Chapter 8

1 Material and Energy Balance

8.1 Reaction

C2H5OH → CH3CHO + H2

Catalyst :Cu -Co-Cr2O3

0
Temperature: 280 – 350 C.

Process

The raw material i.e., ethanol is vaporized and the vapors, so generated, are heated in a heat exchanger
0
to the reaction temperature by hot product stream. The product stream is cooled to –10 C and in doing
it, all un reacted ethanol and acetaldehyde are condensed. The outgoing gaseous stream, containing
hydrogen mainly, is scrubbed with dilute alcohol (alcohol + water) to remove uncondensed products and
the undissolved gas. The remaining pure hydrogen (98%) is burnt in stack.

The material and energy balance in a plant design is necessary because this fixes the relative flow rates
of different flow streams and temperatures in the flow sheet.
Notations used

Msteam = Mass flow rate of steam.

∆Hsteam = enthalpy of steam.

E = Mass flow rate of ethanol.

A = Mass flow rate of acetaldehyde.

H = Mass flow rate of hydrogen.

Cp = specific heat capacity.

λ = Latent heat of vaporization.

Assumptions :

Let us assume an annual production of acetaldehyde 54000 tons per year.

It is assumed that the plant works for 300 days in a year.

Amount of acetaldehyde produced per day =180 tons per day

Basis: One hour of operation.

Amount of acetaldehyde to be produced = 180 TPD = 7500kg/h.

Molecular weight of ethanol = 46 kg/kmol.

Molecular weight of acetaldehyde = 44 kg/kmol.

Molecular weight of hydrogen = 2 kg/kmol.

Therefore, amount of acetaldehyde to be produced = 170.45kmol/h.

Let conversion be 90%.

Taking into account the losses let, the acetaldehyde produced to be some extra.

Let acetaldehyde to be produced = 8000 kg/h.

Amount of ethanol required for 100% conversion = 8363.63 kg/h.

Therefore, ethanol required for 90% conversion = 9292.92 kg/h.

Temperature dependency of Cpwith temperature is given as

T
Cp T 2 −T 20 T 3−T 30 T 4−T 40 T 5−T 50
∫R dT = A ( T −T 0) +B +C + D + E
T0
2 3 4 5

8-1 Values of constants for calculating Cp[22]

Component A B*103 C*106 D*10-5

Ethanol 3.518 20.001 -6.002 0

Hydrogen 3.249 0.422 0 0.083

Acetaldehyde 1.693 17.978 -6.158 0

Water 3.470 1.450 0 0.121

8-2Values of CP for different temperature range (kcal/Kg.C)

Component -25 to 25 to 78.4 to 100 to 200 to 40 to 310
40 oC 100 oC 200 oC 310 oC 232.36 oC
 78.4 oC o
C

Ethanol 0.616 0.587 0.4382 0.471 0.539 0.5415 0.549

----- ------ ----- ------
Acetaldehyd 0.347 0.417 0.528
e
----- ----- ----- ------
Hydrogen 3.399 2.485 2.485
--- ------ ----- ----- ------ ------ ----
Water

8.2 Vaporizer

As shown in the figure,

Ethanol liquid inlet temperature = T i=25oC.

Ethanol leaves as superheated steam at 100 0C = To

Heating fluid is assumed to be saturated steam here and to provide sufficient temperature gradient; it is
taken to be at about 3 atmospheric pressure. At this pressure it condenses at 133.89 0 C and because
process streams are normally available at this pressure.

Condensing temperature of water = 133.89 0 C.

From steam table enthalpy of steam at this temperature = ∆H steam =514.9kcal/kg. [6]
Boiling point of ethanol = Tb = 78.40 C. [6]

Latent heat of vaporization of ethanol= λ ethanol = 200.6 kcal/kg [6]

From heat balance we have,

Msteam = E*[Cpi*(Tb-Ti) +λ ethanol +Cpo*(To-Tb)]

Msteam = 9292.92* [0.5876 * (78.4 – 25) + 200.6 + 0.4382 * (100 – 78.4)]/514.9

= 4357.56 kg.

8-3 Mass Balance Table for Vaporizer

Component Input Feed Stream Output Feed Stream
(Kg) (Kg)

Ethanol 9292.92 9292.92

Water 4357.56 4357.56

Total 13650.48 13650.48

For Water

Heat in =¿ = 2714324.124kcal

Where To=298.15 K and TD=406.15K

Heat out=¿2714324.124 kcal

For ethanol (Tref= 298.15 K)

Heat in= 0 kcal Heat out=470616.48kcal

8-4 Energy Balance Table for Vaporizer

Component StreamIn kcal Stream Out kcal

Ethanol 0 2243710.112

Water 2714324.124 470616.48

Total 2714324.124 2714326.592

8.3 Reactor

The reaction in the reactor:

C2H5OH → CH3CHO + H2

0
Optimum reaction temperature = 310 C.

Conversion = 90%.

From material balance we have,

Amount of acetaldehyde produced = .90 * 44* 9292.92 / 46 =8000kg.

=181.81kmol

Amount of hydrogen produced = .90 * 2* 9292.92 / 46 = 363.63 kg.

Amount of ethanol unreacted = 9292.92 – (8000 + 363.63)

= 929.28kg=20.20kmol
8-5 Mass Balance Table for Reactor
Component Input Feed stream (Kg) Output feed stream (kg)

Ethanol 9292.92 929.28

Acetaldehyde 0 8000

Hydrogen 0 363.64

Dowtherm 32447.6042 32447.6042

Total 41740.5252 41740.5252

0
It is decided to use saturated vapours of dowtherm, at 320 C, for cooling purposes

λdowtherm = 56.5 kcal / kg.

Heat of reaction = ∆Hrxn = 332.64 kcal / kg. [6]

0
Assuming ethanol vapors enter the reactor at 200 C.

From heat balance we can found amount of dowtherm required = M d.

0
Specific heat capacity of ethanol = 0.549 kcal / kg C.

Energy in by ethanol =929.28*[0.5876*(98.2-25)+200.6+0.549*(310-98.2)]

=334439.0624 kcal/kg

Energy in by hydrogen=363.63*2.485*(310-25)=257531.8568 kcal/kg

Energy in by acetaldehyde =8000*0.528*(310-25)

=1203840 kcal/kg

Energy required for the reaction=0.90*9292.92*332.64

=2782077.218 kcal/kg

Q= Amount of heat supplied by dowtherm

Q={Energy out from the reactor+ Heat of reaction }-{Energy entering into the reactor}
 =1833289.639 kcal

Md *λdowtherm=Q

Md=1833289.639 /56.5=32447.6042Kg

8-6 Energy Balance Table for Reactor

Component Stream In (kcal) Stream Out(kcal)

Ethanol 2744598.5 334439.0624

Hydrogen 0 257531.8568

Acetaldehyde 0 1203840

Heat Exchanger

0
This is used only for heat recovery. Since it is assumed vapor is heated up to 200 C by the product
0
stream of the reactor at 310 C.

0
Let outlet temperature = T C.

0 0
Cp of ethanol at 310 C = 0.549 kcal / kg C.
 0 0
Cp of acetaldehyde at 310 C = 0.528 kcal / kg C.

0 0
Cp of hydrogen at 310 C = 2.485 kcal / kg C.

8-7 Mass Balance Table for Heat Exchanger

Component Shell in (kg) Tube in (kg) Shell out (Kg) Tube out (kg)

Ethanol 929.28 9292.92 929.28 9292.92

Acetaldehyde 8000 - 8000 -

Water 363.63 - 363.63 -

Total 9292.91 9292.92 9292.91 9292.92

From heat balance we can find the outlet temperature.

E*Cp,ethanol*(200–100)=E*Cp,ethanol*(310–T) +H*Cp,hydrogen*(310–T)+ A*Cp,acet*(310-T)

9292.92*0.471*(200-100)=929.92*0.549*(310-T)+363.63*2.485*(310T)+8000*0.528*(310-T)

0
Therefore, T = 232.36 C.

8-8 Energy Balance Table for Heat Exchanger

Component Shell side(kcal) Tube side(kcal)

Ethanol 437696 39637.24

Hydrogen - 70157.099

Acetaldehyde - 327951.36

Total 437696 437745.699

8.4 Condenser C1

In condenser 1 it is decided to use cooling water at 30 0 C. the outlet temperature of cooling water is not
allowed to go above 500C, because above this temperature, there is a problem of vaporization. Normally
the approach temp difference is about 10 0C. Since the product can at best be cooled to 40 0C, at this
temperature the product stream would be a two-phase mixture and the mixture composition can be
found out from VLE data.

We make an approximate that; the information given at 699 mmHg is taken.

At 4000C, ethanol in vapor phase = 4.1 mol%. [6]

Ethanol in liquid phase = 55 mol%. [6]

Let, ml = moles of liquid consisting of ethanol and acetaldehyde.

mv = moles of vapor consisting of ethanol and acetaldehyde.

Therefore from mole balance we have

0.55 * ml + 0.041 * mv = 20.20

0.45 * ml + 0.959 * mv = 181.81

On solving above two equations we get, ml = 23.413 kmol.

mv = 178.596 kmol.

Vapor phase composition,

Acetaldehyde = 171.27 kmol = 7536.03 kg.

Ethanol = 7.32 kmol = 336.83 kg.

Liquid phase composition,

 Acetaldehyde = 10.535 kmol = 463.57 kg.

Ethanol = 12.977 kmol = 592.348 kg

Heat Balance

0
At 232.69 C,

0
Cp, hydrogen = 2.485 kcal / kg C.

0
Cp, acetaldehyde = 0.417 kcal / kg C.

0
Cp, ethanol = 0.5415 kcal / kg C.

λ acetaldehyde = 139.5 kcal / kg.

λ ethanol = 200.6 kcal / kg.

3
Heat given out by hydrogen = 363.636 * 2.485 * (232.69 – 40) = 173.823 * 10 kcal.

Heat given out by acetaldehyde = 8000* 0.417 * (232.69 – 40) + 463.57 * 139.5

3
= 706.38 * 10 kcal.

Heat given out by ethanol = 929.92* 0.5415 * (232.69 – 40) + 592.348 *200.6

3
= 215.621 * 10 kcal.

3
Total heat given out = 1095.82 * 10 kcal.

Let, Mw = mass flow rate of cooling water

0
Cp of water = 1 kcal / kg C.
 3 3
Therefore, Mw = 1095.8 * 10 / (1 * (5030)). = 54.79 * 10 kg.

8-9 Mass Balance Table for Condenser 1

Component In (Kg) Vapor Phase Out Liquid phase out (Kg)

(Kg)

Ethanol 929.28 336.83 592.348

Acetaldehyde 8000 7536.03 463.57

Hydrogen 363.64 363.636 --------

Water 54791.29 ---------- 54791.29

Total 64084.21 64083.704

8-10 Energy Balance for Condenser 1

Component Tube side (kcal) Shell side (kcal)

Ethanol 215621 ------

Hydrogen 173823 ------

Acetaldehyde 706380 ------

Water -------- 1095800

Total 1095824 1095800

Condenser C2

In condenser c2, it is desired to condense all ethanol and acetaldehyde. If the working pressure is 1 atm.
0
From the equilibrium data it is seen that for temperatures below 30 C, there is going to be no ethanol in
vapor phase and acetaldehyde would exert its vapor pressure at that temperature. If it is desired to
achieve about 97% recovery of acetaldehyde, the outlet temperature of the product stream should be
0 0
about –25 C.This is because at –22.6 C, its vapor pressure is 100 mmHg and the vapor phase will

consists of 13.15 mol%. In view of this, the cooling fluid chosen is saturated NH 3 at 1 atm. At which it
0
boils at –33.6 C[6].

Heat balance:

0
At 40 C,

0
Cp, hydrogen = 3.399 kcal / kg C.
 0
Cp, acetaldehyde = 0.347 kcal / kg C.

0
Cp, ethanol = 0.616 kcal / kg C.

λ acetaldehyde = 139.5 kcal / kg.

λ ethanol = 200.6 kcal / kg.

λ ammonia = 590 kcal / kg.

3
Heat given out by hydrogen = 363.64 * 3.399 * (40 + 25) = 80.339 * 10 kcal.

Heat given out by acetaldehyde = 7536.03* 0.347 * (40+ 25) + 7309.95 * 139.5

3
= 1189.182 * 10 kcal.

Heat given out by ethanol = 336.83* 0.616 * (40+25) + 336.83 * 200.6

3
= 81.054 * 10 kcal.

3
Total heat given out = 1350.575 * 10 kcal.

Let Mammonia = mass flow rate of ammonia.

3
Therefore, Mammonia = 1350.575 * 10 / 590.= 2289.11 kg.
8-11 Mass Balance Table for Condenser 2

Component Feed In (Kg) Vapor Phase Out (Kg) Liquid Phase out (Kg)

Ethanol 336.83 -------- 336.83

Acetaldehyde 7536.03 226.10 7309.95

Hydrogen 363.64 363.64 ----------

NH3 2289.11 2289.11 ----------

Total 10525.61 10525.63

8-12 Energy Balance for Condenser 2

Component Tube side (kcal) Shell side (kcal)

Ethanol 81.054*103 ------

Hydrogen 80.339*103 ------

Acetaldehyde 1189.182*103 ------

Ammonia -------- 1350574.9

Total 1350.575*103 1350.5749*103

Preheater

The pre heater to the distillation column is necessary because the feed plate will be completely
0
chilled if the feed is not heated. The water stream from condenser c 1 is available at 50 C and is used in
0
the pre heater. If the maximum approach temperature difference is 10 C, the product stream can at
0
best be heated to 40 C. the distillation column pressure is chosen to be 1158 mmHg so that pure
0
acetaldehyde is obtained as liquid product at 40 C. In view of this, the stream coming out of the
preheater is liquid.
Heat balance

At 40 oC

0
Cp, acetaldehyde = 0.347 kcal / kg C.

0
Cp, ethanol = 0.616 kcal / kg C.

Let, Mw = mass flow rate of cooling water.

Mw * (50-30) = 929.178 * (40 + 14.54872)* 0.616 + 7773.52*(40+14.54872)*0.347

Therefore, Mw = 8918.1296 kg

8-13 Mass Balance for Preheater

Component Input (Kg) Out(Kg)

Ethanol 929.178 929.178

Acetaldehyde 7773.52 7773.52

Water 10626.80 10626.80

Total 19329.498 19329.498

8-14 Energy Balance Table for Preheater

Component Tube side (kcal) Shell side (kcal)

Ethanol 31222.249 0

Acetaldehyde 147140.3414 0

Water 0 178362.59

Total 178362.5904 178362.59

8.7 Distillation column

In distillation column acetaldehyde condenses at 40 0C. since vapor pressure data’s of pure gas is not
available, it is estimated using Antoine’s equation.

ln P = A + B/T

Where, A and B are constants, they can be determined from boiling point data at, Pressures
760 mmHg and 400 mmHg.

At 760 mmHg T = 20.20C= 293.20K. [6]

400 mmHg T = 4.90C = 277.90K. [6]

Therefore, ln 760 = A + B/293.2 ln 760 = A +

B/277.9

On solving above two equations we get,

A = 18.29 and B = -3418.2[6]

Therefore, ln P = 18.29 – 3418.2/T

Therefore at 400C, P = 1586.41 mmHg.

Assume 99% acetaldehyde recovery in overhead product and ethanol recovery as 10%.

In overhead:

Acetaldehyde = 7695.78 kg.

Ethanol = 92.917 kg.

Total D = 7788.69 kg.

In bottom:
Acetaldehyde = 77.73 kg. Ethanol = 836.26 kg. Total W = 913.99 kg.

F=D+W

xd= .989

F * x f = D * xd + W * x w

Therefore, xw = F * xf – D * xd

Therefore, xw = .0815

Assume reflux ratio = 0.3

Therefore L / D = 0.3
L = 0.3 * 7788.69 = 2336.60 kg.

Vapor going to the condenser = L + D = 2336.60 +7788.69

=10125.30 kg.

Of this 98.9% is acetylaldehyde

Therefore, vapor composition going to the condenser:

Acetaldehyde = 10013.92 kg, Ethanol = 111.37 kg.

Heat load to condenser

Let L/D=0.3

L=2336.60 kg

Vapor going to condenser = L+D =10125.30kg

Out of this 98.9% is acetaldehyde

Acetaldehyde=10013.92 kg

Ethanol= 111.37 kg.

Heat load to the condenser = Methanol*λethanol + Macetaldehyde*λacetaldehyde

=111.37*200.6+10013.92*139.5 =1419282.662 Kcal

Reboiler load

Let “m” be the amount of liquid vaporized.

Let “L” be liquid going into the reboiler.

Let L/W = 10

L= 9139.9 kg

Therefore, m= L-W

m=9139.9-913.99=8225.91 kg

we know xw = .0815, so

Acetaldehyde=8225.91/45.976*.0815=14.581 kg

Ethanol=8211.32 kg

Heat load to the reboiler = Methanol*λethanol + Macetaldehyde*λacetaldehyde

=8211.32*200.6+14.581*139.5

=1649226.492 kcal.