CHAPTER-1

INTRODUCTION

2-Ethylhexanol is a valuable intermediate product for the chemical industry.

2-EH (2-Ethyl-1-hexanol).

The molecular formula is: C8H18O

Molecular weight is: 130.23.

2-Ethylhexanol ranks after the lighter alcohols (methanol to butanol) as the most

important synthetic alcohols.

Approximately 2 x 106 tons/annum of 2-Ethylhexanol are produced worldwide.

2-Ethylhexanol finds application in a variety of plasticizers and is also used in the

synthesis of specialty chemicals. This alcohol contains one primary hydroxyl group,
which is terminally located.

2-EH is used in the production dioctyl phthalate (DOP) other plasticizers, coatings,
adhesives and specialty. In these end use areas, it contributes significantly to may
high performance characteristics such as flexibility, good adhesion, lower
emissions and fuel performance improvement.
The production of 2-ethylhexanol has recorded a growth of 2.5% per year from
1986 to 2000.
The future of 2-EH is tied to the strength in phthalates, DOP, the largest volume
phthalate ester, is expected to remain flat or decline slightly due to competition
from other phthalates and environmental pressures. Substitutions by non-
phthalates in niche markets and the challenge of metallocene plastomers are
viewed as possible future threats. Modest growth is projected for 2-Ethylhexanol
based intermediates for acrylic surface coatings, dieisel fuel & lube additives.
 CHAPTER-2
PROPERTIES AND USES

Physical properties:

(1.) 2-Ethyl hexanol is clear liquid with a characteristic odor.

(2.) it forms a transparent mixture with other alcohols, ethers and most organic
liquids. Chemical propertis:

2-Ethyl hexanol reacts in the typical manner of 𝛼-branched primary alcohols.

Summary of physical properties.

Property Value
Molecular weight 130.23
2-Ethylhexanol ≥99.5 wt%
Color, Pt- Co scale Max.5
Distillation range (95vol%) at 101.3kPa 184-185°C
Viscosity at 20℃ 9.8 mPa.s
Vapor pressure at 20℃ ca.0.03 kPa
heat of vaporization at 184.8℃ 50.66 kJ/mol
Solubility in water at 20℃ 0.07 wt%
Solubility of water in 2-ethylhexanol at
20℃ 2.7 wt%
Surface tension at 20℃ 0.25 ×10-3 N/.cm
Dielectric constant at 20℃ 7.7
bp at 101.3kPa 184.6°C
Critical temperature 339.8℃
Critical pressure 2.67 Mpa
Critical density 0.2636 g/cm3
Critical compressibility 0.2670
Specific flow resistance at 20℃ 5.8 × 103 MΩ.cm
Azeotrope with water at 101.3kPa, 20%
2-ethylhexanol/ 80% water, bp 183.5℃

2-Ethylhexanol

Physical data specifications

Content (wt%) - > 99
Boiling range (℃) (760 Torr=1013 mbar, 184.8 183.5-185
min 95 vol.%)
Density at 20℃(g/cm3) 0.8323 0.832-0.835
Refraction index nD20 1.4317 1.431-1.433
Hazen color (APHA) - <10
Water content (wt.%) - <0.1
Acid number (mg KOH/gm) <0.1
Carbonyl number (mg KOH/gm) <0.2
Pour point (℃) - -72
Viscosity at 20℃ (mPa.s) ~10
(cP) 9.8 9.5-11
Vapor pressure at 20℃ (mbar) <0.5
Evaporation number 600-690
Evaporation (wt. %) 18
Solubility in water at 20℃ (wt.%) 0.07
Water absorption &wt.%) 2.7
Surface tension at 20℃ (mN/m) (dyn/cm) 25

Dielectric constant at 20℃ 7.7

Flash point (℃) 74-80
Ignition temperature (℃) 250
Property t,℃ Value

Vapor pressure, kPa 78.7 1.333

90.8 2.666
104.6 5.332
113.5 7.998
125.5 13.33
143.5 26.66
164.2 53.32
184.8 101.31

Relative density, d4t 10 0.8396

15 0.8359
20 0.8323
25 0.8286
30 0.8247
50 0.8100
refractive index, 10 1.4356

15 1.4337
20 1.4317
25 1.4298
30 1.4278
50 1.4199

Specific heat, cp,J g-1K-1 0 2.22

20 2.34
50 2.51
80 2.68
 CHAPTER-3

SYNTHETIC ROUTES OF 2-ETHYL HEXANOL PRODUCTION:

The industrially significant synthetic pathways are:

Acetaldehyde route (A)→(F)→(N)

Oxo route (B) → (C) → (G) → (N)

Aldox process (B)→(M)

Shell variant (B)→(L)

The acetaldehyde route starts from ethylene and operates near at atmosphere
pressure. Ethylene is first oxidized to acetaldehyde, which is then converted to
crotonaldehyde via aldol reaction & hydrogenated to n-butyraldehyde. route
(a)→(f)

The most important synthetic route accounting for over 95% of 2-EH production is
based on propylene which after initial hydroformylation is converted into an oxo
crude product. (routes (b)→ (g)). The crude oxo product is a mixture of valuable
products of propylene hydroformylation (n- and iso – butyraldehyde) along with
the byproducts (n- and iso- butanol) and the heavy ends. The individual
components of the mixture can be obtained after distillation.
n- Butyraldehyde is converted into butyraldehyde via an alkali catalyzed reaction
and then crotonized to 2-Ethylhexanol (Route (n)). Thereafter, 2-Ethylhexanol is
ether partially hydrogenated to 2-ethylhexanol or undergoes total hydrogenation
to 2-EH.

The n-component mixture of n- and iso-butyraldehyde can be selectively

converted into 2-Ethylhexanol and then further processed to 2-EH (Route (H)).
However, due to the presence of iso-butyraldehyde and the unavoidable formation
of isomeric n/iso and iso/iso aldols (or C8 diols), the quality of the resulting 2-EH is
interior o that of the product obtained directly from n-butyraldehyde.

Aldox process is a case in which co-catalyst are added to the Oxo catalyst enabling
aldolization to occur in the same phase. Consequently, after hydrogenation a
mixture results consisting of2-EH, isomeric C8 alcohols & isobutanol (Route (m)).

In the shell process a complex (ligand-modified hydroformylation catalyst)

HCO (CO)3 (PR3)3 – is employed. This permits operation at lower pressure and
higher selectivity i.e at a higher n/i ratio. However, the reaction velocity is lower
and part of the propylene is converted to propane.

Basically similar reservations pertaining to the quality of the resulting 2-EH also
apply to the process of the heavy ends of the Oxo synthesis (Route (j)). Which also
yields 2-EH after additional hydrogenation. However one drawback is that in molar
terms only 2/3 of the butanol feedstock is converted into 2-EH, the remaining third
resulting as sodium butanoate.

The reaction of 2-EH with 2-Ethylhexanol in which the very reactive unsaturated
aldehyde can be removed from the reaction mixture via reduction to the saturated
aldehyde (Route (o)) belongs to the more specialized but not industrially operated
methods: Removal of
2-Ethylhexanol prevents its conversion into higher boiling compounds.
 COMPARISION OF COAL BASED ROUTE &
PETROCHEMICAL ROUTE.

The figure clearly indicates that the transition from the Coal based route to the
petrochemical route led to a reduction in the number of processing steps.
Therefore over 95% of the current 2-EH production is based on propylene.
 PROCESS DISCRIPTION

Oxo reactor (hydroformylation):

The first step of the process is hydroformylation (Oxo reaction) from which the
main product is n-butyraldehyde. the reactor operates at 130℃ and 350 bars.
the reactor residence time is 1-2 hours.
The feeds to the reactor are synthesis gas (CO/H2 mixture) and propylene in the
molar ratio 2:1. The catalyst used is cobalt carbonyl in the solution (0.1-1.0 wt%
cobalt concentration).

The synthesis gas may contain several percent methane, which acts as an inert in
the reactor. Traces of water introduced with the synthesis gas are not harmful.
Impurities such as hydrogen sulfide and triethylamine should be carefully excluded,
however the prevent reaction with the active cobalt complex to form catalytically
inactive complexes.

Oxygen should be excluded from the system, during the start up phase when the
active catalyst concentration is being stablished. Oxygen has been shown to inhibit
cobalt Hydrocarbonyl formation, but once the system is operating, concentration
up to 2% can be tolerated carbondioxide acts in the same manner as oxygen, with
concentration up to 4% permissible.

Polymer grade (99+%) pure propylene may be fed. Propylene feed should be
vaporized & fed in to reactor as a gas. Designing for propylene conversion
grater then 95% per pass will minimize propylene losses in the blown vent stream.

The main reaction products are n-and iso butyraldehyde in the ratio of 4:1. The
former being the required product for the subsequent conversion to 2-EH. Within
the reactor, however 6% of n-butyraldehyde product is reduced to n-butanol, 4%
of iso-butyraldehyde product is reduced to iso-butanol & other reactions occur to
a small extent yielding molecular weight compounds.
(heavy ends) to the extent of 1% by weight of the butyraldehyde/ butanol mixture
as the reactor exit.

Separator:
In the separator, which follows the Oxo reactor, the catalyst solution is separated
from the oxo-raw product & recycled to the Oxo reactor.
Stripper:
In the stripper, the unconverted propylene is removed from the Oxo product suing
fresh synthesis gas. This synthesis gas is recycled to the Oxo reactor.

Distillation column (1.): Alcohol/Aldehyde separator

The Oxo product from the stripper passes to a distillation column-1, which gives a
top product of mixed butyraldehyde and the bottom product alcohols.

Distillation column (2.): n- and iso Butyraldehyde separator

The butyraldehydes are passed in to a 2nd distillation column which separates the
two butyraldehydes into an iso-butyraldehyde (top) stream containing 1.3% moles
n-butyraldehyde & an n-butyraldehyde (bottom) stream containing 1.2% mole is
butyraldehyde.

Aldolization:
The n-butyraldehyde stream passes on into an Aldolization reactor. In the
aldolization reactor n-butyraldehyde reacts very quickly to give 2-Ethylhexanol.
2% w/w aqueous NaOH is employed as the standard industrial catalyst. The
conversion efficiency is 90% the temperature is 80-130℃ & pressure 3-10 atm.

Local overheating in the reaction mixture must be avoided since this may cause
secondary reactions & thus decrease yields. Through mixing of the 2-phases in the
system is necessary. The aldolization reactor may be a mixing pump, a packed
column or a stirring vessel.
Separator:
The product from the aldolization reactor passes on to a separator where 2-
Ethylhexanol is separated and then sent to a hydrogenation unit.

Hydrogenerator:
The 2-Ethylhexanol is reduced to 2-Ethylhexanol by hydrogen in the presence of
Raney nickel catalyst with a 99% conversion rate. The selectivity attained is greater
then 99%.

In the subsequent stages 99.8% of 2-Ethylhexanol is recorded at a purity of 99% by

weight.
 CHEMICAL REACTIONS

(1.) Reaction of propylene with synthesis gas:

CH3

130C, 350 bars

2H3C-CH=CH2+2CO+2H2 H3C-CH2-CH2-CHO+H3C-CH3-CHO Catalyst

(n-butyraldehyde) (Iso butyraldehyde) (Oxo-crude)

(2.) the aldolization and subsequent conversion to 2-Ethyl Hexanol:

2% NaOH
80-130c
2CH3-CH2-CH2-CHO CH3-CH2-CH2-CH=C-CHO +H2O
(3-10) atm

CH2-CH3
(n-butyraldehyde)
(2-Ethyl hexenal)

(3.) the Hydrogenation to 2-Ethyl Hexanol:

Nickel
CH3-CH2-CH2-CH-CH=C-CHO+2H2 CH3-CH2-CH2-CH2-CH-CH2OH

CH2-CH3 CH2-CH3
(2-Ethyl hexenal) (2-Ethyl hexanol)
 CHAPTER-4
MATERIAL BALANCE

Basis: 1 hour (Oxo reactor)

100 K-moles of propylene
R = (synthesis reactor + unreacted propylene) per K-mole of propylene feed.
X = mole fraction of propylene in the stripped gas.

Propylene feed= (100 + 100Rx) =100(1+Rx) K-moles

Amount of unreacted propylene = 100(1+Rx) x 0.02 = 2(1+Rx) K-moles
Synthesis gas = 100 R (1-x) K-moles

Assume: 100% of unreacted propylene is stripped in the stripper.

Propylene: synthesis gas = 1:2

100(R) (1-x)
∴ ––––––––––– = 2 ………………… (1)
100 (1+ Rx)

R (1-x)
––––––– = 2
1+ Rx

R-Rx = 2+2Rx

3Rx = R-2
 (R-2)
x = ––––
3R

2 (1+Rx)
x = ––––––––––––––––– ………………… (2)
2(1+Rx) +100 R(1-x)

(1+Rx) 1+Rx 1+Rx

x = –––––––––––––––––– = –––––––––––––––– = ––––––––––––––
(1+Rx) + 50R(1-x) 1+Rx + 50 R – 50Rx 1+ 50R – 49Rx

x( 1+ 50R −49 Rx)= 1+ Rx

x+50 Rx – 49 Rx2 = 1+Rx

x + 49Rx – 49 Rx2 = 1

x{1 + 49R – 49 Rx} = 1

(R-2) 49R (R-2)

–––––– 1+ 49R - –––––– = 1
3R 3R

(R – 2) (98R + 101) = 9R

98R2 +101R – 196R – 202 = 9R

98R2 -104R – 202 = 0

a = 98, b = -104, c = -202

+(
104)
± (−104)2− 4()(
9 8 − 202)
104 ±
2 ()98) 90000
R= = 2 ()98
0

∴ R= 2.061

(R-2) (2.061- 2.0) 0.061

∴ x = ––––––– = ––––––––––– = ––––– = 0.0099
3R 3(2.061) 6.183

Synthesis gas = 100 R(1-x) = 100 x 2.061(1-0.0099) = 204.6 K-moles

Propylene = 100(1+Rx) = 100 {1+2.061(0.0099)} = 102.03 K-moles

Off-gas (unreacted synthesis gas) = 204.06-102.03

= 102.03 K-moles

98% of propylene is converted.

∴ K-moles of butyraldehyde = 0.98 × 102.03 = 99.99 K-moles

n-Butyraldehyde : iso-Butyraldehyde = 4:1

∴ K-moles of n-butyraldehyde = 99.99×0.8 = 79.992 K-moles

6% n-butyraldehyde of is converted to n-butanol
∴ K-moles of n-butanol = 0.06 × 79.992
= 4.800 K-moles
K-moles of iso-butyraldehyde = 99.99-79.992 = 19.998 K-moles

4% of iso-butyraldehyde is converted to iso-butanol

∴ K-moles of iso-butanol = 0.04×19.98

= 0.800 K-moles

Distillation column (1): Aldehyde/Alcohol separator

Assume: all Aldehydes (both n & iso-butyraldehydes leave as the top product) and
all alcohols (both n and iso-butanol leave as bottom product).

Distillation column (2):

Feed: n- Butyraldehyde = 79.992-4.800 = 75.192 K-moles

iso-butyraldehyde = 19.998-0.800 = 19.198 K-moles

More volatile component …………………………....... iso butyraldehyde

(mass balance on the basis of more volatile component)

19.198
ZF = ––––––– = 0.203; XD = 0.987 XW = 0.012
94.39

Over balance:
F= D+W
D= F-W= 94.39-W
Component balance:

F zF = DxD + wxw.
94.39(0.203) = (94.39-W) (0.987) + W (0.012)
19.161 = 93.163 - 0.987W + 0.012W
0.957W = 93.163 - 19.161 = 74.002

74.002
W = –––––– = 75.9 K-moles
0.975

∴ D = 94.39-75.90 = 18.49 K-moles

n-butyraldehyde in W = 0.998×75.9 = 74.989 K-moles

iso-butyraldehyde in W = 75.9-74.989 = 0.911 K-moles

Aldol condensation: (90% conversion efficiency)

K-moles of 2-Ethyl hexanol = 0.90 x 74.989 = 33.745 K-moles

2

Side stream = water + unreacted + iso-butyraldehyde

n-butyraldehyde

= 33.745 + 0.1 (74.989) + 0.911

= 33.745 + 7.499 + 0.911
= 42.155 K-moles
Hydrogenation: (99% conversion)

K-moles of 2-Ethyl hexanol = 0.99 × 33.745 = 33.408 K-moles

H2 required (considering 100% excess) = 2× (2×33.745) = 33.98 K-moles

Propylene 2-ethyl hexanol

102.83 33.408

Production required: (50,000 tons/year)

Molecular weight of 2-Ethyl hexanol = 130.23

Operating period (per annum) = 8000 hours

50000×1000
∴Production (K-moles/hr) = –––––––––––– = 47.99 K-moles
8000×130.23

47.99×102.03
∴K-moles of Propylene required = –––––––––––––– = 146.564 K-moles
33.048

∴Synthesis gas required = 2×146.564 = 293.13 K-moles

Unreacted propylene = 0.02×146.564 = 2.931 K- moles

Off gas = 293.13-146.564 = 146.564 K-moles
K-moles of butyraldehyde = 0.98×146.564 = 143.633 K-moles
K-moles of n-butyraldehyde = 143.633×0.8 = 114.91 K-moles
K -moles of n-butanol formed = 0.06×114.91 = 6.89 K-moles

K-moles of iso-butyraldehyde = 143.633-114.91 = 28.723 K-moles

K-moles of iso-butanol = 0.04×28.723 = 1.149 K-moles

Distillation column:

Feed:
n- butyraldehyde = 114.91-6.89 = 108.02 K-moles
iso-butyraldehyde = 28.723-1.149 = 27.574 K- moles
F = 108.02+27.574 = 135.594 K-moles

27.574
ZF = = 0.203
135.594

Overall balance:
F=D+W
D= F-W = 135.594-W

Component balance:
FzF = DxD + Wxw
135.594 (0.203) = (135.594-W) (0.987) + W (0.012)
27.526 =133.831-0.975 W
W= 109.03 K-moles
n-butyraldehyde in W = 0.988×109.03 = 107.72 K- moles
iso-butyraldehyde in W = 109.03-107.72 = 1.31 K- moles
K-moles of 2-Ethylhexanol = 0.90×107.72/2 = 48.474 K- moles

Side stream = 48.474+0.1 (107.72) + 1.31

= 60.556 K-moles

K-moles of 2-ethyl hexanol = 0.99×48.474

= 47.99 K-moles

H2 = 2×(2×48.474) = 193.869 K-moles.

 CHAPTER-5
ENERGY BALANCE

Let, the reference temperature = 30℃

Heater 1 (to heat propylene): to 100℃
Q = m Cp ∆t

m =146.564 K-moles/hr
= 146.564 ÷ 3600 K-moles/s

Cp=70×103 J/K-mole (K)

∆t = 100-30 = 70°C

∴Q= (146.564÷3600)×70×103 ×(100-30)

= 199.49 KW
i.e., 199.49 KW of heat has to be supplied.

Heater 2(to heat synthesis gas): to 100℃

Q=m Cp ∆t

m = 293.13 K-moles/hr
= 293.13÷3600 K-moles/s

Cp=30×103 J/K-mole(K)
∆t =100-30 = 70°C
Q = (293.13÷3600)30×103 × (100-30) =170.99 KW

i.e., 170.89 KW of heat has to be supplied.

Oxo reactor: Reaction temperature ( Tp) = 130℃

∆HR at 298°C = -136.7 KJ/mole =-136.7x103 J/mole

=-136.7x106 J/K mole
Heat in + heat generation = heat out + heat accumulation

Let the reference temperature (TR) be equal to the feed temperature (Tf)

i.e TR = Tf
= 100℃
∴ heat in term → vanishes
Consider, steady state i.e heat accumulation → vanishes

mpropylene × ∆HR = m Cp(avg), gas (TP -TR) – mw Cpw(TO-TP)

(0.98×146.564) ÷3600 (-136.7×106) = (143.633÷3600) (125×103) (130-100)

+146.564(30×103) (130-100) – Mw (74.7×103) (45-30)

-5.454×106 = 149.61771×103 + 36.641×103 – 1.1205×106 mw

mw= 5.0338 K-moles/s
mw= 90.61 Kg/s
i.e 90.61kg/s of water has to be circulated.
Cooler: (130 ℃ - 72.55℃)
Q= m Cp ∆T
m = 135.594÷3600 K-moles/s

Cp=120×103 J/K-moles/K
∆t = 130℃-72.55℃
= 57.45℃

Q = (135.594÷3600) ×120×103 ×57.45 = 259.66 KW

i.e, 259.66 KW of heat has to be removed.

Overhead condenser:
Q= mλ
m = 26.564 K-moles/s
3600
λ = 3.2×107 J/K-moles

Q= (26.564÷3600) × 3.2×107 = 236.12 KW

i.e, 236.12 KW of heat has to be removed.

Reboiler:
Q= m λ
λ=3.2×107 J/K-mole
m= 109.033÷3600 K-moles
Q= (109.03÷3600)×3.2×107 = 969.16 KW
i.e, 969.16 KW of heat has to be supplied.