TABLE OF CONTENT

No

Title

Pages

.
1.

Executive Summary

2.

Chapter 1 : introduction

3-12

3.

Chapter 2 : Feasibilty study and literature survey

13-18

4.

Chapter 3 : process selection

19-32

5.

References

33

1.0 EXECUTIVE SUMMARY

The project is mainly focused on the background study of 2-ethylhexanol which are general
view, properties of raw materials as well as product, market survey and process to manufacture 2ethylhexanol. Basically, 2-ethylhexanol is a branched, eight-chiral alcohol. This substance exists as
colourless liquid with strong odour at 15 0C and 1 atm. The main industrial application of 2ethylhexanol includes as the feedstock to produce low-volatility esters which then used as plasticizers.
Other applications of 2-ethylhexanol is low-volatility solvents for waxes, animal fats, vegetable oils,
disinfectants and insecticidal sprays. 2-ethylhexanol is widely used as feedstock for many chemical
substances such as 2-ethyhexyl esters of trialkyl phosphites, 2-ethylhexyl sulphate and herbicides. In
industry, 2-ethylhexanol is produced commercially by Oxo process from propylene and synthesis
gases. The market demand for alcohol plastizicers is influenced by the global current economic
situation. This is due to the fact that plasticizer alcohol is associated with a pattern of ups and downs
in the world economy. There are three processes to produce 2-ethylhexanol which are acetaldehyde
route, Oxo process and Aldox process. The selected process for this project is Oxo process. The
justification for the Oxo process to be selected is based on general comparison between the three
processes, economic feasibility and other considerations such as quality of product, efficiency of the
conversion and recovery of process.

CHAPTER 1

INTRODUCTION

2.1 GENERAL VIEW

2-ethylhexanol also known by other names such as 2-ethyl-1-hexanol, 2-ethylhexyl alcohol,
octyl alcohol and octanol. It is a branched, eight-carbon chiral alcohol. Meanwhile, the IUPAC name
is 2-ethylhexan-1-ol and have chemical formula C8H18O. Figure 1 shows the structural formula of 2ethylhexanol.

Figure 1: 2-ethylhexanol Structural Formula (ChemSpider, 2013)

Generally, the observable characteristics of 2-ethylhexanol includes its physical state at 15 0C
and 1 atm as colourless liquid with strong odour. It is very soluble in most organic solvents but
weakly soluble in water.
Even 2-ethylhexanol has a slightly strong odour, it does not indicate a specific health hazard.
However, similarly like other reactive chemicals, it can be hazardous if not handled appropriately.
One of the hazard is acute toxicity. Meaning, it may be harmful if swallowed or in contact with the
skin. Next is irritation. 2-ethylhexanol is irritating to eyes while its vapour and mists is irritating to
respiratory tract. It is also highly irritating to the skin in which may cause local redness and swelling
and in turns leading to scars.

2.2 PROPERTIES
2..2.1 Acetaldehyde Route

n-butyraldehyde (butanal)

Physical

Chemical

Colourless liquid (clear

liquid) turning pale yellow
on contact air or light at
15C and 1 atm.

Highly flammable liquid.

Acrid smell (a pungent

odor).

Insoluble in water.

Vapours are heavier than

air.

Heat of combustion :
353.8105 J/kg.

Latent Heat of Vaporization

: 4.27105 J/kg.

Low molecular weight.

Freezing Point: 96.4C

Flash point : 31 C

Boiling Point at 1 atm:

74.8C

iso-butyraldehyde

Physical

Chemical

Colourless liquid (clear

liquid)

Melting point : 65 C

An extremely unpleasent
smell.

Boiling point : 63 C
Flash point : 33 C
Density : 0.79 g/mL at 25 C

Low molecular weight

Soluble in water.
Highly flammable liquid.

2-Ethyl hexanal

Physical

Chemical

Clear liquid.

Melting point : -76 C

Mild odor.

Boiling point : 55 C at
13.5 mm Hg

Float on water.

Flash point : 108 F

Density : 0.822 g/mL at 25 C

Low molecular weight.

Insoluble in water.
Spontaneously flammable in
air.

Crotonaldehyde

Physical

Chemical

Clear to yellow liquid

Melting point : -76 C

Suffocating odor.

Boiling point : 101 - 102 C

As chemical intermediate in
industry.

Flash point :13 C

Soluble in water.

Low molecular weight.

Spontaneously flammable in air

and light.

2.2.2 Oxo Process

Propylene

Physical

Chemical

In the form of liquid and air.

Boiling point : -47.7 C

Colourless gas/liquid.

Melting point : - 185 C

Good smell.

Density at 70 F : 31.92 lb/ft3

(liquid)
Density at 70 F : 0.1105 lb/ft3

Low molecular weight.

Highly flammable : readily form

explosive mixtures with air.

propane

Physical

Chemical

Colourless gas.

Melting point : -305.8 F

Faint petroleum-like odor.

Boiling point : -43.7 F

Low molecular weight.

Flash point : -156 F

Easily leak.

Easily ignited in air.

2.2.3 Aldox Process

iso-butanol

Physical

Chemical

Clear liquid (neutral liquid).

Melting point : -108 C

Nice smelling.

Boiling point : 107 - 108 C

Use as solvents also.

Flash point : 26 - 29 C

Low molecular weight.

Miscible with all common

solvents.
Highly flammable but stable
under ordinary conditions.
Mobile solvent of medium
volatility

n-butanol

Physical

Chemical

Colourless liquid

Melting point : -89 C

Banana-like, odor smell.

Boiling point : 117 -118 C

Low molecular weight.

Soluble in water.
Flash point : 26 29 C

Moisture sensitive

Highly flammable but stable

under ordinary conditions.

sodium butanoate

Physical

Chemical

White crystalline.

Melting point : 250-253 C

An unpleasent smell.

Soluble in water.

High molecular weight.

Form in butter and animal fats.

2.2 .4 INDUSTRIAL APPLICATION

As esters of 2-Ethylhexanol with dicarboxylic acids are outstanding plasticisers for synthetic
resins and rubbers such as phthalates, adipates and sebacates, 2-ethylhexanol is mainly used as a
feedstock in manufacturing low-volatility esters in industry. The most important one is di-(2ethylhexyl) phthalate (DOP or DEHP). (BASF Petronas Chemical, 1999) which is then used as
plasticizers for PVC and vinyl chloride copolymers. The characteristics of the plasticizers including
its low volatility, great gelling power, strong resistance to high and low temperatures as well as to
water and its excellent dielectric properties. Other than that, 2-ethylhexanol is also used as a solvent
and has a specific ideal use in the development of lacquers and coatings when there is a demand of
slow evaporation. 2-ethylhexanol is a superb defoaming agent which is necessary for uses in varnish,
photographic, rubber latex, ceramic industries and textile printing.
Apart from that, there a numerous of other application of 2-ethyhexanol in industries. It is
utilized as a low-volatility solvent for waxes, animal fats, vegetable oils, disinfectants and insecticidal
sprays and also petroleum derivatives. Besides, 2-ethylhexanol derivatives used as an additive for
diesel fuel to minimize emissions and to enhance the performance of lube oils and mining chemical
and very low concentrations of 2-ethyhexanol is required for aqueous anti-foam formulations in
textiles and paper industries. On the other hand, 2-ethylhexanol is essential to improve flow and gloss
in baking finishes
2-ethyhexanol is widely used as a feedstock in many manufacturing of chemicals. Firstly, it is
used in manufacture of ethoxylates where 2-ethyhexanol is reacted with ethylene oxide. Secondly, it is
used to manufacture herbicieds. Thirdly, it is used as feedstock in manufacturing of 2-ethyhexyl esters
of trialkyl phosphites which is then applied as a thermal stabilizer and anti-oxidant in plastics.
Fourthly, used in the production of remarkably pure grades of DOP which serve as polychlorinated
biphenyl substitutes in heavy-duty capasitors. Fifthly, it is used as a feedstock in production of 2ethylhexyl sulphate which is used as surfactants for electrolytes. Finally, 2-ethylhexanol is used in the
production of diester of maleic acid which is the starting material for surfactants.

2.3 Manufacturing process

2.3.1 Oxo Process from Propylene and Synthesis Gas
Process Description
The production process of 2-ethylhexanol from Oxo process mainly consists of three
conversion steps which are hydroformylation process, aldolization process and hydrogenation
process. The reaction occurs is described in details for each equipment involved in the process.
i.

Hydroformylation

Oxo reactor

The first step in the Oxo process is hydroformylation in which the main product is nbutyraldehyde. The Oxo reactor operates at 130 0C and 350 bars and the reactor residence time is 1-2
hours. The reactor is fed with synthesis gas which is carbon monoxide and hydrogen (CO/H 2 mixture)
and propylene in the molar ratio of 2:1. Cobalt carbonyl in the solution (0.1-1.0 wt% cobalt
concentration) is used as catalyst. A little amount of methane (0.4%) in the synthesis gas acts as an
inert in the reactor. Hydrogen sulfide and triethylamine are the examples of impurities that should be
excluded from entering the reactor to prevent reaction with the active cobalt complex which can form
catalytically inactive complexes. During the start-up phase, oxygen also should be excluded from the
system as the active catalyst concentration is being established.
The feed may consists with polymer grade (99+%) pure propylene. Propylene feed should be
vaporized first and fed into the reactor in a gas phase. Propylene losses in the blowdown vent stream
can be minimized if propylene conversions greater than 95% per pass is designed. The main products
produces from the Oxo reactor are n- and iso butyraldehyde in the mole ratio of 4:1. Also, within the
reactor, 6% of n-butyrablahyle product is reduced to n-butanol, 4% of isobytyraldehyld product is
reduced to iso-butanol and molecular weight compounds (heavy ends) to the extent of 1% by weight
of the butyraldehyde/ butanol mixture is yielded by other reactions at the reactor exit.

Separator

Next, following the Oxo reactor, the reaction is continued in the separator. Here, the oxo-raw
product is separated from the catalyst solution and will be recycled back to the Oxo reactor.

Stripper

Meanwhile in the stripper, fresh synthesis gas is introduced to remove the unconverted
propylene from the Oxo-product. The synthesis gas is then recycled to the Oxo reactor.
10

Distillation Column 1

The first distillation column is focuses on the separation of alcohol and aldehyde components.
The stripper produces Oxo-product and passes them to distillation column where mixed
butyraldehyde is produced as top product and alcohols as the bottom product.

Distillation Column 2

After the first distillation column passed on butyraldehydes into the second distillation
column, the two butyraldehydes now are separated into iso-butyraldehyde which is the top stream that
contains 1.3% moles of n-butyraldehyde and n-butyraldehyde, the bottom stream containing 1.2%
mole of isobutyraldehyde.
ii.

Aldolization

Aldolization reactor

Next, the n-butyraldehyde stream will passes on into Aldolization reactor where Aldol
condensation occurs. In the reactor, n-butyraldehyde reacts vigorously to produce 2-ethylhexanal.
Also, 2% w/w aqueous sodium hydroxide, NaOH is introduced into the reactor as it is the standard
industrial catalyst. The reactor condition includes temperature of 80-130 0C and pressure 3-10 atm
while the conversion efficiency that can be achieved is 90%. Besides, local overheating must not
happening in the reaction mixture because it can develop secondary reaction hence yields may be
decreased and it is necessary for the two phases in the system to be mixed thoroughly. The ideal
equipment to be used as Aldolization reactor may be a packed column, a stirring vessel or a mixing
pump.

Separator

The Aldolization reactor passes on the products which are 2-ethylhexanal and n-butyraldehyde
into a separator. 2-Ethyhexanal is separated and then passed on to the hydrogenation unit.
iii.

Hydrogenation

Hydrogenerator

Hydrogenation unit is basically where the reduction process of 2-Ethylhexanal to 2-Ethylhexanol

by hydrogen in the presence of a Raney Nickel catalyst is occurred with 99% rate of conversion and
the selectivity achieved is greater than 99%. The 2-ethylhexanol produced consists of 99.8% recovery
at a purity of 99% by weight.

11

2.3.2

Chemical equation involves in Oxo process

1) Hydroformylation Reaction of Propylene with Synthesis Gas

H3C
130 OC, 350 bars
2H3C-CH=CH2 + 2CO+2H2
Catalyst

H3C-CH2-CH2-CHO + H3C-CH-CHO
(n-butyraldehyde)

(iso-butyraldehyde)

(Oxo-crude)

2) Aldolization Reaction and Subsequent Conversions to 2-Ethylhexanal

2% NaOH,
(80-130) C
2CH3-CH2-CH2-CHO

CH3-CH2-CH2-CH=C-CHO + H2O
(3-10) atm
CH2-H3C

(n-butyraldehyde)

(2-Ethyl Hexanal)

3) Hydrogenation reaction to 2-Ethylhexanol

Nickel
CH3-CH2-CH2-CH=C-CHO + 2H2

CH3-CH2-CH2-CH2-CH-CH2OH

CH2-H3C

CH2-H3C

(2-Ethyl Hexanal)

(2-Ethyl Hexanol)

CHAPTER 2
12

3.0 FEASIBILITY STUDY AND LITERATURE SURVEY

3.1 Market Survey (demand)
The demand for alcohol plasticizer in the world market is strongly affected by the current world
economic situation. This is because the demand for the plasticizer alcohol is associated with a pattern
of ups and downs in the world economy. platicizer alcohol applied in the construction / remodeling,
production and automotive original equipment manufacture (OEM).
In 2014, the use of 2-ethylhexanol (2-EH) and n-butanol reached to 73% of world consumption of
alcohol plasticizer,. However, the use of n-butanol is expected to rise a bit more drastic than 2-EH,
supported by the growth of n-butanol were higher in China and Asia. In the United States and Western
Europe, the use of 2-ethylhexanol will grow more rapidly than n-butanol.
The pie chart below shows world consumption of alcohol plasticizer:

Asia (including Japan), Europe and North America were the largest market for the plasticizer alcohol
(2-ethylhexanol and n-butanol) which provides nearly 95% of world demand in 2014. Asia is also one
of the largest consume in the 2-ethylhexanol and n- butanol which was 55% of global consumption; In
Asia, China produced 36% of total world consumption. This shows that China was one of the largest
Asian countries to produce 2-ethylhexanol and n-butanol. Western Europe hold about 20% of the
world demand, and North America about 17% of global consumption.

Plasticizers are the largest consumption market for 2-ethylhexanol and n-butanol which was about
48% of world consumption in 2014 based on studies in Chemical Economics Handbook (2015), the
demand will grow slightly less than the demand for alcohol plasticizer in an acrylate / methacrylate
13

and acetate esters. Plasticizer area manufacturers, such as the United States and Western Europe,
experienced a moderate growth rate, while Japan was expected to see a slight decline for plasticizers.
Plasticizer market in China was expected to grow steadily during 2014-2019, although less than other
market segments plasticizer alcohol. The world consumption of alcohol plasticizer for plasticizers was
expected to grow at an average annual rate of 3.6% during 2014-2019, mainly as a result of stronger
growth in China, India, and other Asia
3.2 Production Data (Supply)
Based on statistical data in 2010, the annual production capacity of 2-ethylhexanol was 3,330 kmt/ yr
and the rate of consumption of the year reached 2,869 kmt / yr. The impact on operating rates were
too high .According to the operating rate in 2010 was recorded at 86.2%. According to analysis of
LIU Yuan and XUE Hui-feng, there were three continents that had large production capacity, namely
in Asia, Western Europe and North America, which produced at 51%, 17% and 12% in the world
market. According to the study, Asia was the most important in the use of the product 2-ethylhexanol,
which took about 65% of total world consumption. For Western Europe and North America, each of
which takes about 11%. It explained that the use and production of 2-ethylhexanol more focused on
Asia. Nowadays, the usage and production in North America and Western Europe are static. See detail
in table 1.0 and 1.1.
No
1
2
3
4
5

Company
SINOPEC

6
7
8
9
10
TOTAL

Oxea Group
LG Group
BASF
Eastman Chemical
Company
Formosa Plastics
Group
Kedzierzyn Nitrogen
Work
Mitsubishi Company
Group
Gazprom
Perstorp
All others
3330

Capacity
360
300
265
263
252
190
170
146
131
125
1128

Table 1.0 Global Top 10 manufacturers of 2 ethylhexanol kmt/yr

Table 1.1 shows Supply and Demand of world Market in 2010

14

.In 2010, n-butanol produced in China was 516kmt, net imports are 620kmt, apparent consumption
was 1,139kmt and the subsistence level was 45%. In 2000 ~ 2010 annual average growth rate of the
product is 7.09% and the use clearly is 11.93%. See details in Figure 2-3.

Figure 2.1 Supply and Demand

of n-butanol in China in
Recent years

In 2010, the production of 2-ethylhexanol in China was 440kmt, net imports were of 460kmt,
apparent consumption was 900kmt and self-sufficiency level of 49% [6]. During 2000 to 2010, the
annual average growth rate of the product was 5.61% and the use clearly was 6.69%. See details in
Figure 2.2.

Figure 2.2 Supply and Demand

of 2-ethyl hexanol in China in
Recent years

3.3 Local, regional and Global scenario

15

Nowadays, the mainstream technology for producing OXO in China is carbonyl synthesis method.
Till the end of 2010, there were totally 8 manufactures in China that applied this technology with a
total production capacity of 550,000 tons of n-butanol per year and 875,000 tons of 2-ethylhexanol
per year. There were totally 7 manufactures in China that used this technology in same period with a
production capacity of 215,000 tons of n-butanol per year. See details in Table 3.1.

NO

Manufactures

n-butanol

2-ethylhexanol

Total

I
1
2
3

OXO
Sinopec Qilu Co.
Sinopec Yazi-BASF
Sinopec Yanshan
Co.
CNPC Jilin
ChemicalCo
CNPC Daqing Co.
Shandong Lihuayi
Group
Tianjin Soda Plant
Shandong Jianlan
biological
fermentation
process
Total

550
50
100
20

875
255
110
50

1425
305
210
70

170

70

240

25
85

55
140

80
225

80
20
215

145
50
0

225
70
215

765

875

1640

4
5
6
7
8
II

III

Table 3.1 OXO production capacity in china 2010 kmt/yr

In the total production capacity of n-butyl alcohol in China, Sinopec, PetroChina and local companies
respectively in 30.9%, 35.5% and 33.6%. it was indicating a close pattern.Their production capacity
2-ethylhexanol each take up 47.4%, 14.3% and 38.3%. Sinopec and its main and local enterprises are
predominant. This show in table 3.2

Table 3.2 OXO Supply Pattern in China

3.4 Literature Survey (process technology)

16

Variable
Base condition
Construction investment
Extension of construction
period
Operating food
Price of raw material
Product price

Rate of change
10%
-10%
1 year
1 year

Internal Rate of Return

19.27
17.34
21.51

-10%
10%
-10%
10%
-10%
Table 4.1 Sensitivity Analytical Statement

16.04
18.11
10.60
26.78
28.85
7.30

Based on finance research by Liu Yuan, and Xue Hui-Feng in 2012, the production load decreases
10% and the construction investment, material price and product price respectively fall 10%.
Sensitivity analysis is made for the change on internal rate of return. The results show in Table 4.1

Propane price

IRR
n-butanol
2-ethylhexanol
13%
6150
6580
4000
18%
6550
7010
23%
7000
7490
13%
6750
7230
5000
18%
7200
7720
23%
7660
8200
13%
7370
7890
6000
18%
7860
8410
23%
8290
8870
13%
8000
8560
7000
18%
8520
9110
23%
8970
9600
13%
8630
9240
8000
18%
9240
9880
23%
9690
10370
13%
9350
10010
9000
18%
9960
10060
23%
10420
11150
Table 4.2 : The Impact of Material and Product Price Variation on Benefit

17

Table 4.2 shown, when the price of propylene is certain, the variation of OXO price would causes
benefit change; the multiple slant lines show: when both the prices of propylene and OXO change, the
benefit would change. For instance: if the price of propylene was 7,000 Yuan/ton, the price of nbutanol was higher than 8,000 Yuan/ton and the corresponding price of 2-ethylhexanol was higher
than 8,560 Yuan/ton, the internal rate of return would be higher than 13%; if the price of propylene
doesnt change, the price of n-butanol was higher than 8,520 Yuan/ton and the corresponding price of
2-ethylhexanol was higher than 9,110 Yuan/ton, the internal rate of return will be higher than 18%; if
the price of propylene was 6,000 Yuan/ton, the price of n-butyl alcohol is 8,290 Yuan/ton and the
corresponding price of 2-ethylhexyl alcohol was 8,870 Yuan/ton, the internal rate of return would be
higher than 23%.

4.0 CHAPTER 3 :
PROCESS SELECTION
18

4.1 process comparison

There are three methods to prepare 2 ethyl-hexanol. The three methods are via acetaldehyde
routes or acetaldehyde condensation method, Oxo synthesis of propylene and hydrogen gas and aldox
method or oxo-aldol process method.
Methods production of 2 ethylhexanol :
1. Acetaldehyde route
2. Oxo process
3. Aldox process
1. Acetaldehyde route:

Figure 1.0. : 2 ethylhexanol via the acetaldehyde route

Process description and conditions :
The acetaldehyde route begin from the main product which the oxidization of ethylene which
operates at near atmospheric pressure.The oxidization of ethylene is to convert ethylene to
acetaldehyde. Then, aldolization occurs to convert acetaldehyde to crotonaldehyde. The
crotonaldehyde is hydrogenated to n-butyraldehyde. According to figure 1, oxidation of acetaldehyde
occur in oxidation reactor 1 and then is fractionally distilled to pure aldehydes in columns 2,3 and 4.
The following aqueous acetaldehyde solution can be utilize for further processing to crotonaldehyde.
In reactor 5, aldolization to acetaldol will occur and then goes to reactor 6 for crotonization.
Conditions for the aldolization stage at reactor 5 are usually. The conditions of the aldolization stage
are generally 100kPa and 20c.
The crotonaldehyde which results for the crotonization of reactor 6 is purified in columns 7
and 8 . The purified crotonaldehyde is partially hydrogenated in the gas phase in reactor 9. Ni or Cu
catalyst which is an heterogeneous supporter are favorable for this purpose of hydrogenation. The
19

hydrogenated product is fractionally distilled in column 10 yielding n-butyraldehyde as overhead

along with unsaturated aldehydes. The light ends of column 10 are purified in tower 11. The bottoms
(pure n-butyrldehyde) are then transferred to the 2-EH plant,the bottoms of the distillation column 10
are hydrogenated in 12.
Process route
Oxidation
CH2=CH2
Ethylene

CH3-CHO
Acetaldehyde
Dehydrogenation

CH3-CH2-OH

CH3-CHO

2 CH3-CHO

CH3-CH-(OH)-CH2-CHO
iso-butyraldehyde

CH3-CH-(OH)-CH2-CHO

CH3-CH=CH-CHO +H2O
Crotonaldehyde

CH3-CH=CH-CHO +H2

CH3-CH2-CH2-CHO
n-butyraldehyde

2CH3-CH2-CH2-CHO

CH3-CH2-CH2-CH=C-CHO + H2O

CH3-CH2-CH2-CH2- CH=C-CHO +2 H2
CH2=CH2

2-Ethyl hexanal
CH2=CH2
CH3-CH2-CH2-CH2 CH-CH2OH +
2-Ethyl hexanol

CH2=CH2

2. Oxo route:

20

Figure 1.1 : Production of 2-ethylhexanol via the oxo route

Process description and conditions :
In order to get the first product which is n-butyraldehyde, the first process is hydroformylation
(Oxo reaction).The operation of the reactor are 1300C and 35000 kPa. Synthesis gas (CO/H2) and
propylene are fed into the reactor in molar ratio of 2:1. Cobalt Carbonyl is used in the solution (0.11.0 wt% cobalt concentration. An inert which is methane that contain in synthesis gas acts as inert in
the reactor. In the separator, which follows the Oxo reactor, separation occur between the catalyst
solution and the oxo-raw product and it is recycled to the oxo reactor.
From the stripper, by using fresh synthesis gas , the unconverted propylene is removed from
the Oxo-product. The synthesis gas used is then recycled to the Oxo reactor. Then, it enters the
distillation column 1 which is the alcohol/ aldehyde separator which results in top product of mixed
butyraldehyde and bottom product is alcohol. In distillation column 2, which is n-butyraldehyde and
iso butyraldehyde separator, both butyraldehydes are separated into top stream and bottom stream.
The top stream contains iso- butyraldehyde which contains 1.3% moles of n-butyraldehyde and the
bottom stream contains n-butyraldehyde which contains 1.2% mole of butyraldehyde. The bottom
stream which contains n-butyraldehyde are pass into an aldolization reactor.

The n-butyraldehyde reacrs swiftly to create 2-ethylhexanal. The standard industrial catalyst
which is 2% w/w aqueous NaOH is used that helps the conversion efficiency to 90%. The operating
condition for temperature is between 80c - 1300c and the pressure is between 303.975 kPa - 1013.25
kPa. Overheating of the reaction mixture must be avoided due may cause secondary reaction, hence,
21

decreasing the yields. It is necessary for thorough mixing of the 2-phases in the system. The product
from aldolization reactor passes on to separator where 2-Ethyhexanol is separated and then sent to a
hydrogenation unit. In hydrogenator, by the presence of Raney Nickel, 99% conversion of 2Ethylhexanal to 2-Ethylhexanol can be obtained with selectivity being greater than 99% and 99.8% of
2-Ethylhexanol is recovered at purity of 99% by weight.
.
There are three steps in the oxo process which is important for the production of aldehydes
from alkenes. A formyl group (CHO) and a hydrogen atom to a carbon-carbon double bond is the
addition of this chemical reaction.Oxo synthesis or oxo process is an important homogeneously
catalyzed industrial process for the production of aldehydes from alkenes. The following is reaction
scenario of oxo synthesis.
The reaction includes :

a) Hydroformylation
b) Aldolization
c) Hydogenation
Process route:
a) Hydroformylation

H3C
130C, 100kPa

2H3C-CH=CH2+2CO+2H2

H3C-CH2-CH2-CHO+H3C-CH-CHO

The above is reaction of hydroformylation, which takes place at 130C, 100kpa. The molar ratio of the
feed reactor which is the propylene nad synthesis gas is 2:1.Cobalt Carbonyl is used as the catalyst in
the solution with the percentage of 0.1-1.0 wt% cobalt concentration.

b) Aldolization
2% NaOH and 80C-130C
2H3C-CH2-CH2-CHO

CH3-CH2-CH2-CH=C-CHO +H2O
303.975 kPa - 1013.25 kPa

CH2-H3C
The above Aldolization reaction takes place at80C-1300C and pressures 303.975 kPa - 1013.25 kPa.
22

c) Hydrogenation
CH3-CH2-CH2-CH=C-CHO +2H2
CH2-H3C

CH3-CH2-CH2-CH2-CH-CH2OH
Nickel

CH2-H3C

Hydrogenation takes place in the presence of Raney Nickel catalyst.

3.)Aldox process

23

Figure 1.2 : 2-ethylhexanol via aldox process

Process description and conditions :
Aldox process is where the Oxo catalyst is added with co-catalyst that let aldolization to
happen in the same place. After the hydrogenation, 2 ethylhexanol isomeric c* alcohols and isobutnol
is produced. This process combines hydroformylation of the olefin and the aldolization of the
resulting aldehydes into in a single step. A simplified flow sheet of the Aldox system is shown in fig
3. The oxo reaction proceeds at about 20265kPa and 180c using a catalyst system such as cobalt
acetate and zinc acetylacetonate. A second reactor maybe used as a soaking vessel to allow the aldol
reaction to take up the majority of the normal butyraldehyde produced. Oxo catalyst is separated from
the crude reactor product and recovered for the recycle to the reactor. The C 4 aldehydes and alcohols
are separated from the C8 aldehydes, 2-ethylhexenal are hydrogenated in a two stage system in order
to minimize heavy end formation.

24

Process route
Aldox process combines the oxo reaction with aldol condensation
CH3
HCo(CO)4
CH3CH2=CH2 + H2 + CO

CH3CH2CH2CHO + CH3CHCHO

Catalyst
2CH3CH2CH2CHO

H2
CH3CH2CH2CH2CHCHO

CH3CH2CH2CH2CHCH2CHCH2OH

CH2CH3

CH2CH3

General Comparison of three different process

Type of process

Carbonyl synthesis method/oxo

Acetaldehyde condensation method

Main Materials

Propylene,

Ethylene,

carbon

monoxide,

acetaldehyde,

Caustic

Aldox met
soda
25

Propylene,

By products

hydrogen, caustic soda (NaOH)

Iso-butanol and C4 alcohols

Carbonyl

aldehydes
Cobalt acetate

synthesis

(NaOH)
Iso-butanol and C4 alcohols - aldehydes

Caustic So
Iso-butano

Cobalt acetate, rhodium catalyst

mixture

compoun

catalyst

insoluble
Normal butylaldehyde and isobutylaldehyde

hydride
Normal bu

isobutylaldehyde
20684 34473

3000- 20000

3447 344

(kPa)
Reaction

In range of 100 204.44

In range of 70-150

Around 2

temperature (C)
Percentage
of

99.8

99.8

95

Solvent
Reaction

Normal
pressure

butylaldehyde

and

conversion (%)
Technical
flow, Long flow and many equipments

Longer

number

compared to oxo route

of

equipments
Operation
temperature

medium

flow

and

higher

equipments

Low

Shorter flo

High

and

pressure

Table 1 : comparison between the 3 process

4.2 Economic feasibility

26

Figure 2.0 :
various 2routes

Yields from
ethylhexanol

Figure 2.1 :
production

Isooctanol
Economic Data

Figure
of higher
economic data

2.2 : Production
alcohols

The
various
routes

yields from the

2
are

ethyl

hexanol

summarized

in

figure 2.0. The synthesis of acetaldehyde from ethyl alcohol or acetylene is also included. 70 kg nbutanol per metric ton of 2 ethyl hexanol or acetylene is also included. 70 kg n-butanol per metric ton
of 2 ethyl hexanol results as byproduct from acetaldehyde route, while with the oxo route, the
corresponding values are 130 kg n-and 350 kg iso-butanol. The yield of 85.5 kg of 2 ethylhexanol
from 100kg n-butyraldehyde shown for the oxo route in figure 2.0 is exceeded in modern oxo plants.
The economic superiority of the oxo route compared to those based on ethylene and the low cost of nbutyraldehyde from large modern oxo plants. In the future, acetaldehyde route will only be attractive
where inexpensive ethyl alcohol or inexpensive acetylene is available.

4.3 Other consideration

Quality of product

27

High quality product with percentage of purity is important. This is because the additives may
contain health hazard, Hence, high percentage of purity product would avoid these hazard. It is
important to use high quality, high purity supplements from professional supplement producers.

The efficiency of the conversion

High efficiency conversion will result in saving cost and produce good quality products, these
criteria is important for building a plant due to the production

requires electricity, labor and etc.

The investment cost of the process in economical aspect and consumption of energy

Investment cost must be low to avoid fluctuation of profit, the consumption energy must be low
to save cost.

Operation of the process and control system

Must be stable and short route of process to avoid high maintenance and using lots of manpower.
Recovery of the process
The catalyst and other materials used has a recovery system so that the recovered material can be
used again in following process to avoid increasing in cost.

4.4 justification of selection

Subject
quality

Oxo route
of

High

quality

product

Acetaldehyde route

Aldox route

High quality product with

Less quality product with 95%

28

products
Efficiency

of

conversion

with 99.8% purity

Three conversion

99.8% purity
Same as oxo route but

purity
One-step reaction makes low

process reaction steps

longer reaction

propylene conversion.

yielding high propylene

Economical

conversion
Due to medium reaction

Due to lower reaction

Because

of

aspect, cost of

pressure and medium

pressure and lower

pressure

and

investment

reaction temperature,

reaction temperature,

temperature, process need high

Process needs lesser cost

reduce cost of labor,

high cost of labor due to complex

of labor, because of three

because of complicated

process and unstable operation

simple process and the

process more worker for

that needs to be maintained at all

operation is stable ,

management is needed

time. Also the cost for the

management needed is

and management is

modified

because the catalyst

needed

hydride is expensive.

Medium process flow

Longer process flow but

Shorter

but

stable

flexibility,

process

and

energy

higher

reaction

high

reaction

Cobalt

tetracarbonyl

activity is stable. No
need for management.

Operation

stable

and

high

plant

operation.

flow

but

only

has

no

alcohols

are

catalyst The process has

Also have a recovery obtained,

the

high recovery portion of

system that can recover

intermediate

are

the Cobalt acetate used.

the greater portion of the

isolated.

expensive cobalt and zinc

occurs

compounds.

isomeric aldehydes in the crude

Mixed
due

to

aldehyde
not

being

aldolization
presence

of

oxo product.
Recovery
the catalyst

of

Due to the continuous

operation of Heavy End

Same as the two process

Same as the two processes.

Separation process and

Catalyst Recovery
process, catalyst activity
is high

Table 2 : advantages, similarities and disadvantages of the three process

Selection of Process:
Although there are 3 processes to manufacture 2-ethyl hexanol, the oxo process is
predominant among them. The acetaldehyde process requires huge production of ethanol or ethylene.
Finally due the above mentioned conditions, which are favorable to produce 2-ethyl hexanol by oxoprocess is preferred than other processes. In Essos Aldox process, however, in aldol condensation is
effected by suitable promoters. Magnesium erthoxide and soluble zinc compounds are recommended
29

to promote controlled aldolization which is a serious disadvantages when mixed aldolization with the
branched aldehyde, problem associated with recycling of the additives hence preventing wider use of
aldox process.

30

REFERENCES
1. 2-Ethylhexanol.

(2013).

Royal

Society

of

Chemistry.

Retrieved

from

http://www.chemspider.com/Chemical-Structure.7434.html
2. Technical Leaflet 2-Ethylhexanol. (1999) BASF Petronas Chemicals. Retrieved from
http://www.solvents.basf.com/portal/load/fid245412/Technical%20Spec%20%202%20Ethylhexanol_BPC.pdf
3. 2-Ethylhexanol (2-EH) Uses and Market Data. (2009) ICB Chemical Profile.
Retrieved

from

http://www.icis.com/resources/news/2007/11/05/9075782/2-

ethylhexanol-2-eh-uses-and-market-data/
4. ..MacKetta, J. J. (1984). Encyclopedia of chemical processing and design (Vol. 20).
New York u.a.: Dekker. pp (383 , 384)
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6. MacKetta, J. J. (1978). Encyclopedia of chemical processing and design (Vol. 5). New
York u.a.: Dekker. p.p (373,376,389)
7. .Mitsubishi Chemical Corporation | Oxo Alcohols and Acrylates Dept. (n.d.).
Retrieved from kagaku.co.jp/english/products/business/chemical/oxo/index.html
8. Olah, G. A., & Molnar, A. (1995). Hydrocarbon chemistry. New York: Wiley. pp
(377-378)
9. Borner, A., & Franke, R. (2016). Hydroformylation fundamentals, processes, and
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KGaA.

31