Reactive distillation - a viable solution for etherification of glycerol with

tert-butyl alcohol
E. Vlad, C.S. Bldea
University Politehnica of Bucharest, Department of Chemical Engineering, Str. Polizu 1-7,
011061 Bucharest, Romania; tel. +40 21 4023903, email: s_bildea@upb.ro;
Recently, large amounts of glycerol are available as by-product of increased biodiesel
production. Proper uses of glycerol need to be found in order to achieve waste reduction. Due
its polarity that makes it soluble in water and insoluble in hydrocarbons, glycerol can not be
mixed directly with conventional fuels. Many recent studies looked for new uses of glycerol
as a way to improve the economic efficiency of biodiesel production process. A special
attention was paid to glycerol etherification leading to glycerol tert-butyl ethers (GTBE),
which can be used as diesel and biodiesel additives.
This study considers etherification of glycerol (G) with tert-butyl alcohol (TBA), leading
to a mixture of mono-, di- and tri-ethers:
G TBA MTBG H 2O
MTBG TBA DTBG H 2O
DTBG TBA TTBG H 2O
Although the reaction is suggested in several studies, the design of the entire process has
not been reported yet.
A (conventional) reactor-separation-recycle process performs the reaction between
glycerol and TBA in liquid phase, in a plug flow reactor, in the presence of an heterogeneous
catalyst (Amberlyst 15). The separation of the products from reactants is achieved by a
distillation column operated at atmospheric pressure where pure ethers are obtained, followed
by a section involving extractive distillation with 1,4 - butanediol as solvent, which separates
TBA from the TBA/water azeotrope. The design shows that the purity of the ethers product
exceeds 99% and glycerol and TBA are efficiently used by recycling. However, the large
number of distillation columns necessary for products/reactants separation results in a very
large Total Annual Cost of the plant (for example, 800,000 $/year for a plant processing the
glycerol obtained as by-product of a 15,000 tonnes/year biodiesel plant).
In this work, a new process for etherification of glycerol with tert-butyl alcohol is
proposed and designed. The process employs azeotropic reactive distillation columns as
integrated, multifunctional unit.
The reactions are equilibrium limited. Therefore, increased reaction rate and conversion
can be achieved by removal of the products from the liquid reaction mixture. In particular,
significant amounts of water are formed, but the relative volatility of water (b.p. 100 C) and
TBA (b.p. 80 C) favours the vaporization of TBA. For this reason, n-hexane is used as an
entrainer, enhancing the volatility of water due to formation of the water - n-hexane
azeotrope.
Figure 1 presents the flowsheet, as simulated in AspenPlus. The column has 10 reactive
stages, a rectifying and a stripping section (each of 8 stages). TBA is fed as vapour below the
reactive zone, while glycerol enters as liquid above the reactive zone. n-Hexane (makeup and
recycle) is fed on the top stage. It effectively removes water, due to the formation of a lowboiling water - n-hexane azeotrope. The water - n-hexane mixture is condensed and

submitted to liquid-liquid separation. High purity water is obtained as top product, while the
organic phase is recycled. On the few trays in the stripping section, lighter components are
removed to obtain high-purity GTBE. Temperature, reaction rate and composition profiles are
presented in Figure 2 and Figure 3.

Figure 1. Etherification of glycerol with TBA in azeotropic reactive distillation column

Figure 2. Temperature and reaction rate profiles

along the azeotropic reactive distillation column

Figure 3. Liquid composition profiles along the

azeotropic reactive distillation column

Sensitivity analysis shows that the purity of GTBE and water product critically depends
on feeding the reactants in the stoichiometric ratio. However, this is difficult to be practically
achieved, because the ratio between MTBG, DTBG and TTBG products is unknown, in
addition to the usual measurement and implementation errors. Therefore, the second part of
the paper is devoted to process control. The control scheme developed used glycerol feed rate
as throughput manipulator. It should be noted that the temperature in the stripping section
depends on the amount of TBA existing in the process. Therefore, it can be used as an
indication of TBA inventory, in a control loop manipulating the TBA feed. The performance
of the control structure is proved by dynamic simulation in AspenDynamics.
In conclusion, etherification of glycerol with TBA by in an integrated, multifunctional
unit as azeotropic reactive distillation greatly reduces the investment cost and energy
requirements, comparing very favourable to the conventional reaction - separation - recycle
processes.