Terephthalic acid (TPA), with current annual world capacity of exceeding 50 million

metric
tons, is a commercially important chemical used primarily in the manufacture of
polyesters. A
spray reactor in which the liquid phase, containing dissolved p-xylene (pX) and the
catalyst
(Co/Mn/Br), is dispersed as fine droplets by a nozzle into a continuous vapor phase
containing
the oxidant (O2) is shown to produce high-purity TPA with less than 25 ppm 4-
carboxybenzaldehyde (4-CBA) in the solid TPA product. In sharp contrast, the solid
TPA
product obtained from a conventional stirred reactor similar to the configuration
used in the
conventional Mid-Century (MC) process contains nearly 1000 ppm 4-CBA even though
the
reactor is operated at similar pressure and temperature (15 bar and 200 C) but
with the gas
phase dispersed into the liquid phase. The dramatic improvement in TPA product
quality during
spray reactor operation is attributed to two main factors: the alleviation of
interphase gas-liquid
mass transfer limitations that facilitates more complete oxidation of the pX and
the intermediate
oxidation products to TPA, and reduced backmixing that enhances the oxidation
rates. Kinetic
studies of pX oxidation to TPA performed in a well-stirred 50 mL reactor confirm
that the
intermediate oxidation steps are subject to mass transfer limitations even at the
highest rpm used.
Theoretical calculations show that the time constants for O2 diffusion in typical
spray droplets
(assumed to be 50 m diameter) are one to two orders of magnitude lower than the
kinetic rate
constant confirming complete O2 penetration and saturation of the droplets.
Gas phase concentration measurements show that in the spray reactor gas phase CO
formation
is roughly one-fourth of that in the MC process, indicative of solvent burning.
This decrease is
attributed to the shorter residence times in the spray reactor. Further, the usage
of CO2 as an inert
! iv
gas and the dominance of acetic acid (>50 mol%) in the vapor phase under reaction
conditions
create a gas phase environment that falls outside of the flammability envelope.
Mathematical modeling of the stirred reactor using MC process conditions accurately
predicts
the steady state temperatures observed in industrial reactors (195 C). The model
also clearly
divulges that the cooling provided by partial evaporation of the acetic acid
solvent, upon
absorbing the heat of reaction at the set reactor pressure, is vital to maintain
stable steady state
operation. Experimental results clearly attest to the significance of reliable
pressure control to
prevent undesired temperature rises. Comparative economic analyses and gate-to-gate
and
cradle-to-gate life cycle assessments show that the spray process significantly
reduces capital and
operating costs by 55% and 16% respectively, and also imposes less adverse
environmental
impacts than the MC process. These benefits of the CEBC spray process are mainly
derived from
the non-requirement of the hydrogenation step required in the conventional process
for purifying
the crude TPA. Thus, the spray reactor concept has the potential to be a greener
and more
sustainable process for making polymer-grade dicarboxylic acids in one step. The
results from
this dissertation provide valuable guidance for the rational design and development
of a
continuous spray reactor.