CinChE Material Balance Problems Chapter 5

Semi-Batch Reactor Example

Problem Statement

A new catalyst has been found that will produce styrene monomer at ambient conditions (25ºC and 1
atm). The main reaction converts the reactants of toluene and methanol into styrene monomer, water,
and hydrogen. A side reaction converts the reactants into ethylbenzene and water. The two reactants
in stoichiometric proportion are placed into a capped reaction vessel with the catalyst, and they are
allowed to react isothermally. All chemical components exist in the liquid phase, except hydrogen.
How much material in kg-mol is placed in the vessel initially to produce a desired amount of styrene
monomer? The molar conversion of the toluene is 80%, while the yield of the styrene is 75 mol%.

Conceptual Model

Diagram
initial time, ti final time, tf
capped vessel TG = 25°C
G no capped vessel PG = 1 atm
gas flow G
PhG = gas
Ti = 25°C gas
Why T f = 25°C nG = ?
Pi = 1 atm
define Pf = 1 atm Why xG , H 2 = 1.0
Phi = liquid
the Ph f = liquid define
ni = ?
process the
xi ,TL = 0.50 nf = ?
state? process
xi , ME = 0.50 x f ,TL = ?
state?
x f , ME = ?
x f , SM = ? Finds:
x f , EB = ?
Givens: x f ,WA = ?
ni in kg-mol

Rxn I: C7H8 + CH3OH  C8H8 + H2O + H2

toluene methanol styrene

Rxn II: C7H8 + CH3OH  C8H10 + H2O Assumptions:

toluene methanol ethylbenzene
1. semi-batch process
80 mol% conversion of toluene 2. basis of nf,SM = 150 kg-mol
75 mol% yield of styrene monomer

Based on the procedure in Chapter 4 for developing a conceptual model, the process unit is identified
to be a reactor system with six chemical components. The process unit operates as a semi-batch
reactor, because the reactants of toluene and methanol are placed in the vessel just before the start of
the process, and the hydrogen gas is flowing out of the vessel. Thus, this semi-batch process is being
observed at two points in time (ti and tf), and no material is “flowing into” the system boundary, but
material is flowing out. In the diagram above, the system boundary is the sides of the reactor vessel.

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 CinChE Material Balance Problems Chapter 5

Mathematical Model

CinChE
 Total: − nG + 1 RI = nf – ni
Eq. 5.4i units of nG, nf, ni ? kg-mol
units of RI ? kg-rxns
 TL: – 1 RI – 1 RII = n f , TL – 0.50 ni
 ME: – 1 RI – 1 RII = n f , ME – 0.50 ni units of a stoichiometric
coefficient ? kg-mol / kg-rxns
Eq. 5.5i  SM: 1 RI = n f , SM
 EB: 1 RII = n f , EB
 WA: 1 RI + 1 RII = n f , WA
 H2: − nG + 1 RI = 0
# vars = 10
 mix f: n f = n f , TL + n f , ME + n f , SM + n f , EB + n f , WA # eqns = 7
DOF = 3
0.50 ni − n f , TL
 Conversion: = 0.80
0.50 ni
# vars = 10
n f , SM # eqns = 9
 Yield: = 0.75
0.50 ni − n f , TL DOF = 1

Mathematical Algorithm

ni = reactor  n f , SM 

 1. RI ← n f , SM
 2. nG ← RI
Gaussian Elimination
nf,SM
3. Solve ni , n f , TL , in ni = ------------------------------
 0.50(0.20) ni − n f , TL = 0 0.50 · 0.75 · (1.0 - 0.20)
 0.50(0.75) ni − 0.75 n f , TL = n f , SM
nf,TL = 0.50 · 0.20 · ni
End

 4. RII ← 0.50 ni − n f , TL − RI
 5. n f , WA ← RI + RII
 6. n f , EB ← RII

 7. n f , ME ← 0.50 ni − RI − RII
 8. nf ← ni − nG + RI

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CinChE Material Balance Problems Chapter 5

Numerical Solution

EZ Setup Model, Michael Hanyak, Sept. 5, 2007

/* Semi-Batch Reactor Example, CinChE Manual, pp. 5-18 to 5-23

/* 1 - TM */ - nG + R1 = nf - ni

/* 2 - TL */ - R1 - R2 = nftl - 0.50*ni
/* 3 - ME */ - R1 - R2 = nfme - 0.50*ni

/* 4 - SM */ R1 = nfsm
/* 5 - EB */ R2 = nfeb

/* 6 - WA */ R1 + R2 = nfwa
/* 7 - H2 */ - nG + R1 = 0

/* 8 - conv */ 0.50*ni - nftl = 0.80*0.50*ni

/* 9 - yeild */ nfsm = 0.75*(0.50*ni - nftl)

/* basis */ nfsm = 150 // units -> kg-mol

Click here to solve this math model using the Excel "EZ Setup"/Solver Add-Ins.

Basis: mks, 150 kg-mol of styrene monomer

nfsm = 150 kg-mol

R1 = 150 kg-rxn
nG = 150 kg-mol

ni = 500 kg-mol
nftl = 50 kg-mol

R2 = 50 kg-rxn
nfwa = 200 kg-mol
nfeb = 50 kg-mol

nfme = 50 kg-mol
nf = 500 kg-mol

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 CinChE Material Balance Problems Chapter 5

Heuristic Observations See Page 4-24 in CinChE Manual

Numerical Solution

check: mix f: n f = n f , TL + n f , ME + n f , SM + n f , EB + n f , WA ?????? standard form

Which form do you
use and when? 500 = 50 + 50 + 150 + 50 + 200 OK
See p. 4-23 in this 1.0 = xf,TL + xf,ME + xf,SM + xf,EB + xf,WA normalized form
CinChE manual.

Mathematical Algorithm

Know ni instead of nf,SM, then math algorithm would not have a solve construct.

Could solve problem assuming ni =100 kg-mol and then scale the final answers.
Click here to learn about scaling.

Mathematical Model

Find the volume of the hydrogen gas that was produced in the semi-batch reactor. Why does the nG
not have a dot
Use the ideal gas law; that is, PG ·VG = nG·R·TG , and add it to the mathematical model. over it? See pp.
5-22 to 5-23 in this
CinChE manual.

Conceptual Model

Is a semi-batch process, because hydrogen leaves but does not enter. Everything else is batch.

Is not continuous, because no flow into system boundary.

Is not batch, because flow out of hydrogen exist.

Is not semi-continuous, because no flow into system boundary.

What if the gas stream did not exist; that is, you had a closed batch vessel?
What might happen to the closed vessel?

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