_

class and home prOblems )

Th e objec t of this column is to enhance our readers ' co llectio ns of interesting and novel problems in chemical engineeri ng. Probl ems of the type that ca n be used to motivate the student by present ing a particul ar principle in class, or in a new light , or that ca n be assig ned as a novel home problem , are requ ested , as well as those that are more traditio nal in nature and which eluc ida te difficul t co nce pts. Please submit them to Professor Ja mes O. Wi lkes (e-mail: wilkes@e ngin.umich.edu) or Mark A. Burn s (e-mail: maburns @engin.u mich.edu ). Chemical Engineering Department , University of Michigan , Ann Arbor, MI 48 109-2 136.

AN INTRODUCTION TO PROCESS FLEXIBILITY

Part 2: Recycle Loop with Reactor
W.

E.

J ONES, J.A. WILSON

Uni versity of N ottingham No tti ngha m, N G7 2RD, Engl and

n earlier article!I ] disc ussed teachin g flexibilit y via a simple heat-e xchan ge problem. Heat exc hange is a convenient starting point for flexibility teac hing beca use the equations and res ulting ca lculations are easy to handle. Other process operations can rapidly become complex and a rigorous treatm ent very demanding.!" Hence it is pleasing to find that a potentiall y complex recycle loop with reactor can be simplified to prov ide a thought-p rovokin g, process-flowsheet-based exercise that emphasizes understanding of the sys tem's operation.

reactor. The reactor is part of a recycle loop where product is separated fro m the reac tor effluent and unreacted feed is recycled (see Figure I). It is well known that when designing recycle loops, an eco nomic optimum exis ts for reactor conversion that balances reactor size against the combination of produ ct separa tion load and circulation rate. Having chose n the design conversion, the circulation rate is an immed iate consequence in order to meet the required
Warren Jones holds a s c and PhD degrees in chemica l enginee ring from the Unive rsity of Nottingham and is a registered Chartered Engineer. He has a wide-ranging interest in both frontend process and detailed plant design, developed initially through nine years of experience with a major engineering and construction company. Teaching responsibilities include several design courses, and engineering thermodynamics.

It is important to stress, eve n with simplification, that the recycle loop is still a much broader exampl e than that for heat exchange , makin g the exe rcise more suitable as a basis for proje ct work or a discussion question. One of the authors first became interested in the prob lem when attempting to expl ain the operating bounds of an ammonia or meth anol synthesis loop durin g the course of final-yea r design projects. The reactor used in this exercise is a simpler design than comm only found in amm oni a and methanol plants, but the exerc ise still illustrat es man y of the issues that make design and operation of such process systems so interesting.

BACKGROUND
The exerc ise considers a reversible exo thermic reaction taking place in the gas pha se ove r a catalyst in an adiabatic

Tony Wilson holds a s c and PhD degrees in chemical enginee ring from the University of Nottingham. With industrial and consulting experience in process control and batch process engineering. and with active research in both fields. he coordinates the department's research in computer-aided process engineering and is responsible for process control teaching at the undergraduate level.

Copyrigh t ChE Division of ASEE 1998

224

Chemical Engineering Education

production. The choice of reactor ope rating temp erature is also important and may be opt imized by the desig ner as part of the reactor size-separation load/circulation rate trade-off. In the case of reversible exo thermic reactions. se lection of

a relatively low temp erature per mits a higher conversion, but this must be balanced agai nst a slower rate of reaction leadin g to a large catalyst inventory. The design co nversio n for reversib le exo thermic reactions ofte n approac hes quit e closel y the upper bound impo sed by thermodynamics. Finally, the temp eratu re wil l increa se through the catalyst bed, but a single tem pe rature va lue is needed to c ha racte rize o peratio n; for th is we wi ll use inlet temperatur e. It is assume d that react or inl et temperatu re ca n be adju sted inde pe nde ntly .!!' For a flexi bi lity study . the ca talyst inve nto ry and othe r eq uipme nt will be fixe d ; we are int erested in investigating ho w the plant will per form und er alte rna tive op erating co ndi tio ns. From the earlier discussion. two obvious parameters to character ize operation are circulation rate and reac tor inlet temperature. As noted before, the reactor inlet temperatures ca n be adjusted to maximi ze produ ction for fixed circ ulation rate (illustrated in Figure 2a p l). To the left of the maximum, increasing inlet temperature improves the rate of reaction, lead ing to more production. But as the temperature increases, the deteriorating equilibrium conversion impose d by thermodynami cs "bites," and production peak s. Operation at the optimum inlet tempera ture ensures that the minimum circulation rate to meet production is being used ; we ass ume the optimum temp erature to be selected in each case. A typical industrial exa mple is more complex and invo lves four additional considera tions: Catalyst deacti vation Producing circulation around the loop Loop pressure Presence of an inert component in the make-up gas

~ Iake-up , ) L - - -+ r gas (MU G) (,.

---,

Loop ci rculation Circulation compressor Reactor Pr od uct sepa ra tion

Purge . (o nly needed if M UG co ntai ns a n inert co mpo nent)

.--- ----'----

Product

Fig ure 1.

a
0.125 0.12
u 0.115 Ql .!!l 0.11 "0 E 0.105

,.- ...
,/ /

.........

..".---- ----- .....

20% extra flow

""
(J l:

.-'

'0
0 :;:; :::>
"'0

0.1 0.095 0.09

.-_.- . ' . _' .... ....

k"" 40 t

"

-~

.
30t

a. 0.085
0.08 0.075 500 505

- -- -------- --510 515

20% less flow

--- --525 530 535

520

Re a c to r In le t Te m perature K

EOR Catalyst Ac tiv ity

The catalyst ca n be deacti vated in seve ral ways.!" Here, we are more interested in the ove rall effects of deac tiva tio n than we are in the details of one particular mechanism, so we adopt a simple modelnamely, un iform deac tivation througho ut the ca talyst inventory. Th e norm al respo nse to loss of productio n through ca talyst deactivation is to raise the react ion rate by increa sing the inlet temp erature. For rever sible exo thermic reactions, however, this action further limit s the conve rsion, and unle ss the circulation rate is also increased , the prod uction target will not be met.
-'-_...I

0.08

L-

......

......

......

""-

475

485

515 505 Rea ctor Inlet Te mperature K

495

525

Fig ure 2.
Summer / 998

The effects of catalyst deacti vation are demonstrated in Figure 2b, which compares performance at beginni ng-of-run (BO R) and end-of-run (EOR). Note particularly that the BOR circulation rate is
225

Parts 1 and 2 of this paper introduce flexi bility by providing exercises th at force the student to consider how the system will actually operate-this is an important first step for developing a robust design. Further, a wide-ranging knowledge of ba sic chemical engineering is required, making these exercises (particularly Part 2) ideal as the basis for project work.
15% less than that for Ea R; if the EaR circulation rate were implemented at BaR, ove rpro ductio n wou ld result. Norm al design practice wou ld be to set the loop process parameters for EaR ope ratio n, but produ cing a design sufficiently flexib le to opera te at BaR is clearly very desirable. Loop circulation is norm ally produced using a var iable speed centrifuga l co mpressor, so compressor characteristics become import ant in meetin g process flexibility. Centrifuga l compressor charac teri stics are represe nted by a head-capacity curve and, for recycle sys tems (where the loop pressure drop is 10% or less of the nomin al operating pressure) the loop can be treated as one of constant density, and the compressor characteristics will have roughly the same shape as those obtained for centrifugal pump s. Figure 3 show s the operating point to be defined where the sys tem curve intersec ts the co mpressor characteristic; for a recycle loop the system curve is based solely on fricti on losses beca use the discharge returns to the suction. Also show n in Figure 3 is the implem entation of redu ced circulation rate via co mpressor speed redu ction. The affinity lawslsi ca n be applied to relate compressor performance at different speeds . Sometimes the speed redu ction requi red is quite large, takin g the compresso r close to a critical speed, which indu ces synchro nous whirling of the shaft; this condition must be avo ided and hence places a lower bound on operation. Typically, critical speeds are found in the range of 60 to 80% of normal running speed. Two other constra ints that arise from compresso r opera tion are loop pressure. Varying loop pressure is helpfu l when matching compressor ope ration to process requ irements because

A reduction in loop pressure increases the circulating gas specific volume; hence. circulating the same quantity of gas would require a faster compresso r spee d to cope with the larger volumetric flowrate, i.e., moving operation m vay fro m the critical speed. If the reaction is one where there is volume reduction as the reaction pro ceeds, pressure reduction will give a lower, thermodynami c limited, conversion, and this will lead to a larger circulation rate and a move away fro m the critical speed.
Th e loop pressure ca nnot be set independently, however. In a simple exa mple where the feed contains no inert component , the rate of reac tant consumption (in the reactor) must balance the rate of make-up gas (MU G) flow into the loop in order for the pressure to remain steady. In other word s, at steady-state, the reac tor inlet temp erature and circulation rate (co mbined with the pressure) must give a reaction rate that j ust balances the M UG rate. If the circulatio n rate, say , were smaller, the loop wou ld equilibrate at a higher pressure with the extent of the pressure increase being limited by the relief valve setting on the loop. Finally, we need to consider an inert compo nent in the MUG. In man y indu strial exa mples, the MUG to the synthesis loop is not pure reactant, but contain s I to 2% by volume of an inert component. Unless the inert is removed, it will accumulate in the loop and slow the rate of reaction. In a pressur ized loop, some inert will dissolve in the product, but

Maintenance of sufficient volumetric flowra te through the machine to avoid surge; for a low-head compressor (as considered here) this constraint will lie well to the lef t on the head- capa city curve (aro und 50% of normal capac ity) and hence will not be influential. Overspeed trip. typically set at 10 to 15% above the normal running spee d; this constraint obviously "bites " fo r operating modes requi ring higher circulation rates.
The constraints impo sed by compressor operation lead to the third parameter that required furth er con sid eration-namel y,
226

800

r------------------------ - ---,
EOR Operati on 10000 rpm

700

600

E
'g SOO
ell

Systems Curves 8420 rpm

:I:

400 300

r----2~~--_~
"'--_ _......._ _---''--_ _......._ _......._ _--J

200 ' - - - -.......::;;'O::'--........ 0.6 0.7

0.8

0.9

1.1

1.2

1.3

1.4

Ac tual Vol umetric Flowrate m A3/se c

Figure 3.
Chemical Engineering Education

most has to be purged from the loop (see Figure I). A relatively high purge rate ensure s the inert composition in the recycle loop is low and the rate of reaction high for the pressure beca use the inert has only a small diluti ng effect. A high purge rate, ho we ver , results in a large reactant loss and. in des ig n mode, se tti ng the purg e rat e is an econo mic opti mization that add s the third dimension of MUG rat e to the reactor size- se paratio n load/circulati on-rate balance alread y di scussed . From a flexibility viewpoint. recycle loops with purg e can fully exp loit the interacting trio of parameters (circulation rate. reactor inlet temperature , and pressure ) becau se pressure ca n now be set indepe nde ntly via the purge rate rather than bein g a co nsequence, as previou sly noted. To illustrat e, if the loop is initi all y at steady state, redu cing the purge rate causes the inert composi tion to increase, so the loop press ure must increase to restore the reactant partial pres sure s. T here will be a compensating reduction in MUG demand. If the circulation rate is also increased . it will limit the change in press ure needed. In view of the co mp lexi ty added by con sidering an inert in the MUG, the main part of the exerci se concentrates on pure M UG ; handl ing an inert in the MUG is co nsidered at the end of the exe rcise.

stoichiometric proportions (mixture RMM=50): he nce the recycle stream also contains only A and B, and the purge flowrat e will be zero . The recycl e loop at end-of-run (EOR) is designed to operate at a nomin al pressure of 50 bar, wit h a circulation rate through the reactor of 2.2 kmol sec' . The EO R loop pressure drop is 5 bar; this compri ses 4 bar for all eq uipment excl uding the reactor and I bar for the rea ctor. Th e EO R reactor pressure drop may be furth er dec omposed:

Pressure drop (based 0/ 1 EOR circulation rate) for reactor if catalyst were in good mechani cal condition: 0.7 bar Allowan ce (based on experience) fo r catalyst particle breakdown and loss of voidage: 0.3 bar
Circulation throu gh the reactor is provided by a singlestage centrifugal compressor who se head (He. m) - capacity (Q , rrr' sec') cha rac teristic at 10.000 rpm is rep resen ted by
H e = 530.5 + 149.5 2 Q - 130.58 5 Q 2

The exercises below examine the process tlex ibility requirements for the synthes is loop as the catalyst invent ory of 35000 kg slowly deacti vate s. Catalyst deactivation is modeled by assumi ng EO R k, and k H values are only 30 % of those app lying at BOR (see Tab le I). You may assume the heat exc hanger arra nge ments on the reactor feed have sufficient flexibi lity to prod uce a wide range of reactor feed temperatures and the co mpressor suction operates at 40 C. Also , assume the reacta nts A and B have negligible solubility in the product. I) Determine the maximum production of C ac hievab le at EO R conditions by varying the reactor inlet temperature . 2) Yo u wish to achieve the same produ ction rate of C as that calc ulated in ( I). but using BOR ca talyst. a) Calc ulate the circ ulation rate required if the loop pressure remains at 50 bar. b) If the circulation rate is maintained at 2.2 kmol sec:'. at what pressure wou ld the loop need to operate? c) Use the insight you have gained from so lving 2(a) and (b) to exp lai n the interrelatio nship between loop pressure . circu lation rate. and reactor inlet temp eratur e. How might you ex ploit this flexibility to deal with variation of catalyst activity? 3) a) Co nfir m the co mp ressor speed of 10.000 rpm will satisfy EO R operati ng co ndition s. b) Deter mine the co mpressor speed for 2(a). c) Determin e the co mpressor speed for 2(b). d) Comment on your answer to 2(c) in light of the compressor speeds you have j ust calculated.
227

(-------------)
PROBLEM STATEMENT
The reversible exot hermic chemical reaction
A +B ~ C

takes place in the gas phase over a fixed catal yst bed in a reac tor operated adiabatica lly. T he reac tion da ta are summarized in Tabl e I. Th e reactor form s part of a recycl e loop (show n in Figur e I) where C is totally separa ted from the reac tor eftl uent. For the first three parts of the exe rcise, yo u may ass ume the make-up gas co ntains only A and B in

TA B LE 1
Reaction Data for the Exercise
Heat of reaction

=- 14000 kJ per kmol of C formed

Rate of production of C by the forwa rd reaction = k.P A PH where k, = BOR rate constant. krnol sec" bar" (kg of catalyst)" k, = 100 exp (-94000/8.3 14 T ) Rate of destr uct ion of C by the reverse reaction = kHPc where BOR rate constant. krnol sec" bar" (kg of ca talyst)" 525000 exp(-108000/8.314 T) partial pressures of A. B. and C. bar abso lute temperature of the reactin g mixtur e. K Specifi c heat ca pac ities: CP A' CpR ' Cpc = 30. 40. 70 kl k rno l' K"

Summer /998

4) Th e M UG to the synthes is loop co ntains 2% of an inert co mpound, I, in additio n to equal proportion s of A and B. If the circulation rate is 2.4 kmol sec' I and the pur ge rate is 0.050 91 kmol sec', de term ine the loop opera ting pressure to meet the production target from part I. What wo uld happ en if the purge rate were redu ced further , and how would you mitigate the co nsequences ?

(------

SOLUTION

-----)

dent s should be aware that there are three im portant variables . Reactor inlet tempera ture can and sho uld be optimized for all situations, but circulation rate and loop pressure are related and cannot be set inde pendently. Th e above exe rcises take the two ex treme posit ions of maintain ing loop pressure or maintainin g circulation rate; the co rres ponding maxi mu m red uctio n in circulation rate or loop pressure is then calculated. In practice, an opera tor wo uld use a sma ller change in circulation rate and allow the loop pressure to equilibrate with a red uction some what less than the max imum change previously calculated. 13(a.)1 Plottin g the head -capacit y curve using the given equation produ ces the 10,000 rpm line in Figure 3. The Ea R circulation rate is 2.2 kmol sec" or a co mpressor suction flowrate of [(2.2)(0.08314 )(313)]/50=1.14501 3 sec", and as may be seen fro m the cu rve or equation, this implies that a He of 530 .5m will be thrown up. If the loop pressure drop is 5 b a r, thi s is e q u iva le nt to a n H, o f (5)( I 0 5 )/ [(9. 81)(96.07)]=530.5m, i.e., Hs=H e and the co mpressor speed of 10,000 rpm will satisfy Ea R opera ting conditions (96.07 kg m' is the gas density at the co mpressor suction and is calc ulated from the ideal gas law). 13(b).1 In this case, the sys tem head will be prop ortional to the (circulation rate r' because the loop pressure is main tained at 50 bar and thus the gas de nsity can be assum ed co nstant. We neglect the effect of min or com position and reactor ex it temp eratur e changes. Thu s the sys tem curve passes through the vo lumetric tlowrate [(2)(0.95 1)( 1.145)]/ 2.2=0.9899 rrr' sec' at a head of [(4 .7)(530.5)(0.951 {2/2.2} r ]/ 5=372 .7m. Stable opera tion requ ires the com pre ssor speed to be reduce d such that the head- capacit y curve also passes through this point. Let N be the new compress or speed and the stable operati ng point must map back onto the 10,000 rpm head-capacit y curve . T hus

Th e solution of this probl em requi res a model for the chemica l reactor, which is eas ily generated by integrating the differential mass and energy balances thro ugh the reactor :
dFc = q( k pPAP - kB P ) B C dw
dT
dw q 14000 ( kp PAPB - kB PC) (FAC P A + FBC pB + FcCpc)

where w is the mass of catalyst and q is the mult iplying factor to acco unt for ca talyst deacti vation. At the reactor inlet, the tlow rate s and tem perat ures are FA=F A ' FB =F B ' Fe=O, T=T o, and at any subsequent point , O O FA =F A =F B o-Fe. Ideal gas behavior is assumed to O - Fe, FB calculate the part ial pressures, e.g., PA=PTFA /(FA +F B+Fe), where PT is the nominal loop pressure. Any one of a numb er of numerical integ ration packages can be used.

[!J Setti ng FAo=F so=l. l kmol sec:', q=0.3, and Pr5 0 bar,
the model is run for a range of inlet temp eratures To. Fe is noted after integration thro ugh 35 tons of catalyst and the result s rec ord ed as a plot of Fe aga inst To(see the middl e curve in Figur e 2a). The peak indicat es a maximum produ ction of 0.10206 kmol sec' for C at an inlet temp erature of 517K. (Note the sensitivi ty to circulation rate change s, but relati ve lack of se nsitivity to cata lyst invent ory changes as indicated by the other curves in Fig ure 2a.) 12(a).IFor BaR catalyst q= 1.0 and Pr5 0 bar, the prob lem requ ires a trial-and-error so lution to find FA O and F B O that gi ve the req uired production of Fe. A solution is found for FAo=F B =0.95 I kmol sec' with a reactor inlet temp erature of O 487 K (see Figure 2b). (No te: maintaining the EaR circulation rate gives a large over prod uction .) 12(b).IFor BaR catalyst q= 1.0 and F A o= 1.1 kmol sec:', o=F B the probl em requires a trial-and-error solution to find PT that give s the requi red production of Fe. A solution is found for PT=43.64 bar with a reactor inlet temperature of 495K. 12(c).1By performing the calculations in 2(a) and 2(b), stu228

Solving the quadratic gives N=84 20 rpm ; this is shown as the second compresso r curve in Figure 3. (T his is quite a large speed reduction and may brin g the co mpre ssor qu ite clo se to the critica l speed.) 1 3(c the

)1In this case, the sys tem head will be proportional to

circulation rate )2 ( loop pressur e
Chemical Enginee ring Education

because dropping the loop pres sure has a strong effect on gas den sity. The req uired poi nt on the sys tem cur ve is defined by [( 1. 14 5 ) ( 5 0 ) ]/43 .64 = 1.3 1 19 m 3 se c 1 at a head o f [(4.7 )(530.5 )( {50/43.64 f) ]=654. 6m. Usin g the same approach as that applied in 3(b), but this time anticipating a speed increase, we solve the quadrat ic to give N= 11,160 rpm . (T his is quite a large speed increase and may brin g the machi ne clo se to overspeed trip.) 13(d).1 Answer 2(c) advocates a midd le path- some redu ction in circ ulatio n rate and a corresponding loop pres sure reduction. The answers to sec tion 3(b) and (c) show that if loop press ure or circ ulation rate is mai ntain ed, the extreme s of com pressor speed are also approached, i.e., 2(a) take s opera tion close the critical speed and 2(b ) resu lts in operation near overspee d trip. Hence, the midd le pat h requires a steadier mach ine speed, closer to normal running speed.

remain ; namel y I) flowrates of A or B in the reactor feed, X, and 2) M UG flow rate. M. Wr iting co mponent mas s bala nces for a reactant and the inert at the mixing point ju st before the compresso r gives
X = 0.49M +( X - 0. 1020d 2.1449 7 1 l 2.19588 ) ? 4 - ?X=O O?M (? 4 -? X)( 2. 14497 1 _. . - + _. - l Z.19588)

~ The equat ions represe nting the reac tor must be mod ified
to includ e the presence of the inert. Two changes are needed:
I. Inclu sion of the inert component flowrate, F" in the circ ulation rate (FA +FB+Fc+F,); thi s reduc es the partial pressure of any reactant.

Sol ving for X and M gives X= 1.089976 kmo l sec " and M=0.255028 kmol sec ", and henc e the reactor feed for the simulation is A and B, 1.089976 kmol sec' and I is 0.220048 kmol sec' . Note particularl y that the MUG rate has increa sed by 24 .9%, co mpare d to an inert free MUG , to account for the react ants lost in the purg e. So lving for the loop pressure in this part of the exercise is also by trial and error. A loop operating pressur e of 55 .62 bar will ensure the targe t production is met if the reactor inlet temperature is optimized at 5 17K. Reducing the purge will increa se the inert s com position of the gas in the loop. At co nstant circulation rate, the change must cause the loop press ure to increase in order to restore the reac tan t partial pressures. For hig h-pre ssure systems, the re lief valve is typically set at 10% above norm al run ning pre ssure ; hence the calcul ated loop pre ssure of 55 .62 is prob ably unacceptable if 50 bar is viewed as nor ma l operation . A further reducti on in purge flow would cer ta inly cau se the relief valve to lift. To lim it the pressure increase, the best tacti c would be to increa se the loop circulation rate.

2. Inclusio n of the inert co mponent heat capacity, F,C PI, in the heat capacity (FA CPA +FBCPB+FcCpc+F,Cp,); this provides a greater heat sink and so red uces the temperature rise across the reacto r. Before the reac tor simulation can be used , the effect of the inert co mponent on the recycle loop material balance must be estab lished . In particular we need the reactor feed composition. Fig ure 4 shows all the information easily deri vabl e from the prob lem sta teme nts, but two important unknowns

SUMMARY

l\IUG, 1\1
Co m po nent A 8 1

( ,L- - _ .- - - --,

l\Iole fr ac tion 0.49 0.49

0,02

Part s I and 2 of this paper introduce flexibility by providing exercises that force the student to co nsider how the sys tem will actually ope rate- this is an important first step to de ve lopi ng a rob ust design. Furth er, a wide-ranging knowledge of baReactor fced sic chem ical engineering is req uire d, making Co mpo nent kmol/see A X thes e exerci ses (particularly Part 2) idea l as the 8 X basis for proje ct work . 1 2.4-2X
2.4

2.14497 kmollsec Purge 0.05091 kmol/sec 2.19588 kmollscc Reactor effluent Component kmol/see A X-0. 10206 8 X-0. 10206 C 0.10206 1 2.4-2X 2.29794

REFERENCES
1. J ones , W.E ., and J.A. Wilson , "An In troduct ion to Proc ess Flexibilit y: Part 1," Chem. Eng. Ed., 3 1(3 ), 172 (1997)

2. Swan ey, R.E. , an d I.E . Grossma nn, "An Index for Operational Flexibility in Che mical Proc ess Design," AlChE J ., 31(4), 621 (1985 ) 3. Fromen t , G.F ., and K.B . Bischoff, Chem ical R eactor Ana lys is, 2nd ed., J ohn Wiley , New York , NY, p. 425 (1990) 4. Ibid . p. 219 5. Aer st in , F ., a nd G. Street , Applied Chem ical Process Desig n, Pl enum Press, New York , NY, p. 237 (1978 ) 0

L -_ _....

Pr odu ct kmol/see 0.10206

Component C

Figure 4.
Slimmer 1998

229