1454 ULLETIN OF THER CHEMICAL. SOCIETY OF JAPAN, Vor. 52 (8), 1434—1458 (1979) [Vol. 52, No. 5 Improvement of Acetone Yield in the Oxidation of Propylene Mamoru Ar* and Atsumu Ozaxt Rescerch Laboratory of Resources Utilization, Tokyo Institute of Tecinology, Nagatsuta, Midorisku, Yotohama 227 (Received September 1, 1978) ‘The outstanding property of the SnO;-MoO, catalyst in the oxidation of propylene to acctone was eonfirm- ccd by tests of various oxide catalysts supported on pumice. The optimum. composition was found to be SnO,- 70/MoO,-30 mol‘ for the oxidation at from 170 to 260 °C. It was also found that this pumice-supported catalyst is sufficiently selective for the acetone formation even at a high temperature of 260 °C, and that it gives a high yield of acetone while keeping its high selectivity, The select the pal prams of waiet vapor end with adores in he orem partn premre. On the bs of ich i It has been shown that propylene can be oxidized to acetone in the presence of water vapor on molyb- denum-containing catalysts,-® whereas the acetone yields attained in the previous works were limited ‘because of low conversion at low temperatures or be- cause of low selectivity at higher temperatures. Tas further study is required to. improve the acetone Experimental Catalysis, A muraber of mixed oxide catalysts were prepared by the procedures described in previous papers.‘-® ‘That is, an aqueous solution or slurry containing the required quantity of metal compounds was mixed with 10—20 mesh pumice ina fixed ratio of one g-atom metal per 500.ml of pumice (in apparent volume), followed by evaporation to dryness with vigorous stirring’ and calcination in a stream of air at 500°C for 45h. Procedwes. ‘The catalytic reactions were eartied out in a conventional continuousow system, "The reactor was made of a steel tube coated with aluminum, 50cm in length and 1.8m id., which was mounted vertically and ‘immersed in @Jead bath. The reactant gas was fed from the top of the reactor, with water or isopropyl aleohol (IPA) being introduced into a preheater section by means of an injection syringe pump. "The amount of catalyst in the propylene oxidation was 20,30, oF 40 g, and the feed rates ofthe reactants in a standard run were as follows: propylene-20/aie-20/water vapor-76 rl (volume at 25 °G)/min, "The effluent gas from the reactor vwas led. successively into three chilled water-scrubbers. to recover the water-soluble compounds. At the end of a J-h rum, the contents of the scrubbers (about 50 ml) were callected and analyzed by gas chromatography. ‘The inlet and exit gases were intermittently analyzed. "The reaction of TPA was carried out at a fixed eoncentra- tion of TPA (1.63 mol% in air) and a fixed total flow rate (15i/min), changing the amount of catalyst in the range from 5 10205. Results and Discussion Catalyst Screening. Acatone-ferming Activities of Various Composite Oxide Catalysis: Tt. seems apparent from the previous studies that the propylene oxidation to acetone proceeds through an alcoholic intermediate, requiring two different fimctions for the catalyst: the hydration of olefin and the oxidative dehydrogenation of the alcoholic intermediate, It can, accordingly, be expected that information regard jon, it can be sad that a high yield of aectone ean be obtained by the divided inteduction of oxygen. ing the two functions will be helpful in the exploration of an effective catalyst. Since the hydration activity ‘may be expected to run parallel with the activity for the dehydration of IPA, the catalytic activity for the dehydration and dehydrogenation of TPA in the pres- ence of an excess of air would be relevant as measures of the two fanetions. Since the first function is generally accepted to be associated with acid catalysts, various binary or ter- nary mixed oxide catalysts of an acidic property were tested for the ability to form acetone from. propylene. ‘The amount of catalyst used was 20 g, and the standard feed rates of the reactants were adopted. ‘The results are summarized in Tables 1 and 2 Another series of experiments were carried out with each catalyst using a mixture of IPA and air as the reactant. The rates of IPA dehydration, rp, and de- hydrogenation, r, (mol/h-g-catalyst), were measured at 175°C. ‘They are also shown in’ Tables 1 and 2. ‘The results in ‘Tables 1 and 2 may be summarized as follows. (@) Acetone is obtained, more or less, with every V,O; or MoOyeontaining catalyst, at’ least at a low ‘temperature, The acetone yields is likely to increase with an increase in r., which can be regarded asa measure of the acidity.*-®) (ii) Although it gives a strikingly high value of fm WO--P,O, does not convert IPA to acetone; thus, itis inactive for the propylene oxidation to actone. ‘The SnOsMoO, catalyst gives a strikingly high yield of acetone. It should be noted that both y, andr, are larger on this catalyst than on other catalysis. It is also notable that the high selectivity to acctone is retained at temperatures as high as 220 °C. (iv) The Sn-60/V-40 is the second best catalyst. Effet of the SnOx-MoOy Composition on the Yield of Acione: Five SnO,-MoO, catalysts of different compositions were tested for the yield of acetone as well as for ry and ry, where the feed rate of ait was twice as large as in the standard condition, ‘The yields of acetone at 175, 190, 210, and 240°C are plotted in Fig. 1, together with the values of r; and ny obtained at 140°C, Although the highest yield of acetone is obtained ‘at around 30.atom % Mo at each temperature, it is noticeable that the effect of the temperature inerease ‘on the acetone yield is more marked with the catalystsMay, 1979] Propylene Oxidation to Aectone 455 “Taaun 1. Oxipariow oF PROPYLENE To ADETONE USNG VARIONS MOy-nnen xrai® Oxiation of propylene cual ek Gonveron (92) of propylene to (atone Pale) a T5°C) tae ; = = = ‘ Ga and 00100, Acetone ivy (x33) (xs), Total” Mo-P (9-1) 1.2 330 0.6 (37) 0.25 09 1B Mos (1) mo 08 mo 0s) Mo-W (8-2) 0.8 1.2 920, 0.91 (50) O41 0.8 1.8 (2-8) 25.0 B4 293 3.21 (66) 0.8 14 49 Mo-U (8-2) 34 1.0 369 1.94 (39) 0.8 20 4.9 28) 8.8 05 300 O15 (7) 8. 1.8 2.3 Mo-Ti (5-5) 36.0 5.8 248 2.12 (72) 0.3 0.5 29 290 4.42 (62) 13 2.8 8.5 Mo-Ti-P (5-5-1) 32.0 3.2 250 1.8 (69) 0.2 0.6 26 22 2,66 (4) 0.8 3.0 6.4 Mo-Sn (8-7) 217.0 205 182 19.2 (90) 0.8 14 24 219 45 (87) 1.0 25 28.0 Mo-Fe (2-8) 42.0 22.0 235 3.0 0.9 12 St Bo kas SBS Mo-Bi (8-2) 4.6 0.9 330 1.23 (4) 0.5 LL 2.8 Mo-BEP (9-1-2) 15.0 ot 830 220 4) 2 1 4.8 a) Feed rates=propylene-20/air-20/water vapor-76 ml/min, amount of catalyst wicd=20,g, b) IPA concentration =1.65 mol % in air, ¢) 100x (acetone)/{total). and CO, 4) Calculated as acetic acid. ¢) Sum of acetone, acid, CO, ‘Tanux 2 OXIDATION OF PRORYUENE TO ACETONE RNG vantons ViOy- AxD WOynasen carat?) Oxidation of proprlene ‘erin, Conversion (9%) of propyl Catal or wenion (2%) lene to (oto ft) at 175°C Tene Xow) G0 160, an a” Oy " t Acetone Gig) (2/3) (xfs) Total® ‘V-Mo (85-15) 30.0 7.8 ait Rit (60) ii 03 a5 A 2.40 (38) 19 2.0 6.3 v-w (2) 47.0 140 8 5.0) De 24 428 (49) Lt 34 8.8 es) 5.05 vent 37.0 36.0 mm 032 L708) 37 iad moto TR SR 9) 24 45.0 wr 07) 220 0.87 (33) 0.6 1.0 24 Vvsn (4-6) 80.0 52.0 176 43 @ 12 05 6.0 836 7 TR 88 209 10.0 50) La 20 14.3 mu nas) kg (1-9) 20 105.0 220 0.90 (13) 1.8 42 6.9 about i000 0.0 300 srace 0) trae OS €) 1003 (acetone) (total). with a lower Mo content, suggesting that the rate- limiting step may be different depending on the Mo content, Tn fact, 7, is much larger than r, on the 40% ‘Mo catalyst, while r, is much larger than rp on the 20% Mo catalyst. If and r, represent the two func tions required, the rate-limiting step on the 40% ‘Mo catalyst would be the oxidation of the alcoholic intermediate. The less extensive effect of the tem- perature would be reasonable, because the equilibrium propylene-20/air20)/water vapor-76 ml/min, amount of catalyst wsed=20 i ) Caleulated at acetic acid. fe) Sum of acetone, acid, CO, concentration of the alcoholic intermediate should decrease with an increase in the temperature. On the other hand, the rate-limiting step on the 20% ‘Mo catalyst would be the hydration to form the aleo- holic intermediate; this is in agreement with the more marked effect of the temperature. Thus, 1 and 7, can be regarded a3 parameters for the two functions Effet of the Third Components Added to Sn-70]Mo-50: ‘The effect of the third component to improve the ace-1456 Yield of acetone (mol %) ry and 14X10 (me 0 01 02 02 04 0S ‘Atomic ratio Mo/(Sn-+Mo) Fig. 1. Effect of SnO,-MoO, composition on the yield of acetone and the values of rp and Oxydation of propylene; catalyst used=20, feed rates=propylene-20/air-40|water vapor-76 ml/min (at 25°C). fp and 743 dehydration and dehydrogenation, rates of IPA at 140°C and 1.65 mol % IPA in air. tone yield was tested with P,O,, SO, V:O, UsOy, Tip, AlO,, Fe,O,, and SiO, by adding 2—10 atom% to Sn-70/Mo-30, whereas none of then showed any improvement. Eifect of the Reaction Conditions on the Yield of Acetone. Since the Sn-70/Mo-30 catalyst proved to be the best, the effect of the reaction conditions were investigated fon this catalyst Effect of the Reaction Temperature: The effects of the reaction temperature on the selectivity to acetone and on the yield were tested using different amounts of the catalyst. The results are shown in Figs. 2 and 3. At the acetone yield of around 89 mol%, almost all_of the oxygen fed in was consumed. ‘The results may be summarized as_ follows: (i) The yield of acetone increases with an increase in the temperature up to about 260°C provided the oxygen_is not completely consumed. (ii) ‘The selectivity largely depends on the conver- sion of propylene (Fig. 3), the effect of the temperature being less marked. Eject of the Feed Rate of Oxygen and Nitrogen: ‘Two series of runs were performed, changing the feed rate of oxygen or nitrogen. ‘The results are shown in Table 8. Except for Run 56, the conversion of oxygen was very close to 100%, $0 that the total conversion of propylene increased with the flow rate of oxygen. ‘The results in Table 3 may be summarized as fol lows: (i) The selectivity to acetone decreased as the inlet ‘oxygen concentration increases, so that there is an ‘optimum. value in the oxygen-flow rate to give the highest yield of acetone for a fixed flow rate of propy- ene. An acetone yield of 90mol % was achieved with a selectivity of 78:mol %, (i) The selectivity to acetone can be improved Mamoru Ar and Atsumu Ozaki [Vo 52, No. § %) GF Yield of acetone (mot bys yy 7 700 7 Ho #8 Reaction temperature (°C) Fig. 2. Effect of reaction temperature on the yield of fcetone, Feed rates; propylene-20/axygen-15/nitro- en-24/water vapor-104 ml/min (at 25°C), amount of catalyst used; (0)=20 g, (0)=15g, (@)=10e. ee | Selectivity to acetone (mol %) Reaction temperature (°C) Fig. 3. Effects of reaction temperature and propylene conversion on the selectivity to acetone. Reaction conditians and notations are the same as in Fig. 2. by dilution with nitrogen, suggesting a suppression ‘of complete oxidation in the presence of nitrogen. Effect of the Feed Rate of War Vapor: ‘The acetone- synthesis runs were carried out at different concentra- tions of water vapor. ‘The results, shown in Table 4, indicate that the sclectivity increases markedly with fan increase in the water-vapor pressure. In the ab- sence of water vapor, the catalytic activity was seriously impaired by the deposit of nonvolatile materials, while ‘the catalyst was easily regenerated by air treatment at 500°C. This suggests that the water vapor serves to prevent catalyst poisoning as well as to suppress complete oxidation,“May, 1979) Propylene Oxidation to Acetone 1487 ‘Taste 3, EFFRots OF FEED RATES OF OXXGEN AND NITROGEN ON THE YIELD OF AceTONs*) hun Feel aig ‘Gonvenion (%),of propylene to ‘No, ae ‘Acide CO4 ‘0 oH Ho mG, Ame infect Tae aT a 78 (2) 06 : 82 Dp % % 4 751 8) 14 782 33 0 7% Mw 804 (0) 27 848 ot 2 6 40 10 823 6) 23 88.3 38 0% 7% oT 57 (8) 42 977 36 » % 9 17 532 (a8) Bu v9 a7 » 6 » m6 83) 86 948 wo Ey 6 D o 75a @®) 08 776 59 20 6 o 5 80.6 7) 17 85.1 0 20 6 o 10 90.3 (78) 22 96.1 6 20 6 o 7 87.6 (75) 3.0 96.5 ‘8) Gatalyst=Sn0,-70/MoO,-30, amount of catalyst used=40 g, temperature=215 “0. b) 100% (acctone)/(total). ‘¢) Galeulated as acetic acid. d) Sum of acetone, acid, GO, and CO... ‘Tam 4, Enmucr 0” nHED mATR OF WATER VAPOR ON "MH YiELD OF Acero ‘Feed rates of ‘Conversion -of propylene to Ne (olin) oor CO+G0, GH HO NO, Acme as a8) Gas)” Ts? @ 0 © oz 04 5G 714 68 20 20 20 10, 75.0 S 19 4.0 380.9 oa 0 7% 2» 0 m4 27 4586 5 2 0) m0 (6) 27 52 eo % om 6 4 767 10 16 793 a ne a mo @) 250 41876 6a 2 158 0 ” 35 bet 3.8 56 929 69 sz, 20 40 85.5 41 62 95.8 3 3s0,-70/MoO,80, amount of catalyst wed—10 Spee ‘1005 (acetone) (cal). ‘8 acetic add. d) Sum of acetone, ackl, OO, and GOs, Taste 5. OXIDATION OF PROPYLENE BY DIVIDED INTRODUCTION OF OxvaEN®) Reactor 1 Reactor 2 ‘Conversion (%) of propylene to ‘femp Feed of air ‘Temp — Feed of air ‘Acide’ 00-400, CO) Gallnin} COP “faiminh” —Acstone Ei) CB cifayt Touato 197 0 r 0) 12 16 793 218 20 Without me) LL sia 198 40 Reactor 2 783 0) 14 73.0 216 40 81.0 @) 2.7 878 Without 220 20, 783 (85) 24 793 Reactor 1 220 40 m7 (85) __—-2.0 m5 193, 40. 20 0 790 (86) 25 84.2 it 2» 210 » 7 @8) 286 203 20 210 20 955 (a8) 2.6 13 20 20 25 0 86.5 (67) 2.6 92.7 20 10 25 » a0) 95.1 220 40 2B Oy=10 75) 80 6874 Cstalyst=Sn0,- ‘amount of catalyst uied=20 (Reactor 1) and 20g (Reactor 2), feed rate of Pee ape ed the el mies eee Oe each easaane Teena. Woo feweeh ah Galeolated as acetic seid, d) Sum of acetone, acd, GO, and CO,1458 Improvement of the Acetone Yield. Although a high selectivity to acetone can be obtained by lowering the concentration of oxygen, the yield is limited by the oxygen feed. ‘Thus, the reaction was performed successively in two reactor, with additional air or ‘oxygen supplied to the second reactor. As is shown in Table 5, the yield is markedly improved by such a divided introduction of oxygen, while retaining the high selectivity. In this way, an acetone yield of 48-50 mol % is achieved with a selectivity of about 85 mol %- Although a retardation of acetone forma- tion by product acetone was previously reported”), the above result shows that the retardation by acetone is not strong, Conclusion ‘The selective oxidation of propylene to acetone can be performed on SnO,-MoO,/pumice, particularly with a composition of 30% Mo; a high water partial pressure and a low oxygen partial pressure are requi- sites in improving the acetone yield. ‘The superior ‘of the SaO,-MoO, catalyst is under ‘stood in terms of two functions: the hydration of pro- ‘Mamoru Ar and Atsumu Ozaxt [Vol. 52, No. 5 pylene and the oxidative dehydrogenation of IPA. ‘When the Mo content is varied, both functions, indi- cated by r, and r,, attain maxima at around 20 t0 30% Mo, thus giving rise to an optimum. composition of 30% Mo. References 1) J, Buiten, J. Cate 10, 188 (1968). 2) Y, Moroota, S. Tan, and A, Ozaki, J. Cay 12 291 (1968)3, Bull. Chem. Soe. Jon, 41, 2620 (1968). 3) S, Ogasawara, S, Takahashi, A. Pukai, and Y. Nakata, Kogyo Kagaku Zasshi, 72, 2244 (1969). 4) S. Tan, Y. Morooka, and A: Ozaki, J. Catal, 17 182 (1970). 5) Y. Morooka, Y. Tabita, and A. Ozaki, J: Gata, 23, 185. (1971). ©) M. Ai, J. Gatal, 49, 318 and 327 (1975). 7) M. Ai, J. Gately 49, 305 (1977). 8) M. Ai, J Cuter, 50, 291 (1977), 9) J. Buiten, J. Gaal, 13, 373 (1969). 10) ¥. Motooka, ¥. Takita, and A. Oza 177 (1972). 11) "J, Diten, J. Catel, 27, 282 (1972). 12) Y¥, Takia, Y. Moro-oka, and A, Ozaki, J Cotaly 52, 95 (1978). J- Catal, 27,