucts. Some typical side reactions aze given below: cyto +30,-+6140, + ct = 20,4360, +3140 Therefore, the typical process setup consists of a two-reactor system, with each reactor containing a separate catalyst and operating at conditions so as to maximize the produc- tion of AA. The first reactor typically operates at a higher temperature than the second, As with any reaction involving the partial oxidation of a fucl-like feed material (propylene), considerable attention must be paid to the composition of hydrocarbons and ‘oxygen in the feed stream. In the current design, a fluidized-bed reactor is used, which provides essentially isothermal conditions in the reactor and, with the addition of large amounts of steam, allows safe and stable operation. The second safety concer is associ- ated with the highly exothermic polymerization of AA, which occurs in two ways. First, if this material is stored without appropriate additives, then free radical initiation of the polymerization can occur. This potentially disastrous situation is discussed by Kurland and Bryant [1]. Second, AA dimerizes when in high concentrations at temperatures greater than 90°C, and thus much of the separation sequence must be operated under hhigh vacuum in order to keep the bottom temperatures in the columns below this temperature. B.9.1 Process Description ‘The process shown in Figure B9.1 produces 50,000 metric tons per year of 99.9% by mole AA product. The number of operating hours is taken to be 8000/y, and the process is somewhat simplified because there is only one reactor [5]. It is assumed that both reac- tions take place on a single catalyst to yield AA and by-products. It is imperative to cool‘Turton App® Parti.gud 5/11/12 22:22 aM Page 120 120 Appendix B Tafermation for the Preliminary Design of Fifteen Chemical Processes Figure 8.9.1. Unit 1000: Production of Acrylic Acid from Propylene PFD (The point where Streams 1 and 2 are mixed with Stream 3 to form Stream 4 actually ‘curs within Reactor R-1001,) the products of reaction quickly to avoid further oxidation reactions, and this is achieved by rapidly quenching the reactor effluent with a cool recycle, Stream 8, of dilute aqueous AA in T-1001. Additional recovery of AA and acetic acid (a by-product) is achieved in the absorber, T-1002. The stream leaving the absorption section is a dilute aqueous acid, Stream 9, This is sent to a liquid-liquid extractor, T-1008, to remove preferentially the acid fraction from the water prior to purification, There are many possible solvents that can be used as the organic phase in the separation; high solubility for AA and low solubility for water are desirable. Some examples include ethyl acrylate, ethyl acetate, xylene, di isobutyl ketone, methyl isobutyl ketone, and diisopropyl ether (DIPE), which is used here. The organic phase from T-1003 is sent to a solvent recovery column, T-1004, where the diisopropyl ether (and some water) is recovered overhead and returned to the extrac- tor. The bottom stream from this column, Stream 14, contains virtually all the AA and acetic acid in Stream 9. This is sent to the acid purification column, T-1005, where 95% by ‘mole acetic acid by-product is produced overhead, and 99.9% by mole AA is produced as abottoms product and cooled prior to being sent to storage. ‘The aqueous phase from the extractor, Stream 12, is sent to a wastewater column, 1-1006, where a small amount of DIPE is recovered overhead and returned to the extrac. tor. The bottoms product, containing water and trace quantities of solvent and acid, is sent to wastewater treatment, Process stream information and preliminary equipment summaries are given in Tables B9.1 and B92, respectively. A utility summary is also provided in Table B93.‘Turton App® Parti.gud 5/11/12 22:22 aM Page 121 ‘Appendix 8 Tnformation for the Preliminary Design of Fifteen Chemical Processes aaa pore B.9.2 Reaction Kinetics and Reactor Configuration ‘The reactions taking place are kinetically controlled at the conditions used in the process; that is, equilibrium lies far to the right. 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Carbon stee! Stainless steel Phase Cond. vapor L L (continue) Equipment 1001 4/8 v-1001 v-1002 v-1003, Moc Carbon steel Stainless steel Carbon steel Carbon steel, Power (shaft) (KW) 2260 Efficiency 7% = = _ Centrifugal Type/drive Centrifugal -2 = = - Stage/electric Temperature (°C) 2 Pressure in (ar) 10 = — _ Pressure out (bar) 50 Pressure (arg) - 088 093 oo Diameter (m) = 24 Lo 1s Hleight/length (=) 72 25 45 Orientation = Horizontal Horizontal Horizontal Internals Table 8.9.3 Utility Summary Table for Unit 1000 utility ow ows ws ws ps Equipment F-1001 F-1002 F-10083 F-10048 E-1005 F-1006 F-1007 F-1008 F-1009 E1010 Flow 19950 16820 485 51820 107 543 10.19 S780 385167 Gonne/t)‘Turton App® Parti.gud 5/11/12 22:22 aM Page 129 ‘Appendix 8 Tnformation for the Preliminary Design of Fifteen Chemical Processes 129 B.10 Partial pressures are in kPa, and the activation energies and preexponential terms for re- actions 1-3 are as follows: E; ag i keal/kmol —__kmol/m* reactor hi(kPa)? 1 15,000 159% 1 2 20,000 8.83 10" 3 25,000 181 x10" The reactor configuration used for this process is a fluidized bed, and it is assumed that the bed of catalyst behaves as a well-mixed tank—thatis, itis isothermal at the tempera- ture of the reaction (310°C). The gas flow is assumed to be plug flow through the bed, ‘with 10% of the gas bypassing the catalyst. This latter assumption is made in order to sim- ulate the gas channeling that occurs in real fluid-bed reactors. B.9.3 Simulation (CHEMCAD) Hints The use of a liquid-liquid extractor requires the use of a thermodynamic package (or physical property data) that reflects the fact that two phases are formed and that signifi- ‘ant partitioning of the AA and acetic acid occurs, with the majority going to the organic phase (in this case DIPE). Distribution coefficients for the organic acids in water and DIPE as well as mutual solubility data for water /DIPE are desirable. The process given in Fig- ture B.2 was simulated using a UNIFAC thermodynamics package and the latent heat en- thalpy option on CHEMCAD and should give reasonable results for preliminary process design. Much of the process background material and process configuration was taken from the 1986 AICHE student contest problem in reference [5]. The kinetics presented above are fictitious but should give reasonable preliminary estimates of reactor size. B.9.4 References 1. Kurland, J.J., and D. B. Bryant, “Shipboard Polymerization of Acrylic Acid,” Plant Operations Progress 6, no, 4 (1987): 203-207. 2. Kirk-Othimer Encyclopedia of Chemical Technology, 3rd ed., Vol. 1 (New York: John Wiley and Sons, 1978), 330-354. 3. Encyelopedia of Chemical Processing and Design, ed. J.J. McKetta and W. A. Cunning- ham, Vol. 1 (New York: Marcel Dekker, 1976), 402-428, 4. Sakuyama, S,, T. Ohara, N. Shimizu, and K. Kubota, “A New Oxidation Process for “Acrylic Acid from Propylene,” Chemical Technology, June 1973, 350. 5, "1986 Student Contest Problem,” The AICHE Student Annual 1986, ed. B, Van Wie and R.A. Wills (AICHE, 1986), 52-82, PRODUCTION OF ACETONE VIA THE DEHYDROGENATION OF ISOPROPYL ALCOHOL (IPA) [1, 2, 3, 4], UNIT 1100 ‘The prevalent process for the production of acetone is as a by-product of the manufacture of phenol. Benzene is alkylated to cumene, which is further oxidized to cumene hy- droperoxide and finally cleaved to yield phenol and acetone. However, the process shown in Figure B.101 and discussed here uses isopropyl alcohol (IPA) as the raw