CHAPTER 11

MATERIAL BALANCE
PROBLEMS INVOLVING
MULTIPLE UNITS
Your objectives in studying this
chapter are to be able to:
1. Write a set 01 independent material balances lor a process involving
more than one uni!.
2. Solve problems involving several serially connected units.
If you h ave drive n past a n industrial plant, power station, or waste disposal fa-c ility,
you must have noticed how complex the equipment is . Such plants involve a
large number of interconnect e d processing units. Base d on what you have learned in
Chapters 6--10, are yo u now prepared to solve problems involving an entire plant? Ir
not, s tudy this c hapter to find out what to do .
Looking Ahead
In this chapter we are go ing to discuss how to treat and solve material balance
problems for sy st e ms of serially coupled units . You will be pleased to learn that
principies employed in previous chapters still apply. AH you have to do is apply
them to individual s ubsy s tem s aml/or lo the overall system.
Main Concepts
There are nine and sixty ways 01 constru cting triballa ys,
and every one of them is ri g h l.
Kipling
30S
306 Material Balance Problems Involving Multiple Units Chapo 11
A process flowsheet (flowchart) is a graphical representation of a process. A
flowsheet describes the actual process in sufficient detail Ihar you can use it to formulate material (and energy) balances. Flowsheets are also used for troubleshooting,
control of operating conditions, and optimization of process perfonnance. You will
find that flowsheets are also prepared to represent proposed processes Ihat involve
new techniques or modifications of existing processes.
Figure 11 . 1 is a picture of a seclion of a plan\. Figure 11 .2a is a f10wsheet of
the process indicating the equipment sequence and the flow of materials .
Figure 11 . 2b is a block diagram corresponding to Figure 11.2a. The units ap-pear as
simple boxes called subsystems rather than as the more elaborate portraya!
in Figure 11.2a. You shou ld note that the operations of mixing and splitting are
cIearly denoted by boxes in Figure 11 .2b, whereas Ihe same functions appear only as
intersecting lines in Figure 11.2a.
Figure 11 .3a iIlustrates a serial combination of mixing and splitting stages .
In a mixer, two or more entering streams of different compositions are com-bined. In a
splitter, two or more streams exit, all of which have he same campasi-tion. In a
separator, the exit streams can be of different compositions.
Figure 11 .2 (a) A owsheet of the ammonia plant that neludes major pieces of
equipment and the materials flow . (b ) Block dia gram of the nformation flow corresponding to Figure 11 .
2a .
Examine Figure 11.3a. Which streams must have the sarne composition? Is Ihe
composition ,of sl'eam 5 Ihe sa mio as Ihe composition inside Ihe unit represented by
!: lhe oo,,? It ,W;ill be Ihe same if Ihe contents of the unit are well mixed, the usual as
-

" sqmption in tmUex!. It no reaction takes place in lhe unit , Ihe output composition in
stream 5 is Ihe properly weighted average of the input compositions 3 and 4 . Do 308
Material Balance Problems Involving Multiple Units Chap. 11
6 Figure 11 .3. Serial mixing and
splitting in a system without reaction.
Streams 1 plus 2 mix to form Stream 3.
7
and Stream 5 is spUt into Streams 6 and
7.
streams 5, 6, and 7 have Ihe same composition? Yes, because streams 6 and 7 flow
from a splitter fed by stream 5 .
How many material balances can you formulate for Ihe Ihree proces s units
shown in Figure 11.3a? First, yo u can make overall material balances, namely balances on a system Ihat ineludes al! of the units wilhin Ihe boundary denoted by the
dashed line shown as 1 in Figure 11.3b. In addition, you can make balances on each
of Ihe Ihree units Ihat make up Ihe overall process, 'as denoted by Ihe bound a ries defined by Ihe dashed Iines n, m, and IV in Figure II.3c. Final!y, you can make balances about combinations of two or more units simultaneously, as indicated by th e
boundaries defined by Ihe dashed Iine s V, VI, and VII i n Figure s 11.3d tol1.3f , respectively.
You can c onelude for Ihe three process unit s shown in Figure II.3a Ihat you
can make material balances on seven different systems. The important question is:
How many independent material balance equations can be written for Ihe process?
In general, you can write an ndependent material balance equatlon for each
component present in each unit or subsystem except for splitters_ For splitters,
Figure U.3b The dashed line I
designates the boundlll)' for overall
material balances made on the process
i n Figure 11 .38.
Chap. 11
1
Malerial Balance Problems Involving Mulliple Unils 309
6 Figure 1l . 3c Dashed Iine s n, m, and
IV designate the boundaries foc
material balances around each of the in-dividual units comprising the overall
process,
only one independent mass balance equation can be written regardless of tbe
number of components present in the streams.
As an example, le!' s count Ihe material balances that might be made for the
process shown in Figure 11.3a. For the process shown in Figure 11.3a, assume that 3
components are present in the mixer, and four components present in the unit por-trayed
by the box. How many independent material balances can you wrile for Ihe
process with these assumptions? Did you gel 8? Here is the coun!: mixer: 3, box: 4 ,
splitter: 1, for a total of 8. Next, how many different material balances can you write
in total for Ihe process including both independent and dependent equations. You
can make fiye oyerall balances (one for each component and the total balance) plus a
total of 14 material balances for single units and 15 material balances for pairs of
units . Therefore, you can write a total of 34 material balances of which only 8 are independen!.

For this example , which 8 of the 34 possible material balance equations should
you select? Certainly yon shonld select 3D independent set of equations. As an ex-ample
of what not to do , do not select a component balance for a particular compo -4
6 Figure 11.3d The dashed line V
designates the boundary for material
balances around a system comprised of
the mixing point plus the unit portrayed
by the box.
Material Balance Problems Involving Multiple Units
Figure lJ.3e The dashed line VI
de signales the boundary for material
balances about a system comprised of
the unit portrayed by lh e box plus Ihe
sp litter .
nent for each of lhe individual units in lhe proces s pl us an overall balance for lhe
same componen!. This sel of equations would nol be independenl because, as you
know, lhe overaU balance for each species is jusllhe s um of lhe respective s pecies
balances for lhe individua l uni!. As anolher examp le, don'l use malerial balances for
lhe lotal f10w eilher overall or for an individual unil togelher Wilh aU of lhe respec
-tive species balances for lhe syslem.
Whal s trategy s ho uld you use 10 se lecl lhe particular unit or s ubsy s lem with .
which to start formulating your independent equations fo r a process comprised of a
sequence of connected unils ? A good, but time-consuming , way to decide is to determine lhe degrees of freedom for various subsystems (s ingle units or combinations of
units) selected by inspection. A subsys lem with zero degrees of freedom is a good
starting poin!. Frequently, lhe best way to start is to make material balances for the
overall proc ess, ignoring information about lhe intemal connections. If you ignore
all of lhe intemal streams and variab l es within a set of connected subsystems, you can
treat lhe overall system exactly as you treated a single system in ehapters 7 lhrough
10 by drawing a boundary about the emire set of subsystems as in Figure 11.3b
Figure 1I.3r The dashed line VII
designates the boundary for material
balances about a system comprised of
the mixer plus the spliUer.
Material Balance Problems Involving Multiple Units
EXAMPLE 11.1 Determinadon oC the Number of Independent
Material Balances in a Process with Multiple UnUs
Examine Figure E 11.1. No reac lion lake s place. The syslem is open and s leady
state. The arrows designate flows. The composition of each stream is as follows:
Figure Ell.!
Whal is Ibe maximum Dumber of independenl mass balances Ibal can be gen-eraled lo
solve Ihis problem? Wrile down Ihe possible equalions. Do Ibey form a
unique se t?
Solution
Selecl each of Ihe three units as a syslem. Wilb respecl lo Ibe malerial bal-ances for Ibe
individual unils, you can make 9 species equalions as follows for Ibe
Ibree units (ignoring any 10lal balances for Ibe 3 units, plus overall species and lotal
balance, plus balances for combinalions of units):
However, nol all of Ibe balances are independen!. In Ibe following Iisl, all of Ibe
known concentrations have beco inserted, and F represents the strearn flow desig-

noled by Ibe superscrip!.

If you take as a basis FI = lOO, seven values of pi are unknown, henee only
seven independent equations need to be written. Can you recognize by inspection
that among the entire set Df 9 equations two are redundant. and hence a unique solu
tion can be obtained u s ing 7 independent equations?
If you so lved tbe 9 equations se quentially starting witb Equation (a) and ending witb Equation (i), along tbe way you would notiee tbat Equation ( d) is redundant with Equation (e) and Equation (h) is redundant witb Equation (g). The redundaney of Equations (e) and (d) becomes apparent if you recall tbat tbe suro of tbe
rnass fracHoos in a streaffi is unity, hence ao implicit relation exists between Equations (e) and ( d) so that they are not independent. Why are Equations (g) and (h) not
independent?
If you inspeet the set of Equations (a) tbrough (i) froro tbe viewpoint of solving tbem sequentially, you will find that eaeh one can be solved for one variable.
Look at tbe foll owing lis!:
If you entered Equations (a) through (i) into a software prograrn tb.t solves
equations, you would receive ao error natice of sorne type because they are 001 an
independent set of equations.
Material Balance Problems Involving Multiple Units
"lfthefreshfacrs which come ro our kn o wledge allfir rhemselves inro rhe scheme.
(hen our hypothesis may gradually become a solucion . "
Sherlock Holmes in Sir Arthur Conan Doyle's The Complete Sherlock
Ha/mes, 'The Adventure of Wisteria Lodge"
If you make one oc more component material balances around the combination
of subsystems 1 plus 11, or 11 plus III or 1 plus III in Example !l.!, or around the entire set of three units, no additional independent material balances will be generated .
Can you substitute one of the indicated alternative mass balances for an independent
species mass balance? Yes (as long as the precision of the balance is about the
same) , unless it causes the equation set to be no longer independent.
In calculating the degrees of freedom for problems involving multiple units,
you must be careful to involve only independent material balances and not miss any
essential unknowns. AH the same principies apply to processes with multiple units
that were discussed in Chapters 7 through lO . Table 11.1 is a simplified checklist to
help keep in mind possible unknowns and equations for a process.
Formal preparation of the entries in such a li s t will help you to identify which
variables and equations to employ in solving for the unknowns, and, of course, to
ensure that the degrees of freedom are zero before starting to solve the set of equaTABLE 11.1 Cheddisl ofVarlables and Equatlons lo Conslder
in a Degree-of-Freedom AnaIysis
Variables
F10w variables :
Species (or total flow) entering and leaving for each subsystem
Species (or total flow) entering and Jeaving the overalI system
Reaclion variables:
Extent s of reactiaD (if aoy) in the mini mal set for each subsystem
Equations
Basis for each suhsystem or the overall system
Material balances (species or element):
For each species or elernent (or their total) in each subsystem
Por each species or elernent (or their total) in the overall syste~

Specifications (for each sub system and overall)

Specified composilion s
Specified flow rates
Specified tlow ratios
Specified conversions or extents of reaction
Splitter restrictions
Implicit equations (sum of mole or mass fractions)
Material Balance Problems Involving Multiple Units Chapo 11
tions. ehapter 30 is a detailed diseussion of detennining me degrees of freedom for
a camplieated proeess.
The so/u/ion goes onfamously; bU! JUSI as we have
gol rid o/ Ihe other unknowns. behold! V disappears
as well, and we are left with Ihe indisputable bul
irrilating conclusion
0=0
This is a favorite devi ce ~hat mathematical equations
resort lo, when we propound stupid questions.
Sir Arthur Eddington
Frequently Asked Questions
l. In earrying out a degree-of-freedom analysis. do you bave to inelude at tbe start of
tbe
analysis every ane of the variables and equations that are nvolved in the entire proces
s?
No. What you do is pick a system for analysis. and then you have to take ioto account only the unknowns and equations pertaining to the streams cut by the system
boundary (plus those inside !he system if it is an unsteady state system). For example,
note in Example 11 . 1 that e.eh subsystem w.s treated independently. If you b.d pieked
as
the system the eombin.tion of .11 tbree of!he unit s. then only the variables and
equations
pertaining to stre.ms 1,2, 4,6,7, and 8 would be involved in the analysis.
2. Should you use e le rnent material balances or species material balances in solving
prob-lems that involve multiple unts?
For processes thal do nol involve reaction, use species balances. Element balances
wiU involve redundancy and prove to be quite inefficient. For processes that do involve
reaetion , if you are given the reaerion equations and nformalion lhat will enable you
lo
ealculate th e extent of reaet ion , species balances are easy to use. (If you are nol
specifi-cally given the re actio n equations, sometimes you can formulate them ba s ed
on your ex-perience, s ueb as e buming witb 0 2 to yield e0
2
.) Otherwise use elemenl balances. Just
make sure lhat they are ndependent equations. .
3. D o you have to understand the details of !he elements of equipment in a plant in
order to
make material balances?
No. Collections of elements comprising a unit of equipment can be deemed to be
[he system . rn fa e t , lhe balances do not have 10 represenl any specific physical
elernent of

a unir. For convenience in analysis, a hypothetical system may be designated that has
no
corresponding phy s ical presence. For example, the reactor in Figure 11.2a rnight be
repre-sented as a connected se quence of hypothetical individual reaction systems even
though
the nside of the reactor form s a continuous bed of catalysl.
Material Balance Problems Involving Multiple Units 315 /
We next look at some examples of making and solving material balances for
systems composed of multiple units.
Example 11.2 Material Balances for Multiple Units
in Which No Reaction Occurs
Acetone is used in the manufacture of many chemicals and also as a solvent,
In its latter role, many restrictions are placed 00 the reIease of acetone vapor to the
en'(ironment. You are asked to design an aceto~e recovery system having the flow-sheet
illustrated in Figure E 11.2 , AII lhe concentrations shown in EII.2 of balh lhe
gases and liquids are specified in weighl percenl in this speeial case to niake the calculatiaos simpler. Calculate, A, F, W, B, and D per haur. G = 1400 kg/llr.
Solution
This is an open. steady - state process without reaction . Three subsystems
exist.
Steps 1, 2, 3, and 4
AH the stream compositions are given. AH of the unknown stream flows are
desigoated by letter symbols in the figure.
Step 5
Piek 1 hr as a basis so that G = 1400 kg.
Steps 6 and 7
We could stan the analysis of the degrees of freedom with overall balances ,
but since the subsystems are connecte<! serially, we will stan the analysis with the
absorber column, Unit 1, and then proceed to Unit 2, and then to Unit 3.
Unir J (Absorber)
Variables: 16
W, G, F , A (4 tlow strearns); species mass fractions in each s!rearn = 3
so that 3 x 4 = 12 more variables
Equations: 16
Basis: G
Species material balances: 3 (one for each species)
Specifications: 12
Implicit equations (such as:; "'i = 1): all redundant given the specifications
Degrees of freedom: O
Before proceeding to calculate the degrees of freedom for Unit 2 (the distlla-tion
column), you should note the complete lack of information about the properties
of the stream going from the distillation column to Unit 3 (the condenser). In gen-eral it
is best that you avoid making material balances on systems thal nelude 5uch
streams. as they contain no useful information. Thus, the next system and degree-of
-freedom analysis we select will be for the system composed of Units 2 and 3
combined.
Units 2 and 3 (Distillation Column plus Condenser)
Variables : 9
F, D. B (3 streams); ~pecies mass fractions in each stream ::; 2 so lhat
2 X 3 = 6 more variables

Equations: 9
Species material balances: 2 (one for each species)
Implicit equations: al! redundant
F is detennined by tirst solving lbe equations for Unit 1
(the Absorber)
Degrees of freedom : O if F is known ; 1 otherwise
What would happen if a eorreet analysis of lbe degrees of freedom for a sub-system
gave + I? Then you would hope lbat lbe value for one of lbe unknowns in
the subsystem eould be determined from anolber subsystem in lbe overall system .
In faet, for lbis Example, if you started lbe analysis of lbe degrees of freedom wilb
the eombined Ults 2 plus 3, you would obtain a value of + 1 because lbe value of F
would not be known prior to solving lbe equations for Unit 1.
Step8
Tbe mass balances for Unit I afier introduetion of lbe basis and olber speciti-cations are
as follows:
In
OUI
Air:
(Check to make sore lbat the equations are independen!.)
Step9
Solve Equations (a), (b), and (e) via Polymalb to get
A = 1336.7 kgIhr
B = 221.05 kglhr
e = 157.7 kglhr
Step 10
Step8
Tbe mass balances for lbe eombined Units 2 plus 3 are:
Acetone:
Solve Equations (d) and (e) simultaneausly to get
Chap.11
As a matter of interest, what otber mass balances could be written for!be sys-tem and
substituted for any one of !be Equations (a) through (e)? Typical balances
would be !be overall balances
Equations (1) !brough (i) do not add any extra information lo !be problem; tbe de-grees
of freedom are still zero. Bul any, of !be equations can be substituted for one
of Equations (a) through (e) as long as you mm sure tbal tbe resulting sel of equa-tions
is independen!.
Example 11.3 Material Ba\aIlces for a Process Involving
Multiple Units Bod Reactions
In !be face of higher fuel COSIS and tbe uncertainly of!be supply of a particu-lar fuel,
many companies operale Iwo fumaces, one fired witb natural gas and tbe
otber witb fuel oil. In !be RAMAD 'Corp., eachfUrnace has ilS own supply of oxy-gen.
The gas furnace uses air while tbe oil fumace uses an oxidation stream !bat an-alyzes:
See Figure El 1.3.
Figure EIl.3
(Note that two outputs are shown from the common stack to point out that the
stack gas analysis is on a dry basis but water vapor also exists. The fuel oi! camposition is given in mole fraetioos to save you the bother of converting mass fractions
to mole fractions .)
During one bli z zard , all tran s portation to the RAMAD Corp. was cut off, and

officials were worried abaut the dwindling reserves of fue) oil because the natural
. '.
gas supply was being used at its maximum rate possible. At Ibat time, the reserve of
fuel oil was only 560 bbl. How many ho ur s co uld the c o mpany operatebefore s hutting down if no ' addilional fe! oil was a ttainable? How many lb mol/hr of natural
gas were being consumed? The minimum heating load for the company when trans-lated
into the stack gas oulpul was 6205 lb mo\Jhr of dry s tac k gas. Analysis of Ibe
fuels and stack gas al lh ,al time were :
AIso, calculate the percent increa se in toxic emissions of ars enic and mercury per
hour caused by Ibe combustion of fuel oi! rather th an natural gas.
The molecular weight of Ibe fuel oil was 7 .91 IbIlb mol, and ilS den si ty was 7 .578
Ib/gal .
Solution
This is an open, steady-state process wilb reaction . Two subsystems exis!. We
want to calculate F and G in lb mol/hr and Iben Fin bbllbr .
Steps 1, 2, 3, and 4
We will use elements for Ibe material balances . The unit s of a11 Ibe variables
whose values are unknown will be pound moles. Rather than making balances for
each fumace, since we do not have any information about the individual aUllet
strearns of each fumace, we will make overa11 balances, and thus draw Ibe system
boundary around bolb fumaces.
Step S
Basis: I hr , so Ibat P = 6205 lb mol
Steps 6 and 7
The simplified degree-of-freedom analysis is as fo11ows. You have five elemenlS in Ibe problem and five strearns whose values are unknown : A, G. F, A', and
W; hence, if Ibe elemental mole balances are independent, you can obtain a unique
solution for Ibe problem.
Step8
The overall balances for!he elemenlS are (in pound moles)
Step9
Salve the S balance for F (inaccuracy in !he S02 concentrations will cause
sorne error in F. unfortunately); !he sulfur i. a tie component. Then salve for !he
o!her four balances simultaneously for G. The results are:
EXAMPLE 11.4 Anl!lysis oC a Sugar Recovery Process Involving
Multlple Serial Unlts
Chap.l1
Figure E 11.4 shows tbe process and !he kno",n data. You are asked lo ealeu-late tbe
eomposilions of every flow ,Iream . and tbe fraetion of Ihe sugar in the eane
that is recovered.
Flgure EII.4
AH of tbe known data have becn plaeed on Figure El 1.4. \f you examine the
figure . two questions naluraUy arise , Whal basis should you piek, and whal 'ystem
,hould you pick lo start Ihe analysi, with? Sorne pOlenlial bases and systems lead to
more equalions lo be solved simullaneously tban olhers . You eould, piek as a basis
F = lOO lb. M = IODO lb (Ihe same as I hour), or tbe value of any oflhe intermediale
flow s!reams. You could pick an overaU process as !he syslem witb whieh lO Slart.
or any of the individual units, or any consecutive combinations of units.
Step S
Basis: I hour ( M = IODO lb)

Another importanl decision you musl make is: what are tbe eomppsitions of
slrearns D, E, G, and H? Stream F has tbree eomponents. and 'presumably stream K
eontains only sugar and water. Does stream H eonlain pulp? PTesuniatily nOl, be-cause
if you inspecl Ihe process flowsheel you will nol find any pulp exiting any-where
downstream of tbe evaporalor. Presumably slreams D and G conlain sugar
and waler because Ihe problem implies tbal nol aU of!he sugar in strearn F is recovered. Whal happens if you assume ,!reams D and G conlin no waler or no sugar?
Then you would write a set of material balances that are not ndependent andlor are
nconsistent (have no solution). Try it.
Lel S sland for sugar, P sland for pulp , and W sland for waler.
, Steps 6 and 7
Pick as Ihe inilial syslem Ihe cryslallizer. Why? Because (a) if you check Ihe
degrees of freedom for (he crystallizer , only a smaU sel of unknowns are nvolved
with zero degrees of freedom ; and (h) the crystallizer is al one end of the process.
The unknowns are K, L. and w~. You can make two species balances, S and W, and
know Ihal 0.40 + w~ = 1. Consequently, Ihe degrees of freedom are zero, and Ihe
crystallizer seems lo be a gool! syslem wilh which lO start.
If you pick another basis, say F = 100 lb , and another system, say Ihe mili,
you would have 5 unknowns: D, E, wf, w~, and ww. You could make 3 species balances and employ tWQ implicit equations, LWP = 1 and LWT = 1, hence the degrees of freedom are zera .
Stops 8 and 9
For!he crystallizer Ihe equalions are (using w~ = 1 - 0.40 = 0,60)
Sugar: K (0.40) = L (O) + 1000
Water: K (0.60) = L + O
from which you gel K = 2500 lb and L = 1500 lb .
Step 10
Check using the total flows
2500 = 1500 + 1000 = 2500
The next stage in the solution is to pick the evaporator as the system, and re-peat the
degree-of-freedom analysis
3 variables: R, j, and w{t (w~ ~ O)
3 equatons: 2 independent species ' balances(the P balance is O = O), and
LW
Il
= 1 ,
The degrees of freedom are zer,o . You can solve the eqllations, then proceed upstream one unit, solve the eq~ations for the screen, and lastly solve the eqllations for
the mili. The results for all of the variables are:
lb
mass fraclion
The fraction of s ugar recovered is [1000/(24,574)) (0 . 16) = 0 . 25.
EXAMPLE 11.5 Productioo of a Rormooe lo Coooected Reactors
Figure E 11.5 shows two different reactor configurations to produce a honnone .
Figure E 11.5
The relation that gives Ihe growth (generation in Equation (10 . 1 of Ihe honnone in
eaeh vessel in Ihe steady state is Ihe Monod equation
where Jl. = Ihe specific growth rate, Ilbr
I-'ma x ;:::; maximum specific growth cate (the state at which the concentra-tion of
nutrent becomes the limiting factor in Ihe growlh of cells),

K , = Monod constant , g nutrentIL s ubstrate

The s ubstrate is the Iiquid containing water, nutrients, and ce ll s.
A coefficienl lhal rel a les lhe g of dry eells fo rmedlg nutrienl eonsumed is us ually
given lhe s ymbol Y <ls' and is called lhe biomass yield eoeffie ien!.
Two relaled processes for lhe growlh of a hormone have been proposed. Op-tion I is to
use a si ngle well mixed ve ssel having a volume of 100L. Option 2 is lo
use tWQ wel1 mixed vessels each of volume 50 L connected in serie s so that the out-pul
of vessel I beeomes lhe inpul to vessel 2 .
Whic h oplion will give the highesl eoneentralio n (g ee ll sIL of su bstrate)?
Dala: The subslrale f10w rale into lhe vessel for Option 1, or int o vessel I for
Optioo 2, is 15 Uhr , and contains no cen so but contains a nutrient with a co ncentrati on o f 10 gIL. Y <1, is equal to 0.2 g ee ll slg nutrienl eo ns umed. K, = 2
Figure El1.5 s how s the process stream info rmali o n. Two material balances
are in volved in lh e so lution to this problem. One b alance i s lh e cell balance. The
eon e entralion of eells will be denoled by x wilh the unil s of g cellsIL. The olher balance is the nutrient balance with es being the outri ent co ncentration. Because the
vessels are well mixed. the co ncentration of cell s and nutrient, respectively, in the
effluent is the same as th e concentration n si de the vessel.
Assume each process is in the stea dy- state so that the accum ul atio n in each
vessel (lhe respective syslems) is zero. We will u se Equation (10 . 1) for lhe bal-ances.
The Monod equation applies to eaeh vessel.
Option J
Cells
Nutrient
In lh e literalure of bioleehnolog y lh e ratio FN is termed the dilution rate, D,
e.g. , th e number of culture volumes pass ing through th e vessel per unit time ,
whereas in the chemical engi neerin g lterature the ratio V/F is known as the resi-dence
time .
From Equation ( a ):
From Equalion (b):
Next, introduce the values forthe parameters into the eqllation . F/V is 15/100 .
per hour, and i. equal lo J. so that
from which c~"' = 1.2 g nutrientlL sub"rate. IntrodUce thi. value into equation (d )
to get
1 g nutrient consumed
Option 2
The material balances are essential lhesame as for Op\ion excepl that ,lhe ves-sel volume
is 50 L, and lhe output concentrations from vessel I become the ioput
concentration to vessel2. Thus, F/V = (15 LIhr)50 1,. = 0.31hr .
For vessel 1:
For vessel 2:
The so lution of Equations (e), (f), plus lhe :Monod equatio,n (lhey fonn a non-linear set
of equations) gives c~.'l' = 1.35 g nutrientIL substrate and x~t = 1.73 g
ceJls/L substrate. In view of the number of significant figures in the values given for
the data, the respective answers are essentially the same. How ,can you increase XO
SELF-ASSESSMENT TEST
Questions
1. Can a system be co mprised of more than one unit oc piece of equipment?
2. Can ane piece of equipme nt be treated as a sel of severa l subsystems?

3. Does a flow sheet for a process have to show ane suhsystem for each process unit
thal is
connected la one oc more other process units?
4. lf you eount the degrees of freedom for eaeh individual unit (subsystem) and add
them up.
can their total be different than the degrees offreedom for!he overoU sySlem?
Problems
1. A twostage separations unit is shown in Figure SATl lPI. Given that the input
steeam FI
is 1000 Ib/hr. ealculate !he value of F2 and !he eomposition of F2.
2. A sim plified process for the produetion of SO) to be used in !he manufacture of
sulfurie
acid is illustrated in Figure SATllP2. Sulfur is bumed with 100% excess air in the
bumer, but for the reaetion S + 02 ~ S02' only 90% eonversion of !he S to S02 is
achieved in the bumer. In the converter. th e conversioo of S02 to SO) is 95%
complete .
Caleulate the kg of air required per 100 kg of sulfur bumed, and!he eoncentrations of!he
components in the exit gas from the bumer and fram the converter in mole fractions.
3. In lhe proces s for Ihe produclion of pure acelylene , C
( see Figure SATlIP3), pure
melhane (CH.) , and pure oxygen are combined in lhe bumer, where the following reac- .
tions occur:
a. Calculate lhe ratio of the moles of 0, to moles of CH. fed lo lhe bumer.
b. On lhe basis of 100 lb mol of gases leaving lhe condenser, calculale how many
pounds
of water are removed by the condenser.
c . What is the overall percenlage yield of producl (pure) C
based on lhe carbnn in
the natural gas entering the bumer?
Figure SA TllP3
The gases from the bumer are cooJed in the condenser that removes all of the water.
The
analysis of lhe gase s leaving lhe condenser is as follows:
These gases are senl to aD absorher where 97% of Ihe C,H
and essenlially all lhe CO
are
removed with the solvento The solven t from the absorber is sent to the CO
stripper.
Chapo 11 Material Balance Problems Involving Multiple Units
where aH lhe CO
is removed . The analysis oC lhe gas stream leaving lhe top oC lhe CO,
stripper is as foHows:
The solvenl from lhe CO
stripper is pumped lo the C
stripper, which removes aH lhe
as apure produet.
Thought Problem
1. When choosing a subsystem in a process for which to start making material balances,
what criterion should yon use in making the selection?
Discussion Problems

1. A household can be represenled as a small process. Material (and energy as weH)

flows in
and out. Prepare a flow diagram oC a household thal ineludes lhe kitchen , laundry,
lava-tory. toilets , bathtubs/showers, fumaee, and air conditioners, and look up data so
that yoo
can estimale a1l oC lhe material flows in and oul oC lhe s yslem as weH as reeyele
flows.
2. Look up the description of a process in aD encyclopedia that Deludes a flow
diagram of
the process. Select the systems to be used in making material balances, and explain the
reasons for your choices.
Looking Back
In this chapter you have seen how systems composed of more than one subsys-lem can
be trealed by lhe same principies lhat you used lO treal single syslems.
Whether you use combinalions of material balances from each of several subsystems
or lump all of Ihe units inlo one syslem, all you have lO do is check to see Ihal Ibe
num-ber of independent equations you prepare is adequale lO solve for Ibe variables
whose
values are unknown. Flow sheets can help in the preparalion of Ibe equalion sel.
GLOSSARV OF NEW WORDS
Block diagram A sequence oC boxes, cirdes , and so on used lO represent opera-tiona!
features of Ibe process flowsheel.
Connections Streams flowing belWeen subsystems (units).
F10wchart A graphical representation of Ihe process layout.
Mixer Apparatus to combine two or more flow streams.
Overall process The en tire system composed of s ubystem s (units).
Chap.11
Process flowsheet A graphical representation of the process. See Flowchart.
Separator Apparatus that produces two or more strearos of different composition
from lhe fluid( s) entering the apparatus. "
Splitter Apparatus that divide s the flow into tW Q or more streams of the same
composition.
Subsystem A designated par! of the complete system.
Well mixed Material within the system (equipment) is of uniform composition,
and the exit strearo(s) is of Ihe same composition as Ihe material inside the
system.
SUPPLEMENTARV REFERENCES
In addition to the general references Iisted in the Frequently Asked Questions in the
front material, the following are pertinent.
Baldea, M. "Dynamics and Control of Prceess Networks with RecycJe aud Purge," Paper
252 presented at AIChE mee ting, Indianapolis , IN, November 4 (2002).
Nagiev. M. The Theory 01 Recyc/e Processes in ehemical Engineering. MacMillan, New
York (1964) .
PROBLEMS
'11.1 For Figure PI U how many independent equations "are obtained from !he overall
bal
ance around !he entire system plus the overall balances on units A rid B? Assume
that only one component exists in each stream.
'11.2 What is the maximum number of independenl material balances Ibat can be
wriuen

for the process in Fig. Pl1.2?

11.3 What is the maximum number of ndependent material balances that can be
written
for the process in Fig. Pll.3? The slream f10ws are unknown .
Suppose you find out that A and B are always combined in each of the streams
in the same ratio. How 'maoy indepe~dent equations could you write?
11.4 The diagram in Figure Pll.4 represents a typic.l but simplified dislill.tion column.
Streams 3 and 6 eonsist of steam and water, "and ' do not come in contact with the fluids in the columo that contains t wo components. Write the total and component material balances for the three sections of the colurno. How many ndependent equations
would these balances repres ent? Ass ume th a t s tream 1 contains n components.
"11.5 A distillation process is shown in Figure PI 1.5. You are askOO to solve for all
the val-ues of the stream flows and compositions. How many variables and unknowns
are
there in the system? How many ndependent material balance equations can yau
write? Explain each answer and show all details how yau reached your decision. For
each stream (except F, !he only components !hat occur are labeled below the s!ream .
"'11-6 In Figure PI 1.6 you will see two successive liquid separations columns
operating in
tandem in !he steady state (and with no reaction taking place). The compositions of
the feed and praducts are as shown in the figure. The amount of W 2 is 20% of the
feed . Focus only on the material balances. Write down the names of!he material balances foc each colum" treated as separate units (ane sel foc each columo), along with
!he balances themselves placOO next to!he names of the balances. Also , place an asteri,k in front of the names of the balances that will comprise a set of independent
equations for each column. Write down in symbols !he unknowns for each column.
Calculate the degrees of freedom for each column separately.
Then detennine the number of independent equations for tbe overall syslem
composed of the two columns togelher by Iisling the duplicale variables (by symbols)
and unused specifications as well as tbe redundanl equations. and appropriately
adding or subtracting tbem from tbe values found in tbe first paragraph above. Determine tbe degrees of freedom for Ihe overall syslem .
Check you results obtained in paragraph 2 above by repeating tbe entire analy-sis of
ndependent equations . unknowns, and degrees of freedom for the overall sys-tem o Do
they agree? They should .
Do not solve any of the equations in tbis problem.
'11.7 Examine Figure PII.7 provided tbrough tbe counsey of Professor Mike CUllip.
a. Calculate tbe molar flow rate of DI' D
b . Reduce tbe feed flow rate for each one of tbe compounds by 1% in turn. Calcu-late
tbe flow rates of DI' D
again. Do you notice sometbing unusual?
Explain your results .
'11.8 Figure PI 1.8 shows a schematic for making fresh water from sea waler by
freezing.
The pre-chilled sea water is sprayed into a vacuum at a low pressure. The cooling re
-quired lo freeze sorne of tbe feed sea water comes from evaporation of a fraetion of the
water entering the chamber. The concentration oC th~ brine stream, B, is 4 .8%
salt. The pure salt-free waler water vapor is compressed and fed to a meller al a
higher pressure where the heat of condensation of the vapor is removed through the

heat of fusioD of the ice which contains no salt. As a result, pure cold water and concentrated brine (6.9%) leave the process as products.
(a) Determine the flow rates of streams W and D if the feed is 1000 kg per hoor?
(b) Determine the flow rates of streams e, B and A per hour
11.9 Monoclonal antibodies are used to treat various diseases as well as in diagno,tic tests
.
Figure PIl.9 shows a typical process used to produce monoclonal antibodics. A
stirred tank bioreaclor grows the cells of the antibody of interes~ namely immunoglobulin G (IgG). Afler fermenlation in the reactor, a batch of 2200 L contains
220 grams of the product IgG. The batch is processed though a number oC slages as
shown in Figure PIl.9 before the purified product is obtained. In the diafiltration
slage, 95% oC the IgG cntering the filter is recovered, in the ultra flItration slage 95%
of the entering IgG is recovered, and in the chromatography 90% is recovered.
Tab!e PIl.9 !isls lhe essential components enlenng and !eaving lbe overall
process in kg per batch. What is lbe fraCliona! yield of lbe producl IgG of lhe 220 g
produced in the reactor?
"11.10 Several slreams are mixed as shown in Figure Pll.lO. Caleulale lbe flows of
eaeh
slream in kgls.
Figure Pl1.10
"11.11 In 1988 , lbe U.S. Chemiea! Manufaeturers Assoeialion (CMA) embarked upon
an
ambitious and comprehensive environmental improvement effort-the Responsible
Care inilialive. Responsible Care commiled all of lbe 185 members of the CMA lo
enSUTe continual improvement in the areas of health, safety, and environmental qual - !
ily, as well as in elieiting and responding lo publie eoneerns about Iheir praduets and
operations.
One of Ihe best ways to reduce or eliminate hazardous waste is throu g h souree
reduetion. Generally , this means using different raw materials or redesigning the production process to eliminate the generation of hazardous byproducts . As an exampJe.
eonsider the following eountereurrent extraetion process (Figure P 11.11) lo recov er
xylene from a slream Ihat eontains 10% xylene and 90% solids by weight.
The slream from whieh xylene is to be exlraeted enters Unu 2 al a f10w rate of
2000 kglbr. To provide a solvent for Ihe extraction, pure benzene is fed to Unit I at a
f10w rate of 1000 kglbr. The mass fraetions of Ibe xylene in Ihe solids slream (F) and
Ihe elear liquid slream (S) have Ihe following rel ations : 10 rol('Ylene = ~'Ylene an d
Determine Ihe benrene and xylene eoneenlra tions in all of Ihe slreams. What is
the pereent recovery of Ibe xylene entering Ihe process al Unit 2?
11.12 Fi gure PIl.l2 shows a Ibree-st age separation process. The ratio of PlD , is 3,
Ibe
ratio of P,JDz is 1, and Ihe ratio of Ato B in stream Pz is 4 to 1. Caleulate Ihe
eompo-sition and percent of eaeh eomponent in slream E .
Hint :Allhough Ibe problem eomprises eo nnected unils , applieation of Ihe stan-dard
strategy of problem solv ing will enable you to solve it wilhout solving an exee s -sive
number of equations simultaneously .
11.13 In a tissue paper maehine (Figure PII.13), stream N eontains 85% fiber. Find lhe
un-known fiber values (all values in lhe figure are in kg) in kg for eaeh stream.

11.14 Metallurgieal-grade silieon is purified lO eleetronie grade for use in Ihe

semiconduc-tor industry by ehemieallyseparating il from its impurilies. The Si melal
reaets in
varying degrees wilh hydrogen ehloride gas al 300 C lo form several polyehlorinated
silanes. Triehlorosilane is liquid al room lemperalure and is easily separaled b y fraclional dislillalion from Ihe olher gases. If 100 kg of silieon is reaeled as shown in 'Fig
ure PI 1.14. how much trichlorosilane is produced?
'''11.15 A fumaee bums fuel gas of lhe following campos ilion: 70% Melhane (CH.),
20%
Hydrogen (Hz) and 10% Elhane (Cz!f;) wilh excess airo An oxygen probe plaeed al
Ihe exil of lhe furoaee reads 2% oxygen in Ihe exil gases. The gases are passed lhen
through a long duel lo a heal exchanger. Al lhe entrance lo Ihe heal exehanger lhe
Orsal analysis of lhe gas reads 6% 0z. Is lhe discrepaney due lO lhe fael Ihal Ihe first
analysis is on a wel basis and lhe second analysis on a dry basis (no waler condenses
in lhe duel), or due lo ao air leak in lhe duel?
Iflhe former, give Ihe Orsat aoalysis oflhe exil gas from lhe fumaee. lflhe latter,
calculate lh e amounl of air lhal leaks into lhe duct per 100 mole offuel gas bumed .
11.16 A power com pan y operates o ne of i ts boilers on natural gas and another o n
oil. The
analyses of th e fuels show 96% C H
C.H / .8. for the oi\. The /lue gllSes from both group s enter the same stack, and an
Orsot a nalys is of this combin ed /lue gas s how s 10 .0 % CO
02' What percentage of the total carbon bumed comes from the oil?
"11.17 Sodi um hydroxide is usually produced from common salt by electrolysis . The
es s en-tial element s of the system are s hown in Figure Pll.l7.
(a) What i!iii the perc e nt conversion of salt to sodium hydroxide?
(b) How muc h c hlorine gas is produced pe r pound of product?
(e) Per pound of product, how much water must be evaporated in the evaporatar ?
'''11.18 The f1 0wsheet shown in Fig. PIl.l8 represe nt s the pr ocess for the produc ti o
n of tita nium dioxide (Ti0) used by Canadian Titanium Pigme nt s at Varennis, Quebec.
Sorel s lag of th e foll owi ng anal ys is:
is fed to a digester a nd reacted with H
, which e nters as 67% by weight H
in
a water so lution . The reactio ns in the dige s ter are as follows:
Both reactio ns are co mplete . The theoretically required amount of H
for the Sorel slag is fed . Pure oxygen is fed in the theoretical amount for a ll the Fe
in the Sord,slag. Scrap iron . (p ure Fe) is added to !h e digester to redu ce !he fo
rmation of ferric sulfate lo negligibl e amount s. Thirty-six pounds of scra p iron are
added per pound of Sorel slag.
The produ cts of lhe digester are se nt 10 the clarifier, where aH the inert silica te s
and unreacted Fe are rem oved. The solution of TiOS0
and FeSO, from the clarifier is cooled; crysta llizing!h e FeS04' which is completely
removed by a filter. The prod ucl TiOS0 solulion Cram lbe filter is evaporated down
lo a s lurry lbal is 82% by weighl TiOS0
The slurry is sent lo a dryer Crom whieh a praduel oC pure hydrale, TiOS0
H, O, is oblained. The hydrale eryslals are sent 10 a direel-fired ralary kiln, where lhe
pure Ti0

is produced according to the following reaelion:

Reae lion (3) is eomplele.
On Ihe basis oC 100 lb of Sorel slag Ceed , ea leulale :
Cal The pounds oC water removed by lbe evaporator.
(3)
(b) The exil lb oC H,O per lb dry air fram lhe dryer if lhe air enlers having 0 .036
moles H,O per mole dry air and the air rale is 18 lb mol oC dry air per 100 lb oC
Sorel slag.
(e) The pounds of praduel TiO, produeed.
-11.19 An enzyme is a proteio thal c ataly zes a specific teacti o n, and it s activity is
reported in
a quantit y ca Jl ed " unit s". The specific activity is a meas ure of the purity of ao enzyme. The fraCliona1 re cov ery of ao enzyme can be calc ulat e d from the ratio of the
specific activity ( units pet rng ) after process ing occurs to the initial s pecific activity.
A (hree s tage "process for the purification of an enzyrne involves
l . Breakup of the cells in a biomass to rele ase the intercelluar products.
2 . Separation of the enzyrne from the inter ce l1uar producto
3 . Further separation of {he enzyrne from the o utput of stag e 2.
Base<! 00 !he following data for one batch of biomass, calculate !he percenl recov~
of!he enzyme afier each of!he three stages of !he process. Also caJculate !he purificatian of !he cnzyme !ha. is defined as !he ratio of!he specific activity lo !he ioitial
specific activity. FiIl in !he blank columns of!he following table.
CHAPTER12
RECYCLE, BYPASS,
PURGE, AND THE
INDUSTRIAL APPLICATION
OF MATERIAL BALANCES
12.1 Introduction
12.2 Recycle wlthout Chemlcal Reactlon
12.3 Recycle wlth Chemlcal Reactlon
12.4 Bypass and Purge
12.5 The Industrial Appllcatlon 01 Material Balances
Your objectlves in studying thls
chapter are to be able to:
1. Draw a Ilow diagram or sketch lor problems involving recycle, bypass,
and purge .
2. Apply the 1 Qstep strategy to solve steady-state problems (with and
without chemical reaction) involving recycle, bypass, andlor purge
streams .
3. Solve problems involving a modest number 01 interconnected units by
making appropriate balances .
4. Use the concepts 01 extent 01 reaction , overall conversion, and single-pass (oncethrough) conversion in solving recycle problems involving
reactors.
5. Explain the purpose 01 a recycle stream, a bypass stream, and a
purge stream.
6. Understand in a general sense how material balances are used in
industry.

I/hink /ha/ my friends would agree

How much recycle confuses me
l t's !iomelhing quite new
Only elear /0 a few
J' d ra/her be wa/ching TV
DMH
Looking Ahead
In this chapter we discuss material balances involving recyele-instances in
which material from down stream of the process, retums and reenters the process
again. Cases with and without reaction will be discussed. Purge and bypass will also
be explained along with the industrial uses of material balances.
12.1 Introductlon
In Chapters 9 and 10 we restricted the discussion and examples to a s ingle unit
with stream inputs and outputs as illustrated in Figure 12.1a. In Chapter 11 you encountered multiple units but the stream flows still were all in a forward direction
representing serial sequences as in Figure 12 . 1b . In this chapter we take up
precesses in which material is recyded, that is fed back from a downstream unit to
an upstream unit , as shown in Figure 12 . 1c. The stream containing the recycled material is known as a recyde stream.
Figure 12 . 1 Figure 12.1a shows a single unit with serial flows. Figure 12 .b
shows multiple unit s but still with serial flows. Figure 12 . 1c shows the addition
of recycle .
Whal is a recycle system? A recyele syslem is a syslem Ihal ineludes one or more
recyele s!reams.
You can see in Figure 12.lc Ihal Ihe recyele s!ream is mixed with the feed
stream, and Ibe combination fed lo Process l . Tbe producIs from Process 1 are separaled in Process 2 into (a) the producls and (b) the recycle s!ream . Tbe recyele
s!ream is retumed to Process I for further processing. Figure 12.2 iIlustrates a more
complex process involving several recycle streams.
Figure 12.2 A process involving multiple recycle streams comprised of a debu-tanizer and
three distillation columns. Recycle streams from adjacent processes
are feeds to this process, and sorne of the products of this process become reey-cle
streams fed to O{her processes.
Recycle systems can be found in everyday life . Used newspaper is coIlected
from households , processed to remove the ink, and used to print new newspapers.
Clearly, the more newspapers recycled, the fewer Irees tbal have to be consumed lo
produce newspapers. Recyeling of glass, aluminum cans, plastics, copper, and iron
are also common.
Recycle systems also occur in nature. For example, consider the "water cyele"
shown in Figure 12.3. lf a section of the earth is the system, the recycle s!ream consisls of evaporated water Ibat faIls lO earth as precipitalion, and tbe flow of water in
creeks and rivers brings the water back into the system.
Because of the relatively bigb cost of industrial feedstocks, when cheroica! re-actions are
involved in a process, recyele of unused reactants to the reactor can offer
significan! economic savings for high-volume processing systems. Heat recovery
within a processing unit (energy recyele) reduces the overall energy consumption of
the process. Process integration is lerminology applied lo using material and en-ergy
recyele in process designo
Here are sorne examples of the application of material recyeling in the process
industries.

Figure 12.3
cyele.
A portion of the water
l. Increased reactant converslon. Recycling tbe reactants back to tbe feed to a
reactor can significantly increase tbe overall conversion of tbe reactants. For
certain systems recycle allows tbe reactor to be operated at low conversion lev-els.
yielding improved selectivity. witb recycling of tbe unreacted reactants
making it possible to attain a high overall degree of conversion.
2. Continuous catalyst regeneration. Catalysts are used to increase tbe rate of
chemical reactions. but tbeir effectiveness can diminish witb use (catalyst de-activation).
Processes tbat use catalysts tbat deactivate at a relatively fast rate
may require tbe onsile regeneration and recycling of tbe catalys!. For example,
in a fluidized catalytic cracking (FCC) process (Figure 12.4), tbe cracking cat-alyst
deactivales almost irnmediately upon contact witb tbe gas oH feed at tbe
reaction temperature because of tbe formation of coke on tbe surface of tbe cat-alys!.
Therefore, tbe deactivated (spenl) catalyst is transported lo tbe catalyst
regenerator where mosl of tbe coke is burned off tbe surface of tbe catalysl to
reslore tbe activity of tbe calalys!.
. Clrculatlon oC a working Ouid. A number of processes use the closed circula-lion of a
working fluid for heating or refrigeration. Refrigeration systems (Fig -ure 12.5), including
home air conditioning systems, cireulate a refrigerant gas
by a eompressor so that the gas absorbs heat from the room air and discharges
heat to the outside atmosphere .
Frequently Asked Questions
If you feed material lo a stream conlinuously, as in Figure 12.lc, why docs lhe
arnount of the material in the recycle stream not ncrease and continue to build up1
What is done in this and subsequent chapters is to assume , afien without so staling,
lhat lhe entire process inc1uding .11 units and al1 of the flows of material are in
thesttady
state . As the process starts up or shuts down, the tlows in many of tbe streams change.
but
once lbe steady slate is reached. "what goes in must come out" applies to lbe recycle
stream as weJI as tbe other streams in the process .
You will find that systems involving reeycle stream s can be quantitatively ana-Iyzed
without applying any new principIes. The procedures developed in Chapters 9,
10, and 11 can be directly applied to systems with recyele.
SELFASSESSMENT TEST
Questlons
1. Explain lbe purpose of using recycle in a process.
2. WilI a recycle stream always have lbe same compo s ilion as a product stream?
Problems
l. How many recycle streams occur in Figure SAT12 , lPl?
2. The Hooker Chemical Corporation operates a process in Michigan for the purification
of
. HC!. Figure SAT12 . lP2 shows tbe flow sheet for!he Hookerproces<. The slreams
from
tbe bottoms of tbe five towers are liquido The slreams from tbe tops of tbe lowers are
gases. Hel is insoluble in tbe HCB (hexachlorobutadiens), The various slream compositions are shown in Figure SAT12.1P2.
How many recycle streams are there in the Hooker process ?

12.2 Recycle without Chemical Reaction

R ecycle of material occurs in a variety of pr ocesses th a t do not involve chemi-cal
reaction , including distillation, crystallization , and heating and refrigeration sys-tems.
As an example of a recycle system, look at the process of drying lumber
shown in Figure 12 .6. If dry air is used to dry the wood, Ihe lumber will warp and
crac k . By recycling the moist air that exits from the drier and mixing it with dry air,
the inlet air can be maintained at a sa fe water content to prevent warping and crack-ing
of the lumber
Another example, shown in Figure 12.7, is a di s tillation column u se d to separate
two compounds. Note that a portion of the exit flow from the accumulator is recycled
back into the column as reflux while the reboiler vapo rizes par1 0 fthe liquid in the botto m of the column to create the vapor flow up the column. The recycle of vapor from
the reboiler and retum of the liquid from the accumulator back into the column maintain good vapor and liquid contact on the trays inside the column. The contact aids in
co ncentrating the more volatile components in the overhead vapor stream and concentrating the less vola tile components in the liquid collected in the bottom of the column.
You can formulate material balances for recycle systems without r.eaction ex-actly as yo
u formulated material balances for process e s without recycle , as ex-plained in Chapter
7 and subsequent chapters.
The first step in problem solving is to pick a good system(s) for analysis. Ex-amine
Figure 12.8. You can write material balances for several different s ystems,
four of which are shown by da s hed lines in Figure 12 .8, namely :
1. About the entire process including !he recycle stream, as indicated by !he
dashed lines identified by 1 in Figure 12.8. These balances contain no informa-tion about
the recycle s!ream . Note that the fresh feed enters the overall sys-tem and the overaJl
or Det product is removed.
2, About the junction point (mixing point) at which !he fresh feed is combined
with the recyc\e stream (identified by 2 in Figure 12.8) to produce the total,
or gross, feed. These balances do contain information about !he recycle stream .
3 . About the basic process itself (identified by 3 in Figure 12 .8) . These balances
do not contain any information about the recycle stream. Note !hat !he total
(gross) feed enters the process and the gross product is removed .
4. About the junction point at which the gross product is separated into recycle
and overall (net) product (identified by 4 in Figure 12.8). These balances do
contain information about the recycle s!ream.
In addition, you can make balances (not shown in Figure 12 .8) about combina -tions of
subsystems, such as the process plus the separator (3 plus 4), or the mixing
point plus the process (2 plus 3) . These balances added to !he set of balances for !he
individual units would not be independent balances, but might be convenient to use,
and serve as substitutes for sorne of !he unit balances .
Note tbat in Figure 12.8 tbe recycle s!ream is associated botb wi!h the mixer,
which is located at the beginning of!he process, and wi!h !he separator, which is 10cated at the end of !he process. As a result, recycle problems lead to coupled equations that must be solved simultaneously. Therefore, sets of equations involving re-cycle
typically require robust computer software to avoid trouble in solving tbe
equations . Y ou will find that overall material balances (1 in Figure 12.8), particularly involving a tie component, are usually a good place to 'start when solving recyele problems. If you solve an overall material balance(s), and o calculate aH or sorne
of lhe unknowns, lhe rest of the problem can usually be solved by sequentially applying single unit material balances through the process. If you start solving a recy-

ele problem by writing material balances for individual units, and skip lhe overall
balances, you will probably write an excess ive number of equations lhat have to be
solved simultaneously.
EXAMPLE 12.1 A Continuous Crystallizer Involving
a Recycle Stream
Figure EI2.1a is a sehematie of a process for lhe produetion of flake
NaOH, whieh is used in households lO c1ear plugged drains in lhe plumbing (e.g.,
Drano) .
The fresh feed lo lbe process is 10,000 Iblhr of a 40% aqueous NaOH solution. The
fresh feed is eombined wilb lbe recyeled filtrate from lbe crystallizer , and fed to !he
evaporator where water is removed to produce a 50% NaOH solution, which in tum
is fed to !he crystallizer. The crys tallizer produces. filter cake !hat is 95% NaOH
crystals and 5% so lulion !hat itself consists of 45% NaOH. The filtrate contains
45%N.OH .
a. You are asked to determine !he flow rate of water removed by lbe evaporator,
and the recyc1e rate for !his process .
b. Assume thal lbe same production rate of NaOH flakes oceurs, but !he filtrate i,
not recyc1ed. What would be !he total feed rate of 40% NaOH have to be !hen?
Assume that !he product Solulion from !he ev.porator still contain, 50% N.OH
Solution
Open, steady-state process
a, Steps 1, 2, 3, and 4
Figure E12 . la contains the information needed to salve the problem.
Step S
Basis: 10,000 lb fresh feed (equivalent to I hour)
Steps 6 and 7
Chapo 12
The unknowns are W, G, P, and R. You can make two corriponent balances
about three systems: the mixing point A, the evaporator, and the crystallizer as well
as two overall component balances . You can also make total balances for lhe same
selection of systems. What balances sho uld you choase to salve lhe problem? If you
plan to put four equations in 30 equation solver, it does not make aoy difference as
long as lhe equations are independent. But if you salve the problem by hand, you
should count the number of unknown variables involved for each of the three subsystems and the overall system as follows:
Co mponent balances
Mixing point
Evaporator
Crystallizer
Overall
Unknowns
R plus feed (and compositions) to evaporator
(not labeled)
W, G, and feed to evaporator
G, P, andR
WandP
You can see that by using just two overall component balances (you can substitute
(he overall total balance tor one component balance) you can determne the values
of Wand P. Consequently, you should start with overall balances.
Steps 8 and 9

(or use the overall total balance 10,000 = 4113 + W)

The total amount of NaOH exiting wilh P is
[(0.95) + (0.45)(0 .05)](4113) = 4000 lb
Are you surprised al Ihis result? You shouldn'l be. If you pul 4000 lb of
NaOH into the process, 4000 lb should come out. The amount of water in P is 113
lb . As a check, I i 3 + 5887 = 6O<io lb as expecled.
Steps 6 and 7 (repeated)
Now that you know W and ' p . the next step is to make balances 00 a system
that involves the stream R. Choose either th .e D:lfxin "g poiot A or the crystallizer.
Which one should yau pick? "rtJe crystalliz .?r" inv.<?lves three unknowns, and you
now know the value of P, so tl}.at .o.nly two 'unknowns are nvolved versus introducing a considerable number of new unknown s if you chose mixing poinl A as Ihe
system.
Steps 8 and 9 (repeated)
NaOH balance on the crystallizer
0 .5G = 4000 + 0.45R
H 20 balance on the cryst allizor
0.5 G = 113+ 0.55 R
(or use Ihe lotal balance G = R + 41 13)
R= 38 ,870 lb
b. Now , suppose recyc1e from the crystallizer does not aceUf. but the production
and composition of P remains the same. Then the output of the crystallizer is just
p, as indicaled in Figure EI2.lb. How should you proceed? Do you recognize
Ihal Ihe problem is an.logous lo Ihe ones Ihal you read aboul in Chapler II?
Step 5
The basis is riow P = 4113 lb (the same as l hour)
Steps 6 and 7
TIle unknowns are now F, W, G, and H. You can make two component bal-ances on
the evaporator and two on the crystallizer plus two overall balances . Only
four are independent. TIle evaporator balances would involve F, W. and G. TIle
crystallizer balances would involve G and R while the overall balances would in-volve
F, w: and H. Which balances are best to start with? If you put the equations in
an equation solver, it makes no difference which four equations yon use as long as
lhey are independen!. TIle crystallizer balances are best to start with by hand be -cause
theo you have to salve just two pertinent equations for G and H .
Steps 8 and 9
NaOH balance on Ihe cryslallizer
0.5G = [(0.95) + (0.05)(0.45)](4113) + 0.45H
HP balance on Ihe cryslallizer
O.5G = [(0.05)(0.55)(4113) + 0.55H
H= 38,870 lb
An overall NaOH balance gives lhe new F
Overall NaOH balance
0.40F = 0.45(38 .870) + 4000
F= 53.730 lb
Note !hat wi!hout recycle . tbe feed rate must be 5.37 times larger tban with recycle
to produce tbe same amount of producto not to mention the fact tbat you would have
to dispose of a large volume of filtrate.
SELFASSESSMENT TEST
Questlons

1. Why have we not considered tbe buildup of material in recycle streams in this chapter?
2. Under what circumstances might material be accumulated or depleted in a recycle s
tream?
3. Can you make material balances in botb steady-state and unsteady-state flow processes
that involve recycle?
4. Can you fonnulate sets of equations that are not ndependent if recycling oceues in a
sys-lem?
Problems
l . A ball mili grinds plastic to make a very fine powder. Look at Figure SATl2 .2 PI.
At Ibe present time 10,000 kg of powder are produeed per day . You observe Ibal Ibe
process (shown by Ibe solid lines) is ineffieienl because 20% of!he feed is nol recovered
as powder-it goes to waste.
y ou make a proposa! (designaled by Ibe dashed lines) lO reeycle Ibe uneollecled
malerial
baek lo Ibe feed so Ihal il can be remilled. You plan lo recycle 75% of Ibe 200 kg of
uo-eolleeled material baek lO Ibe feed slream. If Ihe feed eoslS $1.20/kg, how mueh
money
would you save per day while producing 10,000 kg of fine powder?
2 . Sea water is to be desalinized by reverse osmosis using the scheme indicated in
Figure
SAT12 .2P2. Use Ihe dala given in Ibe figure lo delermine: (a) !he rale of wasle brine
re-moval (B) ; (b) Ibe rale of desalinized water (ealled potable waler) produetioo (P);
(e) Ibe
fraction of the brine leaving the reverse osmosis cell (which acts in essence as a
separator)
Ibal is recycled.
3, A maleria! eontaining 75% waler and 25% solid is fed lo a granulalor al a rale of
4000
kglhr. The feed is premixed in Ibe granulalor wilb reeycled prodUCI from a dryer,
whieh
follows Ibe granulalor (10 reduce Ihe waler coneentration of Ibe overall material fed inlo
the granulator to 50% water, 50% salid). The product Ihat lea ves the dryer is 16.7%
water.
In the dryer, air is passed over the salid being dried. The air entering the dryer contains
3 % water by weight (mass), and tbe air leaving the dryer contains 6% water by weight
(mass). .
a. What is tbe ratio of the recycle to the feed entering the granulator?
b. What is the rate of air flow to the dryer on a dry basis? .
4. Benzene. toluene, and other aromatic compounds can be recovered by salvent
extraction
witb sulfur dioxide (S02) ' Figure SATl2 .2P4 is the process schematic. As an example ,
a
catalytic refonnate stre3m containing 70% benzene and 30% nonbenzene material is
passed through the eou nt ereurrent extractive recovery sc heme shown in Figure
SA TI 2 .2P4 . 1000 lb of reformate and 3000 lb of S02 are fed to the system per hour .
The
benzene produet stream eontains 0 . 15 lb of S02 per lb of benzene. The raffinate slream
contains all the initiall y charged nonbenzene material as well as 0 .2 5 lb of benzene per
lb
of nonbenzene material. The remaining component in the raffinate stream is S02- How

many lb of benzene are extracted in the produet slream on an hourly basis? How many
lb
of raffinate are produeed per hour?
. Centrifugal pumps canoOl run dry, and must have a minimum fluid flow to operate
prop-erly-to avoid cavitation, and subsequent mechanical damage to the pump. A s
torage
tank is to be set up to provide liquid flow to a process, but sometimes the demand will
drop below the minimum f10w rate (10--15 % of the rated capacity of the pump) . What
equipment setup would you recommend be implemented so that the pump is nOl
damaged
by the low flows? Draw a picture of the layout so that the minimum flow can go
through
the pump no matter what the level of liquid is in the feed tank and no matter what the
Qul-let pressure and demand may be .
DIscusslon Problems
1. Because of Iimitation s in supp ly as well as economics , many indu s tries reuse their
water
ayer and ayer again. For example. recirculation occurs in cooling towers , boilers , powdered coal tran sport, multistage evaporation, humidifiers. and many devices to wash agri
-cultural products.
Write a brief report di sc ussing one of the se processes, and nelude in the report a de sc
rip-tion of the process, a sim plified tlow s he et. proble ms with recy c ling , the extent
of purge.
and, if you can find the nfacmation, the sav ings made by recycling .
2. A series of unit s with forward and reverse tlow, and reeycle among uoits , is known
as a
cascade. The enrichment of natural uranium by gas diffusion of uranium hexafluoride is
a
well-known example of a process involvi ng a cascade. Develo p a tlow sheet of a
cascade.
and ndicate what the material balances are for individual units at the beginning ,
middle ,
and end of the cascade.
3. The Celane se company appealed to the Supreme Court the applica ti on of an EPA
rule
conceming benzene leakage to the atmosphere . Four of their plants used benzene in their
processes, recycling the benrene over and over in the plants. The cbmpa ny believed
that
the EPA rule on use applied lo Ihe inventory (storage) of benzene, 'which was far le ss
Ihan
the lOOO-metric-ton regulatory threshold for "use," whereas the EPA interpretation of
the
"use" of the benzene was it should be coumed each time it circulated Lhrough a plant.
The
EPA argumenl was Ihat every lime Ihe benzene ci rculated through a planl, il had th e
sa me
chance of leaking into the air as new benzene would. What is your opioion about this
ar-gument ? (The U .S . Court of Appeals agreed with the EPA .)
12.3 Recycle with Chemical Reaction

111e most eommon applieation of reeyele for systems involving ehemieal reae-tion is the
reeyele of reaetam s, an appiication that i s used to increase the oyeraii eon-version in a
reactor. Figure 12.9 shows a simpl e example for the reaction
A->B
From the data in Figure 12.9 you can see that the s teady- state material balances for
the mixer, reactor , and separator are satisfied. Also, note that for the overaii material
balance if you caiculate the extent of reaction you wiil find it is 100 reacting g moVs.
If you ealeulate Ihe extent of reaction for Ihe overall precess in Figure 12.9
based on B
100 - O
1 = 100 moles reacting
If you use material balances to calculate the output P of Ihe reactor (on Ihe basis of I
second) you get
A=900gmol
B= 100gmol
and the extent of reaction based on B for Ihe reactor by ilSelf as Ihe system is
100 - O
~reactor = 1 = 100 moles reacting
In general, the extent of reaetlon Is the same regardless of whelber an overaU
material balance Is used or a material balance Cor lbe reactor is used, This im-portant
faet can be used in solving material balances for reeyele systems wilh reac-tions.
You will eneounter two types of eonversion when reaelions oeeur:
l. Overall Craction conversion:
mass (moles) oC reactant in the fresh feed - mass ( mole s) of reactanl in (he OUlput
oC !he oyeran process
mass (moles) of reactant in Ihe fresh feed
2. Single - pass ("once - lhrough") fraction eonverslon:
mass (moles) oC reaclant red ioto the reactor - mass (moles) ol reactant exiliog the
reactor
mass ( moles) of reac tant fed into (he reactor
As Ihe name indieates, the overall eonversion depends only on what enters and
lea ves Ihe overal! precess, while Ihe single-pass conversion depends on what enters
and leaves the reactor. For Ihe simple recycle reactor in Figure 12.9, Ihe overall con
-version is 100%
100 - O
.:.::..:':::-~ x I 00 = 1 00 %
100
and Ihe single-pass conversion is 10 %
1000 - 900 x 100 = 10%
1000
When lbe fresh Ceed eonslsts of niore lban one reaetan!, lbe eonversion can be ex-pressed
Cor a single componen!, usually lhe IImltlng reactan!, or lbe most Impertan! (expensive) reactant. Rememb er from C hapler lO \hat eonversion in a reactor
(t he single- pass co n vers ion) can be Iimited b y ehemical equili brium aneVor e hemica
l
IOnetics. but \he ove rall conversion is also limited by the efficiency ofthe se parator in
se parating compounds to be recycled from \he com pound s that are not recycled.
The overall conversion (f wi\h a s ubscript OA) and the single-pass conversion
(f wi\h a sub sc ript SP) can be expressed in tenos of th e extent of reaetion , g, \hat was
discussed in Chapter lO. From th e definition of the overall conversion, note \hat \he

numerator is equal to the negative of the product of th e extent of re ac tion times of

Ihe stoichiometric coefficient of the reaClant (A), and the denominator is the moles
of fresh feed of the reactant (A):
-VA
Overall con version of species A = f OA = -n-;-r -'S"" h "'roed"'"
(12.1)
For the single-pass conversion, \he numerator is the same product as in Equation
(12.1) while \he denominator is equal to \he amount of \he reaetant fed to \he reactor :
,
-VA
Single-pass conversion = f Sp = n~actor feed
(12.2)
If you so lve Equations (12.1) and (12.2) for \h e extent of reaction , equale \he ex
-tenis , and use a balance at the mixing point n~~ctor f"d = ntfr r,ed + nL~Ycl" you
can obtain the following relationship between overall and single -pass conversion:
f sp n~esh feed
(12.3)
If you now apply Equation (12.3) to \he simple recyc le example in Figure 12 .9, what
value do you gel for \he ratio of \he si ngle-pass to overall conversion? Do you get
0.1, which agrees wi\h \he resul! stated previous ly ?
EXAMPLE 12.2 Recyde in a Proc!!Ss in Which a Reaction Occbrs
Cyel ohexane (C.H
12
) can be made by the reaetion of benzene (Bz) (C.H.)
with hydr ogen aecording to !he fo llowing reaetion:
For!he proces s shown in Figure E12.2, determine !he ratio of!he re eycle s!ream ti ,
the fresh feed stream if the overall conversion of benzene is 95%, and the single-pass
conversion is 20% . Assume that 20% excess hydrogen is use d in the fresh feed ,
and that !he eomposition of!he recyc1e slream is 22.74 mol % benzene and 78.26
mol % hydrogen .
Figure E12.2 Schernatic of a recycle reactor.
AIso calculate the environmental impact of the product gas by calculating an
environmental index based on the foIlowing threshold Jimit values (TL V) for the respective components:
Solution
The process is open and steady state.
Step5
A convenient basis to choose would be 100 mol (g mol or lb mol) of fresh
benzene feed. althou .gh you could selec- the recycle to be 100 mol.
Steps 1, 2, 3, and 4
Figure E12.2 contains a1l of the information avai1able about the tlowstreams
except the amOllnt of H
2
. which is in 20% excess (fer complete reaction. remember)
n~2 = 100(3)(1 + 0.20) = 360 mol
and the total fresh feed is 460 mol.
Prom Equation (12.1) for henzene (v
you can calculate that ~ = 95 reacting 111oles.
Steps6 and 7
The unknowns are R.II~,.' nk~. snd flt6H12' You can write thl'ee species bal-

ances for each of the three syslems, the mixing poiot, the reactor. and the separator
plus overal! balances (not all of which are independent, of eourse). Whieh systems
should you choose to start with? The oyeran process, because then you can use the
value calculated for the extent of reacrion.
Steps 8 and 9
The species overall balances are nF
The next step is to use the final piece of informatan, me information about
the single-pass eonversion and Equation (12.2), to get R. The system is now the reactor. The amount of the Bz feed to the reactor is 100+ 0.2274R, and ~ = 95 (lbe
same as calculated from the ' overall conversion), Thus, for benzene
and
Finally, the ratio of reeyele to fresh feed is
The higher the TLV, lbe more exposure lbat can be tolerated, henee an index
should use lbe inverse of the TL V values appropriately weighed. You can use relative concentrations oc mole fractions as weights.
Environmental index = l ~5 (0~5) + 1
Note that the benzen. contri bu tes 96% of the indexo
EXAMPLE 12,3 Recycle in a Process witb a Reaction Occurring
lrnmobilized glucose isomerase is used as a catalyst in producing frutase from
glucose in a fixed~bed reactor (water is the solvent). For the system shown in Figure
EI2.3a, what percent conversion of glucose results on one pass through the reactor
when the ratio of the exit strearn to the recycle stream in mass units is equal to 8.331
The reaction is
C12H22011 -> C12H220U
Glucose Fructose
Solution
Tbe process is an ope n. steady-state prccess with a reaction occurring and a
, recyde .
Stops 1, 2, 3, and 4
Figure E12.3b indudes all the known and unknown values of the variables
using appropria te notation (W stands for water, G for glucose. and F for fructose) .
Note that the recycle stream and product stream have the same composition, and
consequently the same mass symbols are used in the diagrarn for each stream.
Step 5
Figure E12.3b
Pick as a ba sis S = 100 kg. given the data shown in Figure EI2.3b.
Step6
We have not provided any notation for the reactor exit stream and composition because we will not be using these values in our balances. Lel f be the
fraction conversion for one pass through the reactor. The unknowns are
R, P, T, w~, w:. w(i,. wb. ww. and J, for a total of 9.
Step 7
Tbe balances are };wf = 1, };wT = 1, R = P/8.33 , plus 3 species balances
each on the mixing point 1 the separator 2 and the reactor as well as overall balances .
We will assume we can find 9 independen! balances among Ihe 101 and proceed. We
do not have to salve aU af the equations simultaneously. The units are mass (kg).
Steps 8and 9
We will slar! wilb overall balances as Ihey are easy lo form and are often decoupled for solution.

o.eraU balances
Overall no water is generated ar consumed, hence
Water: 100(0.60) = pw(l. = loow~
w(l. = 0.60
We now have 6 unknowns left for which lo solve. We start somewhal arbitrarily
wilb mixing poinl 1 lo calculale sorne of Ibe unknowns
Mixing point 1
No reaction occurs so that species balances can be used without involving the
extent of reaction:
or
Next, rather than make separate balances on the reactor and separatar. we will
combine the two into one system (and thus avoid having to calculate values associated with the reactor exit stream).
EXAMPLE 12.4 A Bioreactor with Recycle
Reactors that involve biological materials (bioreactors) use living organisms
t'prOdc~. variety of products. Biore.ctors 'are useel for 'prdducing 'thanT,' antibiotics, and proteins for dietary ~uppTeri;ents and ' medical diagnoSis'. Fi\;ure E12.4
shows a recycle bioreactor in which the overall conversioo of ~e proprietary component in the rresh reed to product i s 100%. The conversion of tite 'pr;rie'tary com ponent to product per pass -in the reactor isAO%. Determine the amollot of recycle'
and the mass percent of component in the recycle stream if the product stream .,c.on- '
tains 90% producto and the feed to the reactor caDtains 3 wt % of the component.
Assume that the component and the product have essentially the same molecular
weighl, and thallhe wasle contains only water and dead cells.
Solution
Steps 2, 3, and 4
AH of lhe dala have been inserted in Figure BI2.4.
Step 5
Pick a convenienl basis of 100 kg of fresh feed (P.
Steps 6 and 7
Pick the overall process as (he system.
Variables (9): 3 slream flows and 2 composilions in each slream
Equalions (9): Basis I
Sum of mass fractions in 3 streams 3
. Specifications: One composilion in F (lbe olber
is redundanl) I
One composition in P 1
Material balances: Componenl and waler (or total) 2
Percent overall conversioo I
Tolal 9
The degrees of freedom are zero .
Steps 8 snd 9
Total balance: lOO = P + W
Componenl balance: O. \O (1 (0) = 0.90 P
P= 11.1 kg w= 88.9 kg
Nexl pick Ihe reaclor plus Ihe producl recovery unit as Ihe syslem.
Steps 6 and 7
The degree-of-freedom analysis can be omitted because all that is needed to
gel lhe kg of proprielary componenl in Ihe recycle slream is a component balance
using Ihe given 40% single-pass conversion. Lel R be the kg of recyc1e and w be the

mass fraction of component in the recycle stream :

Steps 8 and 9
Apply Equation (10.1) using as units kg (Ihe molecular weighl of the componenl can be eliminated from each lerm by division). The consumplion lerm represents conversioo of 40% of the input term o
SELF-ASSESSMENT TEST
Questlons
). If the components in the feed lo a process appear in slOichiometric quantities and the
subsequent separation process is complete so that all of the unreacted reactants are recycled,
what is the ratio tor reactants in the recycle stream? .~
2. Answer the following questions true or false :
a. The general material balance app lies for pracesses thal involve recyde with reaction
as it does for olher processes.
b. The key extra piece of information in material balances on processes with recyele in
which a reaction takes place is the specification of the fractioo conversion or extent of
reaction.
C. The degrees of freedom for a process with recycle that involves chemical reaction
are
the same as for a proces s wilhout recycle .
3. Cite two rcasons for using recyclc in a process .
Problems
and !he tlow i s 24 mollhr.
(a) What is the feed rate, F. and Ibe product flow rate of C
leaving Ibe process?
(b) What is Ibe single-pass conversion ofbutane in the process?
2. Pure propane (C,H
) from El Paso is dehydrogenated catalytically in a continuous process
to obtain pr o pylene (C , H
6
). AII of the hydrogen formed is separated from Ibe reactor exit
gas wilb no loss of hydrocarbon. The hydrocarbon mixture is Iben fractionated to give a
product s!rearn containing 88 mole % propylene and 12 mole % propane. The olber
stream , which is 70 mole % propane and 30 mole % propylene. is recycled. The onepass
conversion in Ibe reactor is 25%, and 1000 kg of fresh propane are fed per hour. Find
(a)
'l, .lbe kg of product stream per hour. and (b) Ibe kg of recycle stream per hour .
'J 3. ' Elbyl elber is made by Ibe dehydration of elbyl alcohol in Ibe presence of sulfuric
acid at
Figure SA T12.3P3 is a simplified process diagram. If 87% conversion of Ibe alcohol
fed
10 Ibe reactor occurs per pass in Ibe reactor , calculate: (a) Idlograrns per hour of fresh
feed, and (b) Idlograrns per hour of recycle.
Discussion Problem
l. Numerous techniques have been proposed for desulfurization of flue gases. The
techniques
can be categorized by the phase in which the reactions occur: gas or solution. What are
sorne of Ibe factors Ibat influence !he choice of!he process for flue gas desulfurization?
12.4 Bypass and Purge

Two additional commonly encountered types of process s!reams are shown in

Figures 12.10 and 12 . 11.
a. A bypass stream-a slream Ihal sldps one or more stages of Ihe proces s and
goes direcUy lo anolher downstream stage (Figure 12.10).
A bypass slream can be used lO control the composition of a final exit s tream
from a unit by mixi ng Ihe bypa ss stream and Ihe un! exit Slream in s uitable
proportions to obtain Ihe desired final composilion.
b. A purge stream-a slream bled off from the process to remove an accumula
tion of inerts or unwanled malerial Ihal might otherwise build up in Ihe reeycle
st ream (Figure 12 . 11).
Figure 12.11 A proces s with a recycle s tr eam with purge.
Many companies have had Ihe unfortunate experience Ihat on startup of a new
process , Irace components nol considered in Ihe material balances used in Ihe design
of the process (because Ihe amounts were so small) build up in one or more recycle
loops.
Look at Figure 12.1 2 for an example of a process involving reeycle wilh a
purge slream .
Note how in the steady slale Ihe argon coneentration is different in eaeh sue
eessive recycle slream so thal 1 % argon oceurs in Ihe feed slream while 25% argon
oeeurs in lhe third reeyele and purge stream. For effective operation, Ihe Ar caneen
tration e a nnO! be al\owed to inerea s e further . Remember Ihal Ihe proeess operales
eontinuously in the sleady stale so Ihal Ihe Ar eoneentration is eonstanl in each indi o
vidual re e ycle stream.
Caleulations for proeesses involving bypass and purge slreams introduce no
new principIes or lechniques beyond Ihose pres enled so faro Two examples will
make thal clear.
Figur e 12 . 12 A process to man ufacture ammonia th at in volves three reaelors
and three distiJlation co lu mns. Note the stepwise r ise in the concentration of Ar
in the recycle streams.
EXAM PLE 12 .5 Bypa ss Ca lcul a tions
In the feedsl ock preparal ion sectio n of a pl a nt manufacturing natu r a l gaso line.
isopentane is removed from butane-free gasoline . Assume for purposes of simplificalio o that the process and components are as shown i n Figu re EI2.5. Wha t. Fraction
of Ibe butane-free gasoline is passed tbrough Ibe isopentane tower? Detailed steps
will not be listed in Ibe analysis and solulion of Ibis problem. The process is in Ibe
steady state and no ~eaction occurs.
Solution
By examining tbe f10w diagram you can see Ibat part of Ibe butane-free gasoline bypasses Ibe isopentane tower and proceeds 10 Ibe next stage io Ibe natural
gasolioe plan!. AII Ibe eomposilions (lbe streams are liquid) are known. Seleet a
basis: 100 kg feed .
Wh.t kind of balances can you write for Ibis process? You can write Ibe followiog:
a. Overall halances (eaeh stream is designated by Ibe letter F, S, or P witb
Ibe units being kg)
Toral materJI halance:
The overall balances will not teH you tbe fraelioo of Ibe feed goiog to Ibe
isopentane tower. For Ibis ealeul.lion you need anotber balance.
b. Balance around isopentane tower: Let x be tbe kg of butane-free gas
going to tbe isopeotane tower, and y be tbe kg of tbe n-C

stream leaving the isopentane tower.

Total materJI halance:
Another approach to this problem is to make a balance at mixing points 1
and 2. Although there are no pieces of equipment at those points , you can see that
streams enter and leave the junctions.
c. Balance around mixing poinl 2:
material into junction = material out
TOlal malerial: (lOO - x) + y = 88.9
Compo nenl (iso-C
5
): (lOO - x)(0.20) + O = 88.9(0.10)
Equation (1) avoids the use of y. Solving yields
x = 55 .5 kg as before
EXAMPLE 12.6 Purge
(e)
(1)
Considerable nterest exists in the conversion of coal into more convenient
liquid products for subsequent production of ehemicals. Two of the main gases that
can be generated under suitable conditions from insitu (in the ground) coal combus
ton in the prese nce of s team (as occurs naturally in Ihe presence of groundwater)
are H
2
and CO. Afier eleanup, these two gases can be combined to yield methanol
according to the following equaton
Figure E 12.6 illustrates a steady-state process for the production of melbanol.
AIl ofthe compositions are in mole fraetioos or percent. The stream flows are in moles.
Figure E12.6
Note in Figure E12.61bat sorne CH. enters Ibe process, but does not partcipate in tbe rcacHon. A purge stream is used to maintain the CH. concentration in !he '
exit from the separator at no more than 3.2 mol%, and prevent hydrogen buildup as
well . The once-Ibrough conversion of Ibe CO in the reactor is 18% .
Compute the moles of recyele, CH
3
0H, and purge per mole of rced, and also
compute the purge gas composition.
Solution
Steps 1, 2, 3, and 4
AII of the known nfarmation has been placed on the diagram, The proc ess is
in the stea dy 5t8te with reaction. The purge and recycle streams have the same composition ( implied by lhe s pliter in the figure). The mole fraction of the component s
in the purge stream have been de signated as x, y , and -z for H
Select a convenient basis: F;;; 100 mol
Step 6
The variables whose values are unknown are x, y. z. E, P, and R. You can ignore the stream between the reactor and separatar as no questions are asked about it.
Step 7
Because me problem is presented in terms of moles, making ao oyeran mass
balance is not convenient. In s tead we will use element balances . You can make
lhree independent element bala nces for the overall prceess: H, e, and o balances .

If you make a CO species balance 00 the r eactor plus separator, you can use the
information about the percent con versian af CO to provide one addrtional balance.
How can you obtain fifth and sixth balances so that the s y stem of equations is determinate? One piece of information given in the problem statement that has not
been used is the iIonnation about the upper Ilmit on the CH
4
concentration in
purge stream . This limit can be expres s ed as z :S 0 .032 . Assume that the purge
s tream contains the max imum allowed CH
4
so that you can get an equation , thus
making
z = 0.032 (a)
Another piece of infQrmation is the implicit mole fraetion balance in the recycle
strearn
x+y+z=l
Steps 8 and 9
The overall element bala nces are (in moles):
For a system composed of th e reactor plus the separ~tor (chosen to avoid calculating the unknown information about the direct output of che reactor), the ca balance l S
co:
Equation (a) can be subs tituted in to Equations (b) through (l) . and !he resulting five equations solved by successive s uhstitution or by using a computer prog ram o The resu lt ing values obtained are (in moles)
Step 10
C heck to see that each of the balances (b}-(I) is satisfie d.
If yo u want to use the extent of reactio n to make the calc ulati ons, you must
first calculate {mM for CO and H
2
and then find that CO was the limiting reactant.
y ou could reach the sa me conclusion by inspection. Theo
SELF-ASSESSMENT TEST
Questlons
1. Exp lain what bypass means in words and also by a diagram.
2. Answer the following questi ons true or false :
a. Puege is used to maintain a concentration of a minor compo nent of a process stream
below sorne set point so that it does not accumulate in the process.
b. Bypassi ng means that a process stream eote es the process in advance of lhe feed to
the
process.
c. A trace compone nt in a stream or produced in a reactor has negligible effee t on the
overall material balance when recyele QCcucs.
3. Is the waste stream the same as a purge stream in a process?
Problems
l. In the famous Haber process (Figure SA Tl2.4PI) to manufacture ammonia. the reaction
is carried out a t pres s ures of 800 to 1000 otm and at 500 to 6OO'C us ing o suitab le
cataly st. Onl y a sma ll fraction of the material entering the reactor reaets on one pass, so
recy-

ele is needed . Also, because the nilrogen is obtained from the air, it contains almos t 1
%
rare gases (chiefly argon) that do not reacl. The rare gases would continue to build up
in
Ihe =ycle until Ibeir effect on Ihe reaction equilibrium would become adverse. There
fore, a small purge stream is used .
Figure SA Tl2.4Pl
The fresh feed of gas composed of 75.16% H
and 0.27% AI is mixed
wilh Ibe =ycled gas and enters Ibe reactor wilh a composition of 79.52% H
2
. The gas
s!ream leaving Ihe ammonia se parator contains 80.01 % H
2
and no ammonia. The product
ammonia contains no dissolved gases. P er lOO moles of fresh foed:
a. How many moles are recycled and purged?
b. What is the pereent conversion of hydrogen per pass?
2. Figure SATI2.4P2 s hows a simplified process to make elhylene dichloride (C
The feed data have been placed on Ihe figure. Ninety percent conversion of the C
2
H. oceurs on each pass through the reactor. The overhead stream from the separator
contains
98% of Ihe CI
2
entering Ihe separator. 92% of the entering C
2
H and 0.1 % of Ihe entering C
. Fi ve percent of Ibe overhead from Ihe separator is purged.
Calculate (a) Ihe flow rate and (b) the composilion of Ihe purge slream.
12.5 The Industrial Application of Material Balances
Process simulators, which initially were used for material and energy balances,
are now used by process engineers for a number of important activities, including
process design , process analysis, and precess optimization. Process design in vol ves
selecting suitable processing units (e .g ., reactors, mixers , and distillation columns)
and sizing them so that the feed to the preces s can be efficiently con verted into the
desired products. Process analysis involves comparing predictions of process vari ables using models of the process units with the measurements made in the operating process. By comparing corresponding values of variables, you can determine if a
particular process unit is functioning properly. If discrepancies exist, the predictions
from the model can provide insight into the root causes of any problems. In addition,
precess models can be used to carry out studies that evaluate alteroate processing
approaches and studies of debotenecking, that is, methods designed to increase the
production rate of the overall precess. Proce ss optimiZa/ion is directed at determining the most profitable way to operate the process. For process optimization, models
of the major processing units are used to determine the operating conditions, such as
product compositions and reactor temperature s , that yield the maximum profit for
the process (subject to appropriate conslraints).

For each of the three precess application s , models of the processing units are
based on material balances . For simple equipment, just a few material balances for
each component in the system are sufficient to model the equipment. For more complex equipment such as distillation columns, you will find the models involve mater
ial balance equations for each component on each Iray in a column, and sorne industrial columns have over 200 Irays. For precess design and most of process analysis,
each processing unit can be analyzed and solved separately. Modero computer codes
make it possible to solve extensive sets of simultaneous equations . For example, the
optimization model for an ethylene plant u s ually has over 150,000 equations with
material balances comprising over 90% of the equations.
12.5-1 Issues In the Solutlon of Equations in Models
The simultaneous solution of the large number of equation s in process models
presents a major challenge for commercial software vendors who develop and maintain the precess models used for process design, process analysis, and process optimization. Computational efficiency and solution reliability (including stability and
convergence of algorithms) are two important factors affecting the use of cornmercial process simulators. If an excessive amount of computer time is required to solve
the model equations, the utility of the simulators can be seriously undermined, particularly for preces s optimization applications , because they involve a large number
of equations and naturally require cOnsiderable computer lime for their solution.
Also, optimization applicaton s are applied eontinuously to many processes so that a
long time to achieve a solution, or fai lure of the algorithm used to solve !he equations , seriously degrades the performance of the software, and can malee it impossible to obtain any expected bene fits.
You s hould be aware that the computational efficiency and reliability of software are affected by the way in which you fo rmulate the process model equations
and the order in which you enter them into the computer. In general , the more linear
is a set of model equations, the faster the set ean be solved, and the more reliable the
soluton. You may reeaH that in Chapter 7 it was pointed out that writing mate rial
balances using the mole fractons as unknown s re s ults in a non linear set of equations
when compared to using the eomponent f10w rates . By writing the model equations
in open equation form, you ca n impr ove the eomputational and reliability aehieved
by equation solvers for large-seale problems.
Con s ider system of equations in whieh al and a2 are known values:
Given the values of YI a nd Y2' the fr s t equation can be used to ealculate xI' Then !he
value of x
2
can be ealculated using the s econd equation. This proeedure is eaHed the
sequential modular approaeh, that is, the equations are s olved individuaHy or in
relatively s maH groups, and the results of one set are used to solve for other unknowns in other se t s.
The open equ a tion form for the example i s written as
1, (x" x2) = y , - a,x,
h (XI, x2)" Y2 - 0lx, - a-X 2
By s peei fy ing the values of YI and Y2 and settingfl=h=O, a sel of two equations and
two unknowns re s ults. The so lution to this se t of equations is the s olution of the
original problem. You so lve the equations simultaneously for both x, and x2' This
proeedure is also eaHed the simultaneous modular approach. Both methods yield
identieal solutions if the eomputer eod e i s robu s t to variations in the eharaeter of the

equation. Why is !he ope n equation form u se d for industrial-seale model applieations? Beeause it is more eomputationaHy efficient ami reliable for large-seale problems . The open equation form affords easier d evelopment of a standardized model
formation so that engineers can combine models and software produeed by different
programmers without difficulty .
In addition , with the open equation form it is ea s ier to use the s ame model to
ealculate various parameters in the equations. For example, fer the previous two
equa ti ons, given Ihe values of YI' Y2' xI ' and x2' Ihe following equations can be
so lved 10 determine Ihe values of al and a2'
No te that the equations have not changed, only the known and unknown .
12.5-2 Material Balance Closure for Industrial Processes
One important way in which individual material balances are applied industrio
ally is to check that "in = out," that is. to determine how well the material balances
balo
ance using precess measurements in Ihe equations. You look for what is called clo
sure. namely that the error between "in" and "ou t" is acceptable. lbe flow rates and
measured co mpositions for all the streams entering and exiting a process unit are s ub sti tuted into Ihe appropriate material balance equations . Ideally , Ihe amount (mass) of
each component entering the system s hould equal th e amount of Ihat component leav
ing th e system. Unfortunately, the amount of a component entering a precess rarely
equals Ihe amount leaving Ihe process when yo u make s uc h calculations. lbe lack of
closure for material balances on industrial process occurs for several reasons :
1. The process is rarely operating in Ihe steady sta te. Indu strial processes are al
most always in a state of flux, and rare ly reach preci se steady-state behavior.
2. The flow and composition measurements have a variety of errors associated
wilh them. First, sensor readings have noise (variations in the measurement
due lO more or less random variations in the readings !hat do not correspond to
changes in Ihe process). The sensor reading s ca n also be inaccurate for a wide
variety of other reasons. For example, a se n sor m ay require recalibration be
cause it degrades, or it may be used for a meas urement for which it was not designed.
3. A component of interest may be generated or cons umed inside the process by
reactions that the process engineer ha s n o t considered.
As a result, material balance closure to wilhin 5% for material balances for
most indu stria l processes is considered reasonable. (Here closure is defined as !he
calculated difference between the amount of a particular material entering and exit
ing the process divided by the amount entering multiplied by 100 .) If special attention is paid to calibrating sensors, material balance closure of 2 to 3% can be at
tained. If specia l high accuracy sensors are used, smaller closure of Ihe material
balances can be attained, but if faulty sensor readings are used, much greater errors
in material balances are observed. In fact, material balances can be used to determine when faulty se nsor readings exisl.
Looking Back
Do the words of th e jingle at lhe s tart of this ehapter still apply to you? From
the explanation and examples presented in lhis section you should have coneluded
lhat problems in vo lving recyele , purge, and bypass are no different from the v iewpoint of how they are analyzed lhan any of lhe problems solved in earHer ehapters of
thi s book . The one new factor brought o ut in this chapter is lhat recyde for a
reactor
usually involves information about lhe fraction conversion of a reactant or extent of

reaction.
GLOSSARY OF NEW WORDS
By-pass stream A slream lhat s kips one or m ore units of lhe process, and gaes directl y 10 a downstream unit.
Fresh feed The ov erall feed to a system .
Gross product The praduct s tream lhat leaves a reactor.
Once-through fraction conversion The conversion of a reactant based on lhe
amount of materia l that enters and leaves lhe reactor.
Open equation form Model equations in which lhe sum of lhe terms of each
equation represe nt a deviation from zero .
Overall Craction conversion The conversion of a reactant in a process wilh recyele ba sed o n the fresh feed oC lhe reactant and lhe overaIl praducts.
Overall products The slream s that exit a process.
Process Ceed The feed s lream that enters the reactor usually used in a process wilh
a reactor and recyele .
Purge A stream bled off fr o m lhe process to remove the accumulation of inerts of
unwanted material th at might olherwise build up in lhe recyele Slreams.
Recycle Material (or energy) that lea ves a process unit lhat is downstream and is
retum ed to lhe sa me un it or an up stre am unit for proces sing agan.
Recycle stream The stream that reeyc le s mate rial.
Recycle system A system lhat ineludes one or more r ecyele streams.
Sequential modular The se quential so lution of model equations .
Simultaneous modular Simultaneous solution of model equations.
Single-pass Craction conversion The co nver s ion based on what enters and leave a
reac to r. See once-through co nver sio n.
SUPPLEMENTARV REFERENCES
In addition 10 the general references listed in me Frequently Asked Questions
in me front material, me following are pertinent.
Cheremisinoff, P . N., and P. Cheremisinoff. Encyclopedia of Environmenlal Control
Technology: Waste Minimization and Recycling , Gulf Publishing, Houston, TX
(1992) .
Lund, H .F .. Ed. M cGraw-HiI/ Recy cling Handbook, 2nd ed., MeGraw-HilI, New
York
(2000).
Luyheo, W.L., and L.A. Wenze!. Chemical Process Analysis:Mass and Energy Balances .
lot!. Ser. lo Phys. & Chem. Eogio. Sei, Preotiee-Hall, Eoglewood eliffs, NJ.
(1988).
Myen;, A.L.. and W.D. Seider. Introduction 10 Chemical Engineering and Computer
Caleulations. Preotiee-HaJI. Eoglewood CHffs. NJ. (1976).
Noll, K.E .. N. Haas, C . Schmidt, and P . Kodukula . Recovery, Recycle, and Reuse 01
Industrial Wasles (Induslrilll Waste Management Series), Franklin-Book Co.
(1985).
Veslind, P. Unil Opera/ions in Resour ce Recovery Engineering, Prentice-HaJI, Upper
Saddle
River, NJ. (1981) .
Web Sltes
http://www.eapec .kt.dtu.dlclmain/36445/simulators .pdf
http://www.dur.ae .ukIa .k .hughes/kptlmodule2 .html
http://www.it.ehe .wust!.eduljoseph/477/homeworksl

http://www.nap.edu/books/0309063779/htm1l28 .html
PROBLEMS
'12.1 How many recycJe streams exis t in eaeh of the following processes?
(a)