Optimising industrial reactor design and operation using high fidelity

predictive modelling

Case study: Terephthalic Acid processes

Praveen Lawrence, Senior Consultant
Juan-Carlos Mani, Vice-President (Sales)

2010 Process Systems Enterprise Limited

Overview

Terephthalic acid (TPA) - background

Need for highly predictive models

PSEs solution approach

Case study: Evaluation of bubble column reactor

performance for TPA process

Conclusions

2010 Process Systems Enterprise Limited

Terephthalic acid - background

Terephthalic acid is a key raw material for

OH

polyester production and ranks 25th in tonnage of

all chemicals produced in the world

It is commercially produced by the oxidation of pXylene

The process is selective (~96%)

As the plant capacities are >200 kt/y, there is huge

potential to save millions of dollars even for
marginal reduction in raw material consumption

2010 Process Systems Enterprise Limited

HO

Typical terephthalic acid manufacture process

Dehydration
tower
Solid-liquid
separation
Purification section
Multi-stage crystallisation

Main oxidation reactor

- Co-Mn-Br catalyst based
-bubble or stirred reactor
- 5 to 15 bar pressure
- 150 225 deg C

Post treatment
- post-oxidation reactor
2010 Process Systems Enterprise Limited- crystallisers

Economic drivers of the process

Raw materials account for

>90% of the total
processing cost
There is significant
incentive in minimising the
wastage of raw materials

Typical breakup of TPA production costs

Need model capable of

predicting <1% change in PX
consumption
key performanceaccurately!
indicators (KPIs)
Stoichiometric
consumption
kg PX/ton TPA
kg AcOH/ton TPA

2010 Process Systems Enterprise Limited

Typical plant Typical change

consumption sought

638

655 665

< 1%

30 40

~ 15%

Modelling solution PSEs approach

2010 Process Systems Enterprise Limited

Reactor performance
Key factors that influence the process performance
Catalyst/
promoter
concentratio
n

Reactor
pressure
/temperature

Reactor
performance
KPIs*

Hydrodynamics

2010 Process Systems Enterprise Limited

Water
concentratio
n

*KPIs

include burning, product

impurities, colour and crystal
size

Bubble column reactor CFD models

Industrial reactors are > 150m3 in

volume

Small bubbles

Large bubbles

Simple gas-liquid, well-mixed reactor

models cannot capture real plant
behaviour

CFD modelling

good understanding of hydrodynamic

behaviour of bubble column
spatial variations in properties

Bubble distribution within reactor

bubble size distribution (shown)

vapour volume fraction etc.

However, CFD cannot capture

phenomenological changes in the
system

2010 Process Systems Enterprise Limited

Bubble column reactor gPROMS Multizonal

results

PSE modelling approach

combines

hydrodynamic information (from

CFD)
phenomenological models (i.e.
reaction, crystallisation)

FLUENT

gPROMS
E

C
B

D
F

Hybrid multizonal approach

Provides detailed insight into

reactors all aspects
E.g.

spatial variation of key

component (PX, left)
effect on undesired side
reactions
many others
PX distribution in
liquid phase

2010 Process Systems Enterprise Limited

Modelling approach to capture impact of

changes to reactor design and operation

Thermodynamics

Kinetics

combine thermodynamics, kinetics and

mass/energy balances

CFD model

Crystal formation and dissolution

crystal size distribution

Reactor model (CSTR)

formation of product, intermediates and

impurities
Reaction in both liquid bulk and film

Hybrid Multizonal approach

CFD model of unit

Multizonal gPROMS model

Total mass conservation

Momentum conservation

Zone population balance

Growth, nucleation kinetics
Network mass/energy balances

Crystallisation

VLE and solubility

take account of effects of changes in

geometry on local energy dissipation rates,
flow profiles, etc.

C
B

D
F

CFD Multizonal

CFD Multizonal

Mass fluxes between zones

Volume-averaged zone energy
dissipation rate

Zone density & viscosity

Hybrid gPROMS Multizonal/CFD model

simultaneously account for

thermodynamics, kinetics and
hydrodynamics

2010 Process Systems Enterprise Limited

10

Plants involve flow recycles: flowsheeting of plant essential

Condensers
Oxidation reactor

Crystallisers

Post oxidation reactor +

condensers

2010 Process Systems Enterprise Limited

Evaluating the effect of modifications to the

bubble column reactor configuration and
operating conditions on process performance

2010 Process Systems Enterprise Limited

Reactor configuration Base Case

vapour
Oxidiser dimensions
Diameter = 3.0 m
Height of liquid level = 18.0 m
Slurry level

Operating conditions
Pressure 5.5 bar
Temperature ~ 153 deg C
P-xylene
Solvent

126 ton/hr

slurry

air
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31.0 ton/hr

23

Reactor configuration Alternative configuration

Spatial distribution of air and liquid feed
vapour
Slurry outlet moved

Oxidiser dimensions
Diameter = 3.0 m
Height of liquid level = 18.0 m
Slurry level

Operating conditions
Pressure 5.5 bar
Temperature ~ 153 deg C
P-xylene
Solvent

126 ton/hr

Second liquid feed

Second air feed

air
2010 Process Systems Enterprise Limited

slurry

31.0 ton/hr

24

Summary of key performance indices (KPIs)

KPI

Unit

Base

Alternative
configuration

Acetic acid consumption

kg/ton TA

36.40

30.59

PX consumption

kg/ton TA

651.09

651.42

4CBA in slurry product

wt ppm

4895

4123

CO in vent

vol %

0.30

0.21

CO2 in vent

vol %

1.32

1.21

O2 in vent

vol %

4.45

4.93

For a 300kt/y plant, this is equivalent to a 1.4M$/y saving

in raw material consumption
Return on investment typically 612 months

depends on capital expenditure

25

2010 Process Systems Enterprise Limited

Summary

PSEs Model-based engineering solutions combines

hydrodynamics and phenomenological behaviour of the
system to provide truly predictive models

The tool helps in identifying the configuration that provides

best improvement to process to ensure maximum ROI with
respect to any capital investment before the investment is
made

Modelling allows businesses to reduce risk of failure and

increase ROI by identifying room for improvement before any
capital investment is made

PSE has successfully carried out performance improvement

studies for 5 industrial customers

2010 Process Systems Enterprise Limited

Thank you!
Mark Matzopoulos Chief Operating Officer

2010 Process Systems Enterprise Limited