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Ind. Eng. Chem. prod. Res. Dev.

1084, 23, 455-458 455

Liquid Phase Oxidation of Toluene to Benzaldehyde by Air
Hemanl V. Borgaonkar, SanJay R. Raverkar, and SampatraJB. Chandalla'
Department of Chemical TechnokJgy, Universffy of Bombay, Mtun@, Bombay 400 0 19, India

Liquid-phase oxidation of toluene by air in acetic acid medium, with cobalt acetate catalyst and sodium bromide
or paraldehyde as promoter, has been investigated with a view to developing a process for the production of
benzaldehyde with benzoic acid as a coproduct. The effects of various process parameters such as temperature,
period of reaction, presswe, and concentrations of the substrate, catalyst, and promoter on the overall conversion
and yield of benzaldehyde were studied. Up to 10% conversion, the use of either sodium bromide or paraldehyde
as a promoter gave more than 90% yield of benzaldehyde. However, at high conversions, the yield of benzaldehyde
decreased markedly. Under suitable conditions. 40% yield of benzaldehyde was obtained at a conversion of 20%
in the presence of sodium bromide.

Introduction sodium bromide was used as a promoter, a glass tube was
Benzaldehyde is widely used in dyestuff, perfumary, and inserted in the stainleas steel reactor tube so that the liquid
pharmaceutical industries. In the latter industry it is used containing sodium bromide did not come in contact with
for the manufacture of intermediates for chloramphenicol, the stainless steel tube. The vapors emerging from the
analgin, ephedrin, and ampicillin etc. For the production reaction mixture did come in contact with stainless steel,
of benzaldehyde, particularly for the grade conforming to but since the vapors were essentially free from bromine-
pharmaceutical and perfumary standards, which is re- containing compounds, it did not pose a problem. A
quired to be free from compounds containing chlorine in compressor was used for passing air continuously through
the nucleus, the vapor phase (Ray and Mukherjee, 1983) the reactor, and the air flow rate and pressure were con-
oxidation of toluene is well established. However, in this trolled by means of needle valves at the inlet and outlet
process, the conversion per pass is restricted to about 15% of the reactor. A rotameter was fitted at the exit to allow
and the yield of benzaldehyde is generally not more than measurement of the air flow rate.
70%, with carbon dioxide as the main byproduct. Further,
the low concentration of toluene in the toluene-air feed
Analytical Procedure
mixture poses problems of recovery. Therefore, with the The major products of reaction were the carboxylic acid
increasing cost of toluene, the process does not appear to and the aldehyde. The reaction mixture was allowed to
be attractive. cool to room temperature and was filtered to remove some
The liquid-phase oxidation of toluene by air mostly of the insoluble carboxylic acid. The aldehyde present in
proceeds to the carboxylic acid, and the amount of benz- the filtrate was analyzed by oxidation with silver oxide,
aldehyde obtained is generally very low, though aldehyde which is formed in situ by reaction of silver nitrate with
is an intermediate product. Morimoto and Ogata (1967), sodium hydroxide (argentometric method). The necessary
Fields and Meyerson (1968), and Kamiya (1968) have re- correction for the silver nitrate consumed by the reaction
ported that high yield of benzaldehyde may be obtained, with sodium bromide present in the reaction mixture was
if oxidation is carried out in acetic acid medium with cobalt made by performing a blank titration without addition of
acetate as a catalyst and sodium bromide as a promoter. sodium hydroxide solution to the sample of reaction
This process also suffers from the disadvantage of rela- mixture. The carboxylic acid present in the filtrate was
tively low yield. Further, the recovery of benzaldehyde analyzed by diluting a sample with water and extracting
from the reaction mixture containing acetic acid, toluene, the aqueous solution with ether. The combined ether
and benzoic acid would be quite involved. However, unlike extracts were washed with aqueous sodium hydroxide so-
vapor phhase oxidation, no carbon dioxide is formed, and lution to extract the carboxylic acid as sodium salt. The
the benzoic acid obtained as a byproduct may be marketed. aqueous layer was neutralized with mineral acid to pre-
The information available on the process is very limited cipitate the carboxylic acid. The latter was dried and
and is found mostly in the patent literature. In this paper, weighed.
the effects of various process parameters on the reaction In the case where paraldehyde was used as a promoter,
rate and yield of benzaldehyde are reported. it was ascertained that all the paraldehyde got oxidized
to acetic acid under the reaction conditions and the same
Experimental Procedure was not present in the reaction mixture.
The flow diagram of the experimental unit has been In a few typical runs, the unreacted toluene in the
reported previously (Kamath and Chandalia, 1973). The product mixture was analyzed by gas-liquid chromatog-
experiments were conducted in a batch manner in a bubble raphy. The ether solution after removal of the carboxylic
column stainless steel reactor (44mm i.d., 330 mm long) acid was used for the purpose. A 2 m long stainless steel
fitted with an air sparger, a thermometer pocket, a pressure column containing 15% Apizion-L on Chromosorb-W was
gauge, and a water condenser. The reactor was heated by used. The oven temperature was varied from 75 to 180
a nichrome wire element and the temperature was con- "C at the rate of 4 OC/min. Injector temperature was kept
trolled by a Variac. The reaction was carried out in a at 195 "C and thermal conductivity detector temperature
medium of acetic acid using cobalt acetate as a catalyst was kept at 210 "C.
and sodium bromide or paraldehyde 8s a promoter. The
presence of sodium bromide in the reaction mixture is Results and Discussion
known to cause severe corrosion, and stainless steel is not Definitions. Conversion to product: amount of reac-
suitable as a material of construction. Therefore, when tant consumed for the formation of a product divided by
Q196-4321I84/1223-Q455$01.5Q/Q 0 1984 Amerlcan Chemical Society

5 30.0 180 0. air flow rate. toluene concentration.2 a Toluene. and above 40% conversion no aldehyde was be chosen for the process (runs 1 to 7. but at version increases.5 9. the overall conversion increased significantly.9 6.6 29.6 7. conv of benzaldehyde. Other byproducts such as benzyl "C. conv.56% w/v concentration of toluene at 10 kg/cm2 Table 11.02 g-mol/L. At higher conversions. temperature.0 'Reaction volume.0 110 1. % w/v reaction conv of conv to yield of of reaction time. When the concen- It is well-known that in consecutive reactions the yield tration of toluene was further reduced to 21. benzaldehyde. the rate of overall con- aldehyde and benzoic acid.9 l l b 11. suitable as a material of construction.0 8 11. obtained (Table I). Most of the work was carried Benzaldehyde and benzoic acid were the only major out at 110 "C. In industrial practice.0 110 3. The yield decreased markedly with the increase in 5b 2.0 92. 0.0 27. Kinetic data were ob- concentration. 300 mL.25 16.7 9. 1 0.5 110 5 33. Effect of Toluene Concentration' concn of overall toluene. pressure.5 20.5 33.8 20.3 27.5 7.167 tained at conversion levels of about 20 to 25%. temperature. CoAc.5 nil nil 10%. 0.8 46.8 4 21. air pressure. For a comparable cobalt acetate Effect of Period of Reaction. 0. mixture h mol % mol % % 1 64. run no.0 110 1. 300 mL.16 g-mol/L. moter.6 4.2 5.6 6 21. Hence sodium bromide was preferred to par- no. In this case also the yield of benzaldehyde was 3 1. 28. sodium bromide. Eng. When the pressure was increased moles of benzaldehyde formed by the moles of benz. Therefore. 23.5 14. air flow rate. About 40% yield of benzaldehyde was ob- 6b 5. Effect of Temperature.16 g-mol/L.88 2. 12 kg/cm2. 10 kg/cm2. 10 kg/cm2. The g-mol/L.56 0.0 8. 3. the of intermediate product will decrease as the overall con.2 8. h mol % mol % % aldehyde in the subsequent work. of conversion. When the concentration of toluene was de- particular product divided by the total amount of reactant creased from 64. 3 L/min.2 1Ob 11. 28.0 50.6 nil nil very high (above go%).88% (w/v of the reaction mix- consumed. kg/cm2. the yield decreased Therefore. 10 and 11.5 38. 110 "C. With further increase in the pressure to 21 zaldehyde in high yield.9 35... it was found that almost quan.8 36. Yield or selectivity: the Effect of Concentration of Toluene in the Reaction amount of reactant consumed for the formation of a Mixture.8 11. 0.0 110 2 19.44 2. overall conversion of toluene increased markedly. toluene.0 4. 0.1 2 3. this range. mixture poses corrosion problems. bCoAc. the reaction rate was less when paraldehyde tained by varying the period of reaction from 0. When the oxidation of toluene was carried out with The yield of benzaldehyde also increased considerably in paraldehyde as a promoter with a view to obtaining ben. pressure.32 2. 1984 Table I.9 96 11.7 31.8 30.7 100 Oxidation of Toluene with Sodium Bromide as a 2 1 19. Therefore. if the conversion was restricted to 4 2.456 Ind. for a given period of reaction the overall conversion defined as the ratio of total moles of reactant reacted to of toluene remained almost the same but the yield of the moles of reactant taken.6 9.7 4. version of toluene increased because a relatively shorter Oxidation of Toluene with Paraldehyde as a Pro.2 7. .0 110 0.4 3 42. No. Dev. cobalt acetate. reaction.5 7b 11.9 2 42.5 3 6. ke/cm2 "C h toluene. Chem. 3 L/min. In the range of 20 to 40% conversion. and stainless steel is not 120 "C. air flow rate.0 5.0 95 3.5 26.5 39. ~~ no. Vol. aldehyde.7 Promoter. the pressure in the range of 10-20 kg/cm2 may markedly.0 49.0 110 2 24. bromide. Overall conversion: the overall conversion is ture).56% w/v.5 27. benzaldehyde increased significantly. temperature. sodium bromide. Effect of Pressure a n d Temperaturea period of overall conv to yield of run press.5 to 2 h was used as compared to that when sodium bromide was for 28.0 40.88 5. the yield of benzaldehyde could be found by dividing the Effect of Pressure. cobalt acetate. aldehyde. temperature.0 35. 42.0 110 0.2 12. Prod. in the following discussion.6 5b 8. aldehyde (run no.486 g-mol/L. Table 111. titative yield of benzaldehyde WBS obtained up to 10% level while the yield of benzaldehyde was almost the same.32 to 42.44% w/v.0 'Reaction volume.6 4 11. Oxidation of Toluene with Paraldehyde Promotera employed.9 9.5 45. % % % l b 1.33 16. of conversion.02 g-mol/L.0 9.1 35. there was no significant effect on the yield of benz- alcohol or benzyl acetate were not obtained.8 4. the amount of reactant taken. paraldehyde. from 1 to 11 kg/cm2 (absolute).4 12. 0.2 5.75 26.88% w/v of reaction mixture. temp. aldehyde.56% w/v. the same level of conversion the yield of benzaldehyde did the yield of benzaldehyde is compared only at similar level not change significantly (Table 11). titanium-lined or glass-lined vessels may be used.0 5.2 19. When the temperature was varied to 180 products of reaction. presence of bromine-containingcompounds in the reaction 110 "C. aldehyde. the yield overall conv to yield of of benzaldehyde was also more in the case of sodium run time. 0.04 g-mol/L.9 9. 110 'C. Concentration of toluene. time of reaction was required to obtain similar conversion. Res.5 26.0 110 2 33.4 5 28. 3 L/min.9 22.5 10. Table 111).8 100 conversion.2 6. Table 111).

4 0. Figure 2.5 h.08 g-mol/L to 0.6 16.5 42. Dev.08 3.9 0.) is directly propor- benzaldehyde accumulates. (0)yield of (0) conversion to acid.883 56 0.3 0.16 g-mol/L. 110 "C. 3 L/min.6 0. 300 mL.5 nil 3 62. It is interesting to note that tional to the concentration of sodium bromide. Thus. Res.16 1.02 0.. indicating that k2 did not in- 0. 0. air flow rate. Table IV). benzaldehyde.1 1. cobalt acetate. order with respect to toluene. Effect of period of reaction: (0) disappearance of toluene. there was not effect . 28.5 0. Figure 1. 4. g-mol/L g-mol/L h mol % mol % % g-mol/(h L) 1 0. Effect of Concentration of Cobalt Acetate and Sodium Bromidea cobalt sodium overall SP acetate bromide reaction conv of conv to yield of reaction run concn. 28. Table IV).3 19.05 0.05 g-mol/L (run no. the rate of formation of 1 and 2. reaction vol.5 38.5 40.5 h. toluene. when overall conversion of toluene was varied from of the limited solubility of sodium bromide in the reaction 20 to 55%. cAssuming the validity of zeroth-order rate expression from zero time instead of from 0. air flow rate.8 6.7 8.6 9.16 g-mol/L. concn. to 0. (0) yield of benzaldehyde. the rate of disappearance of toluene was zeroth crease to the same extent as k l (runs 2 and 3.02. The yield of benzaldehyde it appeared that for most of the time during the run (i. temperature. Kinetic data were also the presence of cobalt acetate and sodium bromide as a obtained at 7 kg/cm2 pressure (Figure 2).56% w/v.02 g-mol/L. 300 mL.02 0. This indicated that during this time interval. air flow rate. cobalt benzaldehyde. In the absence of unaffected. the specific reaction rate (k.640 7b 0.e.4 16.9 0. both overall conversion of toluene as well as yield the rate of formation of benzaldehyde from toluene was of benzaldehyde were found to decrease drastically (runs almost equal to its rate of disappearance to benzoic acid. of 7 kg/cm2 was chosen because glass-lined reactors are Effect of Sodium Bromide and Cobalt Acetate. and thus rate for disappearance of toluene (k. ature. 10 kg/cm2. 7 ume.)was calculated (runs acid (r2). the conversion to benzaldehyde was almost mixture at the operating temperature. 300 mL. 42.5 h Assuming the validity of the zeroth-order rate expression the average rate for disappearance of toluene (rl) is greater from zero time (which is strictly not true) instead of from than the average reaction rate for the formation of benzoic 0.5 nil 0. 110 OC. Still higher with the further increase in the reaction period from 0.7 0. air pressure. sodium bromide 0.0 0. it was seen that the overall conversion of toluene as well as yield of benz- Interpretation of the Kinetic Data aldehyde increased markedly (runs 1 and 2. kg/cm2.5 to 2 h). pressure. A similar observation has With further increase in cobalt acetate concentration to been made by Kamiya (1968) for the oxidation of toluene 0. Eng. 0. k1 increased almost in a linear manner with the Though a detailed kinetic analysis was not carried out. 10 kg/cm2. acetate. reaction volume. rate (hl): no. b28.4 26. toluene.01 the increase in the overall conversion of toluene.8 0.. Vol.02 g-mol/L. and by Ravens (1959) for the oxidation to toluic acid in pressure and 110 "C (Figure 1).337 2 0. concentration of cobalt acetate. 110 "C. period.implying that. benzaldehyde. Ind.319 46 0. the yield of benzaldehyde decreased markedly with When cobalt acetate concentration was varied from 0. bromide. It was observed from the kinetic data that up to 0. sodium bromide.01 0. 6 and 8. toluene. 0.16 3.16 g-mol/L.56% w/v. 3.6 6. Chem. 3 L/min.05 0.5 14.16 1.5 concentraion of sodium bromide could not be used because to 2 h.56% w/v toluene concentration.899 86 0. 23.02 0.2 15. 3 L/min. (A)conversion to benzaldehyde. normally designed to withstand pressures around that When the concentration of sodium bromide was increased range. I t appears that the specific reaction benzaldehyde is more than its disappearance. from 0. Table IV).0 9.8 6.16 2 24.16 2 58. temperature. initially. temper. No. pressure. 1984 457 Table IV.843 6b 0. The pressure catalyst system. toluene.2 0.88% w/v.5 25.2 2. (A)conversion to benzaldehyde.578 3 0. also increased significantly.880 OReaction volume. Effect of period of reaction: (0) disappearance of toluene. (0)conversion to acid. Table IV). reaction conditions. Table IV). Prod.5 23.

provided the (0. Soc. 1973. Chem. Y.02 g-mol/L) as a catalyst and sodium bromide (0. the norbornadiene (N)-quadricyclane (Q) system has been identified as a promising one for the storage of solar energy [Jones et al. Appl. when the overall conversion of p-methoxy. 21(4). Chem. air flow rate 3 L/min) it was oxidized in a medium of acetic acid. 55. (1979)j. (1979). Ser. Scharf et al. 28. Chem. the yield of benzaldehyde was also acetate concentration. Ser. temperature to obtain almost quantitative yield of p. Technol. Introduction It was suggested that the energy transfer from the excited Photochemical conversion and storage of solar energy photosensitizer to N is inversely proportional to the dif- was recently being investigated in various laboratories ference of triplet energy between the excited molecule and around the world [Hautala et al. bornadiene concentration. Res. or paraldehyde as a promoter gave more than 90% yield Morlmoto. The most efficient sensitizers were Michler's ketone. 71-48-7. 395.91 in Theoretical Section pure norbornadiene with acetophenone as sensitizer. 76(2). energy storage. (1979).458 Ind. S. The main criterion which can be used for the screening Acetophenone was found to be the most quantum efficient of various proposed photochemical systems for the storage sensitizer followed by benzophenone and Michler's ketone. E. Sect. be extended to the oxidation of p-methoxytoluene for the 0. 1959. B 1967. (1983)l. S.. In the range of 20 that in this range k1 and k2 are independent of cobalt to 40% conversion. higher with sodium bromide than that obtained with Oxidation of p -Methoxytoluene to p -Anisaldehyde. 23. (1979). efficiency of storage of polychromatic solar radiation under controlled solar simulation in the laboratory and under In particular. 62.16 overall conversion of toluene was restricted to 20%. 1768.p-anisaldehyde. Literature Cited Conclusions Fields. (198311.Jones et al. Chandalia. A mixture of the sensitizers performed worse than the less efficient sensitizer. P. Prod. Y. As has 0196-4321/84/1223-0458~01. 104-93-8. 469.. Soc. Dev. Ray. 1983. Under suitable conditions (toluene. and tem- perature. pressure 10 kg/cm2. B. The kinetics of the thermal reverse reaction were investigated and presented. D. Trans. The rate of conversion and the efficiency of solar energy storage were measured and have been quantitatively correlated. acetic acid. Also other objectives were to study the reverse thermal reaction Q N and to carry out a number of cycles of the process to determine - of norbornadiene upon monochromatic irradiation (A = 254 possible product deterioration. with cobalt acetate possible to get 40% yield of benzaldehyde. K. K. This information is considered to be useful in the development of a photochemical solar energy storage system. of benzaldehyde. J . S. S. National Technlcal University of Athens. the largest value being 0. sodium bromide. 100-52-7. Philippopoulos et al. acetophenone. Athens. The use of sodium bromide was Received for review September 22.02 g-mol/L. It is hoped that this in- nm) in the presence of solvents and photosensitizers has formation may be useful in the development and im- recently been reported [Phdippopoulos et al. Blotechnol. A&. Data have been obtained by exposing the system to the actual sunlight. 123-63-7. N.. sodium bromide. Mukherjee. 1983 preferred to paraldehyde because relatively higher reaction Accepted March 5. implying rates were obtained in the former case. 193. cobalt acetate.16 g-mol/L. Faraday.cobalt acetate. The provement of a viable process for photochemical solar quantum efficiency was found to be a function of nor. benzaldehyde. Toluene. S. paraldehyde. reactant and sensitizer concentrationsJnsolationpower. 1968. Chem. 108-88-3. Kamath. 458-466 on reaction rate as well as yield of benzaldehyde. The efficiency and kinetics of conversion conditions of exposure to the sun. toluene was restricted to about 20%. At higher conversions. Ogata. e e e c e The conversion of norbornadieneto quadricyclane by polychromatic radlation in a solar simulator was investigated. and repeated cycles of photochemical conversion and thermal reverslon of the reaction were made. 1984. 23. Thus p-methoxytoluene was 110 O C . 137. 123-11-5. Part of this interest is directed The present paper aims at studying the kinetics and to the valence photoisomerizations of organic molecules. Up to 10% conversion. perhaps due to a mechanism of intersensitizer energy transfer. J . benzaldehyde decreased markedly and benzoic acid was obtained as a coproduct. the yield of Ravens. Parameters examined were photosensitizers. T. 1968. A.p-methoxytoluene. qw. No. production of p-anisaldehyde. temperature. Meyerson. solvent... Eng. 1984 Kinetics and Efficiency of Solar Energy Storage in the Photochemical Isomerization of Norbornadlene to Quadricyclane Constantine Phlllppopoulor and John Yarangozls Laboratory of Chemlcal Process Engineering. anisaldehyde.50/0 0 1984 American Chemical Society . and benzophenone in that order. of solar energy is the overall storage efficiency. g-mol/L) as a promoter at 10 kg/cm2 pressure and 125 "C Registry No. the use of either sodium bromide Kamiya. No. S. 7647-15-6. Chem. A&. the acceptor. 0. Indian J . 76(2).56 % The process for oxidation of toluene to benzaldehyde could w/v of reaction mixture.paraldehyde.