Introduction to Chemical

Engineering
Teaching by:
Vassily Hatzimanikatis ([email protected])

Assistants:
Denis Joly ([email protected])
Konrad Lagoda ([email protected])
Zi Xuan Ng ([email protected])

Office hours: Mondays 16h-19h (CH H4 625) or schedule by email

Fridays, 14h15 - 17h00
2024-2025
Course Schedule
Date Subject
1. Fundamentals of Material Balances
13-Sep 1.1. Process definition and classification
1.2. Material balance calculations
20-Sep 1.3. Balances on multiple-unit processes
27-Sep Review on Mass Balances (non-reactive)
1.4. Chemical reaction stoichiometry
04-Oct
1.5.1 Balances on reactive processes (part 1)
1.5.2 Balances on reactive processes (part 2)
11-Oct 1.6. Balances on multiple unit reactive processes
Review on Mass Balances (non-reactive & reactive)
2. Energy and Energy Balances
18-Oct 2.1. Energy balances on closed systems Recommended textbook:
2.2. Open systems at steady state Elementary Principles of Chemical
3. Balances on Non-Reactive Processes Processes
3.1. Energy balance calculation Richard M. Felder & Ronald W.
01-Nov
3.2. Changes in Pressure, Temperature, Phases Rousseau
3.3. Mixing and Solution

4. Balances on Non-Reactive Processes

08-Nov
Problems: Mass and Energy Balances on non-Reactive Systems

15-Nov Midterm Exam: Mass & Energy Balances non-Reactive Systems

22-Nov Review Midterm
5. Balances on Reactive Processes
5.1. Heats of reaction/combustion
29-Nov 5.2. Combustion reactions
5.3. Enthalpy of reaction
5.4. Energy balance calculation
6. Energy balances on mixing processes
06-Dec
Review
13-Dec Review and Study Session
 Session IV: Friday 11 October 2024

After studying this session, you will be able to:

1. Perform Mass Balances on Reactive Systems

(atom balance)

2. Understand the concepts of Recycle, Bypass and

Purge, as well as the advantages of applying them

3. Perform Mass Balances on multiple unit processes

with recycle, bypass or purge of streams

3
1. Mass Balance on Reactive Systems
(atom balance)

4
 Mass Balance on Reactive Systems(atom balance)
• Knowing that number of atoms of any given element does not change in any
reaction, how the “mother of all equation” changes for atomic balancing??
0 0 0
In + Gen – Out – Cons = Acc

In – Out = 0 Assume st.st.

• When analyzing a reacting system, you must choose either an

atom balance or a molecular species balance but not both
• An atom balance often yields simpler algebra (especially for multiple reactions)
• When doing atom balances, the extent of reaction does not count as an unknown,
while with a molecular species balance it does
• When you're doing an atom balance you should only include reactive species, not
inerts

5
Example 1: Balance on reactive process on molecular
and/or atomic species
Reaction: Dehydrogenation of ethane is in steady-state continuous reactor

C2H6 → C2H4 + H2

100 kmol C2H6/min is reacting to produce 40 kmol H2/min. Balance it !

• For simplification: n1=ethane, n2=Hydrogen, n3= Ethylene

1)Draw the flowchart

100 kmol C2H6/min ṅ2 =40 kmol H2/min
ṅ1 (kmol C2H6/min)
ṅ3 (mol C2H4/min)

6
 100 kmol C2H6/min ṅ1 (kmol C2H6/min)
a) molecular species balance ṅ2 =40 kmol
H2/min
ṅ3 (mol C2H4/min)

2) Mass balance:

Ethane molecular balance : ṅ1,in – ṅ1,Out + ṅ1,Rct = 0 → ṅ1,in – ṅ1,Out – ξ = 0

H2 balance : ṅ2,in – ṅ2,Out + ṅ2,Rct = 0 → ṅ2,in – ṅ2, Out + ξ = 0

→ ξ = 40
→ ṅ1,Out = 60 kmol / min

Ethylene balance: ṅ3,in – ṅ3, Out + ṅ3,Rct = 0 → ṅ3,in – ṅ3, Out + ξ = 0

→ ṅ3, Out = 40 kmol /min

ntot = 140 kmoles → 42.9 % C2H6, 28.5 % H2, 28.5 % C2H4

7
 100 kmol C2H6/min
ṅ1 (kmol C2H6/min)
b) Balance on atomic species ṅ2 =40 kmol
H2/min
ṅ3 (mol C2H4/min)

Carbon balance:
ṅc,in – ṅc, Out = 0 → 2 × 100 k mol of C2H6 / min = 2 × ṅ1, Out + 2 × ṅ3, Out
→ 100 kmol of C / min = ṅ1, Out + ṅ3, Out

Hydrogen balance:
ṅH,in – ṅH, Out = 0 → 6 × 100 kmol of C2H6 / min = 6 × ṅ1,out + 4 × ṅ3, Out+ 80 kmol of H /min
→ 600 kmol of H / min = 6 ṅ1, Out + 4 ṅ3, Out + 80 kmol of H /min

6 ṅ1, Out + 4 ṅ3, Out = 520 kmol of H /min

ṅ1, Out + ṅ3, Out = 100 kmol of C / min

→ ṅ1, Out = 60 kmol / min, ṅ3, Out = 40 kmol/min

8
 Example 2
Methane is burned with air in a continuous steady-state reactor to yield a mixture of
carbon monoxide, carbon dioxide, and water. The reactions taking place are:
CH4 + 3/2 O2 → CO + 2 H2O (1)
CH4 + 2 O2 → CO2 + 2 H2O (2)
The feed to the reactor contains 7.80 mol % CH4, 19.4 mol% O2 , and 72.8 mol % N2. The
percentage conversion of methane is 90.0%, and the gas leaving the reactor contains 8
mol CO2/mol CO.

• Carry out a degree-of-freedom analysis on the process. Then calculate the molar
composition of the product stream using molecular species balances and atomic
balances.

nCH4 (mol CH4)

nCO (mol CO)
1) Draw a diagram nCO2 (mol CO2)
100 mol
0.0780 mol CH4/mol nH2O (mol H2O)
0.194 mol O2/mol nO2 (mol O2)
0.728 mol N2/mol nN2 (mol N2)
2) Basis:100 mol feed
9
 CH4 + 3/2 O2 → CO + 2 H2O (1)
CH4 + 2 O2 → CO2 + 2 H2O (2)

a) molecular species balance

3) DOF analysis
Molecular species balance: 5 unknown variables + 2 independent reactions – 5 molecular
species balances – relationship between CO and CO2 – 1 specified methane conversion = 0
degree of freedom

4) Calculations with the Mass balances

Methane balance: nCH4,in – nCH4,out + (–1ξ1 – 1ξ2) = 0
Oxygen balance: nO2,In – nO2,Out + (-3/2 ξ1 - 2ξ2) = 0
Nitrogen balance: nN2,In – nN2,Out + 0 = 0 → nN2,In = nN2,Out → nN2,Out = 72.8 mol
Carbon dioxide balance: nCO2,In – nCO2,Out + ξ2 = 0 → nCO2,Out = ξ2
Carbon monoxide balance: nCO,In – nCO,Out + ξ1 = 0 → nCO,Out = ξ1
Water balance: nH2O,In – nH2O,Out + (2ξ1 + 2ξ2) = 0
Conversion of methane: 0.9 = (nCH4 ,In- n CH4,Out)/ nCH4,In → 0.9 = (7.8- nCH4,Out)/7.8 →
nCH4,Out = 0.78 mol
10
 CH4 + 3/2 O2 → CO + 2 H2O (1)
CH4 + 2 O2 → CO2 + 2 H2O (2)

• Relationship between CO and CO2

nCO2,Out = 8nCO,Out → ξ2 = 8ξ1

• By using the methane balance:

7.8 mol – 0.78 mol + (-1ξ1 - 8ξ1) = 0 → ξ1 = 0.78 mol and ξ2 = 6.24 mol
nCO,Out = 0.78 mol of CO
nCO2,Out = 6.24 mol of CO2
nO2,Out = 5.75 mol of O2
nH2O,Out =14.0 mol of H2O

• Final result:
0.78% CH4, 0.78% CO, 6.2% CO2, 14.0% H2O, 5.7% O2 & 72.5% N2

11
 CH4 + 3/2 O2 → CO + 2 H2O (1)
CH4 + 2 O2 → CO2 + 2 H2O (2)

b) Atomic species balance

3) DOF analysis

DOF: 5 unknowns variables – 3 independent atomic species balance – relationship between

CO and CO2 one specified methane conversion = 0

4) Calculations with the Mass balances

Carbon atomic balance:

1nCH4,In - 1nCH4Out – 1nCO,Out – 1nCO2,Out = 0

Hydrogene atomic balance:

4nCH4,In – 4nCH4,Out – 2nH2O,Out = 0

Oxygen atomic balance:

2nO2,In – 2nO2,Out – 1nCO,Out – 2nCO2,Out – 1nH2O,Out = 0

Relation between CO and CO2:

nCO2,Out = 8nCO,Out
12
 CH4 + 3/2 O2 → CO + 2 H 2O (1)
CH4 + 2 O2 → CO2 + 2 H2O (2)

Conversion of methane:
0.9 = (nCH4 ,In- n CH4,Out)/ nCH4,In → 0.9 = (7.8- nCH4,Out)/7.8 → nCH4,Out = 0.78 mole

Carbon atomic balance:

7.8 – 0.78 – nCO,Out – 8nCO,Out = 0 → nCO,Out = 0.78 mol of CO
nCO2,Out = 8 × 0.78 = 6.24 mol of CO2

And we found nH2O,Out = 14.0 mol of H2O

nO2,Out = 5.7 mol of O2

13
2. Concepts of Recycle, Bypass and Purge

14
Terminology and quantification in reactive mass balances

To understand the chemical processes, first we need to understand the words:

Recycle To put or pass through a cycle again, as for further

treatment

Bypass An alternative passage created to divert the flow and

circumvent an obstructed or congested area

Purge To free from impurities, purify

15
3. Mass balance on multiple unit processes

16
 Recycle

A recycle stream (R) sends back a part of the outgoing stream of a process
unit into a fresh feed stream that enters the same process unit.

Example: we want to recycle a fraction of the product stream from a reactor.

How would you draw it?

Recycling
… and mixing it M S implies
with the separating part
reactants. Process of the product
stream …
The mixture will
be fed to the
process unit.

R
17
 Bypass
A bypass stream (B) sends forward a portion of the inlet stream in a
process unit to the product stream from the process unit. This portion of
stream will skip the process unit.

Example: we want to bypass a fraction of the feed stream that would

enter a reactor. How would you draw it?

S M … and mixing it
with the
Process product stream.

Bypassing implies The mixture will

separating part of be the final
the feed stream … output of the
process.
B

18
 Purge
A purge stream (P) sends out of the process a portion of another
stream, in order to eliminate undesired components.

Example: we want to purge a fraction of the recycling stream for a

reactor. How would you draw it?

Purging implies
M S
separating a
portion of a
Process
stream…

…and sending it
P out of the
process.
R

Why purging a recycle stream? to avoid accumulation of undesired

19
materials in a recycled system
 Why recycle, bypass or purge?

Process: Advantages(examples):

Recycle We can separate from the stream the products from

reactants that have not reacted. If we recirculate the
reactants, we can increment the overall conversion
-> ECONOMICALLY AND ENVIRONMENTALLY USEFUL

Bypass Reach final product specifications (concentration of a

component) by mixing streams
-> might improve the quality of the final product ( see
S4E4 orange juice)

Purge We can eliminate undesired substances and avoid

accumulation of them in the system.
-> improves the purity of the product and makes waste
treatment easier 20
 Recycling: Application and Advantages

Recycling is used in a wide variety of processes

M S
Process

The use of recycle makes a great deal of environmental and economic

sense
Using recycle lets achieving a wider range of separations
By using recycle, it is possible to recover expensive catalysts and reagents
Recycle reduces the amount of waste that a company generates
21
 Recycling: Considerations in the analysis

Remember, when recycling:

(1) we separate part of the output stream
(2) and we mix it with the feed

Therefore, we generate two new and important points of study:

(1) The splitting point OR a separator: separation point in product stream
(2) the recombination point: mixing point in feed stream

(2) Recombination M S
point (1) Splitting
Process point

R 22
Recycling: IMPORTANT Considerations in the analysis

Will the composition of the streams that participate in a

recombination point differ?
Yes, unless the feed and the recycle stream have the same
composition (which is not normally the case)

Will the composition of the streams that participate in a

separator (e.g.: distillation column, evaporator, extractor)
differ?

Will the composition of the streams that participate in a

splitting point differ?

23
 Recycling: Considerations in the analysis
• The composition of the streams around the recombination and
splitting point (or separator) should be known.

• These streams are internal in the process, since they don’t cross the
boundaries of the system.

How can we calculate the composition of the new streams?

• The recombinant point and the splitting point or separator will be

considered as new subsystems

• We have to perform mass balances around these points

• The mass balance analysis of these processes follows the same

considerations as explained in the processes with multiple units

24
 Recycling introduces two types of conversion!
R
A B S

Reactant Reactant
input to reactor output to reactor
Single-pass = 100 *
conversion Reactant
input to reactor

Reactant input Reactant output

to overall process to overall process
Global/Overall = 100 *
conversion Reactant input
to overall process

25
 Calculate the two types of conversions

25 mol A/mol
100 mol A/mol 75 mol B/mol
75 mol A/mol R 75 mol B/mol
A B S

25 mol A/mol

Single-pass conversion of A

(100-25)/100 =75%

Global conversion of A

(75-0)/75=100%

26
 Example 3: Recycling after a reactor
Cyclohexane C 6H12 is made from benzene and H2 according to the
following reaction:
C6H6 + 3H2 → C6H12

20% excess H2 is used in the fresh feed/input and the single pass
conversion is 20%, the output goes into a separator and part is recycled.
How much should be the ratio of recycle stream to feed stream in order to
achieve an overall conversion of 95% , if the recycle is 22.74% mol B and
77.26% mol H2.
For simplification: n total , nC mol cyclohexane, nB mol benzene, nH mol H2

0) Units: mol, %-mol n1 n2

nC1 nC2
1) Flowchart, subsystems nB1 nB2
2) Basis: 100 mol B nBF nH1 nH2 n4
nC4
nHF R S nB4
WE NEED TO LOOK FOR : nH4
n3 / (nBF + nHF)
n3, nB3, nH3 27
 Example 3: Recycling after a reactor
KNOWN:
• 20% excess H2
• Single pass conversion 20%
• We want overall conversion 95% n2
n1
• Composition of recycle stream nC1 nC2
nB1 nB2
nH1 nH2 n4
nBF
R S nC4
nB4
nHF nH4
n3, nB3, nH3
Single pass conversion → conversion only around the reactor
0.2 = nB1- nB2 / nB1 → nB2 = 0.8 nB1
Overall conversion → conversion on the overall system
0.95 = 100 - nB4 / 100 → nB4 = 5 mol of B
20% excess H2: 20% more than if all B had reacted
If all 100 mol B reacted we need 300 mol H 2 → 20% excess H 2 →
nHF = 360 mol
28
 Example 3: Recycling after a reactor
n1
S1 n2
nC1 nC2
nB1 nB2
nBF nH1 nH2 n4
nHF R S nC4
nB4
nH4
n3, nC3, nB3, nH3

S1 (global system) :
• Benzene mass balance:
100 – 5 – ξ = 0 → ξ = 95 mol

• H2 mass balance:
360 – nH4 – 3ξ = 0 → nH4 = 75 mol

• Cyclohexane mass balance:

0 – nC4 + ξ = 0 → nC4 = 95 mol
The number of total mol leaving the reactor:
n4 = 5 mol of benzene + 75 mol of H2 + 95 mol of cyclohexane = 175 mol 29
Is ξ in the reactor different
from ξ in overall system?

30
 Example 3: Recycling after a reactor
n1
S1 n2
nC1 S2 nC2
nB1 nB2
nBF nH1 nH2 n4
nHF R S nC4
nB4
nH4
n3, nC3, nB3, nH3

S2 (reactor) :
• Benzene mass balance:
nB1 – nB2 – ξ = 0 → nB1 – 0.8nB1 – 95 moles = 0 → nB1 = 475 mol

• H2 mass balance:
nH1 – nH2 – 3ξ = 0 → nH1 = nH2 + 3 × 95

• Cyclohexane mass balance:

nC1 – nC2 + ξ = 0 → nC1 = nC2 – ξ 31
 Example 3: Recycling after a reactor
n1 n2
nC1
S2 nC2
S1 nB1 nB2
nBF nH1 nH2 n4
S3 (mixing system) : nHF R S nC4
• B mass balance: S3 nB4
100 + nB3 – 475 = 0 → nB3 = 375 mol nH4
• H2 mass balance: n3, nC3, nB3, nH3
360 + nH3 – nH1 = 0
• C mass balance:
0 + nC3 – nC1 = 0 → nC1 = 0
(in the recycle stream, there is no cyclohexane, so nC3 = 0)

From the reactor we find : nC2 = 95 mol

nH3/nB3 = 77.26/22.74 → nH3 = 3.4nB3 → nH3 = 1275 mol
nH1 = 1635 mol, nH2 = 1350 mol, nB2 = 380 mol

SOLUTION: recycle stream /feed stream = (nB3 + nH3 ) /(nHF + nBF ) = 1650/460 = 3.6

-> most of the stream going into the reactor comes from recycled reactants 32