Acrylic acid is produced from propylene which is a byproduct of ethylene and gasoline

production. Ethylene can be carboxylated to acrylic acid under supercritical carbon

dioxide condition.[5]

Because acrylic acid and its esters have long been valued commercially, many other
methods have been developed but most have been abandoned for economic or
environmental reasons. An early method was the hydrocarboxylation of acetylene
("Reppe chemistry"):

This method requires nickel carbonyl and high pressures of carbon monoxide. It was
once manufactured by the hydrolysis of acrylonitrile which is derived from propene by
ammoxidation, but was abandoned because the method cogenerates ammonium
derivatives. Other now abandoned precursors to acrylic acid include ethenone and
ethylene cyanohydrin.[4]

Dow Chemical Company and a partner, OPX Biotechnologies, are investigating using
fermented sugar to produce 3-hydroxypropionic acid (3HP), an acrylic acid
precursor. [6] The goal is to reduce greenhouse gas emissions. [7]
Acrylic acid became commercially available when routes based on the
reaction of acetylene with water and carbon monoxide, or an alcohol and
carbon monoxide to give acrylic acid, were developed. Another early process
was the reaction of ketene, obtained by the pyrolysis of acetone or acetic acid,
with formaldehyde. All these processes are now obsolete.

Modern plants are based on the gas phase catalytic oxidation of propylene via
acrolein. The reaction can be carried out in single- or two-step processes but
the latter is favoured because of higher yields. The oxidation of propylene
produces acrolein, acrylic acid, acetaldehyde and carbon oxides. Acrylic acid
from the primary oxidation can be recovered while the acrolein is fed to a
second step to make acrylic acid. Purification can be carried out by azeotropic
distillation.

Korea's LG Chem has developed a process that employs a new reactor

design and purification technique. The reaction temperature is claimed to be
easier to control under severe conditions, enhancing the stability of the system
and minimising byproducts while improving catalyst life. In the purification
section, the efficiency of the absorption unit has been improved, reducing the
size of the equipment and leading to capital and energy savings, says LG.

A process based on propane, instead of propylene, is being developed

by Rohm and Haas, with support from Englehard, following the award of a
$5.2m grant from the US Department of Energy. Rohm and Haas's expertise
in oxidation catalyst research will be complemented by Englehard's
development work in monolithic catalysts used to control emissions. The
companies will screen and test catalysts with
the University of Delaware providing computational modelling capabilities. The
process is expected to give significant savings in manufacturing costs as well
as reducing pollution.

US ethanol producer Cargill and the Danish enzymes manufacturer

Novozymes are developing a technology that could produce acrylic acid from
3-hydroxypropionic acid using sugar as the feedstock. Engineered
microorganisms ferment the sugar to make 3-hydroxypropionic acid. The
project has received $1.5m funding from the US Department of Energy with
the technology expected to be commercially viable by 2013.