Process Selection (Conventional)

The Oxo conventional route is a series of catalytic chemical reaction processes to

produce 2-Ethylhexanoic Acid and its derivative, 2-ethylhexyl-2-ethylhexanoate. The
series of chemical reaction processes involved are hydroformylation, aldol
condensation, hydrogenation and oxidation. The 2-Ethylhexanoic acid produced will
then undergo esterification to form its derivative, 2-ethylhexyl-2-ethylhexanoate.
The Oxo conventional route started with hydroformylation which having
petrochemicals, propylene and synthesis gas as feed. Therefore, Malaysia is suitable
for building this plant as there are plenty of petroleum industries located in the
country, which can supply raw propylene to the plant. BASF and PETRONAS
Chemicals Group Berhad (PCG) are building a new world-scale production plant for
2-Ethylhexanoic acid in Kuantan, Pahang. This will be the first and foremost 2Ethylhexanoic acid production plant in Malaysia which also shows that there is still
plenty of market needs for this industry.

Process Chemistry
The series of processes of the Oxo conventional route come in a sequence:
Hydroformylation of propylene and synthesis gas to form iso-butyladehyde and nbutyladyhyde, Aldo Condensation of n-butylaldehyde to form 2-ethylhexanal,
hydrogenation of 2-ethylhexanal to form 2-etylhexanol and then oxidation of 2ethylhexanol to form 2-ethylhexanoic acid. At last, esterification of 2-ethylhexanoic
acid will form 2-ethylhexyl-2-ethylhexanoate as its derivative.

Figure 1: Process Flow Diagram

Hydroformylation of Propylene with Synthesis Gas

The Oxo reactor is the reactor for the first reaction of the oxo conventional route,
hydroformylation to take place. The proportion of the propylene feed is about 93% of
propylene and 7% of propane, while the synthesis gas will then consists of 48.5% of
hydrogen, 49.5% of carbon monoxide, 0.4% of methane and 1.5% of nitrogen. The
ratio of the synthesis gas and propylene in the feed stream is 2:1. This process involve
the usage of catalyst, rhodium/cyclohexyl diphenylphosphine (Rh/CHDPP) together
with the solvent, 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate. The operating
condition is set at 120 degree Celcius and 350 bar for optimum conversion rate. The
conversion ratio of the end product from this reactor: n-butylaldehyde to isobutylaldehyde ratio is about 10:1.
Aldo Condensation of n-butylaldehyde
The product stream from the oxo reactor will then undergo separation units to obtain
the pure n-butylaldehyde for the aldol condensation reaction. This is a condensation of
n-butylaldehyde by breaking the double bond to form 2-ethylhexenal. NaOH is
introduced to this reaction as catalyst, which 2% wt of NaOH will be needed for the
reaction to happen in optimum rate. The conversion efficiency for this reaction is
90%.
Hydrogenation of 2-ethylhexenal
The aldol condensation reactors product stream which containing about 10% of
unreacted n-butylaldehyde will then separate by a separator and send back to the aldol
condensation reactor again to optimize the product. The pure 2-ethylhexenal will then
undergo hydrogenation in a reduction reactor with Nickel catalyst added and
hydrogen will be introduce to the reactor for hydrogenation to take place. The
conversion rate to 2-ethylhexanol is up to 99%.
Oxidation of 2-ethylhexanol
The 2-ethylhexanal produce from the previous hydrogenation reaction will then
undergo oxidation by hydrogen peroxide to produce 2-ethylhexanol with the presence

of [CH3(n-C8H17)3N]HSO4 as catalyst. The operating condition for this reaction is

90C in 1 bar.
Esterification of 2-ethylhexanoic acid
2-ethylhexanoic acid will then undergoes esterification with 2-ethyl-1-hexanol to
produce the end product as 2-ethyl-2-ethylhexanoate. The catalytic esterification of 2ethylhexanoic acid with 2-ethyl-1-hexanol in supercritical carbon dioxide operate in
the pressure range about 150-250 bar with the temperature of 75-140 C and the
carbon dioxide stream flowrate of 0.36-0.72 g min-1. The mole ratio of the alcohol to
acid in this process will be around 0.5-2. Novozym 435 is the enzymatic catalyst use
for this esterification reaction with the present of n-hexane as solvent.

Aldox Reaction
Aldox reaction route consist of hydroformylation, aldol condensation and
hydrogenation, oxidation, and esterification to produce ester from propylene. The
advantage of this route is that it combines 2 reactions in 1 single reactor. This is
achieved by introducing a co-catalyst, AMberlyst-15 scCO 2. This catalyst allows the
aldol condensation and hydrogenation to take place simultaneously.

Figure 2: Aldox process for 2-ethylhexanol from propylene

Shell Variant
The shell variant route uses a special catalyst of phosphine ligand modified cobalt
complex for the hydroformylation process. The advantage of this catalyst is that the
resulting aldehydes are directly hydrogenated to fatty alcohols in the same reactor.
This process route offers good selectivity to linear products, and carried out at
pressure of 40 to 80 bar and temperature of 170C. The addition of PR 3 ligands
change the rate and regioselectivity dramatically because of electronic and steric
effect of PR3 substitution where the ratio of linear branch is 9:1.
This reaction however, takes much longer time to complete, 5 to 10 times more timeconsuming than conventional oxo process.
From the alcohol, there will be 2 more reactions to become ester which are the
oxidation and esterification, which use the same operating condition as in the
conventional oxo process.

Summary of Technology
Comparison between various routes of production:
Details of the processes:
Route
Number of

Oxo Conventional
5

Aldox
4

Shell Variant
3

reactor
Operating

130 C

130 C

170 C

Temperature

(Hydroformylation)

(Hydroformylation)

(Shell Variant)

80-130 C (Aldol

60 C (Aldox)

90C

Condensation)

90C

(Oxidation)

130 C

(Oxidation)

75-140 C

(Hydrogenation)

75-140 C

(Esterification)

90C

(Esterification)

(Oxidation)
75-140 C
(Esterification)
Operating

350 bar, 3-10 bar, 1

350 bar, 160 bar, 1

40-80 bar, 1 bar ,

Pressure
Catalyst

bar,150-250 bar
Rhodium/cyclohexy

bar,150-250 bar
Rhodium/cyclohexy

150-250 bar
HCO(CO)3(PR3)3

diphenylphosphine,

diphenylphosphine,

NaOH, Nickel

Pd/AMberlyst-15

scCO2
/

Catalyst
Accessibility

SWOT analysis for the processes:

Process

OxoConventional

Mature establish
technology and
have high yield.

Most number of
reactor needed
as compared to
aldox process
and shell variant
process.

Recycling of the
by-product (e.g.
isobutyraldehyde)
to use for the feed
can increase the
yield.

Aldox

One pot
synthesis

Rare and
expensive cocatalyst used for
the aldox
reaction.

Research on the
possible common
co-catalyst to be
use in this
process.

Competition
between
company in
same industry
which most of
them utilise this
technology.
Less supply in
the market for
co-catalyst used
which may cause
the price to be
high.

Shell Variant

Least number of
reactors needed
as compared to
the oxo
conventional
process and
aldox process.

Long reaction
time, the
reaction is in
batch.

Research on
reducing the
process time by
using CSTR.

Less supply in
the market for
catalyst used
which may cause
the price to be
high.

Process Routes Selection Summary

Oxo Conventional route was chosen due to the mature technology that have been
developed and the high yield of products from this routes. The easy accessibility
(supplier) and the cost concern for the catalyst used in each of the reaction routes have
to take in count also. Thus, Oxo conventional is the suitable route for our plant, in
term of economical concern for the raw material and catalyst costs.
Furthermore, in order to minimize the production waste or by products, isobutyraldehyde which produced by hydroformylation of propylene with syn gas can be
either sell out or recycle as feed. In this plant, the iso-butyraldehyde will be undergo
cracking process to turn into propene, hydrogen and carbon monoxide, which are the
feed for the hydroformylation process. By recycling the by product, iso-butyraldehyde
(by cracking), the yield of final product can able to be optimize.
The operating temperature for this plant is around 70-150 degree Celcius (excluding
the cracking of iso0butyraldehyde which needed a highr operating temperature) which
is consider within a desired operating temperature range. While the operating pressure

range is from 1-350 bar which can be done by installing expander and compressor
valve to the system.
Microwave technology was used in the final process esterification of 2ethylhexanoic acid to 2-ethylhexyl-2-ethylhexanoate by adding 2-ethyl-1-haxanol to
reduce the reaction time from 12 hours to 20 minutes.

Mass Balance
Mass balance is important in any production line or plant design, as the capacity of
the unit operation can be determine throughout the mass balance. The parameter to be
concern in the mass balance calculation is mainly on the flow rate of each stream and
the total flow rate. The principle of mass balance is based on the law of conservation
of mass balance.
The expression of the law of conservation of mass is as shown below:
The +=

The assumptions made to simplify the calculation are:

1. Continuous process at steady-state so accumulation is zero.
2. All streams are in steady state conditions.
3. All mixtures are in homogenous condition.
4. Ideal Mixing in all the unit operations
5. No corrosive compound is formed in any unit operation

The overall mass balance:

Process

In

Hydroformyla
tion

Propylene
Carbon
Monoxide
Hydrogen

Total
Aldo

n-

Flow
Rates
(ton/yea
r)
10000

Out

n-butyraldehyde

Flow
Rates
(ton/yea
r)
15267

10000

iso-butyraldehyde

1527

10000

unreacted propylene
Carbon Monoxide
Hydrogen

200
6503
6503
30000
12057

30000
15069

2-ethylhexanal

Condensation

Total
Hydrogenatio
n

butyraldehyde
isobutyraldehyde

2-ethylhexanal
Hydrogen

Total
Oxidation

Total
Esterification

2-ethylhexanol
Hydrogen
Peroxide

20

n-butyraldehyde

1507

iso-butyraldehyde
Water
15088
12057

2-ethylhexanol

20
1505
15088
12246

189
12246
12246
1052

2-ethylhexanoic acid
2-ethylhexanol

12246
10849
2449

13298
2-ethylhexanoic 10849
acid
2-ethyl-13194
hexanol

2-ethylhexyl-2ethylhexanoate
2-ethyl hexyl ether
2-ethyl-1-hexene

Total

14043

13298
6154
2107
5783
14043