Production of 2-ethylhexanol

Material Balance
The following are the calculations done so as to produce one ton of 2-ethylhexanol in one
day.

Oxo-Reactor
We will start by determining the amount of fed required to achieve this
Let,
R= (synthesis gas + unreacted propylene)/kmol of propylene feed
x= mole fraction of propylene in stripped gas.
Let us take 24 kmol of fresh propylene

(Determined by trial & error)

Total propylene feed = (24+24Rx) kmol

Unreacted propylene = 24(1+Rx)0.02

(assuming reactor has 98% conversion)

= 0.48(1+Rx) kmol
Synthesis gas = 24R(1-x) kmol
Propylene: synthesis gas = 1:2
[24(1+Rx)] / [24R(1-x)] =
Therefore x =(R-2)/3R

(1)

Also x = (unreacted propylene)/( unreacted propylene + synthesis gas)

x= [0.48(1+Rx)]/[0.48(1+Rx)+24R(1-x)]

(2)

Solving for x we get

x = 0.01 & R = 2.06
Therefore total propylene feed = 24+24Rx = 24.49 kmol
Unreacted propylene = 0.48(1+Rx) = 0.49 kmol
Synthesis gas = 24R(1-x) = 48.95 kmol
Unreacted synthesis gas = 48.95-24.49 = 24.46 kmol
Now 98% proplene is converted. Also butyraldehyde formed is a mixture of n-butyraldehyde
and iso-butyraldehyde in the ratio 4:1
So n-butyraldehyde = 4/5 * 0.98 * 24.49 = 19.20 kmol
iso-butyraldehyde = 1/5 *0.98 *24.49 = 4.80 kmol

6% of n-butyraldehyde is converted to n-butanol and 4% of iso-butyraldehyde is converted

to iso-butanol.
Therefore n-butanol = 0.06*19.20 = 1.15 kmol
iso-butanol = 0.04*4.80 = 0.192 kmol
Effectively n-butyraldehyde = 19.2-1.15 = 18.05 kmol
iso-butyraldehyde = 4.8-0.19 = 4.61 kmol

Distillation column 1
5%w/w of butyraldehyde will be in alcohol stream in stripping section.
Feed = 18.05 kmol n-butyraldehyde + 4.61 kmol of iso-butyraldehyde + 0.19 kmol isobutanol +1.15 kmol n-butanol
= 1631.52 kg butyraldehyde + 99.16 kg butanol
Residue = 5.22 kg butyraldehyde + 99.16 kg butanol
Distillate = 1626.3 kg butyraldehyde = 17.992kgmol n-butyraldehyde + 4.56kgmol isobutyraldehyde

Distillation column 2
Feed = 17.992kmol n-butyraldehyde + 4.596 kmol of iso-butyraldehyde
xf= 0.2
xd= 0.99
xw= 0.01
F= D+W
22.588= D + W
Fxf = Dxd + Wxw
22.588*0.2= (22.588-W)0.99 + W*0.01
W= 18.163 kmol
D= 4.425kmol
n-butyraldehyde in residue = 18.163*(1-0.01)
=17.945kmol
iso-butyraldehyde in residue = 0.218 kmol
n-butyraldehyde in distillate=0.404kmol
iso-butyraldehyde in distillate= 4.3395kmol

Aldol Condensation (90% conversion)

2-ethylhex-2-enal = (17.945/2)*0.9
=8.075 kmol
Water= 8.075 kmol

Unreacted n-butyraldehyde = 0.1*17.945

= 1.7945 kmol
iso butyraldehyde = 0.218 kmol

Hydrogenation (99% conversion)

Hydrogen fed (Considering 100% excess) = 2*2*8.075
=32.3 kmol
2-ethylhexanol = 0.99*8.075
= 7.994 kmol
=1039.220 kg

Thermodynamic Feasibility
1. Reaction of Propylene with synthesis gas :

Greaction =Gproducts - Greactants

G= G(n-butyraldehyde+i-butyraldehyde+n-butanol+i-butanol)- G(propylene+syn gas)
= (-149.02-151.46-178.96-158.57)-(2*150.81-2*148.661)
=-642.308kJ/mol

The Aldolization and subsequent Conversion to 2-ethylhexenal :

Greaction =Gproducts - Greactants

G=G(intermediate)-G(n-butyraldehyde)
G= -89.36-(2*-178.961) = 268.562kJ/mol
G=G(2-ethylhex-2-enal+water)-G(intermediate)
G= (-70.19-237.14) (-89.36)
=-217.970kJ/mol

The Hydrogenation to 2-ethylhexanol :

Greaction =Gproducts - Greactants

G= G(2-ethylhexanol)- G (2-ethylhex-2-enal+Hydogen)
G=-140.15-(-70.19+0)
=-69.96kJ/mol