MASS BALANCE

INTRODUCTION OF THE PROCESS

Based on the process flow diagram above, some of the ideas were cited from the resources but the rest
were made from own studies with relevant resources. In the process of producing acetaldehyde, there
are total 5 main equipments which all are reactive processes occur in each unit. To start off, a portion
of ethylene, oxygen and hydrochloric acid were added into the reactor as the raw materials. These
combination of raw materials inside the reactor will produce portions of unconverted ethylene,
acetaldehyde, chloral, carbon dioxide, acetic acid, chloromethane, chloroethane, crotonaldehyde, water,
and hydrogen forming 100 parts from converted ethylene as the main raw material. From the reactor,
all of the components mentioned will enter the expansion valve as in this valve it will increase to
pressure of 1 atm. With the aid of condenser, components with high boiling points such as acetic acid,
crotonaldehyde, chloral, and some portion of water will be condensate and discharged out of the process
which will be no further use in the process. However, in the second heat exchanger, the temperature
inside was reduced to 25ºC in order to prepare a suitable operating condition before being fed to the
extractive distillation column. In the extractive distillation column (EDC), carbon dioxide, ethylene,
chloromethane, chloroethane and hydrogen will be fed inside. Some of the soluble components will be
washed away by water. This will produce acetaldehyde, small portion of chloromethane and
chloroethane and huge amount of water as the bottom product. Later, these components will enter the
solvent recovery unit and will be heated up to 80ºC. From the boiling points of each component, water
will remain as liquid and the rest will be converted into gas. This leads to production of acetaldehyde
with 99.8% purity. As for the top product of EDC, it will produce carbon dioxide, hydrogen, ethylene,
chloroethane and chloromethane with high concentrations. These components will be further washed
in the scrubber that will use a lot of water consumptions. In which, these components will enter the
solvent recovery unit and separate chloromethane and chloroethane as the top product in the unit
whereas the bottom product will be discharge in water tank to be use later. Carbon dioxide, hydrogen
gas and ethylene will be the produced as the top product in the scrubber. Which is the unreacted ethylene
will be further recycle as the raw material.
 REACTOR (R-101)

S1
ṅ1 = Ethylene, C2H4
as R-101
as S4
ds
S2 as
d ṅ2 = Oxygen, O2 as
as
aa ṅ4 = Unconverted Ethylene, C2H4
ds
as
a ṅ5 = Acetaldehyde,
d CH3CHO
ds
dS aaCCl CHO
d ṅ6 = Chloral, 3
1 a
aa S3 ṅ7 = CarbondSDioxide, CO2
a 1
as ṅ8 = Acetic Acid, CH3COOH
dS
as
1 ṅ9 = Chloromethane, CH3Cl
ds
ṅ3 = Hydrochloric Acid, HCl ṅ10 = Chloroetane, C2H5Cl
d
aa ṅ11 = Crotonaldehyde, C4H6O
a
dS ṅ12 = Water, H2O
1 ṅ13 = Hydrogen, H2

Main Reaction:

1) C2H4 + 1/2 O2 CH3CHO ........................................ (ξ1)

Side Reactions:

2) C2H4 + 3 O2 2 CO2 + 2 H2O ................................. (ξ2)

3) C2H4 + O2 CH3COOH ...................................... (ξ3)

4) 2 CH3CHO C4H6O .............................................. (ξ4)

5) C2H4 + HCl C2H5Cl ............................................... (ξ5)

6) C2H + HCl + 3/2O2 CH3Cl + H2O + CO2 ............... (ξ6)

7) CH3CHO + 3HCl CCl3CHO + 3H2 ...................... (ξ7)

Assumptions:

1) Overall conversion of ethylene is 0.45%. (Cite from link)

2) Selectivity is 95%.

3) The reactor is in steady state.

4) No accumulation involved in the reactor.

Sample of Calculations:

The compositions of each component were assumed when 100 parts of Ethylene gives:

1) 0.95 Acetaldehyde (ṅ5)

2) 0.0056 Chlorinated Aldehyde, Chloral (ṅ6)

3) 0.0056 Unconverted Ethylene (ṅ4)

4) 0.0056 Carbon Dioxide (ṅ7)

5) 0.0056 Acetic Acid (ṅ8)

6) 0.0056 Chloromethane (ṅ9)

7) 0.0056 Chloroethane (ṅ10)

8) 0.0056 Crotonaldehyde (ṅ11)

9) 0.0056 Water (ṅ12)

10) 0.0056 Hydrogen (ṅ13)

By using Extent of Reaction Methods:

𝑛𝑖−𝑛𝑖𝑜
ξ=
𝑣𝑖

• Assuming Feed Ethylene (ṅ1) = 50 kmol/hr

• Ethylene Converted = (50 kmol/hr)(0.45) = 22.5 kmol/hr
• Selectivity of Acetaldehyde = (22.5 kmol/hr)(0.95) = 21.375 kmol/hr

All ξ can be calculated as follows

 𝑛5−𝑛5𝑜 21.375−0
ξ1 = =
1 1

= 21.375

𝑛7−𝑛7𝑜 (0.0056)(22.5)−0
ξ2 = =
2 2

= 0.063

𝑛8−𝑛8𝑜 (0.0056)(22.5)−0
ξ3 = =
1 1

= 0.126

𝑛8−𝑛8𝑜 (0.0056)(22.5)−0
ξ4 = =
1 1

= 0.126

𝑛8−𝑛8𝑜 (0.0056)(22.5)−0
ξ5 = =
1 1

= 0.126

𝑛8−𝑛8𝑜 (0.0056)(22.5)−0
ξ6 = =
1 1

= 0.126

𝑛8−𝑛8𝑜 (0.0056)(22.5)−0
ξ7 = =
1 1

= 0.126

From Extent of Reactions Calculated, Molar Flowrate can be Determine:

• Output Molar Flowrates:

1. Unconverted Ethylene, ṁ4
ṁ4 = 27.5 kmol/hr x 28 kg/kmol
= 770 kg/hr
2. Acetaldehyde , ṁ5
ṅ5 = n5o + ξ1 - 2 ξ2 – ξ7 = 22.5 kmol/hr
ṁ5 = 22.5 kmol/hr x 44.05 kg/kmol
= 991.125 kg/hr
3. Chloral, ṁ6
ṅ6 = ṅ6o + ξ7 = 0.126 kmol/hr
ṁ6 = 0.126 kmol/hr x 147.39 kg/kmol
= 18.571 kg/hr

4. Carbon Dioxide, ṁ7
ṅ7 = ṅ7o + 2ξ2 + ξ6 = 0.252 kmol/hr
ṁ7 = 0.252 kmol/hr x 44.01 kg/kmol
= 11.09 kg/hr

5. Acetic Acid, ṁ8
ṅ8 = ṅ8o + ξ3 = 0.126 kmol/hr
ṁ8 = 0.126 kmol/hr x 60.052 kg/kmol
= 7.57 kg/hr

6. Chloromethane, ṁ9
ṅ9 = ṅ9o + ξ6 = 0.126 kmol/hr
ṁ9 = 0.126 kmol/hr x 50.44 kg/kmol
= 6.36 kg/hr

7. Chloroethane, ṁ10
ṅ10 = ṅ10o + ξ5 = 0.126 kmol/hr
ṁ10 = 0.126 kmol/hr x 64.51 kg/hr
= 8.13 kg/hr

8. Crotonaldehyde, ṁ11
ṅ11 = ṅ11o + ξ4 = 0.126 kmol/hr
ṁ11 = 0.126 kmol/hr x 70.09 kg/hr
= 8.83 kg/hr

9. Water, ṁ12
ṅ12 = ṅ12o + 2 ξ2 + ξ6 = 0.252 kmol/hr
ṁ12 = 0.252 kmol/hr x 18.02 kg/kmol
= 4.54 kg/hr

10. Hydrogen, ṁ13

ṅ13 = ṅ13o + 3 ξ7 = 0.378 kmol/hr
 ṁ13 = 0.378 kmol/hr x 2.0159 kg/kmol
= 0.76 kg/hr

Total Mass Flowrate Outlet = 1826.98 kg/hr

• Inlet Molar Flowrates:

1. Ethylene, ṁ1
ṅ1 = 50 kmol/hr
ṁ1 = 50 kmol/hr x 28.05 kg/kmol
= 1402.66 kg/hr

2. Oxygen, ṁ2
ṅ2 = ṅ2o – ½ ξ1 -3 ξ2 – ξ3 – 3/2 ξ6 = 11.754 kmol/hr
ṁ2 = 11.754 kmol/hr x 32 kg/kmol
= 376.128 kg/hr

3. Hydrochloric Acid, ṁ3
ṅ3 = ξ5 + ξ6 + 3 ξ7 = 0.63 kmol/hr
ṁ3 = 0.63 kmol/hr x 36.458 kg/kmol
= 22.97 kg/hr

Total Mass Flowrate Inlet = 1801.758 kg/hr

Inlet Streams (S1,S2,S3)

No Component Formula MW Molar Flowrate Mass Flowrate
(kg/kmol) (kmol/hr) (kmol/hr)
1 Ethylene C2H4 28 50 1402.66
2 Oxygen O2 32 11.754 376.128
3 Hydrochloric HCl 36.46 36.458 22.97
Acid
Total Input 61.8215 1783.59654
Outlet Stream (S4)
No Component Formula MW Molar Flowrate Mass Flowrate
(kg/kmol) (kmol/hr) (kmol/hr)
 4 Unconverted C2H4 28 27.5 770
Ethylene
5 Acetaldehyde CH3CHO 44.05 22.5 991.125
6 Chloral CCl3CHO 147.39 0.126 18.571
7 Carbon Dioxide CO2 44.01 0.252 11.09
8 Acetic Acid CH3COOH 60.052 0.126 7.57

9 Chloromethane CH3Cl 50.44 0.126 6.36

10 Chloroethane C2H5Cl 64.51 0.126 8.13

11 Crotonaldehyde C4H6O 70.09 0.126 8.83
12 Water H2O 18.02 0.252 4.54
13 Hydrogen H2 2.0159 0.378 0.76
Total Output 51.512 1828.351128

CONDENSOR (E-102): NON -REACTIVE PROCESS

Assumption:

1) Assume all high boiling points component condense.

S4 E-102
S6
as as
ṅ4as
= Unconverted Ethylene, C2H4
as
ṅ5ds= Acetaldehyde, CH3CHO ṅ4 = Unconverted Ethylene, C2H4
ds
d ṅ5 = Acetaldehyde,
d CH3CHO
ṅ6 = Chloral, CCl3CHO
aa
ṅ7 a= Carbon Dioxide, CO2 ṅ7 = CarbonaaDioxide, CO2
a
S5 ṅ9 = Chloromethane,
ṅ8dS
= Acetic Acid, CH3COOH dS CH3Cl
1 as 1
ṅ9 = Chloromethane, CH3Cl ṅ10 = Chloroetane, C2H5Cl
as
ṅ10 = Chloroetane, C2H5Cl ṅ13 = Hydrogen, H2
ds
ṅ11 = Crotonaldehyde, C4H6O d CH3COOH
ṅ8 = Acetic Acid,
aa
ṅ12 = Water, H2O ṅ11 = Crotonaldehyde,
a C4H6O
ṅ13 = Hydrogen, H2 ṅ6 = Chloral, CCl
dS 3CHO
1
ṅ12 = Water, H2O
 Boiling Points of Components Streams:

1. Acetaldehyde (ṅ5) = 20.2ºC

2. Chloral (ṅ6) = 97.8ºC
3. Unconverted Ethylene (ṅ4) = -103.7ºC
4. Carbon Dioxide (ṅ7) = -78.46ºC
5. Acetic Acid (ṅ8) = 118ºC
6. Chloromethane (ṅ9) = -24.2ºC
7. Chloroethane (ṅ10) = 12.3
8. Crotonaldehyde (ṅ11) = 102ºC
9. Water (ṅ12) = 100ºC
10. Hydrogen (ṅ13) = -252.9ºC

Inlet Stream (S4)

No Component Formula MW Molar Flowrate Mass Flowrate
(kg/kmol) (kmol/hr) (kmol/hr)
4 Unconverted C2H4 28 27.5 770
Ethylene
5 Acetaldehyde CH3CHO 44.05 22.5 991.125
6 Chloral CCl3CHO 147.39 0.126 18.571
7 Carbon Dioxide CO2 44.01 0.252 11.09
8 Acetic Acid CH3COOH 60.052 0.126 7.57
9 Chloromethane CH3Cl 50.44 0.126 6.36

10 Chloroethane C2H5Cl 64.51 0.126 8.13

11 Crotonaldehyde C4H6O 70.09 0.126 8.83
12 Water H2O 18.02 0.252 4.54
13 Hydrogen H2 2.0159 0.378 0.76
Total Input 51.512 1828.351128
Outlet Stream (S5)
14 Acetic Acid CH3COOH 60.052 0.126 7.57
15 Chloral CCl3CHO 147.39 0.126 18.571
16 Crotonaldehyde C4H6O 70.09 0.126 8.83
17 Water H2O 18.02 0.252 4.54
Total 0.63 39.511
Outlet Stream (S6)
18 Ethylene C2H4 28 27.5 770
19 Acetaldehyde CH3CHO 44.05 22.5 991.125
20 Carbon Dioxide CO2 44.01 0.252 11.09
21 Chloromethane CH3Cl 50.44 0.126 6.36

22 Chloroethane C2H5Cl 64.51 0.126 8.13

23 Hydrogen H2 2.0159 0.378 0.76
`Total 50.882 1787.465

SCRUBBER (T-101)

Assumptions:

1) All acetaldehyde product dissolved in water as it is assumed that the solubility is at infinity.

2) Water absorbs 95% of chloroethane and chloromethane.

3) Carbon dioxide and hydrogen is not absorbed in water.

4) Amount of water = Acetaldehyde feed is added with 10% extra for other components.

ṅ4 = Ethylene, C2H4
ṅ7 = Carbon Dioxide, CO2
ṅ9 = Chloromethane, CH3Cl
ṅ10 = Chloroethane, C2H5Cl
S8
ṅ13 = Hydrogen, H2
as
as
ds
d
S7 aa
ṅ14 = Water fed, H2O
a
as T-101
dS
as S9
1
ds
S6 as
d as
as ṅ5 = Acetaldehyde, CH3CHO
aa ds
ṅ4 = Ethylene, C2H4
as
a ṅ9 = Chloromethane,
d CH3Cl
ṅ
ds
dS5 = Acetaldehyde, CH3CHO aa
ṅ10 = Chloroetane, C2H5Cl
d
ṅ17 = Carbon Dioxide, CO2 a
aa ṅ14 = WaterdSout, H2O
ṅa9 = Chloromethane, CH3Cl
1
dS
ṅ10 = Chloroetane, C2H5Cl
1
ṅ13 = Hydrogen, H2
 Sample Calculations:
Inlet Streams (S7)
Amount of water fed:
ṁ14 = 991.1 kg/hr + (991.1 kg/hr + 0.1)
= 1090.21 kg/hr

Outlet Stream (S8)

ṁ9 = 0.126 kmol/hr x 50.44 kg/kmol

= 6.36 kg/hr x 0.95

= 6.042 kg/hr

ṁ10 = 0.126 kmol/hr x 64.51 kg/hr

= 8.13 kg/hr x 0.95

= 7.7235 kg/hr

Outlet Stream (S9)

ṁ9 = 6.36 kg/hr - 6.042 kg/hr

= 0.318 kg/hr

ṁ9 = 8.13 kg/hr - 7.7235 kg/hr

= 0.4065 kg/hr

Inlet Stream (S6)

No Component Formula MW Molar Flowrate Mass Flowrate
(Kmol/h) (kg/hr)
1 Ethylene C2H4 28 27.5 770
2 Acetaldehyde CH3CHO 44.05 22.5 991.125
3 Carbon Dioxide CO2 44.01 0.252 11.09
4 Chloromethane CH3Cl 50.44 0.126 6.36

5 Chloroethane C2H5Cl 64.51 0.126 8.13

6 Hydrogen H2 2.0159 0.378 0.76
`Total 50.882 1787.465
Inlet Stream (S7)
7 Water H2O 18.02 60.5 1090.21
 Total 60.5 1090.21
Outlet Stream (S8)
8 Ethylene C2H4 28 27.5 770
9 Chloromethane CH3Cl 50.44 0.12 6.042

10 Chloroethane C2H5Cl 64.51 0.12 7.7235

11 Carbon Dioxide CO2 44.01 0.252 11.09
12 Hydrogen H2 2.0159 0.378 0.76
Total 28.37 795.616
Outlet Stream (S9)
13 Acetaldehyde CH3CHO 44.05 22.5 991.125
14 Chloromethane CH3Cl 50.44 0.0063 0.318

15 Chloroethane C2H5Cl 64.51 0.0063 0.4065

16 Water H2O 18.02 60.5 1090.21
Total 83.216 2082.06

EXTRACTIVE DISTILLATION COLUMN (T-102)

Assumptions:

1) Purity 99% of Acetaldehyde at distillate with Water, Chloroethane and Chloromethane.

2) All of low boiling point will be evaporated at distillate.

ṁ2
S10

asas
ṅ5 = Acetaldehyde, CH3CHO
dsd
ṁ1 ṅ9 = Chloromethane, CH3Cl
S9 T-102 aaa
ṅ10 = Chloroetane, C2H5Cl
dS1
as
ṅ5 = Acetaldehyde, CH3CHO ṅ14 = Water, H2O
as
ṅ9ds
= Chloromethane, CH3Cl
ṁ3 ṁ3
ṅ10d= Chloroetane, C2H5Cl S11
aa ṅ15 = Water,
ṅ14a= Water, H2O asas H2O
dsd
dS
aaa
1 Sample Calculations:
dS1
Total Feed = 2082.06 kg/hr
 Total Feed Composition: 1.000

1) Acetaldehyde, CH3CHO = 0.476

2) Chloromethane, CH3Cl = 0.000153
3) Chloroetane, C2H5Cl = 0.000195
4) Water, H2O = 0.5236

Where,

Mass in = Mass Out

Overall Mass Balance:

ṁ1 = ṁ2 + ṁ3

2081.06 = ṁ2 + ṁ3

Acetaldehyde Balance:

991.1 = 0.99 ṁ2

ṁ2 = 1001.11 kg/hr

Total Distillate (D):

991.1 + 0.318 + 0.4065 + ṁ2 Water = 1001.11 kg/hr

ṁ2 Water = 9.2866 kg/hr

Total Bottom Product (B):

1090.21 – 9.2866 = 1080.923 kg/hr

Total Inlet and Outlets:

2082.06 kg/hr = 2082.033 kg/hr

Inlet Stream (S9)

No Component Formula MW Molar Flowrate Mass Flowrate

(kmol/hr) (kg/hr)
1 Acetaldehyde CH3CHO 44.05 22.5 991.125
2 Chloromethane CH3Cl 50.44 0.0063 0.318
3 Chloroethane C2H5Cl 64.51 0.0063 0.4065
4 Water H2O 18.02 60.5 1090.21
Total 83.216 2082.06
Outlet (S10)
5 Acetaldehyde CH3CHO 44.05 22.5 991.125

6 Chloromethane CH3Cl 50.44 0.0063 0.318

7 Chloroethane C2H5Cl 64.51 0.0063 0.4065

8 Water H2O 18.02 0.5153 9.2866
Total 23.028 1001.136
Outlet Streams (S11)
9 Water H2O 18.02 59.985 1080.923
Total 59.985 1080.923

PACKED BED COLUMN (T-103)

Assumptions:

1) Selectivity of Ethanolamine solvent for the Ethylene is low. Thus, it favours absorption of Carbon

Dioxide, Hydrogen, Chloroethane, Chloromethane.

2) 100% removal of absorbed gases.

3) 95% of Ethylene recovered.

4) Ethanolamine flow rate = 1000 kg/hr

 ṅ4 = Ethylene recycled , C2H4

S13

asas
ṁ16 = 1000 kg/hr dsd
S12 aaa
dS1
asa ṅ16 = Ethanolamine, C2H7NO
sds T-103
daa S14
adS asa
S8
1 sds
as
ṅ7 = Carbondaa
Dioxide, CO2
asṅ4 = Ethylene, C2H4 adS
ds ṅ9 = Chloromethane,
1 CH3Cl
ṅ7 = Carbon Dioxide, CO2
d
ṅ10 = Chloroetane, C2H5Cl
aaṅ9 = Chloromethane, CH3Cl
aṅ = Chloroetane, C H Cl ṅ13 = Hydrogen, H2
10 2 5
dS ṅ16 = Ethanolamine
1ṅ13 = Hydrogen, H2

Sample Calculations:

Inlet Stream (S8): Outlet Stream from T-101

ṁ4 = 770 kg/hr
ṁ9 = 6.042 kg/hr
ṁ10 = 7.7235 kg/hr
ṁ7 = 11.09 kg/hr
ṁ13 = 0.76 kg/hr

Inlet Stream (S12):

ṁ16 = 1000 kg/hr

Outlet Stream (S13):

ṁ16 = 770 kg/hr

Outlet Stream (S14):

ṁ9 = 6.042 kg/hr
ṁ10 = 7.7235 kg/hr
 ṁ7 = 11.09 kg/hr
ṁ13 = 0.76 kg/hr
ṁ16 = 1000 kg/hr

Inlet Stream (S8)

No Component Formula MW `Molar Flowrate Mass Flowrate
(Kmol/hr) (kg/hr)
1 Ethylene C2H4 28 27.5 770
2 Chloromethane CH3Cl 50.44 0.12 6.042

3 Chloroethane C2H5Cl 64.51 0.12 7.7235

4 Carbon Dioxide CO2 44.01 0.252 11.09
5 Hydrogen H2 2.0159 0.378 0.76
Total 28.37 795.616
Inlet Stream (S12)
6 Ethanolamine C2H7NO 61.08 16.37 1000
Total 16.37 1000
Outlet Stream (S13)
7 Unreacted Ethylene C2H4 28 27.5 770
Total 27.5 770
Outlet Stream (S14)
8 Chloromethane CH3Cl 50.44 0.12 6.042

9 Chloroethane C2H5Cl 64.51 0.12 7.7235

10 Carbon Dioxide CO2 44.01 0.252 11.09
11 Hydrogen H2 2.0159 0.378 0.76
12 Ethanolamine C2H7NO 61.08 16.37 1000
Total 17.24 1025.612

SOLVENT RECOVERY UNIT (T-104)

Assumption:

1) Solvent 99% recovered, 1% loss due to evaporation.

 ṅ7 = Carbon Dioxide, CO2
ṅ9 = Chloromethane, CH3Cl
ṅ10 = Chloroetane, C2H5Cl
S15 ṅ13 = Hydrogen, H2
asas ṅ16 = Ethanolamine
dsda
aadS
1

S14 T-104
S6
asas as
dsda ṅ16 = Ethanolamine
ṅ7 = Carbon Dioxide, CO2 as
aadS ds
ṅ9 = 1Chloromethane, CH3Cl d
ṅ10 = Chloroetane, C2H5Cl aa
a
ṅ13 = Hydrogen, H2
ṅ16 = EthanolaminedS
ṅ16 = Ethanolamine 1
(Solvent Added)
Sample Calculations:
Inlet Stream (S14):
ṁ9 = 6.042 kg/hr
ṁ10 = 7.7235 kg/hr
ṁ7 = 11.09 kg/hr
ṁ13 = 0.76 kg/hr
ṁ16 = 1000 kg/hr

Outlet Stream (S15):

ṁ9 = 6.042 kg/hr
ṁ10 = 7.7235 kg/hr
ṁ7 = 11.09 kg/hr
ṁ13 = 0.76 kg/hr
ṁ16 = 10 kg/hr

Outlet Stream (S16)

ṁ16 = 10 kg/hr + 990kg/hr

= 1000 kg/hr