SECTIOl'f 'I DECISIONS FOR m~ II'lI'l,n.

()UT'l1l STIlUCTUU 111

TABLE 5.1-1
Bier.relty or decisions
CHAPTER I. Bau:::b Ya5US conbnuolI$

5
1. lnpul-oulput Sl'1lC\Ull: of lbe IIowshtt'
J. Recycle ~'lIChrrt of the lIo..-sb«r
... ~lluuet... t of 'M ~.a".... 5}"~

" '".pol' rec:o~tl'\ 'ylltm

" LIquid Stl'u.'1Of\ ')"ltm
5. lleal<lLch.an&t. ncr .. o,l
INPUT-OUTPUT
STRUCTURE
OF THE order-of-magnitude argumenl to say thaI this rule of thumb is equivalent to
requiring that we complelely recover and lhen recycle all valuable reaclants. Thus,
FLOWSHEET Fig. 5.1-la indicates thai no reactants leave the system.
Of course, if air and water are reactants in a process, they are sufficienlly
mexpensive. compared to organic materials. that il mighl be cheaper 10 lose them
10 an exit slream rather than 10 recover and recycle lhem. lienee, in a few rare cases.
Fig. 5.1-10 mlghl not be complele.
The olher sllualion in .... hlCh commonly reaclanlS have been losl from a
process occurs when we have a gaseous reactant and ellher a gaseous feed impurity
or a gaseous b)-produCt produced by one of the reactions. We wanl to recycle the
gaseous reactant. but the mert-ga~ componenlS mUSI be purged from the process so
Ihat lh(") do not contmue 10 accumulale m the gas-recycle loop. In the past. It was
so expensive 10 separate gaseous mix Iures that some reactant was allowed 10 lea\e
the process in a ~as-r("cycle and purge stream (see Fig. 5.1-lb). Ho.....ever, the new
In Sec. 1.2 we: descnbed a hierarchical decision procedure for inventing process membrane-separation lechnology, such as Monsanto's prism process, has CUI Ihe:
flowshccls and base<ase designs" The decision levels are repealed in Table 5.1-1 COsl of gaseous separations so lhat gas recycle and purge might not be necessary
The batch versus continuous decision of level 1 was discussed in Sec. 4.2, and in the
subsequent chapters we discuss the other decision levels in detail.

5.1 DECISIONS FOR THE

PlIT-OlITPlIT STRUcruR£
To understand Ihe decisions required to fix the input-output structure of a
streams ~L _ _P_'-,OC-,=
(a>
~ :;:::ucu
f10WSheel, we merely draw a box around Ihe total process. Thus, we focus our
auention 00 what raw materials an: fed to the process and what products and by-
products are removed. Since Ihe raw malerials costs normally faU in lhe range rrom r -_. c ,,",g,

=L
3310 85y' of the lotal processing costs., we wanl to calculate these costs before
we add any other detail to the design.
P,oc,,, ~ Pm""'"
Flowsheel Alternatives
streams _ ~ By-prOOucls
(b)
Almost e\ery flowsheel has one of the IWO structures shown in Fig. 5.l-la and b.
There is a rule of thumb in process design (see Sec. 3.4) that it IS desirable 10 recover FIGURE 5..1-1
more than 99 y. of all valuable materials. For initial design calculations .....e use the Inpul-<fu,pu' .lrudu't of I\o..-'!htd IF,."" J 101 D<ougltll. AIO.[ J. JI: JJJ (/98J)-J

116
 SEmON II D£C!SJOI'I5 FOil 11lf INPUT-OUTPUT snocnru 119
TABU; 5..1-1
u,'d-2 decisions If a ked Impurity IS present as an azeotrope with a reactant.
often It IS beller to process the Impuflly. (5.1-5)
I, Should we: punr,
,be: M.c:d SITUIIlli bdOfe: ,be:y C'IIlc:r tbe: Fooas1
1. Should _ umoY<: .... locydc a ,....... tslbk by-prodlK1 If a feed impunly IS lOert but lS easier 10 separate from the
1. SbouId ....e: IlM' aau reqo.:k aad pu,..., IIrQm' product than the feed, II IS betler 10 pr~ Ihe impurilY.
... Should we: DOl bo,be:. 10 n:covu and ~"'" wmr: ruotUnlS' If a feed impunty 15 a C01lotl)st poison, rClllove It.
5.. 110.... /lUDY prOOt>C1 SlfQIDS "In lbe:rC' lx'
6. What arC' tbe: dlOS'ln unables lor lhe: mpul-OUlpul IolnKU1f<:. and ",hal CCOlKlrID<: tndC'·o/h .'C'
aUOClatw .. lib lhae ""n.. hles' PROCESS ALTt.RNAltVE. Unfortunately, not all these dcslgn gUldellncs are
quantttallve, so often we must base our Innial decision on our best judgment
(which might be merely a guess)
We distinguish belween Fig. 5.1-la and b because the presence of a gas
recycle and purge stream adds a design degree of freedom 10 the design problem; If we are nol certam that our decision is correct, we list the
i.e., eilher the reactanl composition of Ihe purge slream or tbe excess ga~us opposite decision as a process alternative. (5.1-8)
reactanl fed 10 the process becomes a new design variable. We discuss the dcslgn
variables later. Wilh Ibts approach, we have a systematic way of generating a Iisl of process
alternall\es

uvel-2 Decisions
ECOl'liOMIC TRADE-OFFS FOR FEED PURltlCATION, Our deciSion of pun~
The decisions ....e must maLe to fix the mput-outpul structure ofttle flowshecl are
given in Table 5.1-2 and arc discussed belo"," (ying tbe feed streams before they arc processed IOvohcs an economic trade-off
bclween bUlldlng a preprocess separation system and mcreasing the cost of the
process because \oloe arc handltng the increased flow rales of men matenal$. Of
PurifiCliltion or Feeds course, the amount of mert materials present and where they will efilet and lea\e
Ihe process may ha\e a great Impact 011 the processing costs. Therefore, it IS not
A decision 10 purify the feeds before:. they eDter the process is equivalent to a
surpnsmg Ihat Ihere IS no simple deSIgn criterion lhat always indicates the corn::cl
decision to design a preprocess purificalion system. This is different from a decl~lon decision.
10 feed the process Ihrough a separation system thaI is required 10 any evenl..Smcc
at this stage of our synthesis and analysis procedure we do nOI kno~ what ~lIld of
separation system WIll be required for the process wilh no feed Impuntlcs, we Reco\er or Rec)'c1e Re\'ersible By-producls
cannol always make a definite: decision. The r.r:.actlons 10 produce benzene from toluene are
Some design guidelines to be considered are as follows:
If a feed Impurity is DOl inert and l$ prescDt in signlficanl, Toluene + Hz ..... Benzene + CH.
(4.1-3)
quantities., remove it (otherwise, it will lead to raw-matenal 2 Benzene ¢Diphenyl + Hz
losses, aDd usually a much more complicated separauon
system is required to recover Ihe additional by-produClS). (5.1-1) Since the second reaction IS rc\-ersiblc, we could recycle the dlpbcnyl back to the
If a feed Impurity is present in a gas feed, as a first IUess reactor and lei II build up In the recycle loop until it eventually reached an
process the Impurity. (5.1-2) equilibnum level. That is, the recycled dlphenyl would decompose to form benzene
at the same rale as ben2ene would be producing diphenyJ.
If a feed Impurity in a liquid feed stream is also a by- If we recycle the reverSible by-producl, we must oversl2e all the eqUIpment in
produci or a ptoduct component, usually it is bener to reed that recycle loop, to accommodate the equilibrium flow of the reversible by-
Ihe process through the separation system. (5.1-3) produci. However, If we remove it from the process, we pay an ecollomlC penally
If a feed impurity is presenl in large amounU, remove it because of the Increased raw-material cost of reactant (toluene) that was conver1ed
(there is no quantitalive cnlenon avaLlabk to indicate how to lbe reverSible by-product (dlphenyl), e.g., the raw-matenal cost of toluene minus
Mlarge" is large), (5.1-4) the fuel value of dlphenyl. Since our decision Involves an a;onomlc trade-off
bet""een raw-material losses to less valuable by-products and IOcreased recycle
120 SECTION,. D£CISlON5 rOl mE INPUl-OllTPUl nlUCTUl..I'. ncnoN 51 DKISIom FOR nu! IN"".()U'T1'VT snUCT\}l£ 121

costs. it should not be surprismg that no iimple design guideline is available to TABu.: 5.1-J
make thIs decLSion The result Will also be sensiti\e to the equilibrium constant of DestiJUltion coda and compoDnit dassificatiOfL'i
the b)'-product reactIon. So we generate another process ahemative

I. V""I G:ascout b,·prodllClJ alld s...:d .... puntMS

Ca!'i Re'C),·de and Purge 1. Recyck and purse Gueous IUClll!lS pNllIICf1 pscs andlor p _ bJ'producu
, R«ydo Rca~ts
If .....e ha\'e a Mlight- reactant and either a Mlight~ feed impurity or a Ulight~ b)- Rcaettoll Ullermedl.ltcs
product produced by a reaction. it used to be common practice to use a gas rec)'cle Auonopcs "'llb reactlnls (oomchmcs)
and a purge stream; Ie. we want to recycle the reactant. but we must purge one or RevnsitHc by·products (somcumcs)
more components from the process. We define a light componenf as one which boils <N~ RUela.nUl-lf complete COnVCl'tI(lD 01 ulUllble rc.lCIJOIl ,ntcnncd'llcs
lower than propylene (-SS"F, -4S"C). We choose propylene as a breakpoint 5. E1cas-venl Gueous resetlnl nOI rco;o'fClCld lnd rco;ydcd
because lower-boiling components normally cannot be condensed at high pressure 6. E1cea- ... ute Liquid readlnl DOt recovered or recycled
with cooling water; i.e.• both high pressure and refrigeration would be required. 1. Prim.a.1)" produn Primll)" Pfoduel
Since gaseous reactants normally are less expensive than organic liquids. and since L Valuable by·produel (I) Separlle dcstUl&tion for ~nnl b,·prodIKUI
refrigeration is one of the most expensive processing operations. it usually was ,. Fuel B,·products 10 fuel
cheaper to lose some of the gaseous reactants from a gas recycle and purge stream 10- Waitt By,pfodu.eu 10 "·Ule 1R:l1lDC1lt
than it was to recover and recycle pure reactant.
However, membrane technology. such as Monsanto's prism process. now
makes gas separations less expensh-e.. Unfortunately. there is not a sufficient optimum amount of eJ:oess that should be used Similarly, at some point. the cost of
amount of published information available concerning tbe costs of membrane noess water used will become significant Moreover, pollution l.tealment costs
prooes~ to be able to develop new design guidelines. Thus, we treat the membrane
must be considered.
separator as another process alternative.. Because of the lack of published informa-
tion. we would base our initial design on a process with gas recycle and purge,
Numbt'r of PToducl Stream!'i
whenever our design guideline is satisfied:
To determine the number of product streams that \\i1lleave tbe process, first we list
Whenever a light rcactant and either a light feed impurity all the components that are expected to leave the reactor. This component list
or a light by-product boil lower than propylene (- 5S"F. usually includes all the components in the feed streams and all reactants and
- 4S"C). use a gas recycle and purge stream. (5.1-9) products that appear in every reaction. Then we classify each component in the list
and assign a destinalion code to each. The component classifications and destina-
A membrane separatIon process also should always be considered. tion codes are given in Table 5.1-3. Finally, we order the components by theIr
nonnal boiling points. and we group neighbouring components with the same
destination. The numbeT of groups of all but the recycle streams is then consKlcred
Do Not RKOver and Rcc)'cle Som~ Readanl!'i to be the number of product streams.
This procedure for determining the number of product streams is based on
One of our design gutdelines states that we should recover more than 99 % of aU the common seme design gukl.eline that
valuable materials. Since some materials, sucb as air and water. are much less
valuable than organic ones, we normally do not bother to recover and recycle It is never advantageoU!'i to separate two streanu and then
unconverted amounts of these components. Of course, we could try to feed them to mix them together. (5.1- 10)
the process so tbat they would be completcl)' converted, but often we feed them as
Also, it is ba!'iCd on the assumptIon tbat the components can be separated by
an excess to try to force some more valuable reactant to complete conversion. distillation and that no azetropes are formed. Thus, in some cases (i e.. solids) a
Forellample. in combustion reactions. we usually use an uocss amount of air different set of rules must be used to estimate the number of product streams.
to ensure complete conversion of the fuel. The greater amount of the ellocss we usc,
the closer to complete conversion of the other reactant we oblain. However, the Example 5.1-1. Suppose we have the 10 components listed ill order of l1lelr boihng
capital and operating costs of Ihe blower used to move the air. as well as preheating points and WIth the dCSllnatlon codes indlCl.led. How many rroduct streams will there
and cooling costs. increase as we increase the ellcess amounl of air Thus there is an "'?
122 UCTtOfII J I DIlCISlOHS HMt nut INPUT-QUTPVT nalJCTUle

c.m..-., ' :iI'",,;

H,. CH,
=L
CompoMJtI Otsri_tioa Dati.luloo.

A Waste F Primary product H2• CH4 Process Benzene

8 WaSle G Recycle
Toluene _ Diphenyl
C Recycle II Recycle
0 F~I I Valuable by-product I
"'IGUR[ 5..1-2
E F~I } F~I
Input-OUlput iUUdUIC 01 HOA pc-oecu. [F,_ J. JJ ~ Ala£J~ 31 ljl (l9,!U~]

$ohniolt. The product streams an:

Evaluation of Ihe F10wsheel
I. A. + B 10 waste (do not separate them and tbeD mix them in the sewer) At each stage of the development of a f1owsheel, this is essential:
2. D + E 10 fuel (do not separate them and tben mix them 10 burn)
1. F -primacy product <to stOr.lse lor sak) Be «nain that all products, by-products, aod impurities
4. I ~valuable by-product 1 (10 storage for sale) leave the process! (5.1-1 I)
S. J to fud (J mwu be separated from 0 and £ 10 recover compoocnlS F. G, H, aDd I,
$0 we Ireal J as a separate product stream) For example. in our HDA process. there mighl be some other impunlies in the
hydrogen feed stream. We would expect them to leave with the purge. We also
expect Ihat Ihere will be some impurities in the toluene feed stream. We altempt to
Example 5.1·2 HydfOlilkyladOil of lolllC~ to pl'"odUtt bf,auoe. Find tbe Dumber of
identify Ihese impurilies by considering the sour« of our toluene, and the:n we look
product streams for the HDA process; ie.. sec Enmpk-4.I-l.
for where tbey will exil the "process. Furthermore, we need to consider the
possibility of other side reactions (such as Ihe formation of terpbcnyl), and we must
Sob<,iOll. Ill. Example 41-1 tbe components in tbc reacbons are loIUC'lK, hydrogen. ensure Ihal tbc:sc new by-products kave the process or can be recycled
bellUM, mc:lhalX', and diphenyl. No addlUonal oomponents arc prC$CII1 In e:uba of If even a trace arnounl of a component IS fed to a req'de loop and is not
the: feed streaJns,. U ...Ie arrange Ihese componenlS In order of their nonnal boiling removed, Ihe process will be inoperable. This is one of Ihe most common mistakes
poiols, we oblain the results shown in Table: 5.1-4. Since both hydrogen (a reaC'lanl) made by inexperienced designers.
and melhane: (bolh a feed impurilY and a by·prodllCl) boil al a lower temperature
Ihan propylen.c:, we decide to usc a ps recycle and purge stream. 8enune is our
primary prodllCl, and loluene (a reactant) is rcqc:kd. Dipbmyl is a revemble by-
prodllCl, and for lhis uampJc we decided to rc:movc: it from tbe process aDd to we it u
pan of our ruel supply. Tbcsc destinatioD c:odc5 also arc given in Table 5.1 ...... 5.2 DESIGN VARlABLES, OVERALL
Thus. lberc: are three prodllCl streams: • purge coDtaininl H J and CH., the MATERIAL BALANCES, AND
primary prodllCl stream conlaining benzene; and a fucl by-prodUCt stream conUliniog STREAM COSTS
dipbenyl. The initial t10wshect is given in Fia- 5.1-2.
To calculale: Ihe overall proocss material balances and the slTeam COSIS. we must
first assess wbetbcr Ibe probkm definilion is complete or whelbcr there are any
degrees or freedom that must be specified to calculate tbe malerial balances. In
TABL£5.J-4
Tol~ to beo.uoe general. lbe pmblem definition is not complele:. Therefore, normally, it 15 impossi-
ble to develop a unique set of material balances ror a process. Only a process wilh a
e.-,I I t singJc reaction and with no loss or reactants from the prooc:ss has no degrees of
freedom.

..
H, Ree:yclc and purac
-2S3-C
-161"'C Ree:ytle and purac
or course, ir tbe: material balances are not unique, Ihen Ihe stream costs will
CH.
~~ ...c Primary product also not be unique. Thus. we must develop the material balances and the: stream
Tol~
O!:pbmyl
lwe
2Sl"'C ."""
F~I
costs in terms of the unkno.....n design variables, and eventually "'e will Jook for the:
economie optimum values or these design variables.
Design Variables TABLE 5.1-1
Procitdures (Of" ieTdoping o~1I malerial balances
1lle vanablcs we select to compkte the: definition 0( the design problems are what
we call the d~gr~~s of fr~~dom.. For compkx reactions., it is usually possible to I. Start ..uh lhe apcCficd productoon ... Ie..
correlate Ihe product distribution measured in the chemist's laboratory as a 1. From lhe uo,cl'lIometry(ancl, for complu leIIChOllS,.lhe COtn,bl\>on fo' prodllCl dostnbuuonl find the
by·prodllCl nows aDd the ruaant requlrementa (in tcmu o/IM destJJl vanablcs)
function of the conversion of the limiling reactant, the molar ratio of reactants, the
J,. Calculatc tM Impurily mlet and outlet Bowa for lhe ~ alreaml wherc the .elIctanlla.c completely
reactor temperature, and/or the reactor pressure. U the activation energies of all the ,«o>'creel and ,ecycled
reactions are equal, then temperature will not appear in this correlation. Similarly, .. Calculatc the OUlla 110.... of reactanla ,ft lerm, of a apccified amount of UCICSa (abo\'e tM n:acllon
if there: are the same number of moles of reactanlS and products for gas-phase fCCjouremauaj fOlIllrc:ama ..bien: lbie reacranll arc 001 1CCO¥'CI..cl and Rqded (rccydc and PU'J'C 0'
reactions, or if we are considering liquid-phase reactions. then pressure wiU not .... or .... tcr).
appear in this correlation. In addition. we usually attempt to correlate the So CaJeWa,lc the: ullcI and oullcllloW1' for the tmpu,nuea enlm.t WIth the reactant lllreams '0 IUCp.
conversion against the space velocity in order to estimate the reactor size..
For preliminary designs, where kinetic data often are not available, we
assume that the reactor configuration used in the process is the same as that used
by the chemist (a batch reactor is equivalent to a plug 80w reactor), because we Material Balance Procedure
cannot evaluale the effect of the reactor configuration on the produci distribution
without a kinetic model. However, if the preliminary design calculations indicate To de:ve:lop the: overall material balances ror single-product plants, we: always slart
that additional development effort is justified, part of that development effort with the give:n production rale.. (If a process in an existing complex is replaced by a
should be directed to determining the best reactor configuration. new process, lhen the: fc:ed rate: may be known instead or the production rate.)
In addition to the design variables which affect the product distributlOll, the From the production rate, the reaction stoichiometry, and (usually) the correla-
other design variables that enter into the overall material balanoes correspond to Hons for the product distribution, we calculale all the by-product flows and the
situations where we do not recover and recycle all the reaetants. Thus, if we use an raw-material requirc:men15 as functions of the desiln variables that appear in the
excess amount of air in a combustion reaction, we must specify the amount of product distribution correlations. Then, Knowing the impurity compositions of the
excess. Similarly, if we have a gas recycle and purge stream present, we must specify feed streams, we calculate the inlet and then the oullet flows of the inert materials.
either the excess amount of gaseous reactant fed (i.e., in eJlccss of the reaction For feed streams where an excess of reactant is fed and not recovered and recycled
requirements) which is lost in the purge stream or the reactant composition in the or a feed stream where the reactant exits through a gas recycle and purge stream.
purge stream. we must specify the excess amount ofreactant that is lost from the process. Then we
A list of the level-2 design variables that might affect the overall material can calculate: the inkt and outlet flows of any impurities from the composition of
balanocs is given in Table 5.2-1. these: feed streams. A summary of the procedure is given in Tabk 5.2-2.

Ov«all Material Balances Limitations

Nonnally it is possible to develop expressions for the overall material balances in Note that the preliminary material balances described above are based on the
terms of the design variables without ever considering any recycle 80ws. Any time assumption of complele recovery of all valuable malerials, instead of the rule-of-
the overall equations are underdetioed. it is necessary to look for one or more thumb value of grealer than 99% recovery. There are no ruks of thumb available
design variables to complete the problem definition, and these design variables to fiJI any 0( the design variables. Moreover, it is aJlIl'ays much more important to
always correspond to sig"ificmtl prOCLSS-Cpfindzotion problems. Henoe, the initial find tbe neighborhood of the optimum values of the design variables which tix the
analysis should always focus on the input-oulput 80ws only. inlet and outlet nows than it is to include the losses early in the analysis. Howe:ver.
we v.iU want to revise our initial material balances at some point to include the
TABLE 5.l-t J=.
Possible design variables for level 2 Our approach focuses on processes that produce a single product. There are a
number of processes that produce multiple: products, e.g., chlor;nalion or methane,
ReaaOf oon¥'Cf'SlOn, motar rallO of rcactuta, amine: prooesscs, glycol plants. refineries, etc. The overall material balance ca.lcula-
'eactlOn temperatun and,tu< ptCBWC
tions ror these: processes are usually more diffkult than the procedure described in
R_nU not '_\'enld...- au 'CICY'* aad ...'tc
Table 5..2-1 because the product distribution must match the market demand.
126 ~u..'ION II nOI(,N ~''''IAIiI "-S. U~UAII I'o!AIUIAL llALANCE.S. AI'U HlEAM CO~TS SECflON H lH:.SI<iN ~A.IAILES, O~UALL MATEliAL BAlANCES. AND STlUM COSTS 127

~ll.I"'plc .5.2-1 T"h"'M W knLt'ne. lk... dop lhe o~eralJ m;olenal bal,mCCi (or lhe process, this hydrogen will leave with the purge stream. Thus, the IOtal amount of
II DA process hydrogen fed to the: process Will be
Sulurju". The reactions of mll:rC:S1 arc p.
FE. + 2S(1 +S)-YFHFG (5.2-4)
Toluc:ne + II J ~ 8c:0zc:0c: + CII.
(41-))
28c:0zeoc::;:. Dipheo)'1 + II J which IS equal 10 Ihe amount of hydrogen to the makeup gas stream YrHfc;.
and we arc 1I\e:o thaI the: dc:smcd proouclioo nlte of bc:nzcoc: 1$ p. _ 265 mol/hr Similarly, the methane flow rate leaVing the process will be the amount of melhane
(ElIImple: 41-1) If we usc a gas recycle: and purge: nrc:am for the: H J Ind CI-I.,lnd If entering the process. (I - YrHWG' plus the amounl of melhane producro by lhe
we: recover Ind re:mo~e lhe dlpbenyl, lhen there are three: product Ilrc:ams; see reaetJons, P It.CH. = P.IS, or
E10Impie 51-2 Ind tbe: 6o......ihect lI\eo In Fig.. 5.1-2-
p.
We nole from Fl!. 51-2 that aU the toluene we feed 10 the process gelS POI. - (I - YrJl)Fc; +S (5.2-5)
convc:ned (I.e.. no lolu.eoc: lea... es the system). However, dUI does DOt mean that the
con..-erswn of loluene: lD the reac!or is unity A low conver-non per pass stmply means
thlt there .....111 be I large inlernll reqck flow of loluene.. H01O'ever, we eVlluale: tbc:se The t01a1 purge flow rate PG will then be Ihe c:xocss H J , FE, plus the tOla! methane
rttyde: flows III later stage of our desIgn procedure:. Of course:. our lS5umptlon lhlt POI.. or
aU !he fc:e:d loJuene is con\er1c:d negJc:eu any IOII1C:DC 1055CS lD any of tbe product
II reams, bUI IhlS COtTesponds to Our Initial design assumpllQn of complete: recovery (5.2-6)
~ersus I!lfClter than 99~. reoovenes.

Rather thao uSing the excess hydrogen feed F £ as a design variabk, we

SELECflVITV AND REACTION srOICIUOMETRY. We ddioe the ulectivity S normally use tbe purge composJllon of the reactanl 1'H' wMre
as the fraction of loluene converted In lhe reactor that corresponds 10 the benzene
flow al lhe reactor oUllet Also, we recover and remove aHlms benzene. Hen«, for F,
)"H = - (5.2-7)
a production of p. mollhr, tbe toluene fed to the process F FT must be p.
p. This purge composmon IS always bounded belween zero and unity (aclually there
FrT=~ (5.2-1)
S is a smaller upper bound which depends on the feed composition and sometlmes on
lbe conversion). The use of bounded variables makes the preparalion of graphs
Also, from Ihe StOIChlomelry (Eq. 5.1-3), the amount of melhane produced PIt.CII.
simpler.
must be We can develop expressIons for the makeup gas rail' F G and the purge rate
p. Pc; explicitly ID tenns of the purge composition of reactant }'rN either by using
PIt.Ol.. = S (52-2) Eq. 5..2-7 to eliminate F£ from Eqs 5,2-4 and 5.2·7 or by writing balances for the
hydrogen and methane and then combining them. That is, the amount of hydrogen
If a fraclion S of toluene is con ..erted to benzene, a fraction J - S must be 10SI to in the feed must supply the net reaction reqUirements as well as the purge loss
diphenyl. However, from the stoichiometry of Eq. 5.1-3, the amounl of diphenyl
produced PD musl be
(5.2-8)
(5.2-3)
and the melhane in the fec:d plus lhe methane produced must all leave with the
Since the toluene stream contains no impurities, we find Ihc: tnluene fresh feed purge
rale and the diphenyl by-product flow rale in tenns ofselcctivity from the reaclion p.
stoichiomelry and the given production rate. A relationship between selectivity and (1 YtH)FG + S = (1 Y'II)PG (5.2-9)
conversion is given ill Example 4 I-I.
Addmg these expressions gives
RECVCI.£ AND PURGE. The stoichiometry also indicates the amount of H J r. I- S (5.2-10)
required for Ihe reaclion If we feed an excess amounl of hydrogen, "-1;' inlo Ihe P.. -FG + S 2
 We can thcn solve for Fr;: of the desired component divided by thc production of thc undesired component
For the HDA process. in the first case we would ha\c

(52-II) s
. = ~_I_ -:: 2~l
(,
(5.2-18)

whcreas in the second case we would ha\c

If we are given valucs of p •• S. and either F[or Y'H' we can use the abO\e
equations to calculate the fresh feed rate of toluene. FH (Eq 5.2.1), the production ~l - 2~l
rate of diphenyl, Po (Eq. 5.2·3), the makeup gas rate Fr; (F..q. 5.2-4 or 5.2.11), and S. = (5.2-19)
(,
the purge f1owrate. PG (Eq 5.2-6 or 5.2-10). Thus. we have detennined all the input
and output flows in tenns of the unknown design variables S and either F £ or )"H' II is essential 10 ensure that the definition of seleclivit~· that IS reported by a chemist
(or in the litcrature) is clearly defined. but it is a simplc matter to COfl\'ert from one
definition to another.
MATERIAL BAUNCES IN TERMS OF EXTENT OF RUCTION. It is becom-
ina common practice 10 describe material baJance: calculations in tcrms of the Enmpk 5.1--2 Tor_ to kurer.. De\~lop tbe apressioas relauD@ lbe utcnlS of
utcnt of reaction ~ I (or fractional extent of reaction). Thus, for tbe HDA process. reacuon to prodtlClion ratc and $ClcctivlI) for tbe HDA process.
we would say that ~I mol (or molesjhr) of toluene react witb ~I mol of H 1 to
produce ~l mol of benzene plus ~I mol ofCH ... Also, 2~1 mol ofbenune produces SoIMtioll. From Eq~. 5.2-15 and 5.2-1 we: find that
C1 mol of diphenyl plus ~l mol or hydrogen. Then, we combine these statements to p.
5ay that C· s (52-20)

Net benzene produced - ~I - 2~l (5.2-12) Also from Eq 5.2-12 "'c find Ibat
Methane produced _ ~I (5.2-13) (5.2-21)

Diphenyl produced .., ~l

Tbu.s \III'e: can \III rilc
(52-14)
Toluene consumed - ~l (5.2-15) (52-22)

Hydroaen consumed - <I - ~l (5.2-16)

Stream Tables
We can generahze these expressions and say that the number of moles (or
moles per hour) of any component is given by It is common practice to report material balance calculations In tenns of stream
tables. That is. the streams are numbered on a flowsheet, and then a table is
(5.2-17) prepared that gives tbe component flows in cach of these streams which correspond
to a particular set of values of the design variables.. An e:xample is given in Fig.
where the II IJ arc the stoichiometric coefficients, which are positive for products and S.2-1. Tbe temperatures., pressures, and enthalpy of eacb stream also are normally
negative for reactaol5.. Normally (for tbe purposes of initial design calculations) no listed_ Since we do Dot consider energy balances until thc end of thc synthesis
products are fed to tbe process, II; = O. and no reactants are aUowed to lea\'c, procedure. we add th~ \·alues to the stream tables later
"J "'=' O. Experience: indicates that it normally is possible to correlate tbe extent of One major difficulty with this conventional practice: is that the designer is
<,
each reaction aaa-iost the per·pass conversion of tbc limiling reactant., although forced to select values of design \'ariables without knowinatbe optimum values.
in some: cases the molar ratio of reactants, reactor temperature, and/or reactor Moreover. once a sct of values has been selected, it is orten difficult to remember
pressure: must be included in the correlation. tbat they were selected arbitrarily. For this reason, we recommend tbat the stream
tables list the: values of the design variables and that the appropriate material
balance equalions. such as Eqs. 5.2-1. 5.2-3. 5.2-4 5.2-6. etc.. be programmed on fI
EXTENT VERSUS Sf:L.ECT1VITI. For lhc case or only two reactions. It often is ~pread~heet such as LOTUS. With this approach it is very easy to change: the
simpler to describe the product distribution in terms or selectivity. Selectivity can production rate and the design vanablc:s and then recalculate: all the stream nows.
be described in a number of different ways, such as the production of the desirable We can use this same table as the basis for calculating the: stream costs a~ a functi(>n
component divided by the amount oflimiling reactant converted or the production of the design variabks.
 130 SECTION S! DeilON V"II"aLES., OVaAlJ.. W"TUI"L ......... NCeS. "NO s.-."".. COSTS
UCTION H Of.SKiN V"kl"lu.s. OVUAU M"TUI"L II"LANCES, "ND srlEA.M COSTS 131

TAllLE U-3
5 Purge
Cost datil for HOA process
H 2, CH 4
I
I I H2, C H,
Value of berw::n~
Vilue or lolll~n~·
SO.8S/gal = S904/mol
so SO/gal _ S6 4O/mol
3
Benzene Valll~ of H J feed S3 00/1000 fl' .. Sl l>l/mol
Process Fud ~ Sot 0/10· Blu
2 4
Diphenyl Flld valu~, H, o12l " 10" lilli/mol
ToJuen , CII. 0.383 " 10· Bill/mol
Benzene 141 " 10· Blu/mol
Production rale = 265 Tolu~nc 1.68 " 10" Blu/mol
DipbCllylt 2.688 " 10" Blu/mol
Design variables: FE and x
• A .. u.... lIP 'Dlemaltran.f~r·,,",," value v...... the cun~QI
pnca. nl U.l6/pJ.
Componem 2 3 4 5 t w. a.Ioo ......"'" wt the fuel val... nl d,pbe..yl .. SSJI/IDO!.
H, FH , 0 0 0 FE
The economic polential is the annual profit we could make if we did not have
CH. FM 0 0 0 FM + PsiS to pay anything for capital costs or utilities costs, Of course, if the economic
Be=~ 0 0 p. 0 0 potential is negative, i.e.• the raw materials are wOrlh more than the products and
Toluene 0 PsiS 0 0 0 by·products, then we want to tenninate the design project. look for a less expensive
source of ra..... materials, or look for another chemistry route that uses less
Diphenyl 0 0 0 Ps(l - S)/(2S) 0 expensive raw malenals.
Temperature 100 100 100 100 100
Pressure 550 Example 5,2-3 HDA Siream CMIS. If we use Ihe coS( dala given in Table 5.2-3.
15 15 15 465
""here tbe values of H l ' CH., and dlphenyl in the produci Streams are based on the
where S I 0.0036/(1 X)U44 FH1 _ FE + PB(I + S)/25 healS of combusllon of lhe compollc:nls and a fuel value of S4/I06 BlU. we can
FM = (1 - YFH)(FE + P8 (1 + S)/S))IYFH calculale Ihe economic polential for lhe HDA process in terms of lhe design variables
Fa = FHI + FM
(""e use reactor conver~ion per pass x, instead or S. and YI'H). The results arc sho... nlll
FIGURE 5.2-1 Fig. 52·2. The graph indicates lha' al high conversions Ihe process is llnpt"ofilable
Siream ur.bk HDA prOOCSli.

4,000,000
Stream Costs: Economic Potential
3,000,000
Since the Kbest" values of the design variables depend on the process economics, we
want to calculate the stream costs, i.e" the cost of all raw materials and product 2,000,000 YPH
streams in tenns of Ihe design variables. Normally, we combine these costs into a
single term, which we call the economic potential (EP). We define Ihe economic
potential at level 2 as ~
"
1.000,000
0
---.. "'" ~
~
~
...... 0.1
-+- 0.7
___ 0.9
-1,000,000
EP l = Product Value + By-product Values i".. 'li
- Raw-Material Costs, Slyr (5.2-23) -2,000,000
which for an HDA example would be
EP = Benzene Value + Fuel Value of Diphenyl + Fuel
Value of Purge - Toluene Cost - Maleeup Gas Cost (5.2-24)
-3.000,000
-4,000,000
0.1 0.2 0.3 0.4 0.5 0.6
" 0.7
Conversion x
We would also subtract tbe annualized capital and operating cost of a feed FlGURE 5.2·2
Eco"omK POI~DuaJ-lcvel 2.
compressor, if one is needed. (fhe calculations required are discussed in Sec. 6.5.)
 SECTlQN,. 'l-'loll.MIlY. VIllOSE$, .....-n NOIoIE"ClATU." 133

TABLE s.J.t 1. Should we purify the feed stream?

Alternatives for the UOA 2. Shouk! we remove or recycle a re\'ersiblc by-product?
p<oc""
3. Should we use a gas recycle and purge stream?
I. Punfy the bydrOlC'D r-t JlrcanL 4. Should we use: an excess of some reactant that we discard?
1. Rcqdc 1M dlpheTl)'llo ulJnctK>n.
S. How many product $Ireams will there be?
J. Punfy lhc U.-rceyCH. JlIam
6. What are the design variables and the economic trade-ofTs al this Je\d of
analysis?
(u~..•'C con"crt so much loluene 10 dlphen}l Ihal lhls selccuvllY loss ucecds the In some ca§eS heunstJCS can be used to help make these decisions. When no
mcrcucd value of the benzene Ihal ~ produce). Also. al hIgh pur!C composItiOns of heuristics are available. we make a guess and then hst the opposile decision as a
hydrogen ..~ lose money (~lose so much hydrogen to fucllhal"~ cannol mue up process alternative. We complcle • tint desigo based 00 ow original guess before
for IhlS )os;s). we consider any other alternatives. (Since Ic:ss than 1 ~ ofidcas for new designs arc
Aocordm! 10 the gnlph. the mosl dcsu'lIbie vall.lCS (i.e., the Wellesl profil) of suca:ssful. we might learn something about the process thai will make all the
lhe design vllnables corrcspond to x _ 0 (i.e.. no sc:lCClivily loss) and a reactant
alternatives unprofitable.)
composlIion or lhe purge slream Y'B equal to tero (i.e~ purge pure rm:thane),
As we prooeed lhrough the design, ho...·ever, we find lhal a tero conversion per Some of the heurislics and design guidelines that were presented include Ihc
pass (x - 0) corresponds to an infimtdy large recycle 801" of toluene and that purpng following:
no hydrogen lI,. - 0) corresponds 10 an Infinuely large gas-KC}'C1e Row Hena:, ...e If a feed impurity is not inert, remo"e it
develop Ibc:.opumum vall.lCS or x and Y"" as "'~ proc:eed througb the design.
If an impurity is present in a gas feed stream. as a first guess process the
unpurity.
5.3 PROCESS ALTERNATIVES If an impurity in a liquid ked stream is a product or b)·product. usually f~
In our development ofa design for the HDA process (see Fig. 5.1-2), we made the the process through the ~paralion system_
decisions (I) nol 10 purify the hydrogen reed srream, (2) 10 remove the diphenyl an impurity is present in large amounts. remove it
[f
from the process. and (3) to use: a gas recycle and purge stream. If we change any of If an impurity is prese:nt as an a7.cotropc with a reactant. process the
these: decisions, we generate process allernatives. It is always good practice to make Impurlly,
a lisl of Ihese alternauves. Such a hSI tS given in Table 5.3-1. If a feed impurity IS an inert. but is easier to ~parale from the product and
bl-product than from the feed. il is beUer to process the impurit}·
Evaluation of Alternath"es Whenever there is a light reactant aod a light reed impurity or by-produci
We could attempt to SImultaneously develop designs that corresponded to each (where ligbt components boil lower than propylene, _48°C), use a gas recycle and
process alternative Ho....ever. if we remember that less than I ~ of ideas for new purge stream for lhc first design. Also consider a membrane separator later.
designs ever become commercialized, our initial goal should be to eliminate, with If O 2 from air or water is a reactant, consider using an elcen. amount of this
as little effort as possible. projects that will be unprofitable. Thus. we prefer to reactant.
complete the design for one alternative as rapidly as possible before we give any For single-product. vapor-liquid processes. we determine the number or
consideration to tbe other alternatives, for we might encounter some faclor that product streams by grouping components with oeigbboring boiling points that
will make all the alternatives unprofitable. Then, aner ViC have compleled a base- have the same exit destinations; i.e.. we never separate streams aod then remiJL:
case: design, \\'e examine Ihe alternatives.. In the terminology of artificiallOteUigeooe th<m.
(AI), we arc using a tI~pfh-first, rather Ihao a br~odlh-firsl. stnJl~gy. Be certain thai all by-products and impurities leave the process!
The: significant design variables are those that affect the product distribution
5.4 SUMMARY, EXERCISES. AND and purge compositions of gas streams
NOMENCLATURE Raw-material co~ls arc often in the range from]J to 85~~ of the lotal COsl~

Summary Exercises
The queslions we must answer 10 fix the mput-oulput structure of the flowshect 5.4-1. Draw the inpul-outpul no...sheEt .nd plot lhe CIODfK)I'Tl;C rolenhal rot'" the IIDA.
include the follo.... in~ rorOOCft for the cue wherr. the dlphc:n)t Os rec:yclaI