PROCESS CALCULATIONS

TERM PAPER

TOPIC: PRODUCTION OF ETHANOL

FROM ETHYLENE

SUBMITTED BY:
19BCH002 (ADITYA JANI)
19BCH023 (KUNJAN PANDYA)
 PROCESS DESCRIPTION

• Ethanol for use as an industrial feedstock or solvent (sometimes

referred to as synthetic ethanol) is made from petrochemical feed
stocks, primarily by the acid-catalysed hydration of ethylene.
• The reaction is carried out in the presence of high pressure steam at
300 °C (572 °F) where a 5:3 ethylene to steam ratio is maintained.
• The entire flow diagram for this simulation can be found in the
flow sheet. The first step in the production of ethylene to
anhydrous ethanol is to react water with ethylene over a catalyst.
• This reaction is simulated using a well mixed reactor model. One
reactor is required with a volume of 9.2 m3. The reactor will
operate at 300 °C and a pressure of 7.0 bar with an overall
conversion of 96.5% .The incoming ethylene stream is mixed with
water and an ethylene recycle stream which contains unreacted
ethylene recycled from the product stream from the reactor.
• The mixing stream is represented by icon M-108 in the process
flow diagram. After the reaction takes place, the product stream is
cooled to separate the ethylene from the ethanol using a flash
drum.

• The separation step is represented by icon CS-102 in the process

diagram. The ethylene is recycled back to the reactor and the
 96.5% ethanol is dehydrated using a series of distillation towers
and the addition of a small amount of benzene.
• During the cooling and separation step a small amount of ethylene
is purged from the system. This purging is represented in the
process flow diagram by icon M-101.
• This process was used on an industrial scale by Union Carbide
Corporation and others in the U.S., but now only LyondellBasell
uses it commercially.

Figure 1: Flow sheet of Ethanol producing plant

There are three different processes to produce ethanol:

1) Hydration of Ethylene
2) Fermentation of Corns or Sugars
3) From cellulose
 For this term paper we have chosen first of the above listed
methods which is hydration of Ethylene. It is the oldest of the
methods and it is believed being started on large scale in 1960s.

Figure 2: Flow sheet of Ethanol producing plant with unit operations

The raw materials needed for this process are basically ethylene and
water. It is nearly works at 300°C. There are many unit operations
involved in this ethanol producing process. The following are the unit
operations involved:

1) Mixing
2) Heat transfer
3) Cooling
4) Separating
5) Distillation
 MATERIAL BALANCE

Basis: 1000 kg/hr (given)

Material balance over Mixer:

The compositions of are as follows:

C2H 4= 600 kg/hr

H2O = 400 kg/hr

C2H 4(recycled) = 21 kg/hr

Total flow rate of feed in the mixer = Total flow rate of liquor after
mixing = 600+400+21 = 1021 kg/hr

Therefore,

C2H 4in liquor = 621 kg/hr

H2O in liquor = 400 kg/hr

Material balance over Reactor:

The product stream contains: C 2H 5OH, C 2H ,4 H O2

Composition of C2H 4= 621 kg/hr

Composition of H2O = 400 kg/hr

Therefore,

Number of moles of C 2H 4= 22.178 kmol

Number of moles of H2O= 22.22 kmol

As the given reaction has a 96.5% conversion ratio of C H

2 ,4

mol of C2H4 reacted

% conversion = * 100
mol of C2H4 fed

Hence,

Moles of C2H 4reacted = (96.5/100) * 22.178 = 21.394 kmol

Moles of H2O reacted = 21.394 kmol ( As per stoichiometry)

Moles of Ethanol formed = 21.394 kmol

Therefore,

Weight of Ethanol formed = moles*molecular weight = 984.126 Kg

Now,

Unreacted moles of C 2H 4= No. of moles fed – No. of moles reacted

= 22.178 – 21.394 = 0.7845 kmol

2 4 Weight of C H in product stream =

moles*molecular weight
= 0.7845*28= 21.966 kg
Unreacted moles of H2O= No. of moles fed – No. of moles reacted

= 22.22 – 21.394 = 0.826 kmol

Weight of H2O in product stream = moles*molecular weight

= 0.826*18= 14.868 kg

Total weight of output stream from reactor = 984.126+21.966+14.868

= 1020.96 kg

Material balance over cooler:

Moles of C2H 5OH = 21.394

Moles of C2H 4= 0.784

Moles of H2O = 0.828

There is no transfer of mass in the cooler so the output will be equal

to input

Material balance over separator:

Assuming 99.5% ethanol gets separated from ethylene

Moles of ethanol in ethanol rich stream

99.5 = * 100
Moles of ethanol fed
Moles of ethanol in ethanol rich stream = 0.995*21.394

= 21.287 kmol

Weight of ethanol in ethanol rich stream = moles * mol. wt

= 21.287 *46 = 979.202 kg

Moles of water in ethanol rich stream = 0.828

Weight of water in ethanol rich stream = moles * mol. wt

= 0.828*18 = 14.904 kg

Moles of ethanol in ethylene rich stream = 21.394-21.287

= 0.107 kmol

Weight of ethanol in ethylene rich stream = moles * mol. wt

= 0.107 *46 = 4.922 kg

Weight % of ethanol in ethylene rich stream = 18. 3009

Moles of ethylene in ethylene rich stream = 0.784 kmol

Weight of ethylene in ethylene rich stream = moles * mol. wt

= 0.784 *28 = 21.952 kg

Weight % of ethylene in
ethylene rich stream =
81.699
This ethylene rich stream is then sent for purging and recycling and
ethanol rich stream is sent for separation of ethanol and water

Material balance for Purging:

During cooling and separation step a small amount of ethylene is

purged from the system

About 5% ethylene rich stream is purged here,

Moles of ethylene before purging = 0.784

Total weight of ethylene rich stream = 4.922 + 21.952 = 26.874 kg

Weight of ethylene rich stream purged = 0.05 * 26.874 = 1.344 kg

Therefore,

Weight of ethylene purged = 81.699 % of 1.344 kg

= 1.098 kg

Moles of ethylene purged = 1.098/28 = 0.039 kmol

Weight of ethanol purged = 18.3009 % of 1.344 kg

= 0.246 kg

Moles of ethanol purged = 0.246/46 = 0.005 kmol

Moles of ethylene after purging = 0.784 – 0.039 = 0.745 kmol

Weight of ethylene after purging = 0.745 * 28 = 20.86 kg

Moles of ethanol after purging = 0.107 – 0.005 = 0.102 kmol

Weight of ethanol after purging = 0.102 * 46 = 4.692 kg

Therefore,

Purge ratio of ethylene =

weight of ethylene purged
weight of ethylene in ethylene rich stream

= 1.098 / 21.952 = 0.05

weight of ethylene after purging

Recycle ratio =
weight of ethylene fed initially

= 20.86 / 600 = 0.0347

Material balance for Fractional Distillation:

Moles of ethanol fed = 21.28 kmol

Weight of ethanol fed = 979.21 kg

Moles of Water fed = 0.828 kmol

Weight of water fed = 14.91 kg

Now,
Moles of ethanol entering = Moles of ethanol leaving = 21.28 kmol

After distillation we get 99% w/w ethanol,

Therefore,

wt of ethanol
0.99 =
wt of ethanol + wt of water

Let us assume weight of water to be x kg,

979.21
= 0.99
979.21 + x
On solving, x = 9.891 kg

Total weight = 979.21 + 9.891 = 989.096 kg

Hence,

Water obtained as by-product = 14.91 – 9.891 = 5.016 kg

Overall Mass Balance:

Mass entering the system = Mass leaving the system

Feed + Recycle = Product + By-product + Purge + Recycle

1000 + 21 = 989.096 + 5.016 + 1.344 + 20.86 + 4.674

1021 = 1020.9997

Hence we can say that the mass is balanced.

 ENERGY BALANCE
Energy Balance in reactor:

Feed is entering at a temperature of 303 K (30˚C)

Reactor heats up to 573 K (300 ˚C)

298 K or 25⁰C is the reference or datum temperature

aT 2+( b * T + c * 2)dT (eqnT1)

Specific Enthalpy = ∫
T
1

Total Enthalpy = Mass flow rate *( Specific Enthalpy + Heat of

formation)

Total Heat for reaction and Power for reaction according to industrial
data = 11567717.85 KJ/hr

Enthalpy of Entering Feed:

 Gases and their constants
Chemical a b c
H2O 32.4921 0.0796 * 10-3 13.2107 * 10-6
C2H4 4.1261 155.0213 *10-3 -81.5455* 10-6
Table :- Gases and their
constant values

Chemical ni° (kmoles/hr) ∆Hi° (KJ/kmol) ni °×∆Hi °

(KJ/hr)
C2H4 22.17857 52746.73126 1169847.071

H2O 22.222 -290571.4551 -6457142.801

Table :- Molar Enthalpy and total Enthalpy of product

Chemical ∆H formation (KJ/kmol) Specific Enthalpy (KJ/kmol)

C2H4 52530 216.7312586
H2O -290740 168.5448842
Table :- Specific Enthalpy and Enthalpy of formation of products

Calculations for C2H4

After integrating eqn 1 from Tref to T

Specific Enthalpy = (4.1261(T – T ) +ref(155.0213×10 -3)/2(T2-T 2)- ref

81.5455×10-6/3(T3-Tref3)
Putting Limits -Tref = 298 K and T = 303K

We get ,

Specific Enthalpy = 216.7312586 KJ/kmol

∆H = (Specific Enthalpy) + (∆H )
C2H4 C2H4
formation
C2H4
∆HC2H4 = 52746.73126 KJ/kmoles

(Enthalpy) = n °×∆Hi ° = 1169847.071

C2H4 i KJ/ hr

Similarly we calculate for Enthalpy of water

(Enthalpy) = n °×∆H
H2O i ° = i-6457142.801 KJ/ hr

Total Enthalpy of Entering Feed

= 1169847.071 + ( -6457142.801)KJ/ hr = -5287295.73 KJ/hr

Enthalpy of Leaving Feed:

Gases and their constants

Chemical a b c
H2O 32.4921 0.0796 * 10-3 13.2107 * 10-6
C2H4 4.1261 155.0213 *10-3 -81.5455* 10-6
C2H 5OH 6.296 231.5 *10-3 -118.56 * 10-6
Table :- Gases and their constant values

Chemical ni° (kmoles/hr) ∆Hi° (KJ/kmol) n °×∆H °

ii
 (Molar Enthalpy) (KJ/hr)

C2H4 0.784521 67835.95817 53218.73374

H2O 0.82817 -281083.2195 -232784.6894

C2H 5OH 21.39405 301067.2628 6441048.074

Table :- Molar Enthalpy and total Enthalpy of product

Chemical ∆H formation (KJ/kmol) Specific Enthalpy (KJ/kmol) at

573K
C2H4 52530 15305.95817
H2O -290740 9656.780484
C2H 5OH 278000 23067.26283
Table :- Specific Enthalpy and Enthalpy of formation of products

Total Enthalpy of Leaving Feed

= 53218.73374 + (-232784.6894) + 6441048.074 KJ/ hr

= 6261482.118 KJ/hr

∆H for the reaction = Total Enthalpy of Leaving Feed -

Total Enthalpy of Entering Feed
= 11548777.85 KJ/hr

For energy balance

∆H = Q + W (eqn 2)

Q + W – heat and power for providing heat in reactor =

11567717.85 KJ/hr ( from industrial data )

For energy to be balanced eqn 2 should be equal

∆H = 11548777.85 KJ/hr ~ Q + W = 11567717.85

KJ/hr

The reason ∆H is not exactly equal to Q + W

is because no system can be 100% closed and
also we have considered every gas as ideal
which is also not true

Energy Balance in Cooler :

In a cooler no chemical reaction takes place and only energy in form
of heat is exchanged. The liquor exiting the reactor at 573K enters
cooler at same temperature. The leaving temperature of liquor is
303K. In the cooler the phase change of both Ethanol and Water takes
place at 351K and 373K respectively. The C H2 (ethylene)
4 is cooled
down to 303K without any phase change as its Boiling point is 170K.

As no chemical reaction is taking place so we can take the input state

of chemicals as reference states.

INLET OUTLET

Chemical n °(kmoles/hr)
i ∆Hi°(KJ/kmol) n °(kmoles/hr)
i ∆Hi°(KJ/kmol)
& Phase Molar Enthalpy Molar Enthalpy

Liquid 0 0.784521 -51294.235

×
Water
Water 0.784521 0 0 ×
Vapour (Reference)
Liquid 0 21.39405 -63627.404
×
Ethanol
Ethanol 21.39405 0 0
×
Vapour (Reference)
Ethylene 0.82817 0 0.82817 -15089.073
Vapour (Reference)
 Chemical Enthalpy ( ni° × ∆Hi°) (KJ/hr)

Ethanol -1361247.863
Water -40241.40454
Ethylene -12496.31759
Total -141398.585

For Ethanol

∆H1+ ∆H2 +∆H3 = ∆H

Ethanol Ethanol Liquid
Vapour
303 K
573K

∆H1 = -19415.266
KJ/kmol

∆H3 = -5652.138
KJ/kmol

Ethanol Ethanol Liquid

Vapour
 ∆H2 = -38560
Similarly we KJ/kmol calculate values
for other
∆H2 is Enthalpy of Vaporisation
T
chemical
∆H1 = ∫
T 2 (a + b * T + c * 2)dT T ( a,b,c, for Ethanol s and
vapour) 1

find their
∆H3 = ∫T2
T1 a + b * T + c * 2)dT T (a,b,c for Ethanol energy.
(
liquid)
Accordin
g to industrial data the energy required for cooling the liquor was =
147862.788 KJ/hr

For energy to be balanced eqn 2 should be equal

∆H = -141398.585 KJ/hr ~ Q + W = -147862.788

KJ/hr

The reason ∆H is not exactly equal to Q + W

is because no system can be 100% closed and
also we have considered every gas as ideal
which is also not true
Energy Balance in Separation in Distillation:

The Water and Ethanol can easily be separated by Distillation. The

boiling point of Ethanol anr Water are 78°C and 100°C respectively.
As the temperature reaches 78°C the Ethanol starts evaporating and
by the time temperature reaches 98°C it is 100% evaporated. This
leaves water behind and we have successfully separated the Ethanol
and Water mixture.

Image 3: Laboratory setup of Separation of ethanol and water

 INLET OUTLET

Chemical n °(kmoles/hr)
i ∆Hi°(KJ/kmol) n °(kmoles/hr)
i ∆Hi°(KJ/kmol)
& Phase Molar Enthalpy Molar Enthalpy

Liquid 0.82817 0 0.82817 51294.235

Water (Reference)
Liquid 21.28707 0 0 ×
Ethanol (Reference)
Ethanol 0 × 21.39405 45700.392
Vapour

Chemical Enthalpy ( ni° × ∆Hi°) (KJ/hr)

Ethanol 972827.4457
Water 2885.236988
Total 97562.6826

According to industrial data the energy required for cooling the liquor
was = 114590.788 KJ/hr

For energy to be balanced eqn 2 should be equal

∆H = 97562.6826 KJ/hr ~ Q + W = 114590.788
KJ/hr

The reason ∆H is not exactly equal to Q + W

is because no system can be 100% closed and
also we have considered every gas as ideal
which is also not true

REFERENCES

➢ https://www.google.com/search?q=all+unit+operations&oq=all
+unit+ope&aqs=chrome.1.69i57j0j0i10i22i30j0i390.4091j0j7&
client=ms-android-xiaomi&sourceid=chrome-mobile&ie=UTF-
8
➢ https://www.google.com/search?q=all+unit+operations&oq=all
+unit+ope&aqs=chrome.1.69i57j0j0i10i22i30j0i390.4091j0j7&
client=ms-android-xiaomi&sourceid=chrome-mobile&ie=UTF-
8
➢ https://www.sciencedirect.com/science/article/abs/pii/S2210271
X20300669#:~:text=In%20the%20direct%20hydration%2C%20
ethylene,%5B21%5D%2C%20and%20etc
➢ https://www.sciencedirect.com/science/article/abs/pii/S2210271
X20300669#:~:text=In%20the%20direct%20hydration%2C%20
ethylene,%5B21%5D%2C%20and%20etc
➢ https://www.britannica.com/science/ethanol
➢ A comparison of anhydrous ethanol production from ethylene
and fr.pdf
➢ article_publication_ethanol.pdf
➢ https://m.youtube.com/watch?v=phQtK41YRo0