Biobased Terephthalic Acid Technologies

Terephthalic acid (TPA) is a chemical compound produced on a large scale through the aerobic
catalytic oxidation of para-xylene (PX), which is obtained from non-renewable sources. An
essential aromatic chemical substance of aromatic is typically condensed as core raw material
with glycols to manufacture polyethylene terephthalate and polyester fibers as a result of the
condensation process. As the demand for polyester continues to grow, the expansion of the
TPA market is expected. High consumption is triggered by its wide range of application areas,
including, packaging, plastic containers, films, bottles, textiles, and furnishings. (Gregorius R.
Harviantoa, 2017)
Considering the production path, there is a strong need to improve the environmental impact of
TPA either by enhancing the environmental aspects of the PX oxidation process or by
generating TPA from renewable sources, which is referred to as biobased TPA, such as
carbohydrates, lignin. Currently, approximately 30% of biobased materials are biobased PET.
The Coca-Cola Company’s PlantBottle PET is a biobased MEG product introduced in 2009.
Manufacturing biobased TPA will facilitate PET production from 100% biobased content. Both
companies and academia are developing technology pathways to make this applicable to the
industry. In mid-2012, Ford Motor Company, The Coca-Cola Company, H.J. Heinz Company,
Nike Inc., and The Procter & Gamble Company joined hands to form the Plant PET Technology
Collaborative aimed at accelerating the development and utilization of 100% renewable PET.
(Dimitris I. Collias, 2014)
The AMOCO process is a widely used technique for terephthalic acid production, whereby a
significant majority of the production occurs through the aerobic catalytic oxidation of p-xylene
with air in an acetic acid solution catalyzed by manganese, cobalt, and bromide compounds.
The first record of para-xylene oxidation goes back to 1912 – to the studies of Ciamician and
Silber to analyze the influence of light on certain derivatives of benzene, including para-xylene.
One-year lasting exposure of those derivatives to sunlight in the presence of molecular oxygen
as an oxidant resulted in the production of terephthalic acid together with p-toluic acid. Stephen
modified this oxidation process by replacing sunlight with dimmed light a decade after in 1926.
This study contributed to investigating the oxidation mechanism, after which the stepwise
oxidation of hydrocarbon and alkene, yielding ketones and aldehydes as intermediates, was
revealed. Because of the long reaction time, studies of Stephens and Ciamician & Silber were
not applicable to the industry. Consequently, the application of a homogeneous or
heterogeneous catalyst for the oxidation of para-xylene to terephthalic acid has been met with
considerable approval in academic and industrial sectors alike. (Nor A.M. Fadzil, 2014)
Considerable efforts have been devoted to improving renewable polymers derived from biomass
sources. Recent advancements in catalytic processes for converting biomass have facilitated
the development of technically effective and cost-efficient methods for synthesizing green PET
monomers. Due to carbon content, fossil-derived TPA production causes greenhouse gas
emissions. Additionally, as fossil resources, such as natural gas, coal, and crude oil, are formed
over hundreds of thousands of years, however, consumed quickly, they are considered as non-
renewable materials. Materials that are created through natural processes and are able to
replenish themselves at a rate similar to their consumption, such as plants (sugar beets, sugar
cane, potatoes, corn, citrus fruit, and woody plants), lignocellulose, carbohydrate, hemicellulose,
cellulosic waste, animals, fish, bacteria, fungi, and forestry products, are referred to as
renewable or biobased resources. As the availability of fossil resources diminishes, and they
become more expensive, volatile in price, and regulated for CO2 emissions, there is an
increasing need for biobased TPA to serve as a replacement for fossil-derived TPA. Technology
pathways are categorized based on the intermediate chemical used to obtain biobased TPA:
a) Biobased PC, via 2,5-dimethylfuran (DMF; C 6 H 8 O )
b) Other intermediate chemicals, via 2,5-furandicarboxylic acid (FDCA; C 6 H 4 O5 ) and
limonene (C 10 H 16)
c) No intermediate, directly from carbohydrate
The primary chemical goal when utilizing carbohydrates is to convert glucose, fructose, or furan
derivatives (containing a ring with 4 carbon atoms and 1 oxygen atom) that have functional
groups into an 8-carbon TPA molecule containing a 6-carbon aromatic ring. In the case of lignin,
the primary chemical objective is to break it down into smaller units while preserving its aromatic
content, which accounts for approximately 45% of the lignin polymer. (Dimitris I. Collias, 2014)
Biobased TPA via Biobased PX Intermediate
In this section, the pathway developed by Virent Inc. for commercialization is reviewed. This
technology utilized soluble pentose and hexose sugars as carbohydrates and transfers them to
a Benzene-Toluene-Xylene (BTX) steam, which has rich PX content. This steam is the
feedstock for the separation and purification of PX. In Virent’s process, once the sugars are
solubilized, the hydrogen is then introduced for the hydrodeoxygenation of the sugars in the
presence of deoxygenation catalysts, such as Pd, Ni, Fe, and Co to generate different
oxygenated intermediates, such as aldehydes, alcohols, and ketones. Then, the oxygenated
intermediates are reacted in the presence of acid condensation catalysts such as alumina,
carbide, and silica to yield an aromatics stream consisting of benzene, toluene, xylenes, and
ethyl benzene. Consequently, with the help of the present infrastructure for fossil-derived TPA,
PX is oxidized to TPA.
Biobased TPA Production via Biobased Intermediates Other than PX
The intermediates employed for the current TPA production technology are muconic acid,
FDCA, limonene, and methyl coumalate. Muconic acid can be prepared from the microbial
synthesis of biomass, in which process biomass-derived carbohydrates are converted to a
mixture of muconic acid isomers. The conversion of muconic acid to biobased TPA on an
industrial scale happens at dilute reaction conditions and the theoretical weight yield of the
overall reaction from glucose to TPA through muconic acid is 92% if ethylene is fossil-based, by
61% with biobased ethylene. To derive FDCA, fructose is initially dehydrated to HMF, which is
subsequently oxidized to FDCA. Fructose is obtained from the isomerization reaction of glucose
through enzymatic or chemical catalysis. The process from fructose to TPA contains 4 stages;
the theoretical weight yield from fructose with biobased and fossil-derived ethylene is 61% and
92%, respectively.
Biobased TPA via Direct Fermentation (Smith, 2015)
This method involves either biological processes to get biobased TPA or its precursors, which
can then be oxidized to TPA chemically or biologically. These procedures utilize advanced
genetic technology to create microorganisms that are not naturally occurring and have
novel metabolic pathways to transform carbohydrates into TPA or its precursors. The
technical challenge in the development of methods of renewable TPA production was
the natural degradation of toluene and other aromatic compounds by certain bacteria.
However, recombinant technology allows the creation of new microorganisms with
different biosynthetic pathways using sustainable biomass as carbon sources, which ac
be obtained through various processes like extraction, enzymatic or acid hydrolysis.
Biobased TPA via Lignin Processing (Daobin Tang, 2021)
Interest in renewable plastics and chemicals is increasing and lignin is now being considered a
viable starting material. Lignin was previously seen as a by-product and overlooked in favor of
sugars and oils. However, developing new technologies to convert lignin into useful chemicals is
essential for improving the economics of bio-sourced materials and biorefineries. Lignin
feedstock is attractive for being available agricultural waste and it is the second most abundant
naturally occurring polymer. Breaking down the C-C and C-O bonds of lignin through non-
selective depolymerization and de-oxygenation can create aromatics like BTX, phenol, and
aliphatic. BTX can be transformed into other chemicals using existing petrochemical processes.
The main form of xylene derived from lignin is usually meta isomer, but selective oxide catalytic
isomerization of mixed xylenes can enhance the yield of the PX isomer, a reaction currently
applied in the market.
Numerous pathways are being investigated by researchers to produce biobased TPA. This
review paper examined several of them utilizing different feedstocks and intermediate
chemicals. The success of the technology pathway will depend on its ability to deliver economic
and environmental benefits.

References
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