Soran university

Faculty of engineering

Chemical engineering department

[Design of production 2-ethylhexanol from propylene and synthesis gas]

Name of student;

Ali Muhammad qadir

Supervised by :

Ali hosen alibag

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Oxo reaction
 Propylene synthesis gas

H.E separation

Catalyst recovery

Iso-butyraldehyde N/I separation

n-butyraldehyde

hydrogen gas
condensation

hydrogenation hydrogenation hydrogenation

iso-butanol 2-ethylhexanol n-butanol

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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 + 100 Rx) =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 striper.

Propylene: Synthesis gas = 1 : 2

100(R) (1-X) / 100(1+RX)= 2 ………………………… (1)

R (1-X) / 1+RX= 2

R-Rx = 2+2Rx
3Rx = R – 2
x= R-2/3R

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

x = (1+Rx) / (1+Rx) + 50R(1-x)

= 1+RX / 1+RX + 50R-50RX
= 1+RX / 1+50R-49RX

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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) / 3R*1+49R – 49R (R-2) / 3R = 1

(R – 2) (98R + 101) = 9R
98R2 +101R – 196R – 202 = 9R
98R2 -104R – 202 = 0
a = 98, b = -104, c = -202

R = ( 104 ) +or- ROOT SQUARE[(104)^2 – 4(98)( -202)] / 2(98)

R=2.061

X=(R-2)/3R==(2.061-2)/3(2.061)==0.061/6.183= 0.0099

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 x 102.03 = 99.99 K-moles
∴n-Butyraldehyde : iso-Butyraldehyde = 4 : 1
K-moles of n- butyraldehyde = 99.99 x 0.8 = 79.992 K – moles
∴6% n- butyraldehyde of is converted to n-butanol
K-moles of n-butanol = 0.06 x 79.992 =4.800 K moles

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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 x 19.998 = 0.800 K moles

Distillation column (I) : Aldehydes/Alcohol separatorAssume: all Aldehydes (both n & iso-
butyraldehydes leave as the top product) and allalcohols (both n and iso-butanol leave as
bottom product ).

Distillation column (II) :

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)

Zf =19.198 / 94.39 = 0.203;

Xd =0.987 : Xw =0.012

Over all material balance:

F=D+W
D = 94.39-W

Component balance:
F ZF = DxD + W.xw.
94.39(0.203) = (94.39 – W) (0.987) + W(0.012)
19.161 = 93.163 – 0.987W + 0.012W
0.975W = 93.163 –19.161 = 74.002

W = 74.002 / 0.975 = 75.9 K mole

So D = 94.39 – 75.9 = 18.49 K mole

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n-Butyraldehyde in W = 0.988 x 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

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 x 33.745 = 33.408 K-moles
H2 required (considering 100% excess) = 2 x ( 2 x 33.745) =134.98 K-moles
Propylene 2-ethyl hexanol

Production required :
40,000 tons/year
Molecular weight of 2-Ethyl hexanol = 130.23
Operating period (per anum) = 8000 hours

Scaling factor = moles product per hour specified / moles product produced per 100 k mole of
principle raw material

So production ( k moles / hr) = 40000 * 1000 / 8000 * 130.23 = 38.39 k moles

K moles of propylene required = 38.39 * 102.03 / 33.048 = 118.53 k moles

Synthesis gas required = 2 x 118.53 = 237.07 K-moles

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Unreacted propylene = 0.02 x 118.53 = 2.3706 K- moles
Off gas = 237.07-118.53 = 118.54 K-moles
K-moles of butyraldehyde = 0.98 x 118.54 = 116.16 K-moles
K-moles of n-butyraldehyde = 116.16 x 0.8 = 92.93 K-moles
K -moles of n-butanol formed = 0.06 x 92.93 = 5.58 K-moles
K-moles of iso-butyraldehyde = 116.16 – 92.93 = 23.23 K-moles
K-moles of iso-butanol = 0.04 x 23.23 = 0.9292 K-moles

Distillation column:
Feed: n- butyraldehyde = 92.93 – 5.58 = 87.35 K-moles
iso-butyraldehyde = 23.23 – 0.9292 = 22.30 K- moles
F = 87.35 + 22.30 = 109.65 K-moles

Z F= 22.30 / 109.65 = 0.2034

Over all material balance:

F=D+W
D = F- W = 109.95 – W
Component balance:

FZF= DxD + Wxw109.85 (0.2034) =(109.65 - W) (0.987) + W (0.012)

W = 88.169 K- moles
n- butyraldehyde in W = 0.988 x 88.169 = 87.11 K- moles
iso- butyraldehyde in W = 88.169 – 87.11 = 1.06 K- moles

k mole of 2-ethylhexanol = 0.90 * 87.11 / 2 =39.2 k mole

Side stream = 39.2 + 0.1 (87.11) + 1.06
= 48.971 K- Moles
K- moles of 2-ethyl hexanol = 0.99 x 39.2 = 38.81 K- moles

H2 = 2 x (2 x 39.2 ) = 156.80 K-moles.

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Energy balance:
Let, Reference Temperature = 30°C

Heater 1 (To heat Propylene): to 100°C

Q = m Cp ∆t
m = 146.564 k mole / hr =146.564 /3600 k moles / S

Cp=70 x 103 J/K-mole (K)

∆t = 100-30 = 70°C

146.546
Q=
3600
*70 * 1000 * (100-30) = 199.49 KW

So 199.49 KW of heat has to be supplied

Heater 2 (To heat synthesis gas): to 100°C

Q=m Cp ∆t
k mole 293.13 K mole
m = 293.13 =
hr 3600 S
Cp =30 x 103 J/K-mole(K)

∆t = 100-30 = 70°C

Q= 293.13 / 3600 * 30* 1000 * 70 = 170.99 KW

So 170.89 KW of heat has to be supplied

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Oxo Reactor: Reaction temperature (Tp) = 130°C
∆HR, at 298°C = -136.7 KJ/mole =-136.7x10^3 J/mole
=-136.7x10^6 J /K mole

Heat in – heat out + generation heat = heat accumulation

Heat in + heat generation = heat accumulation + heat out

Let the reference temperature (TR) be equal to the feed temperature (Tf)
TR = Tf = 100°C
∴ heat in → vanishes term
Consider, steady state . heat Accumulation → vanishes

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

0.98∗146.564 143.633
(-136.7 * 10^6) = (125 * 10^3)(130 – 100 )
3600 3600

146.564
+ (30 * 10^3)(130 -100 ) – Mw (74.7 * 10^3)(45 -30 )
3600

-5.454 x106 = 149.61771 x 103 + 36.641 x 103 –1.1205 x 106 Mw

mw=5.0338 K-moles/s
mw=90.61 Kg/s

so 90.61 kg/s of water has to be circulated.

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Cooler : (130°C – 72.55°C)

Q= m Cp ∆T
135.594 K moles
m=
3600 S
Cp=120x103 J/K-moles/K
∆t=130-72.55 = 57.45°C
135.594
Q= * 120 *10^3 *57.45 = 259.66 KW
3600

259.66 KW of heat has to be removed.

Overhead condenser :
Q=m λ
26.564
m= k moles /S
3600

λ=3.2 x 107 J/K-moles

26.564
Q= 3.2 * 10^7 = 236.12 KW
3600

236.12 KW of heat has to be removed.

Reboiler:
Q=m λ
λ=3.2 x 10^7 J/K-mole
109.03
m= K moles /S
3600
109.03
Q= 3.2 * 10^7 = 969.16 KW
3600

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So 969.16 Kw of heat has to be supplied.

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