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Suggestion: Start using the second approach immediately, even on the simple problems, so that youll be
used to it when the problems start getting harder (which they will very soon). This handout guides you
through the basics of that approach. We also suggest that you read through pp. 4-1 to 4-6 of the Student
Workbook. If you follow all the guidelines laid out in those pages, it may not guarantee a good grade in
the course but it will increase the odds significantly.
The labeled flow chart of the process described in the first paragraph might appear as follows:
m 2 (kg/h)
0.95 kg B/kg
0.05 kg T/kg
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Copyright Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Semi-batch process: Neither batch nor continuous; e.g. allow contents of gas tank to escape;
slowly blend liquids in a tank from which nothing is withdrawn
Balance equation
We can write a balance on any quantity entering or leaving a system mass, moles, energy, people:
(a)
Input
What
comes
in across
system
boundary
Generation
What is
produced
within the
system
(reaction)
I+GOC=A
Output
What
leaves
across
system
boundary
(4.2-1)
Consumption
What is
consumed
within the
system
(reaction)
Accumulation
Change in amount
contained in the system
Simplifications
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
(kg/s) denote the unknown mass flow rate of the stream. The labeling would then be
Suppose we let m
m (kg/s)
0.85 kg CH4/kg
0.15 kg C2H6/kg
The stream is now completely labeled, since we can express the mass flow rates of methane and ethane in
terms of what is written on the chart:
Methane flow rate: m CH 4 (kg CH 4 /s) = _____________________
Ethane flow rate: m C2 H 6 (kg C 2 H 6 /s) = _____________________
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
You may label either a total flow rate (or amount) and component mass or mole fractions, or
individual component flow rates (amounts).
m(kg)
x1 (kg NaCl/kg)
x2 (kg KCl/kg)
(1 x1 x2 )(kg H 2 O/kg)
OR
m1 (kg NaCl)
m2 (kg KCl)
m3 (kg H 2 O)
Once you have one, you can always calculate the other:
In terms of m, x1, and x2, m1 = _____________________________
In terms of m1, m2, and m3, m = _______________ and x1 = __________________________
Label in the way that builds in given information about the stream. (For instance, if you know
or can easily calculate either a total flow rate or values of component mass or mole fractions,
label the total and fractions; otherwise label individual component flow rates or amounts
(likely to get easier algebra that way).
Suppose you know that a gas stream containing sulfur dioxide and air (21 mole% O2, 79%
N2) flows at a rate of 125 mol/s. The stream might be labeled
125 mol/s
x (mol SO2 / mol)
(1-x) (mol air/mol)
0.21 mol O2/mol air
0.79 mol N2/mol air
__________________________________
__________________________________
If volumes or volumetric flow rates of streams are either given or required, include labels
both for them and for mass or molar quantities.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
O2 (g)
Air
0.21 mol O2/mol
0.79 mol N2/mol
Evaporator
Completely label the flow chart (including the molar flow rate of the liquid water stream),
following the rules given above.
Evaporator
0.015 mol H2O(v)/mol
0.21 mol O2/mol
0.79 mol N2/mol
20.0 cm3 H2O(l)/min
Convince yourself that your labeling is complete. (For example, what is the flow rate of oxygen
in the outlet stream in terms of labeled values and variable names.)
Basis of Calculation and Flowchart Scaling. At least one stream quantity or flow rate (mass, moles,
volume) should be specified before any calculations are done. If the problem statement doesnt do it, you
should choose a convenient basis (an amount of a stream with known composition.) Having degrees of
freedom = 1 is often a reminder that you must choose a basis.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Mixer
m2 (g)
0.60 g E/g
0.40 g W/g
m3 (g)
0.35 g E/g
0.65 g W/g
Solution: The problem statement does not specify a stream amount or flow rate. There is enough
information to calculate the required stream ratio without specifying one, but arbitrarily choosing a basis
of calculation (an amount or flow rate of one of the streams) makes the required math easier. We might
proceed as follows:
Basis of calculation: 100 g of Stream 1 (m1 = 100 g):
100 g
0.30 g E/g
0.70 g W/g
Mixer
m2 (g)
0.60 g E/g
0.40 g W/g
m3 (g)
0.35 g E/g
0.65 g W/g
We could then write balance equations on ethanol and water, solve for m1 and m2, and determine the
requested ratio as 100/m2. The same result would be obtained if we chose any other basis of calculation:
the values of m1 and m2 might be different, but the ratio would be the same.
Read Section 4.3b to see how to scale a flow chart from one basis to another, and work through the
Test Yourself on p. 95.
DF = 0 number of equations equals number of unknowns can solve for all unknowns
DF > 0 (more unknowns than equations) either youve overlooked some equations, problem is
underspecified, or you can solve for all requested quantities without knowing all the unknowns.
DF < 0 (more equations than unknowns) either flowchart is not fully labeled or problem is
overspecified.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
____ unknowns
- ____ independent equations
-----------------------------____ DOF
x + y = 10
xy=0
____ unknowns
- ____ independent equations
-----------------------------____ DOF
x + y = 10
2x + 2y = 20
____ unknowns
- ____independent equations
-----------------------------____ DOF
x + y = 10
xy=0
xy = 3
____ unknowns
- ____independent equations
-----------------------------____ DOF
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
For a non-reactive process, the number of independent material balance equations equals the number
of independent species involved in the process.
Independent molecular species: We discussed this in the context of how many balances we can do
around a process. If two molecular species are in the same ratio everywhere in the process and the
ratio is incorporated in the flowchart labeling, the species are not independent, and neither are
balances on them.
100 mol CH4/s
n1 (mol air/s)
Gas blender
n2 (mol/s)
x1 (mol CH 4 / mol)
(1 x1 )(mol air / mol)
0.21 mol O 2 / mol air
Looks like 3 unknowns 3 equations (balances on CH4, O2, N2) = 0 D.F., but it wont work. Write
balances on O2 & N2 & see what happens.
O2 balance:
N2 balance:
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
0.95 kg B/kg
0.05 kg T/kg
__ unknowns
__ balances
1 ___________________
1 ___________________
= 0 DOF
(_______, ________)
Since the problem is solvable, we may proceed to write out the equations. All balances have the form
(_________).
Feed density: m 1
2000 L _____________ kg
m 1 (kg/h) (2000)(0.872)
h
L
(1)
8%: m B 3 _____________________
(2)
Mass balance: m 1 m 2 m B 3 m T 3
(3)
(4)
Either do the algebra and arithmetic manually (easy in this problem, not so easy in problems to come) or
use Excels APEx or Solver to calculate the unknown quantities.
Equations:
m1 = 2000*0.872
mB3 = 0.08*m1*0.45
m1 = m2 + mB3 + mT3
m1*0.45 = m2*0.95 + mB3
m 1 1744
kg
h
, m 2 760
kg
h
B 3 =62.8
, m
kg B
h
T 3 =921
, m
kg T
m B 3
m
kg B
kg overhead
= 0.0638
xB
, ROF 2 0.436
kg
kg feed
m B 3 m T 3
m 1
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Scale the flow chart: Now suppose we are asked to calculate the volumetric feed rate needed to produce
2500 lbm/day of overhead product. The scale factor (see Example 4.3-2) is the desired value of the
specified quantity (overhead product rate = 2500 lbm/day) divided by the value of the same quantity
corresponding to the original basis of calculation (= 760 kg/h).
2500 lb m /day
lb /day
3.29 m
760 kg/h
kg/h
lb /day
kg
3 lb m feed
(m 1 )new (m 1 )old SF 1744 3.29 m
5.74 10
h
kg/h
day
Work through Problem 4.11 in the Student Workbook. Follow every step. Fill in the blanks yourself,
then check the solutions.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Weve looked at processes represented by single boxesmixer, distillation column. Think about plants
youve seen from the highwayall those towers & stacks & pipes running all over the place.
How do you analyze something like that?
Overall system: large box around system enclosing all units, recycle & bypass streams. Subsystems:
individual units or combinations of units, stream mixing points & stream splitting points. DOF
analyses as with single units.
Go through Ex. 4.4-2 on your own or in groups. If you just read it you think you get it but you dont.
Ask questions about each step, dont go on until you can answer it.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Solution. First, fully label the chart and mark systems about which balances might be written.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Degree-of-freedom analysis:
Overall system:
Mixing point:
_______ Unknowns:
_______ Unknowns:
=
_______ Degrees of freedom
Unit 1:
_______ Unknowns:
_______ Unknowns:
=
_______ Degrees of freedom
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Overall balance of A:
Balance of A on Unit 1:
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
100 kg A/min
100 kg B/min
Dump
90 kg A/min
Whats wrong with this picture? How would you redraw it to be more cost efficient and environmentally
conscious?
Notes:
Real reaction and real separation are always less than perfect. There is always some
unreacted raw material, and some unwanted material in the product.
Recycling is not free (requires pumping, pipes, etc.) but is only a one-time cost and usually
pays for itself quickly
Reasons to recycle:
o Recovering a catalyst
o Diluting a process stream
o Controlling a process variable
o Circulating a working fluid
o Increasing the overall percent conversion of a reaction
Sometimes a stream might bypass a process unit, where a fraction of the stream is diverted around the
unit and combined with the output stream. This allows us to vary the composition and properties of the
product stream. A stream that bypasses a unit introduces a splitting point in which a stream is split into
two streams.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
100 mol/s
0.70 mol A/mol
0.30 mol B/mol
60 mol/s
x1 (mol A/mol)
(1 x1 )(mol B/mol)
m 2 (mol/s)
x2 (mol A/mol)
(1 x2 )(mol B/mol)
Do a degree-of-freedom analysis:
Did you get 1 DOF? Wrong. If all were doing is splitting a stream, the compositions of the outlet
streams must be the same as that of the feed stream.
OK, so heres the revised flow chart.
100 mol/s
60 mol/s
Q: Why?
A: Because # balances = # independent species, which A and B are not in this case. Try writing the
possible balances
Mass Balance:
A Balance:
B Balance:
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Forty-five hundred kilograms per hour of a solution that is one-third K2CrO4 by mass is joined
by a recycle stream containing 36.4% K2CrO4, and the combined stream is fed into an
evaporator. The concentrated stream leaving the evaporator contains 49.4% K2CrO4; this stream
is fed into a crystallizer in which it is cooled (causing crystals of K2CrO4 to come out of solution)
and then filtered. The filter cake consists of K2CrO4 crystals and a solution that contains 36.4%
K2CrO4 by mass; the crystals account for 95% of the total mass of the filter cake. The solution
that passes through the filter, also 36.4% K2CrO4, is the recycle stream.
1. Calculate the rate of evaporation, the rate of production of crystalline K2CrO4, the feed rates
that the evaporator and the crystallizer must be designed to handle, and the recycle ratio
(mass of recycle)/(mass of fresh feed)
2. Suppose that the filtrate were discarded instead of being recycled. Calculate the production
rate of crystals. What are the benefits and costs of the recycling?
Solution.
1. First, fully label the chart and mark systems about which balances might be written.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Degree-of-freedom analysis:
Overall system:
_______ Unknowns:
_______ Unknowns:
=
_______ Degrees of freedom
Evaporator:
Crystallizer/filter:
_______ Unknowns:
_______ Unknowns:
=
_______ Degrees of freedom
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
95% specification:
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
2SO2 + O2 2SO3
The stoichiometric coefficients define conversion factors from moles of one species consumed or
formed in the reaction to moles of another species consumed or formed. For instant, if 50 mol/s of
SO3 are produced in the reaction
oxygen consumed
Feed reactants in stoichiometric proportion (e.g., 2 mol SO2/1 mol O2) all reactants run out at the
same time. What if theyre not in stoichiometric proportion?
2SO2 + O2 2SO3 (Sulfuric acid production, acid rain)
n1 (mol SO3/s)
n2 (mol SO2/s)
n3 (mol O2/s)
Limiting reactant: reactant that runs out first, fed in less than stoichiometric proportion to all other
reactants. In example, SO2 limits. (Stoichiometric proportion = 2 SO2 : 1 O2, actual feed proportion =
10 SO2 : 9 O2)
Excess reactants: all other reactants but limiting one. In example, O2 is in excess.
Theoretical (stoichiometric) requirement of an excess reactant: How much would be required to react
completely with the limiting reactant.
Theoretical oxygen =
90 mol O 2 50 mol O 2
100% 80% excess O 2 (=80%XS air if O2 comes from air)
50 mol O 2
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Suppose you are told that oxygen is now fed in 60% excess (instead of at a rate of 90 mol/s). Then
(nO2 )fed (nO2 ) theoretical (nO2 )excess ( nO2 ) theoretical 0.60( nO2 ) theoretical
( nO2 ) theoretical (1 0.60) 1.60 (50 mol O 2 /s) 80 mol O 2 /s
% XS
or in general, if A is fed in excess, (n A )fed (n A ) theoretical 1
100
Note: The theoretical and excess quantities depend only on the feed amounts and the stoichiometric
reaction, not on what actually happens in the reactor.
mole fed
moles in
2SO2 + O2 2SO3
80(mol SO3/s)
20 mol SO2/s
50 mol O2/s
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
n1 (mol N2)
n2 (mol H2)
n3 (mol NH3)
200 mol N2
300 mol H2
____________________________________________________
Now suppose the percentage conversion of nitrogen is 25%
(d) n1 = _____________________ , n2 = _____________________ , n3 = _________________
(e) The percentage conversion of hydrogen is ________________
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
We have three unknowns and three species ( 3 balances), so it looks like we should have zero
degrees of freedom. We dont, howeverno matter how hard you try, you cant calculate any of
those unknown variables without getting more information. Try using 0 = In-Out+Gen-Con
Independent reactions (Section 4.7b). Chemical reactions are not independent if we can get one in
terms of the other by adding, subtracting, and multiplying them.
AB
2A 2B
(1)
(2)
A 2B
BC
(1)
(2)
A 2C
(3)
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
SO 2 balance : I G O C A C I O 80
mol SO 2 consumed
s
SO 3 balance : I G O C A O G
n1
80 mol SO 2 consumed
_____
mol SO3
s
O 2 balance : I G O C A O I C
n3 90
mol O 2
s
80 mol SO 2 consumed
50 mol O 2 / s
The original system must therefore have had ________ degree(s) of freedom.
2
2
1
where (mol/s) is the extent of reaction (same for all species, must be positive). It follows that
ni nio i (Batch)
ni nio i (Continuous, steady - state)
(4.6-3)
where i is the stoichiometric coefficient of species i (+ for products, for reactants). One of these
equations may be written for every independent molecular species involved in the process. For
nonreactive species ( = 0), the equation reduces to ni nio ).
Q: What is ?
A. Its a dummy variable that reflects how far each reaction proceeds. It reflects the stoichiometry
of the reaction and helps us keep up with generation and consumption.
2SO2 + O2 2SO3
n1 (mol SO3/s)
20 mol SO2/s
n3 (mol O2/s)
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
DOF = #unknowns (2) #extent of reaction equations (3) #other equations (0)
+ #independent reactions(1) = 0
Apply extent of reaction equation ( ni nio i ), starting with the species we know most about:
SO2: 20 mol/s = 100 mol/s 2 = 40 mol/s
O2: n3 = ___________________________________________= 50 mol O2/s
SO3: n1 = __________________________________________ = 80 mol SO3/s
Instead of writing balances on the molecular species involved in the process (SO2, O2, SO3), lets do it
on the atomic species (S, O). Since atomic species are neither generated or consumed (except in
nuclear reactions, which we dont consider), all balances reduce to I = O.
With atomic species balances,
DOF = #unknowns (2) #independent atomic balances (2) #other equations (0)
S balance :
100 mol SO 2
___ mol S
1 mol SO 2
20 mol SO 2
___ mol S
1 mol SO 2
90 mol O 2
___ mol O
1 mol O 2
n1 (mol SO3 )
___ mol S
1 mol SO3
n1 80 mol SO3 / s
O balance :
100 mol SO 2
___ mol O
1 mol SO 2
n1 (mol SO3 )
___ mol O
1 mol SO3
+
n3 50 mol O 2 / s
Independent atomic species: If two atomic species are in the same ratio everywhere in the process,
they are not independent. Look at TY #1 on P. 128.
Q: How many independent atomic balances are there?
A: Two. Write balances on C and H and see what happens.
For more practice, do the Test Yourself on p. 119.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Atomic species
balances
Extents of
reaction
#DF
(# unknowns on chart)
+ (# independent reactions)
(# independent molecular species balancesa)
(# other equations)
(# unknowns on chart)
-- (# independent atomic species balancesb)
(# other equations)
(# unknowns on chart)
+ [# independent reactions: (1 per reaction)]
(# independent species balancesa)
(# other equations)
If two molecular species are in the same ratio everywhere in the process
and the ratio is incorporated in the flowchart labeling, the species are not
independent
b
If two atomic species are in the same ratio everywhere in the process,
they are not independent
DOF: If youre confident about independence of atomic species, use the atomic species balance
approach, & if youre more confident about independence of reactions, use the extent of reaction
approach. Note that all DOF approaches should give the same answer, so if youre unsure, use
more than one to confirm.
Balances:
Dont use molecular species balances for reactive species (especially for multiple reactions
it gets hairy fast)
Hand calculationsatomic balances
Solver or chemical equilibriumextents of reaction. (Be sure reactions are independent)
Note: You can use one method for the DOF analysis & another for the calculations.
Work through Example 4.7-1 on p. 131. If you fully understand the solution, you can solve any
single-unit reactive balance problem you are likely to encounter on homework and tests.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
If you are given an initial composition of a mixture of A, B, and C and an expression for the equilibrium
constant K(T), and you are told that the reaction proceeds to equilibrium at a final temperature T, you can
calculate the final composition using extents of reaction. See Example 4.6-2 for an illustration.
Multiple reactions (4.6d)
C2H6 C2H4 + H2
The second and third reactions both consume ethylene and so are undesired. Sometimes byproducts
can be sold, and at other times they are worthless and possibly hazardous and have to be disposed of
(another cost).
Yield = mole of desired product / [moles that would have been formed if there were no side reactions
and the reaction went to completion (the limited reactant was completely consumed)]
If yield and selectivity are high, then we have successfully suppressed the undesired reactions.
Note: in the ethylene example, H2 is not an undesired byproduct. An undesired byproduct is the
result of a competing reaction that results in less of the desired product.
A 2B + C
BD
B: Desired product, D: Unwanted byproduct
20 mol A
120 mol B
80 mol C
40 mol D
100 mol A
Maximum possible B produced = _______ mol (All A fed reacts, no side reaction)
Yield (Eq. 4.6-4): YB = _____________________
Selectivity B/D (Eq. 4.6-5): SBD = _____________________________________
A process engineer might take two different approaches to this reaction system:
Maximize yield: Get most B you can, even if it means producing more D.
Maximize selectivity: Hold down production of D, even if it means producing less B.
Q: Why would you want to suppress production of a byproduct if it means getting less of the product
youre selling? (Think of several possible reasons.)
A:
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Batch:
ni ni 0
ij
ij
Cont., St.State: ni ni 0
(4.6-6)
Recall is positive for products, negative for reactants, and ZERO for inerts (N2, etc.) that go
through the process without reacting.
Example:
A 2B + C
BD
[Rxn 1]
[Rxn 2]
A1 = 1, B1 = +2, C1 = +1
B2 = 1, D2 = +1
(All others = 0)
n A
n B
n C
n D
(mol A/s)
(mol B/s)
(mol C/s)
(mol D/s)
nI (mol I/s)
n A 100 1 ,
nB ____________________, nC ____________________
nD ____________________,
nI ____________________
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Single pass conversion: based on what goes into and comes out of the reactor. In this case
it is 75%.
A fed to reactor A leaving reactor
Single-pass conversion of A =
A fed to reactor
=
Overall conversion: Based on what comes in and out of the overall process.
Overall conversion of A =
Note: only 10% of the propane entering the reactor is converted to propylene in a single pass.
99% of the unconsumed propane is recovered in the separation unit and recycled back, where it
gets another chance to react. Net result = 95% of propane entering the process is converted to
propylene and 5% leaves with final product.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
(b) Purge
Inert gases (e.g. nitrogen, argon) are used in processes because they undergo chemical reactions
under given conditions
Using an inert gas in a system prevents undesirable chemical reactions from occurring (e.g. oxidation,
hydrolysis, combustion)
Purging with nitrogen minimizes fire hazards of residual solvents or process fluids
If an inert gas is introduced to the system and it doesnt react, it has to exit the system somewhere
otherwise, it builds up and would shut down the process
Look at Fig. 4.7-2 on p. 138production of ethylene oxide from ethylene. N2 is an inert. How did it
get in the process?
Purge stream: note it also contains ethylene and O2. Why are we throwing away product and
reactant?
Note there is a cost to discard. But there is also a cost to separate and recycle the last little bit. Gas
separation is hard and expensive. Engineers must evaluate the options based on economics,
environmental regulations, etc. Note that purge stream take-off is a splitter (we can only write one
balance one equation in the DOF).
Work through Example 4.7-3. If you understand Example 4.7-3, you know how to do recycle
problems, which are the hardest problems to solve. The key is flowcharting & systematic DOF
analysis.
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
20
95
940
70
10
160
mol CH4/s
mol O2/s
mol N2/s
mol CO2/s
mol CO/s
mol H2O/s
A1: 2CH4 +
O2 CO + CO2 + 4H2O
WRONG! If that really were the reaction, what would the ratio of CO to CO2 in the product be?
A2:
3
2
O2 CO + 2H2O
Theoretical air
%XS air
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Richard M. Felder, Lisa G. Bullard, and Michael D. Dickey (2014)
Q: What about the fact that not all the methane reacted and some CO was formed?
A: Doesnt matterby definition, the percent excess air is based on complete combustion.
Q: What are the wet-basis and dry-basis compositions of the product gas?
A: Wet: (20+95+940+70+10+160) = 1295 mol/s, xCH 4
20 mol CH 4 / s
mol CH 4
, etc.
0.0154
1295 mol/s
mol
20 mol CH 4 / s
mol CH 4
, etc.
0.0176
1135 mol/s
mol
Most material balance problems on combustion reactors are no different from those on any other
reactor. Go through Example 4.8-3 for an illustration.
Sometimes composition of fuel may be unknown, but if you know the atomic constituents of the fuel
you can determine their ratio. Example 4.8-4 illustrates such a computation.
Read Section 4.9. It outlines the differences between this course and the real world.
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