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Material Balances Without Chemical Reaction
Material Balances Without Chemical Reaction
Material Balances Without Chemical Reaction
without chemical
reactions
Objectives
• Classify processes as batch, semibatch,
continuous, transient, and steady-state.
• Draw and label process flowcharts.
• Select a calculation basis.
• Perform a degree of freedom analysis.
• Define/solve equations to calculate process
variables.
Process Classification
• Batch process
No mass crosses system boundaries between
the time feed is charged and the time product
is removed.
Typically used for making small quantities,
particularly those products of manufacture.
• Continuous process
Feeds and effluents continuously flow across
the system boundary through the duration of
the process.
Suited for the production of large quantities.
• Semibatch process
Any process that is neither batch nor
Process Operation
• Steady state
There is no change in the value of all process
variables (temperature, pressure, flowrates,
heat-transfer rates) except for minor
flucctuations about the mean value.
Continuous processes may be steady-state.
• Transient (Unsteady-State)
The values of process variables change with
time.
Batch and semibatch process are transient by
nature.
Continuous processes may be transient.
The General Balance
Equation
•Consider the following continuous process
unit for which methane is a component of
both the input and output, but the
measured methane inlet and outlet mass
flowrates are not the same.
A = -22,000 P/yr
accumulation
input = output
Continuous steady-state
system
•Benzene/Toluene distillation
continuous process
steady-state operation
no reactions occurring
input = output
Continuous steady-state
system
input = output
• Benzene balance
500 kg B/h = 450 kg B/h + m2
m2 = 50 kg B/h
• Toluene balance
500 kg T/h = m1 + 475 kg T/h
m1 = 25 kg T/h
• Total mass balance
1000 = 450 + m1 + m2 + 475 (all with units of
kg/h)
1000 kg/h = 1000 kg/h ✓
Integral Balances on Batch
Processes
consider the reaction N2 + H2 → NH3 in a
batch reactor
at t=0, there is n0 moles of NH3 in the reactor
at t=tf, there is nf moles of NH3 in the reactor
between 0 and tf, no NH3 crosses system
boundary
NH3 accumulation in system from 0 to tf is ∴ nf
– n0 .
• therefore, for a batch process,
accumulation = final output – initial input
= generation – consumption
⇒ initial input + generation = final output +
Batch Mixing Process
Balance
• Two methanol-water
mixtures are contained
in flasks of amounts and
concentrations shown.
• If the flasks are mixed, what is the mass
and concentration of the resulting
product?
no reactions, ∴ generation = consumption = 0
input = output
Batch Mixing Process
Balance
•Total Mass Balance
200 g + 150 g = m = 350 g
• Methanol balance
0.400 g CH3OH 0.700 g CH3OH
x g CH3OH
200g
g
150g
g
mg
g
g CH3OH
x 0.529
g
• Water balance
200(0.6) + 150(0.3) = 350(1-0.529)
165 g H2O = 165 g H2O ✓
Integral Balances on
Semibatch and Continous
Processes
• Air is bubbled through a drum of liquid
hexane.
• Gas stream leaving contains air and
hexane.
• How long does it take to vaporize 10.0 m3
of liquid?
Integral Balances on
Semibatch and Continous
Processes
• differential air balance
input output
kmol air 0.900 kmol air kmol
0.100 n
min kmol min
kmol
n 0.111
min
Integral Balances on
Semibatch and Continous
Processes
• integral hexane balance
accumulation input generation output consumption
accumulation output
30.659kg 103 L 1kmol
accumulation n 10.0m 3
L m 86.2kg
accumulation n 76.45 kmol C6 H14
output 0.100nt1 0.100 0.111 kmol t1
min
t1 6880 min
Process Flowcharts
• A process flowchart is a method for
organizing information about a process in
a format that permits convenient and easy
to understand.
• A process flowchart uses boxes and lines
with arrows to represent inputs and
outputs of a process.
Labeling Process
Flowcharts
1. Write the values of all known stream
variables on the locations of the streams
on the chart.
400 mol/h
0.21 mol O2/mol
0.79 mol N2/mol
320°C, 1.4 atm
water balance:
molH2O mol 0.15molH2O
2
n n3
min min mol
molH2O mol 0.15molH2O mol
1 .11 n
3 n
3 74.1
min min mol min
Air Humidification and
Oxygenation
1 60.8mol
n min
Air Humidification and
Oxygenation
nitrogen balance:
n 1 mol
min 0 .79 molN
2
mol n 3 0.985 y mol
molN
2
y 0.337mol
O2
mol
Flowchart Scaling
• A kilogram of benzene is mixed with a
kilogram of toluene. The output of this
process is 2 kilograms of a mixture that is
50% mass of each component.
• Balances:
m2 = 250 kg
= 250 kg NaOH
Balances on a mixing unit
6. Total mass balance (INPUT = OUTPUT):
100 kg + m1 = m2 =250 kg
m1 = 150 kg
= 250 kg
= 150 kg
Balances on a mixing unit
7. Diluent water volume:
V1 = 150 L
= 250 kg
= 150 kg
= 150 L
Balances on a mixing unit
7. Ratios:
= 150 kg
= 150 L
Degree of Freedom Analysis
• Process used to determine if a material
balance problems has sufficient
specifications to be solved.
a) draw and completely label the flowchart
b) count the unknown variables on the chart
c) count the independent equations relating
these variables
d) calculate degrees of freedom by subtracting
(b) from (c)
1. basis is given as a
volumetric quantity
3 m
m B3 m
T3
xB m 3 ; xT 1 xB
B3 m
Distillation Column
example
• Ex. 4.3-5
4. Convert mixed units in overhead product stream
95.0kmolB 78.11kmol
kgB
B 7420kgB
5.0kmolT 92.13kmol
kgT
T 461 kgT
7420kgB 461kgT 7881kgmixture
yB2 7420kgB 7881kgmixture 0.942kgkgB
yT2 1 0.942 0.058kgT
kg
Distillation Column
example
• Ex. 4.3-5
5. Perform degree of freedom analysis
=0.94
2 =0.05
8
4 unknowns
-2 material balances
-1 density relationship
-1 process specification
0 degrees of freedom
Distillation Column
example 6. Write system equations iv. total mass balance (check)
• Ex. 4.3-57. Solve 1 m
m 2 m
B3 m
T3
h 1744h
1744kg kg
=766 kg/h
=0.94
2 =0.05
=1744 kg/h 8
yB3 m 3 62.8kghB
B3 m h 0.064kg
978kg kgB
=62.8 kg B/h
3 62.8 kghB 915kghT 978kg
m h =915 kg T/h
Balances on Multiple Unit
Ops
•A system is any portion of a process that
can be enclosed within a hypothetical box
(boundary). It may be the entire process,
a single unit, or a point where streams
converge or combine.
Balances on Multiple Unit
Ops
•Boundary A encloses the entire process.
inputs: Streams 1, 2, and 3
products: 1, 2, and 3
Balances on A would be considered overall
balances
internal streams would not be included in
balances
Balances on Multiple Unit
Ops
• B: an internal mixing point (2 inputs, 1
product)
• C: Unit 1 (1 input, 2 products)
• D: an internal splitting point (1 input, 2
products)
• E: Unit 2 (2 inputs, 1 product)
Balances on Multiple Unit
Ops
•The procedure for solving material
balances on multi-unit processes is the
same as for a single unit; though, it may
be necessary to perform balances on
several process subsystems to get enough
equations to determine all unknown
stream variables.
Two-Unit Process Example
• Variables for Streams 1, 2, and 3 are
unknown
Two-Unit Process Example
• Variables for Streams 1, 2, and 3 are
unknown
• Label unknown stream variables
Two-Unit Process Example
• Degree-of-freedom analysis
overall system: 2 unknowns – 2 balances = 0 (find m 3,
x 3)
mixer: 4 unknowns – 2 balances = 2
Unit 1: 2 unknowns – 2 balances = 0 (find m 1, x1)
mixer: 2 unknowns – 2 balances = 0 (find m2, x2)
Extraction-Distillation
Process
Extraction-Distillation
Process
Simultaneously solve
total mass and acetone
balances to determine m1
and m3.
underspecified
Extraction-Distillation
Process
underspecified
Recycle
• It is seldom cost effective to waste
reactant fed that does not react to
product. More often, this material is
separated (recovered), and recycled
(returned to its point of origin for reuse).
Balances on an Air
Conditioner
• process cools and dehumidifies feed air
• unknowns: n1, n2, n3, n4, n5 (requested by
problem)
• degree-of-freedom analysis critical to
solution
basis
Balances on an Air
Conditioner
•Overall system
ndf = 2 variables (n1, n3) – 2 balances = 0
Balances on an Air
Conditioner
•Mixer
ndf = 2 variables (n2, n5) – 2 balances = 0
Balances on an Air
Conditioner
•Cooler
ndf = 2 variables (n2, n4) – 2 balances = 0
Balances on an Air
Conditioner
•Splitter
ndf = 2 variables (n4, n5) – 1 balances = 1
• only 1 independent balance can be written on the
splitter because the streams entering/leaving have
the same composition.
Balances on an Air
Conditioner n n n
• overall mole balance 1 5 2
• water balance 0.04n1 0.017n5 0.023n2
n2 392.5mol; n5 290mol
solved simultaneously:
Reasons to recycle
• recover catalyst
typically most expensive chemical constituent
• dilute a process stream
reduce slurry concentration
• control a process variable
control heat produced by highly exothermic
reaction
• circulation of a working fluid
refrigerant
Evaporative Crystallization
Process
•Calculate:
rate of evaporation
rate of production of crystalline K2CrO4
feed rates to evaporator and crystallizer
recycle ratio (mass or recycle/mass of fresh
feed)
Evaporative Crystallization
Process
•Overall system:
ndf = 3 unknowns (m2, m4, m5) – 2 balances – 1
spec = 0
specification: m4 is 95% of total filter cake
mass
4 0.95 m
m 5
4 m
Evaporative Crystallization
Process
•Feed/recycle mixer:
ndf = 3 unknowns (m6, m1, x1) – 2 balances = 1
underspecified
4 0.95 m
m 5
4 m
Evaporative Crystallization
Process
•Evaporator:
ndf = 3 unknowns (m3, m1, x1) – 2 balances = 1
underspecified
4 0.95 m
m 5
4 m
Evaporative Crystallization
Process
•Crystallizer:
ndf = 2 unknowns (m3, m6) – 2 balances = 0
solvable
Once m3, m6 are known, mixer or evaporator
balances can be solved.
4 0.95 m
m 5
4 m
Evaporative Crystallization
Process
•Overall system:
solve simultaneously for m and m 4 5
4 1470kgKcrystals
m h
5 77.5kgsolution
m h
0.364kgK/kgsolu
0.636kgW/kgsolu
Evaporative Crystallization
Process
•Overall system:
solve for m with knowns m and m 2 4 5
4 1470kgKcrystals
m h
5 77.5kgsolution
m h
0.364kgK/kgsolu
0.636kgW/kgsolu
Evaporative Crystallization
Process
•Overall system:
only 3 equations are independent
K2CrO4 balance 0.333 4500 kghK m
4 0.364m
5
water balance 0.667 4500 kghK m
2 0.636m
5
total mass balance 4500kgh m2 m4 m5
specification m 2950
2
kgH2O
h
4 0.95 m
m 4 m 5
4 1470kgKcrystals
m h
5 77.5kgsolution
m h
0.364kgK/kgsolu
0.636kgW/kgsolu
Evaporative Crystallization
Process
•Crystallizer:
solve simultaneously for m and m 3 6
3 7200kg
m 4 1470kgKcrystals
m h
h
5 77.5kgsolution
m h
0.364kgK/kgsolu
6 5650kg
m h
0.636kgW/kgsolu
Evaporative Crystallization
Process
•feed/recycle mixer:
total mass balance 4500kg
h m
6 m
1 m
1 kg
10150
h
1 10150
m kg
h 3 7200kg
m 4 1470kgKcrystals
m h
h
5 77.5kgsolution
m h
0.364kgK/kgsolu
6 5650kg
m h
0.636kgW/kgsolu
Evaporative Crystallization
Process
•If recycle is not used,
crystal production is 622 kg/h vs 1470 kg/h (w/
recycle)
discarded filtrate (m4) is 2380 kg/h,
representing 866 kg/h of potassium chromate
• What are cost consequences of using
recycle vs not?
Bypass Stream
• Similar to a recycle, but a fraction of a
stream is diverted around a process unit,
rather than being returned to it.
• Calculation approach is identical.
Balances on Reactive
Systems
•Material balance no longer takes the form
INPUT = OUTPUT
n A stoich
5 4
A + 2B → 2C
4
0.25
Limiting and Excess
Reactants
• fractional conversion (f) – ratio of the
amount of a reactant reacted, to the
amount fed. f
nA
reacted
nA
fed
A + 2B → 2C
0 0
fA 0.0 f B 0.0
5 8
Limiting and Excess
Reactants
• fractional conversion (f) – ratio of the
amount of a reactant reacted, to the
amount fed. f
nA
reacted
nA
fed
A + 2B → 2C
1 4
fA 0.2 f B 0.25
5 8
Limiting and Excess
Reactants
• fractional conversion (f) – ratio of the
amount of a reactant reacted, to the
amount fed. f
nA
reacted
nA
fed
A + 2B → 2C
2 4
fA 0.4 f B 0.5
5 8
Limiting and Excess
Reactants
• fractional conversion (f) – ratio of the
amount of a reactant reacted, to the
amount fed. f
nA
reacted
nA
fed
A + 2B → 2C
3 6
fA 0.6 f B 0.75
5 8
Limiting and Excess
Reactants
• fractional conversion (f) – ratio of the
amount of a reactant reacted, to the
amount fed. f
nA
reacted
nA
fed
A + 2B → 2C
4 8
fA 0.8 f B 1.0
5 8
Extent of Reaction
• extent of reaction (ξ) – an extensive
quantity describing the progress of a
chemical reaction .
n i ν n– i0stoichiometric
i coefficients: νA= -1,
0 νB = -2, νC =
2
A + 2B → 2C
n A n A0 n B n B0 2 nC nC0 2
Extent of Reaction
• extent of reaction (ξ) – an extensive
quantity describing the progress of a
chemical reaction .
n i ν n– i0stoichiometric
i coefficients: νA= -1,
0 νB = -2, νC =
2
A + 2B → 2C
nA 5 5 n B 8 2 8 nC 0 2 0
Extent of Reaction
• extent of reaction (ξ) – an extensive
quantity describing the progress of a
chemical reaction .
n i ν n– i0stoichiometric
i coefficients: νA =-1,
1 νB = -2, νC =
2
A + 2B → 2C
nA 5 4 n B 8 2 6 nC 0 2 2
Extent of Reaction
• extent of reaction (ξ) – an extensive
quantity describing the progress of a
chemical reaction .
n i ν n– i0stoichiometric
i coefficients: νA= -1,
2 νB = -2, νC =
2
A + 2B → 2C
nA 5 3 n B 8 2 4 nC 0 2 4
Extent of Reaction
• extent of reaction (ξ) – an extensive
quantity describing the progress of a
chemical reaction .
n i ν n– i0stoichiometric
i coefficients: νA= -1,
3 νB = -2, νC =
2
A + 2B → 2C
nA 5 2 n B 8 2 2 nC 0 2 6
Extent of Reaction
• extent of reaction (ξ) – an extensive
quantity describing the progress of a
chemical reaction .
n i ν n– i0stoichiometric
i coefficients: νA= -1,
4 νB = -2, νC =
2
A + 2B → 2C
nA 5 1 n B 8 2 0 nC 0 2 8
2C2 H 4 O2 2C2 H 4O
• Assume an equimolar reactant feed of 100
kmol:
What is the limiting reactant?
What is the percentage excess of each reactant?
If the reaction proceeds to completion: (a) how
much of the excess reactant will be left? (b) How
much C2H4O will be formed? (c) What is the
extent of reaction?
If the reaction proceeds to a point where the
fractional conversion of the limiting reactant is
50%, how much of each reactant and product is
present at the end? What is ξ?
If the reaction proceeds to a point where 60 mol
Reaction Stoichiometry
• Acrylonitrile produced by reaction of
ammonia, propylene, and O2 at 30%
limiting
conversion
C H NH of 3 limiting reactant:
O C H N 3H O
3 6 3 2 3 3 3 2
nNH 3
nC H 3
stoich
1 1 1
6
nO 2
nC H 0.780 0.21 100 0.100 100 1.64
3 0 6
nO 2
nC H
3 stoich6
1.5 1 1.5
Reaction Stoichiometry
• Acrylonitrile produced by reaction of
ammonia, propylene, and O2 at 30%
limiting f 0.20 f 0.093
conversion
C H NH of
XS
3 limiting reactant:
XS
O C H N 3H O
3 6 3 2 3 3 3 2
determine fractional excesses
1 mol NH 3
stoich
n NH 3 10.0 mol C3 H6
1 mol C 3 H 6
10.0 mol NH 3
NH NH
f XS NH NH 3
3 0 3 stoich
12.010.0 0.20
10.0
3 stoich
O O
XS O
f
2
O
2 0
2 stoich
16.415.0
15.0
2 stoich
0.093
Reaction Stoichiometry
• Acrylonitrile produced by reaction of
ammonia, propylene, and O2 at 30%
limiting f 0.20 f 0.093
conversion
C H NH of
XS
3 limiting reactant:
XS
O C H N 3H O
3 6 3 2 3 3 3 2
nC 3 H 6 1 f nC 3 H 6 0 1 0.3010.0 mol C3H6 7.0 mol C3 H6
use fractional
conversion to
determine amount of
propylene that leaves
the reactor
Reaction Stoichiometry
• Acrylonitrile produced by reaction of
ammonia, propylene, and O2 at 30%
limiting f 0.20 f 0.093
conversion
C3 H6 NH3 of
XS
3 limiting reactant:
XS
O C3 H3 N 3H2O n i n i0 i
2 3
determine extent of
nC 3 H 6 7.0 mol C3 H 6 3 mol reaction by applying
mole balance to
propylene
nC 3 H 6 nC 3 H 6 0 1
7.0 mol 10.0 mol
3 mol
Reaction Stoichiometry
• Acrylonitrile produced by reaction of
ammonia, propylene, and O2 at 30%
limiting f 0.20 what use are these calculated values?
f 0.093
conversion 3of limiting reactant:
XS XS
C H NH O C H N 3H O n i n i0 i
3 6 3 2 2 3 3 2
1 2 yCOyH O
nCO2 0.667 ni
2
yi
nH2 0.667 2 1 2 ntotal
ntotal 3 2 2 2 2 ni ni0 i
0.667mol
1 2 yCOyH O
yCO2 0.667/ 3 0.222 ni
2
yi
yH2 0.667/ 3 0.222 2 1 2 ntotal
ntotal 3 2 2 2 2 ni ni0 i
0.667mol
molesdesired
productformed
y
selectivit
molesundesired
productformed
Multiple Reactions
• 100 moles A fed to a batch reactor
• product composition: 10 mol A, 160 B, 10
C A 2B
What is A C
1. fA?
100 10
2. YB? fA 0.9
3. SB/C? 100
4. ξ1, ξ2
Multiple Reactions
• 100 moles A fed to a batch reactor
• product composition: 10 mol A, 160 B, 10
C A 2B
What is A C
1. fA?
160
2. YB? YB 0.889
3. SB/C? 100 10 21
4. ξ1, ξ2
Multiple Reactions
• 100 moles A fed to a batch reactor
• product composition: 10 mol A, 160 B, 10
C A 2B
What is A C
1. fA?
160
2. YB? SB/ C 16
3. SB/C? 10
4. ξ1, ξ2
Multiple Reactions
• 100 moles A fed to a batch reactor
• product composition: 10 mol A, 160 B, 10
C A 2B
What is A C
1. fA? nB nBo B11 nA nAo A11 A22
2. YB? 160 0 21 10 100 1 2
3. SB/C? 1 80 2 90 1 10
4. ξ1, ξ2
Balances on Reactive
Processes
• Continuous, steady-state dehydrogenation
of ethane
• Total mass balance still has INPUT =
OUTPUT form
• Molecular balances contain
consumption/generation
• Atomic balances (H and C) also have
C2H6 C2H4 H2
simple form
Balances on Reactive
Processes
• Continuous, steady-state dehydrogenation
of ethane
• First consider molecular balances:
1000 kmolC2H6
min n
1 40 kmolH2
min 1kmolC2H6
1kmolH2
kmolC2H6
1 60
n min
Molecular Species Balances
C2H6 C2H4 H2
at steady state
2 40
n kmolH2
min 1kmolC2H4
1kmolH2
kmolC2H4
2 40
n min
Atomic Species Balance
C2H6 C2H4 H2
100kmolC2H4
min 2kmolC
1kmolC2H6 n 2kmolC
1 1kmolC2H6 n 2kmolC
2 1kmolC2H4
100kmol n
1 n
2
Atomic Species Balance
C2H6 C2H4 H2
100kmolC2H4
min 6kmolH
1kmolC2H6 40kmolH2
min 2kmolH
1kmolH2
n 6kmolH
1 1kmolC2H6 n 4kmolH
2 1kmolC2H4
600kmol 80kmol+6n
1 4n
2
Atomic Species Balance
C2H6 C2H4 H2
Solve simultaneously
C: 100kmol n
1 n
2
H: 600kmol 80kmol+6n 1 4n
2
1 60kmolC2H6 / min
n
2 40kmolC2H4 / min
n
Extent of Reaction
• The 3rd method by which to determine
molar flows in a reactive system is using
expressions for each species flow rate in
ni ni 0 ij j
terms of extents of reaction (ξ).
j
ndf = 5 unknowns
+ 2 independent reactions
- 5 expressions for ξ (CH4, O2, CO, CO2,
H2O)
- 1 nonreactive species balance (N2)
- 1 specified methane conversion
=0
Incomplete Combustion of
CH4
CH
CH4 1 0.900 0.0780
n 4 conversion molCH
mol 100mol 0.780molCH
specification:
4
4
Incomplete Combustion of
CH4
nCO nCO 0 1 2
nCO 8nCO 2
2
2 2
nH O 21 22
nH O nH O 0 2 1 2 2
2
2 2 nO 19.4 3 1 22
nO nO 0 2 1 2 2
2 2
3
2 2
Product Separation and
Recycle
•Two definitions of reactant conversion
are used in the analysis of chemical
reactors with product separation and
recycle of unconsumed reactants.
overall inputtoprocess
- outputfromprocess
reactant
conversion inputtoprocess
overall inputtoprocess
- outputfromprocess
reactant
conversion inputtoprocess
overall 75molA/min- 0
100% 100%
conversion 75molA/min
Catalytic Propane
Dehydrogenation 95% overall
conversion
Overall
Process
ndf = 3 unknowns (n6, n7, n8)
– 2 independent atomic balances (C and H)
– 1 relation (overall conversion)
=0
consider n6, n7, n8 known for further DOF analyses
Catalytic Propane
Dehydrogenation
ndf = 2
95% overall
conversion
Mixing
point
ndf = 4 unknowns (n9, n10, n1, n2)
– 2 balances (C3H8 and C3H6)
=2
Catalytic Propane
Dehydrogenation
ndf = 2
ndf = 3
95% overall
conversion
reactor
separator
overall
conversion
relationship
n6 5 molC3H8
overall
C atomic balance
100mol 1mol
3molC
CH
3 8
5mol
C H 3molC
3 8 1molC H
3 8
n7 1molC H
3molC
3 6
n7 95molC3H6
Catalytic Propane
Dehydrogenation 95% overall
conversion
n6 5 molC3H8
n7 95molC3H6
overall
H atomic balance
100mol 1mol
8molH
CH 5mol C3 8 1molC H
H 8molH
6molH
CH
3 6
n 2molH
2
n8 95molH2
Catalytic Propane
Dehydrogenation 95% overall
conversion
n6 5 molC3H8
n7 95molC3H6
n8 95molH2
C3H8 C3H6 H2
separator
given relations
n3 900molC3H8 n6 5 molC3H8
n7 95molC3H6
n8 95molH2
C3H8 C3H6 H2
separator
propane balance
n10 4.75 mol C
3H6
n3 n6 n9 n9 895mol C
3H8
Catalytic Propane
Dehydrogenation 95% overall
conversion
n3 900molC3H8 n6 5 molC3H8
n7 95molC3H6
n8 95molH2
C3H8 C3H6 H2
mixer
n9 895mol C3H8 propane balance
n10 4.75 mol C
3H6
Catalytic Propane
Dehydrogenation 95% overall
conversion
mixer
n9 895mol C3H8 propylene balance
n10 4.75 mol C
3H6
Catalytic Propane
Dehydrogenation 95% overall
conversion
reactor
n9 895mol C3H8 C atomic balance
n10 4.75 mol C
3H6
3molC
CH n 3molC
3 8 3 6
n4 99.75molC3H6
Catalytic Propane
Dehydrogenation 95% overall
conversion
reactor
n9 895mol C3H8 H atomic balance
n10 4.75 mol C
3H6
8molH
CH 99.75
3 8
mol C H 6molH
3 6 1molC H n 2molH
3 6 2
n5 95molH2
Catalytic Propane
Dehydrogenation 95% overall
conversion
single-pass
n9 895mol C3H8
n10 4.75 mol C
3H6 conversion
fsinglepass
995molC3H8 900molC3H8
100% 9.55%
995molC3H8
Catalytic Propane
Dehydrogenation fsinglepass 9.55% 95% overall
conversion
n1 995mol C n3 900molC3H8 n6 5 molC3H8
3H8
n4 99.75molC3H6 n7 95molC3H6
n2 4.75 mol C
3H6
n5 95molH2 n8 95molH2
C3H8 C3H6 H2
recycle
n9 895mol C3H8
n10 4.75 mol C
3H6 ratio
Methanol Synthesis
• ndf = 7 unknowns (n0, x0C, np, x5C, x5H, n3,
n4) + 1 rxn
- 5 independent species balances =
3
fsinglepass 60%
CO2 3H2 CH3OHH2O
Methanol Synthesis
• ndf = 4 unknowns (n1, n2, n3, n4) + 1 rxn
– 4 independent species balances
– 1 single pass conversion = 0
fsinglepass 60%
CO2 3H2 CH3OHH2O
Methanol Synthesis
• ndf = 3 unknowns (n5, x5C, X5H)
– 3 independent species balances
=0
fsinglepass 60%
CO2 3H2 CH3OHH2O
Methanol Synthesis
• ndf = 3 unknowns (n0, x0C, nr)
– 3 independent species balances
=0
fsinglepass 60%
CO2 3H2 CH3OHH2O
Methanol Synthesis
investigate
• ndf = 1 unknowns (np) mole balances and
their solution in
– 1 independent species balance
the text
=0
fsinglepass 60%
CO2 3H2 CH3OHH2O
Combustion Reactions
• Combustion - rapid reaction of a fuel with
oxygen.
• Valuable class of reactions due to the
tremendous amount of heat liberated,
subsequently used to produce steam used
to drive turbines which generates most of
the world’s electrical power.
• Common fuels used in power plants:
coal
fuel oil (high MW hydrocarbons)
gaseous fuel (natural gas)
liquified petroleum gas (propane and/or
Combustion Chemistry
• When a fuel is burned
C forms CO2 (complete) or CO (partial
combustion)
H forms H2O
S forms SO2
N forms NO2 (above 1800°C)
• Air is used as the source of oxygen. DRY
usually safe to assume:
air analysis: 79 mol% N2
78.03 mol% N2 21 mol% O2
20.99 mol% O2
0.94 mol% Ar
0.03 mol% CO2
Combustion Chemistry
• Stack (flue) gas – product gas that leaves
a furnace.
• Composition analysis:
wet basis – water is included in mole fractions
dry basis – does not include water in mole
fractions
• Stack gas contains (mol) on a wet basis:
60.0% N2, 15.0% CO2, 10.0% O2, 15.0% H2O
Dry basis analysis:
• 60/(60+15+10) = 0.706 mol N2/mol
• 15/(60+15+10) = 0.176 mol CO2/mol
• 10/(60+15+10) = 0.118 mol O2/mol
Combustion Chemistry
• Stack gas contains (mol) on a dry basis:
65% N2, 14% CO2, 10% O2, 11% CO
xH2O = 0.0700 (humidity measurement)
lbmolH2O lbmoldry gas lbmolH2O
0.0700 0.9300 0.0753
Wet basis analysis: lb wet gas lb wet gas lb dry gas
Theoretical and Excess Air
• The less expensive reactant is commonly
fed in excess of stoichiometric ratio
relative to the more valuable reactant,
thereby increasing conversion of the more
expensive reactant at the expense of
increased use of excess reactant.
• In a combustion reaction, the less
expensive reactant is oxygen, obtained
from the air. Conseqently, air is fed in
excess to the fuel.
Theoretical and Excess Air
• Theoretical oxygen is the exact amount of
O2 needed to completely combust the fuel
to CO2 and H2O.
• Theoretical air is that amount of air that
contains the amount of theoretical oxygen.
• Excess air is the amount by which the air
fed to the reactor exceeds the theoretical
air. moles air fed
- moles air theoretical
% excess air
= 100%
moles air theoretical
Theoretical and Excess Air
C4H10 13O2 4CO2 5H2O
2
6.5molO2
nO2 theoretica
100molC4H10
hr
650
molO2
molC4H10 hr
l
50003094
% excess air 100% 61.6%
3094
Combustion Reactors
• Procedure for writing/solving material
balances for a combustion reactor
1. When you draw and label the flowchart, be
sure the outlet stream (the stack gas)
includes
a. unreacted fuel (unless the fuel is completely
consumed)
b. unreacted oxygen
c. water and carbon dioxide (and CO if combustion is
incomplete)
d. nitrogen (if air is used as the oxygen source)
2. Calculate the O2 feed rate from the specifed
percent excess oxygen or air
3. If multiple reactions, use atomic balances
Combustion of Ethane
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2
degree-of-freedom
analysis
fC2H6 = 0.9
ndf = 7 unknowns
- 3 atomic balances
- 1 nitrogen balance
- 1 excess air specification
- 1 ethane conversion specification
- 1 CO/CO2 ratio specification
=0
Combustion of Ethane
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2
excess air
specification
fC2H6 = 0.9
100molC2H6 3.5molO2
nO2 theoretica 350molO2
molC2H6
l
0.21n0 1.5 350molO2
n0 2500molair
Combustion of Ethane
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2
ethane
conversion
fC2H6 = 0.9
specification
n0 2500mol air
CO/CO2 ratio
specification
fC2H6 = 0.9
n0 2500mol air
2molCOgen
n4 0.25 0.9 100molC2H6 45.0molCO
1molC2H6 react
Combustion of Ethane
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2 n1 10.0 mol C
2H6
nitrogen
balance
fC2H6 = 0.9
n4 45.0 mol C
O
n0 2500mol air
atomic C
n3 1975mol N
balance
fC2H6 = 0.9
2
n4 45.0 mol C
O
n0 2500mol air
100molC2H6 1mol
2molC
CH
2 6
n1 2molC
1molC H n4
2 6
1molC
1molCO n5 1molCO
1molC
2
n5 135molCO2
Combustion of Ethane
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2 n1 10.0 mol C
2H6
atomic H
n3 1975mol N
balance
fC2H6 = 0.9
2
n4 45.0 mol C
O
n5 135mol CO2
n0 2500mol air
100molC2H6 1mol
6molH
CH
2 6
10mol
C 2H6 6molH
1molC H n6 1molH O
2molH
2 6 2
n6 270molH2O
Combustion of Ethane
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2 n1 10.0 mol C
2H6
atomic O
n3 1975mol N
balance
fC2H6 = 0.9
2
n4 45.0 mol C
O
n5 135mol CO2
n0 2500mol air n6 270molH2O
ethane burned forms CO
25% of the
525molO2 12mol
molO
O n 2molO
2 1molO 45molCO 1molCO
1molO
molO 1molO
2 2
n2 232molO2
Combustion of Ethane
C2H6 7 O2 2CO2 3H2O
2
C2H6 5 O2 2CO3H2O
2 n1 10.0 mol C
2H6
n2 232mol O
stack gas 2
n3 1975mol N
composition
fC2H6 = 0.9
2
n4 45.0 mol C
O
(dry basis) n5 135mol CO2
n0 2500mol air n6 270molH2O
ethane burned forms CO
25% of the
sum102321974 45135 2396
270mol H2O
y1 10 2396 0.00417molC2H6 mol
2396mol dry stack gas
y2 2322396 0.0970molO2 mol
mol H2O
y3 19742396 0.824molN2 mol 0.113
mol dry stack gas
y4 45 2396 0.019molCOmol
y5 1352396 0.0563molCO2 mol