Alkyl formate hydrolysis in the presence of formic acid catalyst

Olatunde Jogunola, bo Akademi University, bo/Turku, Finland; Tapio Salmi, bo Akademi University, bo/ Turku, Finland; Jyri-Pekka Mikkola, Ume University, Ume, Sweden & bo Akademi University, bo/Turku, Finland e-mail: jolatund@abo.fi Formic acid (FA), a versatile, environmentally benign chemical is now finding new uses due to its relatively strong acidity, reducing power and eco-friendliness. More than 70% of the world capacity of the acid is produced by carbonylation of methanol (MeOH) and then hydrolysis of methyl formate (MeF0) produced in the first step. MeFo hydrolysis is a slow, endothermic and equilibrium-limited reaction. FA and MeOH are produced almost in equimolar amount in the process. However, the FA product obtained from the reaction catalyses that same reaction. The process is called autocatalysis. Mineral acids such as HCl and H 2 SO 4 have been reported to speed up the reaction. However, these acids have to be separated from the reaction solution and this adds to cost of energy. This drawback can be eliminated by using FA as an initial charge to catalyst its own reaction. Experimental section The hydrolysis experiments (both autocatalysed & FA-catalysed) were performed in a stirred autoclave operating isothermally at 80-110oC with a constant initial water-toester molar ratio (H 2 O/MeFo = 1.8) with or with the formic acid catalyst. Kinetic modelling The hydrolysis of methyl formate can be simply represented as: A + B C + D where A = MeFo, B = H 2 O, C = FA and D = MeOH. In the absence of catalyst (neutral aqueous medium), the reaction is autocatalysed and the reaction rate can be expressed as:
r = (k + k C C )(C A C B 1 CC C D ) KC

In the presence of FA catalyst as an initial charge, the reaction rate is

r = k (C A C B

CC C D )( K d C C ) 0.5 KC

The model equations were solved numerically by backward difference method. The software, ModEst solved the model equations and minimized the objective function (SSQ = (y model y exp )2 by adjusting the three parameters, k0 , K C , and Ea with the Levenberg-Marquardt-simplex method. H ro was fixed at +5.44 kJ/mol. Results and discussion In the absence of the catalyst, there is an induction period as shown in Fig 1. However, the period ceases to exist in the presence of formic acid catalyst. It can also be deduced from the figure that as acid catalyst is added, the reaction rate increases but the acid product yield was suppressed. A comparison of the model prediction of the reaction rate between the autocatalysed reaction and FA-catalysed reaction is shown in Fig 2.
30
Conversion (mol-%)

0.02

ri (mol/g min)

0.016 0.012 0.008 0.004 0 0 50 100 Time (min) Autocatalysis Formic acid catalysed 150

20
FA/MeFo FA/MeFo FA/MeFo FA/MeFo FA/MeFo = 0.0 = 0.1 = 0.2 = 0.05 = 0.15

10

0 0 50 100 150 200 250

Time (min)

Figure 1. Effect of the catalyst on reaction rate & equilibrium conversion at 80oC

Figure 2. Model prediction of the rate of reaction of the 2 processes at 90oC

From Fig. 1., FA/MeFo = 0.1 is the optimum molar ratio required to accelerate the reaction without having a drastic effect on the equilibrium conversion. The result of the modelling for the two systems are depicted in Table 1. Table 1. Comparison of the parameters between autocatalyzed and FA-catalyzed reactions at average temperature (95oC) ' Reaction types KC k k k Ea Ea Ea
(kg/mol min) (kg2/mol2 min) (kJ/mol) (kJ/mol) (kJ/mol)

Autocatalysed FA-catalyzed

0.03

0.12

0.39

88.2

67.8

66.4

0.2 0.2

The FA-catalysed reaction is more than three times faster than the autocatalysed reaction and their activation energies are in the correct range. The equilibrium constant remains the same. Conclusion The models developed for the batch reactor was able to predict the experimental results successfully. This approach can also be used for other alkyl formates.