PKC4050

Petrochemical Technology II

PURIFIED TEREPHTHALIC ACID

(PTA)
ZOYA FATMA
MARYAM HABE EB
 Purified Terephthalic Acid
• Terephthalic acid is an organic compound with the formula C₆H₄(CO₂H)₂.
• It is in the form of a freely flowing, white crystalline powder.
• Used principally as a precursor to the polyester PET, used to make clothing
and plastic bottles.
• Poor solubility in water and alcohol.
 Properties
Benzene-1,4-dicarboxylic
IUPAC Name
acid
Chemical Formula C₆H₄(CO₂H)₂

Molecular Weight 166.13 g/mol

Boiling Point 300°C

Melting Point (sublimes) >300°C

Flash Point 260°C

Specific Gravity at 25°C 1.522

 Precaution and Handling

• Wear personal protective equipment/face

protection.
• Ensure adequate ventilation.
• Avoid contact with skin, eyes, or clothing.
• Avoid ingestion and inhalation.
• Avoid dust formation.
• Keep containers tightly closed in a dry, cool,
and well-ventilated place.
 Market Size

• The purified terephthalic acid global market stands at $50.13 billion.

• It is expected to reach $62.11 billion in 2027 at a CAGR of 5.5%.
• The total production globally is 107 million metric tonnes. (2023)
• Consumption of pure terephthalic acid globally is 87 million metric tonnes
(2022)

• The Indian PTA market is currently estimated to be around US$ 4 billion.

• It is expected to reach US$ 4.10 billion by 2025.

[Link]
[Link]
[Link]
 KEY PRODUCERS
GLOBAL INDIA
SABIC, Saudi Arabia Reliance Industries Ltd, Gujarat
Sinopec Corp, China Indian Oil Corp Ltd, Panipat Refinery
Lotte Chemical Corp, South Korea BP India Pvt Ltd, Maharashtra
BP p.l.c, UK MCPI, West Bengal
Eastman Chemical, USA JBF Industries, Karnataka

INDIA PS&D DATA (2021)

DATA QUANTITY (1000 MT)
Installed Capacity 3873
Production 2996.76
Consumption 3487.24
Export 135
Import 490.5
• Succinic acid
• Malic acid Routes for PTA Production
• Ethylene
1. BIO- BASED ROUTES
• Monoterpenes
• Muconic acid PRODUCTION OF PTA

5%
15%

2. SYNTHETIC ROUTES
80%
• OXIDATION OF p-xylene
• Hydrolysis of dimethyl
terephthalate (DMT)
• Oxidation/disproportionation of
toluene
• Rearrangement of benzoic acid OXIDATION OF P- XYLENE HYDROLYSIS OF DMT OTHER SOURSES
and phthalic anhydride
Executive summary of PTA 2018
MAJOR ROUTES TECHNOLOGY RAW MATERIAL CATALYST OPERATING YIELD %
OF TPA LINCENSOR CONDITION
PRODUCTION

cobalt acetate
(enhanced with
• AMOCO P- Xylene, acetic 470 K
bromine), 95%
PROCESS acid, and air 25 atm
palladium on
OXIDATION OF carbon
p-xylene
• Cobalt
• Methyl ethyl
• MOBIL
p-Xylene and air ketone is 400K 90%
PROCESS
used as
activator
Hydrolysis of • WITTEN
dimethyl PROCESS
Cobalt 430K
terephthalate (DMT is P-Xylene and air 80%
Napthenate 6 atm
(dmt) produced then it
is hydrolyzed)
As we can obtain PTA directly from the extensively commercialized AMOCO Process, thus we are going to
discuss that only. Its conversion is 98%.
 AMOCO Process
• It is a largely adopted worldwide technology.
• Catalyst used : Cobalt-Manganese-Bromide.
• Bromide is obtained either from NaBr, HBr or C₂H₂Br₄
• Bromine acts as a regenerative source of free radical, acetic acid as solvent, compressed air as
oxidant.
• Combination of bromine and acetic acid is highly corrosive, requiring a specialized reactor lined with
titanium.
AMOCO Process Flowsheet
 AMOCO Process Description
• In the oxidation reactor(at 470K and 25 atm), p-xylene, acetic acid and catalyst(cobalt acetate, enhanced by
bromine) are introduced. By injecting air from the bottom, the reaction liquid is stirred. Extra air is supplied
to optimize p-xylene conversion.

• The reaction occurs with acetic acid as the catalyst’s solvent. The generated heat is dissipated through the
evaporation of a portion of the solvent thereafter condensation and reflux to the reactor. The generated
steam can be utilized in the plant’s distillation process.

• Scrubber extracts acetic acid from exhaust fumes(nitrogen, unused oxygen, and carbon dioxide resulting
from over-oxidation).

• Due to low solubility in acetic acid (0.13 g/Kg at ambient temperature and 15 g/Kg at 470K), the majority of
TPA crystallizes during its formation.

• The slurry is evacuated from the reactor bottom and transferred to a surge vessel, which works at a lower
pressure than the reactor. Here more TPA crystallises.

• After filtering the suspension, the crude TPA is dried and transported for purification.
• Crude TPA and water are fed to a mixing tank to form a slurry of at least 15 wt.% terephthalic acid.

• The slurry is pumped to heat exchangers, which raise the slurry temperature for the terephthalic acid to dissolve.

• The solution flows through a hydrogenation reactor that contains a palladium-on-carbon support catalyst.

• Hydrogen is added to the reactor, where it dissolves in the feed solution.

• In the reactor, 4-carbonbenzaldehyde is hydrogenated to p-toluic acid, and various colored impurities are hydrogenated

to colorless products.

• The overall effect of the hydrogenation is the conversion of impurities to forms that remain in the mother liquor during

the subsequent crystallization step.

• The terephthalic acid is purified by crystallization in a series of vessels where the pressure and temperature is

sequentially decreased.
• Crystals are recovered by centrifugation or filtration, followed by drying of the wet cake. A white, freely flowing powder
is obtained (conversion of 98%)
 Major Engineering Problems
1. Formation of 4-CBA

❑ Production of 4-carboxybenzaldehyde(4-CBA) intermediate which co-crystallises with TPA act as a

contaminant.

❑ 4-CBA discolors PTA polymers and In the synthesis of PET, 4-CBA terminates the esterification chain,
necessitating a purification step.

❑ Fixed Bed Reactor : Selective catalytic hydrogenation can minimize the concentration of 4-CBA.

❑ Palladium catalyst is used to convert 4-CBA to p-toluic acid. The solubility of p- toluic acid is greater than that
of 4-CBA, and it does not co-crystallize with TPA.

❑ As Palladium catalyst is used, this makes the process expensive

2. Extremely corrosive

❑ Due to the Presence of acetic acid and bromine which act as potential oxidants.

❑ Usage of specific materials such as Hastelloy C or titanium is required.

 REFERENCES
1. Jocab A. Moulijin, Michiel Makkee, and Annelies E. Van diepen. Chemical Process Technology Second Edition
© 2013 John Wiley& Sons, Ltd.

2. Studies in Surface Science and Catalysis, volume 159 293 Hyun-Ku Rhee, In-Sik Nam and Jong Moon Park
(Editors) © 2006 Elsevier B.V.

3. PROCESS FOR PREPARATION OF TEREPHTHALIC ACID By Kelly Knight Miller (PDF) Process for Preparation of
Terephthalic Acid ([Link]).

4. PETROCHEMICAL TECHNOLOGY-II ([Link])