CHEE2001

Process Principles

Week 6
Week 6 – plan for today
• Recap on key reaction terminology

• Mass balance with reaction questions

 Some reaction definitions from week 4
Limiting and excess reactants: The limiting reactant is the substance that is totally
consumed when the chemical reaction is complete The other reactant/s are excess.

% Excess reactants: (actual reactant flow - theoretical requirement) / theoretical requirement * 100

Fractional conversion: Moles of reactant reacted/ moles reactant fed to the system.

Extent of reaction/ rate of reaction R: In simple terms, this term is used to quantify how
far a reaction has proceeded.

CHEE2001
3
CRICOS code 00025B
 New reaction definitions from lecture week 6
Single pass conversion: Conversion across the reactor. Moles of reactant reacted/ moles fed
to the reactor.

Overall conversion: Conversion across the multi-unit system. Mole of feed reactant reacted/
moles reactant fed to the system.

Selectivity: Ratio of moles desired product vs moles undesired product.

Yield: For CHEE2001, we define yield as ratio of desired product formed vs theoretical amount of
product that could have been formed with complete reaction and no side reactions.

CHEE2001
4
CRICOS code 00025B
 Q1. Combustion of methane, single reaction
Methane is burned to form carbon dioxide and water in a batch reactor. The feed to the reactor
and the products obtained are shown in the following flowchart:

Reactor
100 mol CH4 40 mol CH4
250 mol O2 130 mol O2
60 mol CO2
120 mol H2O
CH4+2O2 →CO2 + 2H2O
1. How much methane was consumed? What is the fractional conversion of methane? 60 mol; 0.6

2. How much oxygen was consumed? What is the fractional conversion of oxygen 120 mol; 0.48
CH : 0 = 100 - 40 + R * -1
3. Write the balance equations for methane and oxygen (Accum = In – Out + Rσ). Use so,4R = 60 mol
each equation to determine the extent of reaction, R, substituting inlet and outlet
values from the flowchart. O2: 0 = 250 - 130 + R * -2
So, R = 60 mol
4. How many independent molecular species balances can be written?
Molecular: 4 (CH4, CO2, H2O and O2)
5. Write the mass balances for carbon dioxide and water and verify that they are all CO2: 0 = 0 mol - 60 mol + 60 mol
satisfied.
H2O: 0 = 0 mol - 120 mol + 120 mol
 Q2. Combustion of methane, multiple reactions
Fuel
100 mol/h methane enters a reactor. It burns in the reactions: 100 mol CH4 Reactor

CH4 + 2O2 → CO2 + 2H2O (desired reaction) Air

CH4 + 3/2O2 → CO + 2H2O (undesired reaction)

1. What is the theoretical O2 flow rate if complete combustion occurs in the reactor? 200 mol O2/h

2. What is the theoretical O2 flow rate assuming that only 70% of the methane reacts? 200 mol O2/h

3. What is the theoretical air flow rate? 200 / 0.21 = 952 mol air /h

4. If 100% excess air is supplied, what is the flow rate of air entering the reactor?
2 * 952 = 1904 mol air/h
5. If the actual flow rate of air is such that 300 mol O2/h enters the reactor, what is the percentage
excess air? % excess = (actual – theoretical)/ theoretical = (300-200)/200 = 50%
Q3. Dehydrogenation of Ethane
Ethane is dehydrogenated to form ethylene in a catalytic reactor according to the following
reaction: C2H6  C2H4 + H2. The process is designed for a 95% overall conversion of
ethane.
The reaction products enter a separator which produces two streams: a product stream
which contains H2, C2H4, and 1.5% of the ethane that leaves the reactor, and a second
stream which contains the balance of the unreacted ethane and 5% of the ethylene that
leaves the reactor. This stream is recycled back to the reactor.
Calculate:
a) the composition of the product
b) the ratio (moles recycled/ mole fresh feed) Method:
• Fully labelled flowchart
c) the single pass conversion. • DOF analyses – overall and sub-units
• General mass balance equation
• Assumptions and simplified mass balance equation
• Component balances and other independent equations
• Solve and communicate outcomes
 Dehydrogenation of Ethane

Ethane 1 2 Reactor 3 5 Legend

Separator
Mixer R E3 E5
Ex Flow of Ethane (mol/h)
E1 E2 Lx Flow of Ethylene (mol/h)
L2 L3 L5 Hx Flow of Hydrogen (mol/h)
H3 H5 X Stream number
4 R Rate of reaction (mol/h)

E4
L4

C3H8 C3H6 + H2 R
-1 +1 +1

DOF Analysis - overall

unknowns = 5 (E1 E5 L5 H5 R)
component bal = 3 (E L H)
other relations = 1 (conversion of ethane)
DOF =1 underspecified, therefore can’t be solved
 Dehydrogenation of Ethane

Legend
Ethane 1 2 Reactor 3 5 Ex Flow of Ethane (mol/h)
Separator
Mixer R E3 E5 Lx Flow of Ethylene (mol/h)
E2
E1 L3 L5 Hx Flow of Hydrogen (mol/h)
L2
H3 H5 X Stream number
R Rate of reaction (mol/h)
4
E4
L4

DOF Mixer unknowns = 5 (E1 E2 L2 E4 L4)

component bal = 2 (E L)
DOF =3 underspecified
DOF Reactor unknowns = 6 (E2 L2 E3 L3 H3 R)
component bal = 3 (E L H)
DOF =3 underspecified

DOF Separator unknowns = 8 (E3 L3 H3 E4 L4 E5 L5 H5)

component bal = 3 (E L H)
other = 2 (ethane split, ethylene split)
DOF =3 underspecified
 Dehydrogenation of Ethane

Legend
Ethane 1 2 Reactor 3 5 Ex Flow of Ethane (mol/h)
Separator
Mixer R E3 E5 Lx Flow of Ethylene (mol/h)
E2
E1 = 100 L3 L5 Hx Flow of Hydrogen (mol/h)
L2
H3 H5 X Stream number
R Rate of reaction (mol/h)
4
E4
L4

Assume a basis of 100 mol/h feed

DOF Analysis - overall

unknowns = 4 (E5 L5 H5 R)
component bal = 3 (E L H)
other relations = 1 (conversion of ethane)
DOF =0 therefore can be solved
Dehydrogenation of Ethane
General Mass Balance (GMB):
Accumulation = Input – Output + Generation – Consumption

Assumptions:
• Steady state, so no accumulation
• Single reaction
Simplified GMB: 0 = Input – Output + R ó

Overall Balances:
E: 0 = 100 – E5 + R * -1
L: 0 = 0 – L5 + R * 1
H: 0 = 0 - H5 + R * 1
Other E5 = 0.05 * 100

Solving:
E5 = 5 mol/h
R = 95 mol/h
L5 = 95 mol/h
H5 = 95 mol/h
 Dehydrogenation of Ethane

Legend
Ex Flow of Ethane (mol/h)
Ethane 1 2 Reactor 3 5 Lx Flow of Ethylene (mol/h)
Separator
Mixer R = 95 E3 E5 = 5 Hx Flow of Hydrogen (mol/h)
E2
E1 = 100 L3 L5 = 95 X Stream number
L2
H3 H5 = 95 R Rate of reaction (mol/h)

4
E4
L4

DOF Separator unknowns = 5 (E3 L3 H3 E4 L4 )

component bal = 3 (E L H)
other = 2 (ethane split, ethylene split)
DOF =0 can be solved
Dehyrogenation of ethane
General Mass Balance (GMB):
Accumulation = Input – Output + Generation – Consumption

Assumptions: Steady state, no reaction

Simplified GMB: 0 = Input – Output

Separator Balances:
E: 0 = E3 – 5 – E4
L: 0 = L3 - 95 - L4
H: 0 = H3 - 95
Other: E5 = 5 = 0.015 * E3
L4 = 0.05 * L3
Solving:
H3 = 95 mol/h
E3 = 333 mol/h
E4 = 328 mol/h
L3 = 100 mol/h
L4 = 5 mol/h
 Dehydrogenation of Ethane

Legend
Ex Flow of Ethane (mol/h)
Ethane 1 2 Reactor 3 5 Lx Flow of Ethylene (mol/h)
Separator
Mixer R = 95 mol E3 = 333 E5 = 5 Hx Flow of Hydrogen (mol/h)
E2 X Stream number
E1 = 100 L3 = 100 L5 = 95
L2 R Rate of reaction (mol/h)
H3 = 95 H5 = 95

4
E4 = 328
L4 = 5

DOF Mixer unknowns = 2 (E2 L2)

component bal = 2 (E L)
DOF =0 can be solved

Balances:
E2 = 100 + 328 = 428 mol/h
L2 = 5 mol/h
 Dehydrogenation of Ethane

Legend
Ex Flow of Ethane (mol/h)
Ethane 1 2 Reactor 3 5 Lx Flow of Ethylene (mol/h)
Separator
Mixer R = 5 mol E3 = 333 E5 = 5 mol Hx Flow of Hydrogen (mol/h)
E2 = 428
E1 = 100 mol L3 = 100 L5 = 95 mol X Stream number
L2 = 5
H3 = 95 H5 = 95 mol R Rate of reaction (mol/h)

4
E4 = 328
L4 = 5

Answers
Composition of product: 2.6 mole% ethane, 48.7 mol% ethylene and 48.7 mol% hydrogen

Recycle ratio: 328/100 = 3.33 mol recycle/ mol feed

Single pass conversion: (428 – 333)/ 428 = 0.22 or 22%

Q4. Production of Nitric Oxide

Ammonia is burned to form nitric oxide in the following reaction:

4NH3 + 5O2  4NO + 6H2O

a) Calculate the ratio (lb mole O2 react/ lb mole NO formed)

b) If ammonia is fed to a continuous reactor at a rate of 100 kmol NH3/h, what oxygen feed rate
(kmol/h) would correspond to 40% excess O2?

c) If 50 kg of ammonia and 100 kg of oxygen are fed to a batch reactor, determine the limiting
reactant, the percentage by which the other reactant is in excess, and the extent of reaction (mol)
and mass of NO produced (kg) if the reaction proceeds to completion.
 Nitric Oxide - solution
Ammonia is burned to form nitric oxide in the following reaction

4NH3 + 5O2 →4NO + 6H2O

a) Calculate the ratio (lb-mole O2/lb-mole NO formed).

b) If ammonia is fed to a continuous reactor at a rate of 100 kmol NH3/h, what oxygen feed rate (kmol/h) would
correspond to 40% excess O2?
Nitric Oxide - solution
Ammonia is burned to form nitric oxide in the following reaction

4NH3 + 5O2 →4NO + 6H2O

a) If 50 kg ammonia and 100kg oxygen are fed to a batch reactor, determine the limiting reactant, the percentage by
which the other reactant is in excess, and the extent of reaction (mol) and mass of NO produced (kg) if the reaction
proceeds to completion.
Q5. Pentane combustion – single unit, single reaction
n-Pentane is burned with excess air in a continuous combustion chamber.

C5H12 + 8O2 → 6 H2O + 5 CO2

σ1x = -1 -8 6 5
A technician runs an analysis and reports that the product gas contains 0.27
mole% pentane, 5.3% oxygen, 9.1% carbon dioxide and the balance nitrogen
(on a dry basis).

a) Assume 100 mol of dry product gas as a basis of calculation, draw and label
a flowchart, perform a degrees of freedom analysis (based on component
balances) and show that the system has -1 degree of freedom. Comment on
this result.

b) Relax one piece of data for product composition and use mass balances to
prove that the reported percentages could not possibly be correct.

c) Using the calculated values from b) determine percentage excess air fed to
the reactor and the fractional conversion of pentane.
a) Fully labelled flowsheet and DOF
Note: this flowsheet presents the molar flow of each component

Legend
P1 Px = Pentane mole flow stream x
P3 = 0.27 mol
Reactor Ox = Oxygen mole flow stream x
O3 = 5.3 mol Nx = Nitrogen mole flow stream x
O2 R
N3 = 85.33 mol Cx = CO2 mole flow stream x
Wx = Water mole flow stream x
N2 C3 = 9.1 mol
R = Extent of reaction mol
W3

Degrees of Freedom
Unknowns: 5 (P1 O2 N2 W3 R)
Independent Balance Equations: -5 (P, O, N, C, W)
Composition Equations: -1 (Composition of Air: N2 = 3.76 O2)

DOF = -1 Overspecified, so no unique solution

Does the Data Conflict?
 b) Relax one constraint e.g. the mol frac CO2 in flue

P1
P3 = 0.27 mol
Reactor Legend
O3 = 5.3 mol
Px = Pentane mole flow stream x
O2 R
N3 = 85.33 mol Ox = Oxygen mole flow stream x
N2 C3 Nx = Nitrogen mole flow stream x
Cx = CO2 mole flow stream x
W3
Degrees of Freedom Wx = Water mole flow stream x

Unknowns: 6 (P1 O2 N2 W3 C3 R) R = Extent of reaction mol

Independent Balance Equations: -5 (P, O, N, C, W)

Composition Equations: -1 (Composition of Air: N2 = 3.76 O2)

DOF = 0 We have relaxed 1 constraint – now solve!

 General mass balance and assumptions

P1
Reactor R P3 = 0.27 mol
O3 = 5.3 mol
N3 = 85.33 mol
O2
C3
N2
W3

C5H12 + 8O2 → 6 H2O + 5 CO2 R

σ1x = -1 -8 6 5
General mass balance:
Accumulation = Input – Output + Generation – Consumption

Assumptions:
Steady state, so accum = 0
One reaction only

Simplified mass balance:

0 = Input – Output + Rσ
 Solve the balances

C5H12 + 8O2 → 6 H2O + 5 CO2

σ1x = -1 -8 6 5
0 = In – Out + σ R

Nitrogen Balance: 0 = N2 – N3 + 0R Water Balance: 0 = 0 – W3 + (6)R

0 = N2 – 85.33 mol 0 = 0 mol – W3 + (6)2.17 mol
N2 = 85.33 mol W3 = 13 mol

Air Ratio: N2 = 3.76 O2 CO2 Balance: 0 = 0 – C3 + (5)R

85.33 mol = 3.76 O2 0 = 0 mol – C3 + (5)2.17 mol
O2 = 22.7 mol C3 = 10.85 mol

Oxygen Balance: 0 = O2 – O3 + (-8)R

0 = 22.7 mol – 5.3 mol – 8R
R = 2.17 mol Note C3 = 10.85 mol ≠ 9.1 mol
Pentane Balance: 0 = P1 – P3 + (-1)R
0 = P1 – 0.27 mol + (-1)2.17 mol
P1 = 2.44 mol
c) Pentane combustion
Calculate Excess Air:

𝑂1 − 8(𝑃1 ) 22.7 𝑚𝑜𝑙 −19.52 𝑚𝑜𝑙

% Excess Oxygen = (𝐴𝑐𝑡𝑢𝑎𝑙 − 𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙)/ 𝑇ℎ𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 =
𝑂1
=
19.52 𝑚𝑜𝑙
= 16%

Fractional Conversion of Pentane:

In – Out 𝑃1 −𝑃3 2.44 𝑚𝑜𝑙 −0.27 𝑚𝑜𝑙

Conversion Fraction = = = = 0.89
In 𝑃1 2.44 𝑚𝑜𝑙