SOLUTIONS MANUAL FOR

Principles
of
Chemical Engineering
Processes

by
Nayef Ghasem
Redhouane Henda

8769X.indd 1 8/6/08 8:28:09 AM

8769X.indd 2 8/6/08 8:28:09 AM
 SOLUTIONS MANUAL FOR
Principles
of
Chemical Engineering
Processes

by
Nayef Ghasem
Redhouane Henda

Boca Raton London New York

CRC Press is an imprint of the

Taylor & Francis Group, an informa business

8769X.indd 3 8/6/08 8:28:09 AM

 CRC Press
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 2

Chapter 1

1.1 Process classification

Classify the following processes as batch, continuous, or Semibatch, and transient or steady-

state.

a. A balloon is being filled with air at a steady rate of 2 g/min. (Answer: Semibatch)

b. A bottle of milk is taken from the refrigerator and left on the kitchen table. (Answer:

Batch, transient in heat).

c. Carbon monoxide and steam are fed into a tubular reactor at a steady-rate and react to

form carbon dioxide and hydrogen. Products and unused reactants are withdrawn at the

other end. The reactor contains air when the process is started up. The temperature of

the reactor is also constant, and the composition and flow rate of the entering reactant

stream are independent of time. Classify the process initially (Answer: Continuous,

transient) and after a long period has elapsed (Answer: Continuous, steady state).

1.2 Types of processes

Water (ρ = 1000 kg/m3) enters a 2.00 m3 tank at a rate of 6.00 kg/s and is withdrawn at a rate

of 3.00 kg/s. The tank is initially half-full.

(a) Is the process continuous, batch or semi-batch? (Answer: Continuous)

(b) Is it transient or steady-state? (Answer: Transient)

(c) Use the general material balance equation to determine how long it will take the tank

to overflow. (Answer: 1000 kg/(3 kg/s))

Solution:

Mass of water in the tank = 2.0 m3 (1000 kg/m3) = 2000 kg

 3

The tank is half full 2000 kg/2 = 1000 kg

The time necessary to fill the tank = 1000 kg /(3 kg/s) = 333.3 sec

1.3 Unit conversion

How many seconds are in a year? (3600 s/h, 24 hours/day, 365 days/year).

Solution:

365 days 24 h 3600s

year
year day h

There is 3.1536E7 seconds/year

1.4 Flowrate through horizontal pipe

Natural gas is flowing through a horizontal pipe at a flowrate of 50 ft3/s. What is this

flowrate in m3/s, gal/hr? (Use conversion table)

Solution:

Flow rate in m3 = (50 ft3/s)(1 m3/35.3145 ft3) = 1.41585 m3/s

Flow rate in gal/hr = (50 ft3/s)(264.17 gal/35.3145 ft3)(3600 s/h) = 1.34649E6 gal/h

1.5 Molar flow rate

Propane gas (C3H8) flows to a furnace at a rate of 1450 m3/h at 15°C and 150 kPa (gauge),

where it is burned with 8% excess air. Calculate the molar flow rate (moles/s) of propane gas

entering the furnace. (Hint: assume ideal gas and use PV& = nRT
& )

Solution:
 4

Using ideal gas low PV& = nRT

&

PV&
n& =
RT

Pabs = Pgage + Patm

Pabs = 150 kPa + 101.32 kPa

Pabs = 251.32 kPa

( 251.32 kPa ) 1000

kPa
Pa
(1450 m /h )3 h
3600s
&
n=
m3 . Pa
8.314 (15+273 K )
mol. K

n: number of moles = 42.2218 mol/s

1.6 Dimensional homogeneity

A quantity k depends on the temperature T in the following manner:

æ mol ö æ Ea ö
k ç 3 ÷ = A expçç - ÷÷
è cm .s ø è R Tø

The units of the quantity Ea are cal/mol, and T is in K (Kelvin). What are the units of A and

R. (hint: note that the exponent is of unitless values; Ea / RT = [ ] ).

Solution:

The units of A [=] mol/cm3s

R [=] cal/mol.K

1.7 Calculation of mass for specific gravity and volume

The specific gravity of gasoline is approximately 0.7. What is the mass (kg) of 10 liters of

gasoline? (Answer: 7 kg)

 5

Solution:

Mass = density * volume

Mass = (0.7 *1 kg/L)*10 L = 7 kg

1.8 Convert of equation to other units

The heat capacity of ammonia, Cp = 2.5 J/g.o C . Convert the expression for Cp to

Btu/(lb m .o F) .(Hint: note that the o C and o

F here is the difference in temperature;

1 o C 1K 1 o C 1 o C
; ; ; ).
1.8 o F 1.8 o R 1K 1K

Answer:

J 453.593g 9.486×10-4 Btu/s 1o C

Cp = 2.5
g.o C 1lbm 1J/s 1.8 o F
Btu
Cp = 0.597609
lbm.o F
 6

Chapter 2

2.1 Absorption of acetone from air

Air contains 3% acetone and 2 % water is fed to an absorber column. The mass flow rate of

air is 1000 kg/h. Pure water is used as absorbent to absorb acetone from air. The air leaving

the absorber should be free of acetone. The air leaving the absorber was found to contain

0.5% water. The bottom of the absorber is send to a distillation column to separate acetone

from water. The bottom of the distillation column was found to contain 4% acetone and the

balance is water. The vapor from the head of the absorber was condensed. The concentration

of the condensate was 99% acetone and the balance water. Draw and label process flowchart

and perform degree of freedom analysis

Solution:

The labeled process flowsheet is shown below

Degree of freedom analysis

 7

Systems
Degree of freedom analysis Overall
Absorber Distillation
process
Number of unknowns 3 3 4
Number of independent equations 3 2 3
Number of relations - - -
DF 0 1 1

2.2 Separation of liquid mixture

A liquid mixture containing 35.0 mol% toluene (T), 27.0 mol% xylene (X) and the remainder

benzene (B) is fed to a distillation column. The bottoms product contains 97.0 mol% X and

no B, and 93.0% of the X in the feed is recovered in this stream. The overhead product is fed

to a second column. The overhead product from the second column contains 5.0 mol% T and

no X, and 96.0% of the benzene fed to the system is recovered in this stream.

a) Draw and completely label a Flowsheet of the process.

b) Perform the degree of freedom analysis

Solution:

Draw and completely label a Flowsheet of the process.

n&2 (kmol / h)
X T 2 mol T / mol
X X 2 mol X / mol
n&3 (kmol / h)
(1 - X T2 - X X 2 ) mol B / mol
0.05 mol T / mol
0.95 mol B / mol
j

Distillation column k
Distillation column

n& f ( kmol / h)
0.35 mol T / mol
0.27 mol X / mol
0.38 mol B / mol n&4 (kmol / h)
n&1 ( kmol / h) X T 4 mol T / mol
0.97 mol X / mol X X 4 mol X / mol

0.03 mol T / mol (1- X T4 - X X 4 ) mol B / mol

 8

Perform the degree of freedom analysis

Systems
Degree of freedom analysis Overall
Column 1 Column 2
process
Number of unknowns 5 7 6
Number of independent equations 3 3 3
Number of relations 1 1 1
DF 1 3 2

2.3 Absorber-stripper process

An absorber-stripper system is used to remove carbon dioxide and hydrogen sulfide from a

feed consisting of 30% CO2 and 10% H2S in nitrogen. In the absorber a solvent selectively

absorbs the hydrogen sulfide and carbon dioxide. The absorber overhead contains only 1%

CO2 and no H2S. N2 is insoluble in the solvent. The rich solvent stream leaving the absorber

is flashed, and the overhead stream consists of 20% solvent, and contains 25% of the CO2 and

15% of the H2S in the raw feed to the absorber. The liquid stream leaving the flash unit is

split into equal portions, one being returned to the absorber. The other portion, which

contains 5% CO2, is fed to the stripper. The liquid stream leaving the stripper consists or

pure solvent and is returned to the absorber along with makeup solvent. The stripper

overhead contains 30% solvent.

a) Draw and completely label a Flowsheet of the process.

b) Perform degree of freedom analysis

Solution

a) The labeled process flowsheet is shown below

 9

11
solv solv CO2
H2S
CO 2 0.01 m r Solv 0.3
s
N2
k
CO2 0.05
H2S
Solv

Absorber

Stripper
CO 2 0.3 l
j
H 2S 0.1
q
N2

n
CO2
o
CO2 H 2S
H 2S Solv 0.2
Solv
Relation: The overhead stream of Fileter
the flash contains 25% of the CO2
and 15% of the H2S in the raw p
feed to the absorber

b) The degree of freedom analysis

Degree of Freedom Analysis (DFA)

Degree of Freedom Analysis Absorber Flash Stripper Splitter Mixer Overall

Number of unknowns 8 7 5 4 3 7
Number of independent equations 4 3 3 1 1 4
Number of relations 0 2 0 1 0 2
DF 4 2 2 2 2 1

The lowest degree of freedom value is for the overall process, taking basis will reduce it to
zero

2.4 Filtration processes

From the following process description draw a flowchart that concisely summarizes each

stage of the process (properly labeling all streams and species within those streams). An

important, naturally occurring chemical, A, is to be removed from its ore (composed of A and

various insoluble other junk). 100 kg/hr of ore is fed to a dissolution tank where it is mixed
 10

with a stream of pure water, W, and a recycle stream. The tank is heated to 90 oC so that all

of the A (but none of the other junk, J) dissolves, forming a saturated solution. The material

exits the tank and is sent to a filter (separator) where all of the junk and a small portion of the

(still saturated) solution are removed. Finally the remaining solution is fed to a crystallizer

where it is cooled to 25 oC in order to form some solid As which is shipped off to be

packaged and sold (some filtrate also leaves with the solid). The remaining filtrate, now

saturated at 25 oC is recycled to the dissolution tank. Upon analyzing the products of from the

filter and crystallizer, it is determined that the waste stream from the filter contains 40.0kg/hr

of junk (J), 12 kg/hr of A, and 4 kg/hr of water (W) and that the final product stream from the

crystallizer contains 42 kg/hr As, 6 kg/hr A, and 6 kg/hr W.

Solution

2.5 Evaporation processes

Fresh feed containing 20% by weight KNO3 (K) in H2O (W) is combined with a recycle

stream and fed to an evaporator. The concentrated solution leaving the evaporator, containing

50% KNO3, is fed to a crystallizer. The crystals obtained from the crystallizer are 96% KNO3
 11

and 4% water. The supernatant liquid from the crystallizer constitutes the recycle stream and

contains 0.6 kg KNO3 per 1.0 kg of H2O. Draw and label the process flow chart and perform

degree of freedom analysis.

Solution:

The process flow sheet is shown below

Degree of Freedom Analysis

Overall
Degree of Freedom Analysis Evaporator Crystallizer Union
process
Number of unknowns 4 4 3 2
Number of independent equations 2 2 2 2
Number of relations 0 1 0 0
DF 2 1 1 0
 12

Chapter 3

3.1 Separation of ethanol/methanol process stream

One thousand kg/h of an ethanol/methanol stream is to be separated in a distillation column.

The feed has 40% ethanol and the distillate has 90% methanol. Eighty percent of the

methanol is to be recovered as distillate. Determine the % methanol in the bottoms product.

Solution

The process labeled flowchart is shown in Figure E3.21

What does eighty percent of the methanol is to be recovered as distillate mean?

The feed contains Xm*F = 600 kg/h on methanol.

Of this amount, 600, 80% must be the methanol in stream D.

Thus, 0.8(600)= 480 kg/h MeOH is in D as a 90% stream,

480 = 0.9*(D) à D = 533 kg/h

P-2
Distillate, D =?
90% Methanol
(100-90)% Ethanol
80% of the methanol is to
be recovered as distillate
Feed, F= 1000 kg/h P-1
40% Ethanol
60% Methanol

Bottom, B kg/h
P-3 x Ethanol
(1-x) Methanol

Figure P3.1 Flowsheet of ethanol/methanol separation process

 13

Figure P3.1b Results using E-Z solver software

3.2 Wet leather drying process

Two hundred kg of wet leather are to be dried by heating and tumbling. The wet leather

enters the drier with 60% moisture and 90% of the water is removed. Determine the mass of

the dried leather.

Solution:

The process labeled flowchart is shown in Figure P3.2

 14

Figure P3.2 flowsheet of wet leather drying process

What does 90% of the water is removed mean?

Is the dried leather 100% BDL?

Often, the amount of a feed chemical (or a % of a feed chemical) is specified to go to a

specific exit stream.

Solution:

Basis: 200 kg/h of wet leather

Total mass balance: 200 = W + B

Component balance (DL): 0.4* 200 = (1-x)*B

Relation: W = 0.9 * (0.6*200)

 15

Figure P3.2a Solution of the set of equation E-Z solver

3.3 Separation of ethanol/methanol/propanol mixture

Twelve hundred lbm /h of an ethanol/methanol/propanol stream are fed to a distillation

column. The feed is 20% methanol. Ninety percent of the methanol is to be recovered in the

distillate along with 60% of the ethanol. All of the 400 lbm/h of propanol fed to the process

must be sent to the bottom. Calculate all unknown stream flow rates and composition

Solution:

The process labeled flowchart is shown in Figure P3.3

 16

Figure P3.3a Tertiary separation processes

Component Feed Distillate Bottom

Methanol (m) 0.2*(1200) = 240 0.9*(240)= 216 ?

Propanol (p) 400 0.0 400

Ethanol (e) 1200-240-400 = 560 0.6*(560) = 336 ?

Total Feed, F = 1200 Distillate, D = ? Bottoms, B = ?

Components = 3 Unknowns = 4 Relations = 1

Cannot be solved?

from the methanol balance: 240=216 + Bm; Bm = 24

from the propanol balance: 400 = Bp + 400; Bp = 0

from the ethanol balance: 560 = 336 + Be; Be = 224

from D = Bp + 552 = 552

B = 400 + Bm + Be = 400 + 24 + 224 =648

* Finally, check using the total balance: F=D+B

1200 = 552 + 648 = 1200

 17

Figure P3.3b Solution using E-Z solve

3.4 Ethanol water separation

One thousand kg/h of an ethanol/methanol stream is to be separated in a distillation column.

The feed has 40 wt% ethanol and the distillate has 80% methanol by weight. Eighty percent

(weight) of the methanol is to be recovered as distillate. Determine the wt% methanol in the

bottoms product.

Solution

The process labeled flowchart is shown in Figure PE3.4

 18

Figure P3.4 Ethanol/water separation

Remember, for a non-reactive system with N species, there are N independent equations. It is

possible to formulate N+1 material balance equations but only N of them will be

independent.

Solution:

Basis: 100 kg/h of feed

Assumption: - Steady state, no reaction

Degree of freedom analysis

Number of unknowns 3 (D, B, Xe)

Number of independent equations 2 (two components)

Number of useful relations 1

DF = 3-2-1 = 0

Material Balance:

Total balance: 100 kg/h = D + B

Ethanol Balance: 100 (0.6) = 0.8 D + Xe B

Relation: 0.8 *(0.6*100) = 0.8 * D

From the relation D = 48/0.8 = 60 kg/h

 19

From the total balance after substituting of the calculated value of D

100 = 60 + B from this equation B = 40 kg/h

Substituting the calculated values of B and D in the ethanol balance equation

0.6(100)=0.8(60) + X e (40) . From this equation the value of Xe = 0.3

1 = Xe + Xw
1 = 0.3 + X w Þ X w = 0.7

3.5 Mixing of hydrochloric acid with water

A stream of aqueous hydrochloric acid that is 57.3 wt% HCl is mixed with water to produce

a stream of 16.5% acid. What ratio of water to concentrated acid should be used?

Solution:

The process labeled flowchart is shown in Figure P3.5

Figure P3.5 Mixing process flowsheet of HC and water

Total Mass Balance: M1 +M2 =M3 (1)

Component Mass Balance (HCl): 0.573 M1 +0 M 2 =0.165M 3 (2)

Substitute M3 in eq (2) with M3 = M1+M2

 20

0.573M1 = 0.165(M1 +M 2 )

0.573M1 =165M1 +0.165M 2

M1 (0.573-0.165)=0.165M 2

M 2 /M1 =(0.573-0.165)/0.165=2.473

3.6 Removal of acetone from nitrogen using an absorber

An absorber is used to remove acetone from a nitrogen carrier gas. The feed, with acetone wt

fraction of 0.213, enters at a rate of 200 kg/h. The absorbing liquid is water, which enters at

a rate of 1000 kg/h. The exit gas stream is 0.8 wt% acetone and 2.9% water vapor.

Determine the mass flowrates and composition of the bottom stream.

Solution: The process labeled flowchart is shown in Figure P3.6

Figure P3.6 Flowsheet of absorber for acetone

Degree of Freedom Analysis Absorber

Number of unknown 3
Number of independent equation 3
Number of relation ‫ـــ‬
D.F 0

Basis =1200 Kg/hr

 21

Total mass balance:

m& 1 + m& 2 = m& 3 + m& 4

200 + 1000 = m& 3 + m& 4

Component mass balance:

(CH 3 )2 CO : (0.213)*(200) + (0.0) = (0.008) m& 3 + x m& 4

H 2O : (0.0) + 1000 = (0.029)* m& 3 + (1- x) * m& 4

Result: m& 3 = 164 kg / hr , m& 4 = 1036 kg / hr , x = 0.04, 1- x = 0.96

3.7 Separation of benzene/toluene mixture

One thousand kilograms per hour of a mixture containing equal parts by mass of benzene and

toluene are distilled. The flow rate of the overhead product stream is 488 kg/h, and the

bottom stream contains 7.11 wt % benzene. Draw and label a flowchart of the process.

Calculate the mass and mole fractions of benzene and the molar flow rates of benzene and

toluene (mol/h) in the overhead product stream.

Solution
 22

3.8 Dilution of methanol mixture

A stream containing 25 wt% methanol in water is to be diluted with a second stream

containing 10% methanol to form a product containing 17% methanol.

(a) Choose a convenient basis of calculation, draw and label a flowchart of this process, and

calculate the ratio (kg 17% solution/kg 25% solution).

(b) What feed rate of the 10% solution would be required to produce 1250 kg/h of the

product?

Solution:

Basis: 100 kg/h of stream 1 (the 25% stream)

 23

Overall material balance

100 + m2 = m3

Component balance
0.25*100 +0.10*m2=0.17*m3

m2 = 114.286 kg/h

m3 = 214.286 kg/h

3.9 Humidification chamber

Liquid water and air flow into a humidification chamber in which the water evaporates

completely. The entering air contains 1.00 mole% H 2 O (v) , 20.8% O 2 , the balance consists

of N 2 , and the humidified air contains 10.0 mole% H 2 O. Calculate the volumetric flow rate

(ft 3 /min) of liquid required to humidify 200 lb-moles/min of the entering air.

Solution:

The process flowsheet is shown in below

 24

Degree of freedom analysis

Number of unknowns = 3

Number of equations = 3

Degree of freedom = 3-3 =0

Material balance:

Total balance:

200+ n3 = n2

Component balance (water)

0.01* (200) + n3 = 0.1 * n2

Component balance (O2)

0.208 * 200 = XO2 * n2

 25

Answer:

The amount of water required = 20 lbmol/min

Volumetric flow rate of water = (20 lbmol/min)(18 lb/lbmol)(1/62.4 lb/ft3) = 5.77 ft3/min

Amount of exit humid air = 220 lbmol/min

Mole fraction of oxygen in the exit stream = 0.19

3.10 Absorption of water from gas mixture

A gas containing equal parts (on a molar basis) of H 2 , N 2 , and H 2 O is passed through a

column of calcium chloride pellets, which absorb 97% of the water and none of the other

gases. The column packing was initially dry and had a mass of 2.00 kg. Following 6 h of

continuous operation, the pellets are reweighed and are found to have a mass of 2.21 kg.

Calculate the molar flow rate (mol/h) of the feed gas and the mole fraction of water vapor in

the product gas.

Solution:

The schematic diagram of the process flowsheet is shown below

 26

As shown from the diagram; knowing n1, one can no all the inlet molar feed rate, the exit

moles of hydrogen and nitrogen are the same, while exit molar feed rate equals inlet minus

0.011 the amount of moles adsorbed

Solution:

Basis: 6 hours of operation

Number of unknowns = 4

Number of independent equations = 3

Number of relations = 1

Number degree of freedom = 4-3-1= 0

Moles of water absorbed = (2.0 – 2.21 kg )/(18 kg/kmol)(1000 mol/kmol) = 11.67 mole
 27

Using the relation

0.97(0.333*n1) = 11.67

N1= 40 mol

Moles of inlet stream

H2O = O2 = N2 = (1/3) 40 = 12.0 mol

Overall water balance:

12.0 – 11.67 = moles of H2O leaving = 0.36 mol

Mole fraction of H2O out = 0.36/(0.36+12+12) = 0.014

3.11 Drying of wet sugar

Wet sugar that contains 20% water is sent through a dryer in whom 75% of the water is

removed. Taking a basis of l00 kg feed calculate the mass fraction of dry sugar in the wet

sugar that leaves the dryer. Calculate the ratio kg H 2 O removed/kg wet sugar leaving the

dryer. If 1000 ton/day of wet sugar are fed to the dryer, how much additional water must be

removed from the outlet sugar to dry it completely, and how much revenue can be expected if

dry sugar sells for $0.25/lb?

Solution:

Number of unknowns = 3

Number of independent equation = 2

Number of relations = 1

Degree of freedom analysis = 3-2-1 = 0

Basis: 100 kg/h of feed

Total balance:

100 = W + np
 28

Sugar balance:

0.8 *100 = (1-Xw)*np

Relation:

0.75(0.2*100) = W

Xw = 0.0588235

np = 85

W=15
29
 30

Chapter 4

4.1 Separations of benzene, toluene, xylene mixtures

Benzene (B), molecular weight = 78, toluene (T), molecular weight = 92, and xylene (X),

molecular weight = 106, are to be separated using the two stage process. The feed to this

process contains 50 wt% benzene, 30 wt% toluene and 20 wt% xylene. The feed enters the

process at a flow rate of 30,000 kg/hr. The overhead stream from the first unit contains 95

wt% benzene, 3 wt% toluene, and 2 wt% xylene. The overhead stream from the second unit

contains 3 wt % benzene, 95 wt % toluene, and 2 wt% xylene. The flow rate of the overhead

from the first unit is 52% of the feed flow rate. The amount of benzene in the overhead from

the second unit is 75% of the benzene that enters the second unit coming; the bottom stream

from the first unit. (a)Determine the flow rates for all of the streams leaving both units.

(b)Determine the compositions of the bottoms stream from both units.

Solution:

The process flowsheet is shown in the figure below

M2
B 0.95 M4
T 0.03 B 0.03
X 0.02 T 0.95
k m X 0.02

M3
30,000 kg/h B
Column 1

Column 2

B 0.50 j
T
T 0.30 X
X 0.20

M5
l n B
T
X
 31

Relations

1. The flow rate of the overhead from the first unit is 52% of the feed flow rate.

2. The amount of benzene in the overhead from the second unit is 75% of the benzene that

enters the second unit coming from the bottom of the first unit

Degree of freedom Analysis

Column Column Over all process

Degree of Freedom Analysis (1) (2)
Number of unknown 4 7 5
Number of independent equation 3 3 3
Number of relations 1 1 1
D.F 0 3 1

Starting with system with zero degree of freedom

System: Column 1

Material balance:

Total balance

35,000 kg/h = M2 + M3

Component balance (B)

0.5(35,000) = 0.92*M2 + XB3* M3

Component balance (T)

0.3(35,000) = 0.03*M2+XT3*M3

Relation

0.52*(35,000) = M2
 32

Answer:

M3 =14400 kg/h

XB3 = 0.0125

XT3 = 0.5925

XX3 = 0.395

M2 =15600 kg/h

System: Column 2

Total balance:

14400 = M4 + M5

Component balance (B)

0.045*(14400) = 0.03*M4 + XB5*M5

Component balance (T)

0.5925*14400 = 0.95*M4+XT4*M5

Relation;
 33

The amount of benzene in the overhead from the second unit is 75% of the benzene that

enters the second unit coming from the bottom of the first unit

0.03*M4=0.75*(0.0125*14400)

Results

M4 = 4500 kg/h

M5 = 9900 kg/h

XB5 = 0.0045

XT5 = 0.43

XX5 = 0.565
 34

4.2 Filtration processes

Slurry consisting of CaCO3 precipitate in a solution of NaOH and H2O is washed with an

equal mass of a dilute solution of 5 wt% NaOH in H2O. The washed slurry, which leaves the

unit, contains 2 kg solution per 1 kg of solid (CaCO3). The clear solution (clear solution

contains no CaCO3 precipitate) withdrawn from the unit can be assumed to have the same

concentration as the solution withdrawn with the solids. The feed slurry contains equal mass

fractions of all components. Based on 100 kg/h of feed slurry: Draw and label the process

flowchart and calculate the composition of the clear solution.

Solution:

Degree of freedom analysis

Number of unknowns = 4

Number of independent equations = 3

Number of relations = 1

Material balance

Total balance
 35

100 + 100 = m3 + mc + ms

Component balance (CaCO3)

(1/3)*100 = mc

Component balance (NaOH):

(1/3)*100 + 0.05*(100) = XN3*ms

ms/mc = 2

Solution using E-Z solve

4.3 Concentration of orange juice

Fresh orange juice is concentrated prior to freezing by the process illustrated in the flow

chart below. Ninety percent of the water entering the evaporator in stream 2 is evaporated.

Assume that only water evaporates and that none of the volatile components of the orange

juice evaporates. Calculate the total mass flow rates of streams 2, 3, 4, and 5.
 36

Figure P4.3 Evaporator process block diagram

Solution:

Relation:

90% of water entering the evaporator in stream 2 is evaporated

Material balance

Overall balance

0.25*(200 kg/h) = 0.75*m5

Component balance (water)

0.75*200 kg/h = m4 + 0.25 *m5

Relation 1

0.9*m2 = m4

Balance around splitter

200 kg/h = m2+m3

Solution using EZ solve

 37

4.4 Separation of NaCl and KCl mixture

A solution containing 15.0 wt% NaCl, 5.0 wt% KCl and the balance water is fed to the

separation process shown below. The feed rate is 18.4 metric tons per hour. The evaporator

product (P) stream composition is 16.8 wt % NaCl, 21.6 wt% KCl, and the balance is water.

The recycle (R) stream contains 20 wt% NaCl, the balance is KCl, and water. The bottom

products of the evaporator and the crystallizer are pure and dry KCl and NaCl. Calculate the

total flow rate and the weight percentage composition of all streams indicated on the flow

chart.
 38

Figure P4.4 Process block diagram of evaporator crystallizer process

Solution:

Material balance

System: overall

Component balance (NaCl)

0.15* 18400 kg/h = N

Component balance (KCL)

0.05* 18400 kg/h = K

System: Crystallizer

Overall balance

P=R+K

Component balance (NaCl)

0.168 * P = 0.2 R

Component balance (KCL)

0.216*P = K + XkR*R
 39

4.5 Sulfur removal system

The raw feed to a sulfur removal system contains 15 mol% CO2, 5% H2S, 1.41% CO, the

balance is CH4. The original absorber design placed a maximum flow limit of 820 kmol/h

and yielded a product stream with only 1% H2S and 0.3% CO2. The feed to the unit is 1000

kmol/h. The excess feed flow is bypassed. To maintain the same product quality, the

absorber was operated with an enhanced removal of the sulfur-containing species. Draw and

label the process flowchart. Find the fowrates and compositions of all unknown streams.

Solution:

The process flow sheet is shown below

 40

Solution

Basis: 1000 kmol/h of fresh feed

System: overall

820 = n2+n5

Component balance (CO2)

0.15 * 820 = 0.003*n5 + X2C*n2

Component balance (H2S)

0.05*820 = 0.001*n5 + (1-X2C)*n2

Component balance (Methane)

(1-0.15-0.05-0.0141)*820 = X5M*n5

Result

Solving using E-Z solve

 41

4.5 Separation of DMF/Nitrogen mixture

A separator is designed to remove exactly 75% of the DMF (Dimethyl Formamide) that is

fed to it. The DMF is removed from the bottom of the separator. The exit composition of

stream leaving the separator should contain maximum 10% DMF and the balance is

nitrogen. To achieve the goal, a recycle stream is used, where part of the exit of the

separator is recycled back. Draw and label for process flowchart. Calculate the flow rate and

compositions of all unknown streams. Compute the fraction of the separator exit stream that

must be recycled. The fresh feed contains 50% DMF and the balance Nitrogen.
 42

n5
DMF 0.10
N2 5

1 2 3 4

Purifier
n1 n4
n2 n3
DMF 0.50 DMF 0.10
DMF x2 DMF 0.10
N2 N2
N2
N2 1 - x2
6 n6 DMF

Degree of Freedom Analysis

DFA Mixing Purifier Splitter Overall
Number 0f unknowns 4 4 3 3
Number of independent equations 2 2 2 2
Number of relations - 1 - -
DF 2 1 1 1

Bases: 100 moles

System: Overall process

Over all material balance:

100 = n6 + n4

DMF component balance:

0.50(100) = n6 + 0.1 n4

n4 = 55.6 mole
n6 = 44.4 mole

System: purifier

Total mass balance : n2 = n6 + n3 (1)

DMF balance : x2 n2 = n6 + n3 *(0.1) (2)

Relations:
 43

n6 = 2/3 n 2 *x 2
50 = 2/3 n 2 *x 2
n2 *x 2 = 75

from equation (1):

75 = 50 + n 3 (0.1)
n3 = 250

System: splitter

n3 = n5 + n4
250 = n5 + 50

Solving for n5
n5 = 200 mole
n5 = 200 mole

4.6 Separation of Benzene/Toluene mixture

A distillation column separates a mixture of 100 kg/hr of 50% benzene and the balance is

toluene. The distillate at the top of the column was found to contain 95% benzene, and the

bottom products contain 96% toluene. The vapor flow rate from the top of the column is 80

kg/hr. The condenser condenses vapor completely. A portion of the condenser product is

recycled to the column as reflux. The rest of the condensate is withdrawn as product.

Calculate all unknown streams flow rate and compositions?

 44

O, Overhead
Condenser
5% H
95% P
R D
5% H

Distillation Colum
F = 100 5% H 95% P
kg/h 95% P Splitter
50% H
50% P

B, Bottom
96% H
4% P
Relation: 0.6 = R/D

4.7 Separation of potassium nitrate

Given the process shown, find the recycle flow in kg/hour, the production rate of potassium

nitrate, and the recycle ratio.

 45

Figure P4.7 Process flow sheet of evaporator crystallizer system

Solution

You are asked to find three things:

(i) the recycle flow (labeled R on the drawing),
(ii) the production rate (labeled C on the drawing)
(iii) the recycle ratio, which will be calculated as R/10000, if we don't change the
basis.

The sketch is already done, so we need to label the variables. Let's call the fresh feed F. If we
look over the compositions, we'll note that they are not consistently represented. Two are
given as %KNO3, one as %H2O, and one as lb KNO3 per lb H2O. We'd usually prefer all the
numbers to be in percent, so let's do the problem using percent nitrate. Shifting the water
percentage to nitrate is easy, just subtract from 100.

Given the process shown, find the recycle flow in pounds/hour, the production rate of
potassium nitrate, and the recycle ratio.

Basis: 1000 kg/h of feed stream

Degree of freedom analysis

 46

DFA Evaporator Crystallizer Overall process

# of unknowns 3 3 2
# of equations 2 2 2
# of relations 0 0 0
NDF 1 1 0

Composition of the recycle stream

Assume 1 lb of water

1.0 lb H 2O + 0.6 lb KNO3 = 1.6 lb total

0.6 lb KNO3 lb KNO3
X KNO 3 = = 0.375
1.6 lb total lb total

System: overall
Total balance:
1000 = W + C
Component balance (KNO3)
0.20 * 10000 = 0.96 * C
C = 2083 kg/h
W = 7917 kg/h

System Crystallizer

Total balance

M = 2083 + R

Component balance (KNO3)

0.5 * M = 0.96*2083 + R* 0.375

M = 9748 kg/h
R = 7666 kg/h

It is now simple to determine the recycle ratio

4.8 Production of instant coffee

Coffee beans contain components that are soluble (S) in water and others that are insoluble

(I). Instant coffee is produced by dissolving the soluble portion in boiling water in large
 47

percolators, then feeding the coffee to a spray dryer in which the water is evaporated,

leaving the soluble coffee as a dry powder. The insoluble portion of the coffee beans (the

spent grounds) passes through several drying operations, and the dried grounds are either

burned or used as landfill. The solution removed from the grounds in the first stage of the

drying operation may be fed to the spray dryer to join the effluent from the percolators. A

flowchart of this process is shown below (Figure P4.8). The symbols S and I denote the

soluble and insoluble components of the coffee beans, W are water, and C is a solution

containing 35% S and 65% W by mass. Calculate the flow rates in kg/h of each of streams 1

through 8.
 48

Figure P4.8 Block flow diagram of for the synthesis of instant coffee.

Solution:

System: spray dryer

m4 *0.35 = 500 kg/h

m4= 500 +W

System: Dryer

0.7*(1400) = 0.5*m7

m7 = m8+1400

System: Press
 49

Component balance (I)

0.5*m7= 0.2*m3
m3 = m7+m5
 50

Chapter 5

5.1 Butane incomplete combustion

Butane (C4H10) is fed at a rate of 100 mol/s to a boiler with 50% excess air. 50% of the
butane is consumed, and the product gas contains 10 moles CO2 per mol CO. Calculate the
molar composition of the stack gas.

Solution:

13
C4 H10 + O2 ® 4CO2 + 5 H 2O x1
2
9
C4 H10 + O2 ® 4CO + 5 H 2O x2
2

The process flowsheet is shown in Figure 5.1

Figure P5.1a Flowsheet of butane combustion process

Basis: 100 mole of butane

13/2 mole O 2
Theoretical oxygen: 100 mole Butane ´ = 650 mole O2
1mole Butane

Total inlet oxygen: 1.5 ´ 650 mole O2 = 975 mole

Component mole balance:

nC4 H10 = 100 - x1 - x 2

 51

13 9
nO2 = 975 - x1 - x 2
2 2
nCO2 = 0 + 4x1
nCO = 00 + 4x 2
nH 2O = 0.0 + 5x1 + 5x 2

100 - nC4 H10

Conversion = 0.5 =
100

mole CO 2 10
Relations: =
mole CO 1

The set of equation is solved using E-Z solves (Figure E5.12b).

Figure P5.1b Solution using E-Z solve

5.2 Butane complete combustion

Butane is burned completely in a process fed with 25.0% excess air. Determine the
composition in mole fractions of the (complete) combustion product stream to 3 decimal
places.

Solution:

13
C4 H10 + O2 ® 4CO2 + 5H 2O
2
 52

Basis: 1 mole of butane

The process flowsheet is shown in Figure E5.13

Figure P5.2 Butane complete combustion process flowsheet

X.S air = 25 %

Calculate moles fed

æ 13 CO 2 ö
O2 fed=1 mole C4 H10 ç ÷ (1.25 ) =8.125 mole O 2 fed
è 2 C4 H10 ø

0.79N 2
8.125 mole O 2 =30.6 mole N 2 fed
0.21O 2

Since nitrogen is inert gas and does not involve in the reaction. The outlet moles of nitrogen
is 30.6 moles.

Molecular balance for CO 2 H 2 O and O 2 in outlet stream

4CO2
1 mole C4 H10 = 4 mole CO2
C4 H10

5 H 2O
1 mole C4 H10 = 5 mole H 2O
C4 H10

13 CO2
8.125 mole O2 - 1 mole C4 H10 = 1.625 mole O2
2 C4 H10

The mole fraction of the outlet stream

n Total = n N2 + n O2 + n CO2 + n H2 O

nTotal = 30.6 + 1.625 + 4 + 5

 53

nTotal = 41.225

ni
yi =
nTotal

Results:

( Answer : yCO2 = 0.097, yH 2O = 0.121, yN2 = 0.742, yO2 = 0.04 )

5.3 Methane combustion

Methane in the amount of 55 moles per minute is combusted with dry air at 90 °C and 770
mmHg. A partial analysis of the stack (exit) gas reveals that the mole fraction of nitrogen is
0.8477 on a dry basis and the molar flow rate of the dry stack gas is 683 mol/min. The
fractional conversion of methane is 97.5%, and the molar ratio of CO2 to CO is ~ 9.9. Based
on the given information determine the percent excess air fed to the combustion chamber.
(Answer: percent excess air 40% XS air)

Figure P5.3 Methane combustion process flowsheet

Solution:

We are given information about nitrogen in the outlet stream, so let us write an overall
balance for molecular nitrogen

Input + Generation = Output + Consumption

But we know that nitrogen is neither generated nor consumed, so

Input = Output

nN2 1 = xN2 1n1 = xN 2 2 n2

 54

æ mol ö
nN2 1 = 0.8477 ç 683 ÷
è min ø

mol
nN2 1 = 578.9
min

The air consists of 21 mol% oxygen and 79 mol% nitrogen

mol N 2 0.21 mol O2

nO2 1 = 578.9 = 153.9 mol O2 fed
min 0.79 mol N 2

We have the following tow chemical reactions

CH 4 + 2 O2 ® CO2 + 2 H 2O
3
CH 4 + O2 ® CO + 2 H 2O
2

The theoretical oxygen (required) is based on the complete combustion reaction only, so 2
moles of O2 is required for every one mole of methane (CH4)

2molO2
55molCH 4 = 110 molO2 required
molCH 4

mol O2 fed - mol O2 required

Theoretical Excess =
molO2 required

153.9 mol O2 - 110 mol O2

X .S .Air = X .S .O2 =
110 mol O2

X .S .Air = X .S .O2 = 0.40 = 40 %

The dew point of the wet gas stream leaving the combustion chamber:

Given that the conversion of methane is 97.5%, we can calculate the methane I the outlet
stream as follows:

molesCH 4 IN - molesCH 4OUT

0.975 =
moles CH 4 IN

55 molCH 4 - nCH 2
0.975 = 4

55 mol CH 4
 55

nCH 4 ,2 = 1.375 mol CH 4

Now, we have so many molecular species to keep track of, it will be easier to solve by atomic
balance:

H atom balance:

Atoms are neither generated nor consumed so:

Number of H atoms in = Number of H atoms out

æ 4H ö æ 4H ö æ 2H ö
55 mol CH 4 ç ÷ = 1.375 mol CH 4 ç ÷ + nH 2O ,2 ç ÷
è CH 4 ø è CH 4 ø è H 2O ø

nH 2O ,2 = 107.25 mol H 2O

nTotal ,2 = 107.25 mol H 2O + 683 mol dry gas

nTotal ,2 = 790.25 mol

Given that the dry gas flow rate is 683

nTotal ,2 = nO2 ,2 + nCO ,2 + nCO2 ,2 + nH 2O ,2 + nCH 4 ,2 + nN2 ,2

nH 2O ,2 107.25 mol H 2O
y H 2O = = = 0.136
nTotal ,2 790 mol

Using Raoult’s law and Antoine’s equation, we may calculate the temperature of the dew
point

yH 2O P = xH 2O PHsat2O (Raoult's Law)

B
(
log PHsat2O [ mmHg ] = A - ) T [°C ] + C
(Antoine's Equation)

B
A-
T [° C ]+ C
yH 2O P = xH 2O 10

1750.286
8.10765 -
0.136 ( 770 mmHg ) = (1.0 )10
T [° C ]+ 235.000

TDew = 52.5 °C
 56

5.4 Burning ethyl ketone with excess air

A gaseous mixture containing 80 mole percent methane and the balance methyl ethyl ketone
(C4H8O) is burned with 50% excess air. Ninety-five percent of the methane and 75% of the
methyl ethyl ketone burns. However, some of the methane that burns forms CO. The
exhaust gas contains 0.5 mole percent CO on a dry basis. Calculate the molar composition of
the exhaust gas.

Solution:

Flow diagram of the above problem is shown in Figure P5.4 below

Figure P5.4 Flowsheet of multicomponent combustion process

We have three reactions to consider:

CH 4 + 2O2 ® CO2 + 2 H 2O
3
CH 4 + O2 ® CO + 2 H 2O
2
11
C4 H 8O + O2 ® 4CO2 + 4 H 2O
2

Basis: 1 mole hydrocarbon

Feed:
0.8 mole CH4
0.2 mole C4H8O

Excess Air: X.S. air = 50%

 57

The total moles of oxygen fed to the burner equal the theoretical oxygen plus the excess
oxygen.

ì 2O2 11 O2 ü
O2 fed = í( 0.8) CH 4 + ( 0.2 ) CH 4 ý (150% ) = 4.05 mole O2 fed
î CH 4 2 CH 4 þ

0.79 N 2
4.05 mole O2 = 15.24 mole N 2 fed
0.21O2

Calculate the moles of each species in the furnace outlet, since N2 is an inert gas

15.24 moles nitrogen in the outlet stream

Molecular balances for CH4, C4H8O, H2O

0.8 CH 4 (1 - 0.95) = 0.04 mol CH 4

0.2 C4 H 8O (1 - 0.75 ) = 0.05 mol C4 H 8O
2 H 2O 4 H 2O
nH 2O = 0.8CH 4 ( 0.95 ) + 0.2C4 H 8O ( 0.75 )
CH 4 C4 H 8 O
nH 2O = 2.12 mol H 2O

Now find three remaining unknowns nO2 ,nCO2 ,nCO . Wee need three equations or other pieces
of information to solve

C atomic balance:

C 4C C 4C C C
nCH 4 + nC4 H8O = nCH 4 + nC4 H8O + nCO + nCO2
CH 4 C 4 H 8O CH 4 C 4 H 8O CO CO2

C 4C C 4C C C
0.8 + 0.2 = 0.04 + 0.05 + nCO + nCO2
CH 4 C4 H 8 O CH 4 C4 H 8O CO CO2

nCO2 = 1.36 - nCO Equation 1

O atomic balance

ì 2O2 11 O2 ü
O2 fed = í( 0.8) CH 4 + ( 0.2 ) CH 4 ý (150% ) = 4.05 mole O2 fed
î CH 4 2 CH 4 þ
 58

O 2O O 2O O 2O O
nC4 H8O + nO2 = nC4 H8O + nO2 + nCO + nCO2 + nH 2 O
C4 H 8O O2 C4 H 8 O O2 CO CO2 H 2O

2O
0.2 + ( 4.05 ) 2 = 0.05 + 2nO2 + nCO + (1.36 - nCO ) + 2.12
CO2

3.41 = 2nO2 - nCO Equation 2

CO is 0.5 mol% on dry basis

nCO nCO
0.005 = =
nTotalDry nCH4 + nC4 H8O + nN2 + nCO + nCO2 + nO2

nCO
0.005 =
0.04 + 0.05 + 15.24 + 1.36 + nO2

nCO
0.005 =
16.69 + nO2

nO2 = 200nCO - 16.69 Equation 3

Substitute equation 3 into equation 2:

3.41 = 2 ( 200nCO - 16.69 ) - nCO

nCO = 0.0922 mol CO

nCO2 = 1.36 - 0.0922 = 1.27

nO2 = 200 ( 0.0922 ) - 16.69 = 1.75

nTotal = nCH 4 + nC4 H8O + nN2 + nCO + nCO2 + nO2 + nH 2O

nTotal = 0.04 + 0.05 + 15.24 + 0.0917 + 1.27 + 1.75 + 2.12

nTotal = 20.56 mol

ni
yi = ; yCH 4 = 0.002; yC4 H8O = 0.0024; yN 2 = 0.741; yCO = 0.0045, yCO2 = 0.0618;
nTotal
 59

yO2 = 0.085; yH 2O = 0.103

5.5 Roasting of iron pyrite

In one of the earliest processes used to make sulphuric acid, an ore containing iron pyrite
(FeS2) is roasted (burned) with air. The following reactions take place in the furnace (s
denotes a solid species and g a gaseous species):

FeS2 (s) + 15/2 O 2 (g) ® Fe 2O3 (s) + 4 SO3 (g)

2 FeS2 (s) + 11/2 O 2 (g) ® Fe 2O3 (s) + 4 SO 2 (g)

(In later stages of the process, not to be considered here, the SO2 is further oxidized to SO3,
which is then absorbed in water to produce the H2SO4 product.)

A solid ore containing 82 wt% FeS2 and 18 wt% inerts is fed to the furnace. Dry air is fed in
40% excess of the amount theoretically required to oxidize all of the sulphur in the ore to
SO3. A pyrite conversion of 85% is obtained, with 40% of the FeS2 converted to form sulphur
dioxide, and the rest forming sulphur trioxide. Two streams leave the roaster: A a gas stream
containing SO3, SO2, O2, and N2, and a solid stream containing unconverted pyrite, ferric
oxide (Fe2O3), and inerts.

a) Draw and completely label a flowsheet of the process, using 100 kg/min of ore as a basis.
b) Calculate the rate of Fe2O3 production (kg/min) in the outlet solid stream, and the total
molar flow and composition of the outlet gas stream.

Solution:

Figure P5.5 Flowsheet of Roasting of iron pyrite

I 2 FeS2 ( s ) + 11 O2 ( g ) ® Fe2O3( s ) + 4 SO2 ( g )

2
 60

II 2 FeS 2( s ) + 15 O2 ( g ) ® Fe2O3( s ) + 4 SO3( g )

2

MW (FeS2) = 55.847 + 2(32.064)

= 119.98 g/mol

MW(Fe2O3) = 2(55.847) + 3(15.999)

= 159.69 g/mol

Input streams

1mol
n1 =82000 g FeS2 × = 683.5 mols FeS2
119.98g

15 / 2
Theoretical O2 based on SO3 reaction = ( 683.5) = 256301mols O2
2

Actual O2 ( 40% excess ) =1.4 ( 2563) =3588.2 mols O2

Air stream 0.21 n 2 =3858.2 n 2 =17086.9 mols

Specification:

FeS2 conversion 85%

\n 7 = (1-0.85) 683.5=102.5 mols FeS2

SO2 0.4 n 3
= = n 4 Þ 11.5 n 3
SO3 0.6 n 4

Atomic Balances:

Fe atomic balance:
n1 = n 7 + 2n 8
n1 = n 7 are known
n 8 =290.5 mols Fe 2 O3
n1 =683.5
n 7 =102.5

S atomic balance

2n1 = n 3 +n 4 +2n 7
but n 4 =1.5n 3
 61

2.5n 3 =2 ( 683.5-102.5 )
n 3 =464.8 molSO 2
n 4 =1.5n 3 = 697.2 molSO3

O atomic balance

2 ( 0.21n 2 ) =2n 3 +3n 4 +2n 5 +3n 8

There is only one unknown in the above equation

n 5 =1642.1mol

N2 atomic balance

n 6 =0.79n 2 =13498.6 mol

kg
Amount of Fe2O3 produced = 290.5 mol ´ 159.69 g/mol´ = 46.4 kg
1000g
Total molar gas flow = n 3 +n 4 +n 5 +n 6 =16302.6 mols
464.8
Molar fraction of SO2 = = 0.079
16302.6
657.2
Molar fraction of SO3 = = 0.043
16302.6
1642.1
Molar fraction of O2 = = 0.100
16302.6
13498.6
Molar fraction of N2 = = 0.828
16302.6

5.6 Water gas shift reaction

100 kmol/hr of a stream containing 20 mol% CO, 20 mol% H2O, and 60 mol% H2 is
combined with additional steam and fed to a water-gas-shift reactor to produce more
hydrogen. The equilibrium constant of the water-gas-shift reaction is 200, and the mole
fraction of hydrogen at the outlet is 0.75.

a. Write and balance the chemical equation.

b. How much additional steam is fed to the water-gas-shift reactor?

a) The balance chemical reaction is shown below

CO + H 2O ® CO2 + H 2

b) The additional steam fed to the water-gas shift reactor is calculated as follows

Basis: 100 kmol/hr of feed

 62

IN OUT
-----------------------------------------
CO 20 20-x
H 2 O 20 + n 2 ( 20 + n 2 ) -x
CO2 0 0 +x
H2 60 60 + x
=========================
nTotal 100 + n2

Π product nCO2 nH 2 x (60 + x )

K eq = 200 = = = (1)
Π reactants nCO nH 2O (20 - x )(20 + n2 - x )

nH 2 60 + x
yH 2 = 0.75 = = (2)
nTotal 100 + n2

There are two equations and two unknowns

75+0.75n 2 =60+x (1)

n 2 =1.333x -20 (2)

Substitute equation 2 in equation 1

x (60+x )
200=
(20-x )(20+1.333x -20-x )

(60 + x )x
200 =
(20 - x )(0.333x )

(60 + x )
200 =
(20 - x )(0.333)

1.333 - 66.6x = 60 + x

67.66x = 1273.33

kmol
x = 18.8
hr

kmol
n2 = 5.09
hr
 63

5.7 Production of Sulfuric acid

Sulfuric acid (H2SO4) is formed by first burning sulfur in air to produce sulfur dioxide (SO2):

S + O2 ® SO2

The sulfur dioxide then is catalytically reacted with more air to form sulfur trioxide:

1
SO2 + O2 ® SO3
2

Finally the sulfur trioxide is combined with water to form sulfuric acid:

SO3 + H 2O ® H 2 SO4

The flow diagram for this process is shown in Figure P5.7. The components in each
stream are as shown in the flow diagram. The concentrated sulfuric acid that is produced is
98% sulfuric acid and 2 wt% water. This process is to produce 200,000 kg/day of the
concentrated acid. How much air, water, and sulfur must enter the process in order to meet
this production demand? Use the following molecular weights when solving this problem

N 2 = 28, O 2 = 32,S =32 g/mol

SO2 = 64, SO3 =80, H 2SO 4 = 98g/mol

Figure P5.7 Flow sheet of sulfuric acid production process

Solution:

If the concentrated acid stream is 98% H2SO4 then the flow rates of the components in the
concentrated acid stream are

H 2SO 4 : 200,000kg/day(0.98)=196,000kg/day
 64

H 2 O:200,000kg/day(0.02)=4000kg/day

Conversion of the mass of H2SO4 into moles gives

æ 1 kmol H 2 SO4 ö
196, 000 kg H 2 SO4 / day ç ÷ = 2, 000 kmol H 2 SO4 / day
è 98 kg H 2 SO4 ø

The flow diagram would look like the following

Figure P5.7b The overall process flowsheet

Also add all of the reactions together to get an overall stoichiometry

3
S + O2 + H 2O ® H 2 SO4
2

The stoichiometry tells us that for every mole of H2SO4 produced one mole of sulfur must be
consumed. Thus

Flow of sulfur (S) =

2000 kmol 32 kg S
Flow of H2SO4 = 2000 kmol/day = = 64 000 kg S/day
day kmol S

Flow of O2 =
æ 32 kg O 2 ö
3/2 flow H 2SO 4 = 3/2 (2,000 kmol/day)=3,000 kmol/day ç ÷ =96,000 kg/day
è kmole O 2 ø

Flow of H2O = flow of H2SO4

æ 18 kg H 2O ö
= 2,000 kmol/day=2,000 kmol/day ç ÷ =36,000 kg H 2 O/day
è kmole O 2 ø

The flow of H2O is that needed for the chemical reaction. There is also the 4000 kg/day that
exists in the concentrated acid stream. Thus the total flow rate of H2O is 36000+4000 =
40,000 kg. Finally, oxygen is 21% of the air flow, so the flow rate of nitrogen is
 65

3000kmol O2 0.79 kmol æ 28000 kg N 2 ö

= 11290 N2 ç ÷ = 316, 000 kgN 2 / day
day 0.21 day è 1 kmol N 2 ø

Thus the flow rate of the air is 316000+96000 = 412000 kg/day. The flows are thus

S = 64,000 kg/day
H 2O = 4,000 kg/day
Air = 412,000 kg/day
 66

Chapter 6

6.1 Chemical Reactor Analysis

In the production of propylene oxide, CO2 (at high pressure) is used as solvent since the
reactant gases (H2, O2, and C3H6) and the propylene oxide products are soluble in CO2 and
CO2 does not react with these gases. A Pt/Pd/Ti catalyst promotes the propylene oxide
synthesis. A byproduct, propane, is also produced in this system.

The desired reaction is:

C3H 6 (propylene)+H 2 +1/2O 2 ® C3 H8O(propylene oxide)
The byproduct reaction is:
C3H 6 +H 2 ® C3H8 (propane)

In the test system, 35 mol/hr air (79 mol% N2, 21 mol% O2) are mixed with 4 mol/hr C3H6,
1.26 mol/hr H2, and 20,000 mol/hr CO2. The mixture is fed to a continuous reactor and the
reactor output is monitored. The percent single pass conversion of C3H6 is 90.5%. The
fractional selectivity of C3H6 to C3H8O is 0.771.

1. What is the limiting reactant in this system? Justify your answer.

2. Calculate the mol% of each component in the effluent stream? .

3. You notice that the process wastes unreacted reactants, and want to recycle components as
well as the solvent. Draw a block flow diagram of a process that recycles CO2, O2, N2, H2 and
C3H6. Individual air, CO2, H2, and C3H6 streams are mixed prior to their entry to the reactor.
C3H8O and C3H8 are separated from the reactor effluent and removed. Assume this separator
is prefect. You want to recycle the remaining components such that the reactor can operate at
steady state. Draw the block flow diagram and indicate how many additional specifications
(if any) will be required to solve for flow rates and compositions of all streams in the system.
Do not solve for flows or compositions.

Solution

C3H 6 (propylene)+H 2 +1/2O 2 ® C3 H8O(propylene oxide) x1

C3H 6 +H 2 ® C3H8 (propane) x2

ni
Limiting reactant has lowest
vi
 67

4
C3 H 6 : =4
1
1.26
H2: = 1.26
1
35(0.21)
O2 : = 14.7
1/ 2
H 2 is limiting

Limiting H 2 diminishes conversion of C3H6 to C3H8

Figure E6.11a Production of propylene oxide

The resultant mole balance set of equations

n&Pe ,out = n& Pe,in - x1 - x 2 = 4 - x1 - x 2 (1)

n&H ,out = n&H ,in - x1 - x 2 = 1.26 - x1 - x 2 (2)
1 1 1
n&O ,out = nO ,in - x1 = 35(0.21) - x1 = 7.35 - x1 (3)
2 2 2
n& N ,out = n& N ,in = 35(0.79) = 27.65 (4)
n&C ,out = n&C ,in = 20, 000 (5)
n&Po ,out = x1 ( 6)
nPa ,out = x 2 (7)

Conversion = 9.5 %

n& Pe,in - n&Pe ,out

0.905 = (8)
n& Pe,in

n&Pe ,out = n& Pe ,in (0.905) = 4(0.905) = 3.62

Selectivity = 77.1%
 68

moles of C3H 6 reacted to produce C3H8O x1

0.771 = = (9)
total moles of C3H 6 reacted x1 + x 2

From equation 1

3.62 = 4 - x1 - x 2 Þ x1 + x 2 = 0.38

x1 x
0.771 = = 1 Þ x1 = 0.29
x1 + x 2 0.38

x1 = 0.29, x 2 = 0.09 , n&Pe ,out = 3.62 , n&H ,out = 0.88 , n&O ,out = 7.21 n& N ,out = 27.65 , n&C ,out = 20, 000 ,
n&Po ,out = 0.29 , n&Pa ,out = 0.09

3. Purge stream required to remove N2 to prevent accumulation

Figure 6.1b Propylene oxide production process

Since the problem is solved up to splitter, only one additional spec is required. Splitter always
requires one additional specification for the system to be fully specified.
 69

6.2 Laundry detergent synthesis process

Butanal C4H8O (used to make laundry detergents) is made by reacting on of propylene

(C3H6) with CO and H2: C3H 6 + CO + H 2 ® C 4 H8O

In an existing process, 180 kmol/h of C3H6 (P) is mixed with 420 kmol/h of a mixture

containing 50% CO and 50% H2 and with a recycle stream containing propylene and then fed

to a reactor, where a single-pass conversion of propylene of 30% is achieved. The desired

product butanol (B) is removed in one stream, unreacted CO and H2 are removed in a second

stream, and unreacted C3H6 is recovered and recycled. Calculate the production rate of

butanol (kmol/h), the flow rate of the recycle stream (kmol/h).

(Answer: n&P , fed to reactor = 600 kmol/h. From a balance on the mixer, we can find that the
recycle rate must be (600-180) = 420 kmol/h).

Figure P6.2 Laundry detergent process

Solution

(i) First choose the entire process as the system. Since no propylene leaves the process, the
overall conversion is 100% (fractional conversion = 1.0).
 70

x& x&
Therefore: 1 = , or x =180 kmol/h.
=
n&P , fed 180
The balance on butanol is simply

n&B ,out = x& = 180 kmol / h . The butanal production rate is 180 kmol/h.

(ii) Now choose the reactor as the system. The fractional conversion = 0.3. The extent of
reaction is the same as in (i), because the reactor is the only unit where a reaction takes place.
Therefore:

x& 180
0.3 = =
n&P , fed to reactor n& P , fed to reactor

or, n&P , fed to reactor = 600 kmol/h. From a balance on the mixer, we can find that the recycle
rate must be (600-180) = 420 kmol/h.

6.3 Butanol production

A company contacts you and claims that they can supply you with a cheaper source of

propylene that could replace your current supply. Unfortunately, the cheaper source is

contaminated with propane at a 5:95 ratio (propane: propylene). The cheaper source is

economically attractive if the butanal production rate is maintained at the current rate and if

an overall conversion of 0.90 can be achieved. Under your reactor conditions, propane is an

inert, and it is too expensive to separate propane from propylene so you decide to install a

purge stream. Assume the CO+H2 stream remains the same (420 kmol/h, 50 mol% CO) as

does the single-pass conversion of propylene in the reactor (0.3). Given this, show how the

block flow diagram must be modified to accommodate the cheaper source of propylene, and

calculate

(i) The flow rate of the contaminated propylene stream to the process (kmol/h).

(ii) The mol% inert and the total flow rate (kmol/h) of the purge stream.

(iii) The mol% inert and the total flow rate (kmol/h) of the feed to the reactor.
 71

A splitter and purge are now essentials. We no longer know the incoming flow rate but we fix

the butanol production rate at 180 kmol/h, from Example P6.3.

Figure P6.3 flowsheet of butane production process

(Answer: (i) n&P , fed = 200 kgmol/h, (ii)34.5 mol%., (iii)17.8 mol% inert.)

Solution:

(i) We first group the entire process into a single system. The overall fractional conversion
for the process is fixed at 0.9. Therefore

x& 180
0.9 = = , or n&P , fed = 200 kgmol/h
n&P , fed n& P , fed

This stream is 5% inert/95% propylene, so the flow rate of the inert to the process is
(5/95)*200 or 10.5 kgmol/h and the total flow of the contaminated propylene stream is 210.5
kgmol/h

(ii) Unreacted propylene exits the system in the purge stream. From a material balance on
propylene with the entire process as the system, propylene flow rate in the purge stream =
200 – 180 = 20 kgmol/h. All the inert flowing into the system needs to leave in the purge, so
the inert flow in the purge = 10.5 kgmol/h. Total purge flow is therefore 30.5 kgmol/h and
the mol% inert is (10.5/(10.5+20)) or about 34.5 mol%.

(iii) Since the extent of reaction and the single-pass conversion is the same as Example 6.14,
then, the propylene fed to the reactor is the same or 600 kgmol/h. A balance on propylene
around the mixer tells us that 600 – 200 or 400 kgmol/h propylene must be in the recycle
stream. Since the composition of the recycle stream equals that of the purge stream, the
 72

recycle stream must contain (400(10.5/20)) = 210 kgmol/h inert. Again, a balance on the
mixer tells us that 210 + 10.5 = 220.5 kgmol/h inert must flow into the reactor. Therefore, the
total flow into the reactor is 220.5 + 600 + 420 (from CO and H2) = 1240.5 kgmol/h, and this
stream contains (220.5/1240.5)x 100% = 17.8 mol% inert.

n&P , fed = 200 kgmol/h, 34.5 mol%., 17.8 mol% inert.

6.4 Hydrodealkylation process

Hydrodealkylation is a process where short organic side changes are removed from larger

molecules using hydrogen. In the Hydrodealkylation of toluene (C6H5CH3) both benzene

(C6H6) and methane (CH4) are produced: C6 H 5CH 3 + H 2 ® C6 H 6 + CH 4

In an industrial process 100 lb-mol/h of pure toluene (liquid) is fed to the process along with

200 lb-mol/h of pure hydrogen (gas). These streams are combined with recycle stream and

fed to a reactor. In the reactor, 75% of the toluene fed to the reactor reacts. The effluent from

the reactor enters a vapor-liquid separator. All of the hydrogen and methane (gas) leave this

separator in the vapor phase; all of the toluene and benzene (liquid) leave the separator in the

liquid stream. The liquid stream then enters a second separator in which all of the benzene

leaves in one stream and all of the toluene leaves in a second stream. The benzene stream

leaves the process as a product stream. The toluene stream is completely recycled by mixing

it with the toluene fed to the process. The vapor/liquid separator is split into two equal

streams. One of these streams is combined with the hydrogen fed to the system to give the

gaseous stream entering the reactor. The other stream is sent to another process for further

processing.

a) Draw a process flow diagram for this process.

b) How much benzene is produced (lb-mole/h)? (200 lbmol/h)

c) What is the composition of the vapor stream sent to the other process for further

processing? (Answer: 50 mol% CH 4 and 50 mol% H 2 )

 73

d) How much toluene is actually fed to the reactor? (133.3 lb-mol/h).

What is the composition of the vapor stream fed to the reactor (NOTE: the answer is not

100% Hydrogen)? (Flow of H 2 in = 200 + 100 = 300 lb-mole/h, Flow of CH 4 in = 100 lb-

mol/h).

Solution

a) The flow diagram would look like the following figure.

Figure P6.4a Flowsheet of hydrodealkylation process

b) Draw a flow diagram for the overall process

H2
200 lb-mol/h H2/CH4

Toluene
100 lb-mol/h Benzene

Figure P6.4b Overall hydrodealkylation process

 74

Notice that the stoichiometry tells us that for every mole of H 2 consumed a mole of toluene is
also consumed. Since there are twice as many moles of H 2 fed as toluene, toluene must be the
limiting reactant. The stoichiometry also tells us that for every mole toluene consumed a
mole of benzene is produced. Thus the production rate of benzene must be

1lb-mol benzene produced 200 lb-mol toluene consumed

= 200 lb-mol benzene produced
1 lb-mol toluene consumed

c) The stoichiometry also tells us that for every mole of toluene consumed a mole of
hydrogen is consumed. Also for every mole of toluene consumed a mole of methane produce.

1lb-mol methane produced 200 lb-mol toluene consumed

= 200 lb-mol methane produced
1 lb-mol toluene consumed

Moles of hydrogen consumed

1lb-mol H 2 consumed 200 lb-mol toluene consumed

= 200 lb-mol H 2 consumed
1 lb-mol toluene consumed

Moles of hydrogen out = moles of hydrogen in – moles of hydrogen consumed

= 200 lb-mol hydrogen in – 100 of hydrogen consumed
= 100 lb-mol hydrogen out

Thus, the steam leaving the system is 50 mol% CH 4 and 50 mol% H 2 .

d) All of the benzene that leaves the system must also be in the stream leaving the reactor
since no benzene is recycle. Thus the stream leaving the reactor must have a benzene flow
rate of 100 lb-mol/h. The stoichiometric of the reaction also tells us that for every mole of
benzene produced a mole of toluene is consumed. Thus 100 lb-mole/h of toluene must be
reacted. The problem statements tell us that 75% of toluene entering the reactor reacts. Thus
the toluene fed to the reactor must be

Toluene reacted 100 lbmol / h

Toluene fed to the reactor = = = 133.3 lbmol / h
0.75 0.75

e) The vapor stream leaving the vapor/liquid separator is split 50/50. We found out in part c)
that the stream going to further processing is 50 mol% H 2 and 50 mol% CH 4 . Since there is
no separation in a splitting operation the composition of the vapor stream leaving the
vapor/liquid separator and that of the vapor recycle stream must -also be 50mol% H 2 and 50
mol% CH 4 . In addition of the flow rate of the two components in the recycle stream must be
the same as that in the stream going to other processing unit. This is mixed with the fresh
H 2 feed to give the reactor feed. Thus, the flow rate of vapor into the reactor must be

Flow of H 2 in = 200 + 100 = 300 lb-mole/h

Flow of CH 4 in = 100 lb-mol/h
 75

6.5 Uranium and Zirconium as nuclear fuels

One route toward separating the uranium, U, and zirconium, Zr, contained in spent nuclear

fuel involves the reaction of these elements with HCl. In the simplified flowsheet shown

below, 10 mol/h of a 90% Zr-10% U mixture is reacted with a HCl stream containing some

water to produce metal chlorides via the reactions

U + 3HCl ¾¾
® UCl3 + 3/2 H 2
Zr + 4HCl ¾¾
® ZrCl 4 + 2H 2 .

The U and Zr are completely converted to chlorides, provided the total HCl fed to the reactor

is twice the amount required by the reaction stoichiometry. The UCl3 produced is a solid and

hence is readily removed from the remaining gaseous reaction products. The vapors from this

first reactor are passed to a second reactor where the ZrCl4 vapor is reacted with steam to

produce solid ZrO2 according to the reaction: ZrCl 4 + 2H 2 O ¾¾

® ZrO 2 + 4HCl

The reaction goes to completion and the ZrO2 solid is separated from the gaseous reactor

products. The remainder of the process is concerned with the concentration of the residual

HCl for recycle back to the first reactor. The gases leaving the second reactor are sent to an

absorber which uses a 90% H2O -10% HCl solutions as a solvent to absorb HCl. This results

in an absorber liquid containing 50% HCl and 50% H2O and an overhead gas containing 90%

H2 and 10% HCl. The absorber liquid is sent to a stripper which boils off most of the HCl to

produce a 90% HCl - 10% H2O recycle vapor. The remaining stripper bottoms is cooled and

recycled to the absorber for use as solvent. Calculate all flows and compositions, assuming all

specified compositions are in mol% (see Figure P6.5).

(Answer: n8 = 80.926 mol / h & n9 = 161.852 mol / h )

 76

Solution

Figure E6.6 Uranium and Zirconium as nuclear fuel process

Solution:

Reaction took place in reactor 1:

U + 3HCl ¾¾
® UCl3 + 3/2 H 2 x1
Zr + 4HCl ¾¾
® ZrCl4 + 2H 2 x2

Reactions took place in reactor 2:

ZrCl 4 + 2H 2 O ¾¾
® ZrO 2 + 4HCl x3

Degree of freedom Analysis is shown in Table E6.6

 77

Table E6.6 Degree of freedom analysis of example E6.6

DOF Reactor 1 Reactor 2 absorber Stripper Mixnig pt Block
Number 7+2 9+1 6 3 4 5+3
unknowns
Number of 7 5 3 2 2 7
independent
equations
Number of 1 0 0 0 1 1
relations
DF 1 5 3 1 1 0

Block Balances

U: 0 = (0.1)(10) - x1 so x1 = 1 mol/h

Zr: 0 = (0.9)(10) - x 2 x 2 = 9 mol/h

UCl3: n 2 = 0 + x1 = 1

ZrCl 4 : 0 = 0 + x 2 - x3 x3 = x 2 = 9 mol/h

ZrO 2 : n 5 = 0 + x3 n 5 = 9 mol/h

HCl: 0.1 n 7 = n11 - 3 x1 - 4 x 2 + 4x3

H2: 0.9 n 7 = 0 + 3/2 x1 + 2x 2 = 19.5 mol/h n 7 = 21.67 mol/h

H 2 O: 0 = n 4 - 2x3 n 4 = 18 mol/h

HCl balance:

n11 = 2.167 + 3 + 36 - 36 = 5.167 mol/h

Now that n11 is known, the degree of freedom for the mixing point has been reduced to zero,
and we can do balances around the mixing point.

Mixing Point Balances

n12 = 5.167 + 0.9 n10

n12HCl = 2[(3)(1) + (4)(9)] = 78 mol HCl/hr

Solving these two equations simultaneously yields:

 78

n10 = 80.926 mol/h & n12 = 86.093 mol/h

With n12 known, DF = 0 for the reactor 1. Likewise, DF = 0 for the stripper because n10 is
now known. We can use either unit to continue with the solution.

Stripper Balances

stripper HCl: 0.5n 9 = 0.1n 8 + (0.9)(80.926)

stripper overall: n 9 = n 8 + 80.926

Solving these equations yields: n8 = 80.926 mol / h & n9 = 161.852 mol / h

Finally, with n 7 , n 8 and n 9 are known, the DF = 0 for the absorber. You should be sure that

you can finish the problem from here.

P6.6 Hydrogenation of ethylene into ethane

Consider a system designed for the hydrogenation of ethylene into ethane:

2H 2 + C2 H 2 ® C2 H 6
(2 A + B ® C )

The reaction takes too long to go to completion (and releases too much heat) so the designers
decided to implement a recycle system in which, after only part of the reaction had finished,
the mixture was sent into a membrane separator. There, most of the ethylene was separated
out, with little hydrogen or ethylene contamination. After this separation, the cleaned stream
entered a splitter, where some of the remaining mixture was returned to the reactor and the
remainder discarded.
The system specifications for this process were as follows:
· Feed: 584 kg/h ethylene, 200 kg/h hydrogen gas
· Outlet stream from reactor contains 15% hydrogen by mass
· Mass flows from membrane separator: 100 kg/h, 5% Hydrogen and 93% ethane
· Splitter: 30% reject and 70% reflux

What was the extent of reaction for this system? What would the extent of reaction be if there
was no separation/recycle process after (assume that the mass percent of hydrogen leaving
the reactor is the same)? What limits how effective this process can be?
 79

0.3 m5
Reject x A5 , xB 5 , xC 5
m5, A, B, C
Splitter

Reflux
0.7 m5
x A5 , xB 5 , xC 5

Separator
FEED
2A+B à C
584 kg/h B m3
200 kg/h A 15% A
xB 3
m4=100 kg/h
1- xB 3 -0.15 5% A
93% C

Figure E6.6 Block flow diagram of the dehydrogenation process

Solution

Degree of Freedom Analysis

On reactor: 6 unknowns (m& 5 , xA5 , xB 5 , x , m& 3 , xB 3 ) - 3 equations = 3 DOF
On separator: 5 unknowns (m& 3 , xB 3 , m& 5 , xA5 , xB 5 ) - 3 equations = 2 DOF
On splitter: 3 unknowns - 0 equations (we used all of them in labeling the chart)à 3 DOF
Overall System: 4 unknowns ( m& 5 , x A5 , xB 5 , x ) - 3 equations = 1 DOF.
Duplicate variables: 8 ( m& 5 , x A5 , xB 5 twice each and m& 3 , xB 3 once)
Total DOF = 8 - 8 = 0 DOF
Plan and Solution

Generally, though not always, it is easiest to deal with the reactor itself last because it usually
has the most unknowns. Lets begin by looking at the overall system because we can often get
some valuable information from that.

Overall System DOF (overall system) = 4 unknowns ( m& 5 , x A5 , xB 5 , x ) - 3 equations = 1

DOF. We cannot say that total mass of A and B is conserved because we have a reaction
here. Therefore, we must include the extent of reaction x in our list of unknowns for both the
reactor and the overall system. However, the total mass in the system is conserved so we can
solve for m& 5

Let us go ahead and solve for m& 5 though because that will be useful later.

784 = 100 + 0.3(m& 5 )

 80

m& 5 = 2280 kg / h

We can't do anything else with the overall system without knowing the conversion so lets
look elsewhere.

DOF (separator) = 4 unknowns ( m& 3 , xB 3 , xA5 , xB 5 ) - 3 equations = 1 DOF Let us solve for
those variables we can though.

We can solve for m3 because from the overall material balance on the separator:

m& 3 = m& 4 + m& 5

m& 3 = 100 + 2280

m& 3 = 2380 kg / h

Then we can do a mass balance on A to solve for xA5 :

m& 3 x A3 = m& 4 x A 4 + m& 5 xA5

2380(0.15) = 100(0.05) + 2380(xA5)

xA5 = 0.154

Since we don't know xB5 or xB3, we cannot use the mass balance on B or C for the separator,
so lets move on. Let's now turn to the reactor:

Reactor Analysis

DOF: 3 unknowns remaining (xB3, xB5, and x ) - 2 equations (because the overall balance is
already solved!) = 1 DOF. Therefore, we still cannot solve the reactor completely. However,
we can solve for the conversion and generation terms given what we know at this point. Let
us start by writing a mole balance on A in the reactor.

n& A1 + n& A, recycle - 2x = n& A3

To find the three nA terms we need to convert from mass to moles (since A is hydrogen, H2,
1mol
the molecular weight is ):
0.002016 g

kg 1mol mol A
n& A1 = 200 * = 99206
h 0.002016 kg h

m5 * x A5 0.7(2280)(0.1544) mol A
n& A,recycle = 0.7 * = = 122000
MWA 0.002016 h
 81

Thus the total amount of A entering the reactor is:

mol A
n& A,in = 99206 + 122000 = 221428
h

The amount exiting is:

m& 3 * xA3 2380 * 0.15 mol A

n& A,out = = = 177083
MM A 0.002016 h

Therefore, we have the following from the mole balance:

221428 - 2x = 177083

moles
x = 22173
h

Now that we have this we can calculate the mass of B and C generated:

mol B kg kg B
mB , gen = -x * MWB = 22173 * 0.026 = -576.5
h mol B h

mol C kg kg C
mC , gen = +x * MWC = 22173 * 0.030 = +665.2
h mol C h

At this point you may want to calculate the amount of B and C leaving the reactor with the
mass balances on B and C:

584 + 0.7 * xB5 * 2280 − 576.5 = xB3 * 2380

(1) 0.7 * (1 − 0.1544 − xB5) * 2280 + 665.2 = (1 − 0.15 − xB3) * 2380

However, these equations are the same! Therefore, we have proven our assertion that there is
still one DOF in the reactor. So we need to look elsewhere for something to calculate xB 5 .
That place is the separator balance on B:

m& 3 * xB 3 = m& 4 * xB 4 + m& 5 * xB 5 (1)

(2380)*xB3 = 0.02(100) + (2280)*xB5 (2)

Solving these two equations (1) and (2) yields the final two variables in the system:

xB 3 = 0.00856, xB 5 = 0.008058

Note that this means the predominant species in stream 5 is also C ( xC 5 = 0.838). However,
the separator/recycle setup does make a big difference, as we will see next.
 82

Comparison to the situation without the separator/recycle system

Now that we know how much ethane we can obtain from the reactor after separating, let us
compare to what would happen without any of the recycle systems in place. With the same
data as in the first part of this problem, the new flowchart looks like this:

2A+B à C m3
15% A
B
m2 m1 C
584 kg/h B 200 kg/h A

Figure 6.6b overall process balance

There are three unknowns ( m& 3 , xB 3 , x ) and three independent material balances, so the
problem can be solved. Starting with an overall mass balance because total mass is
conserved:

m& 1 + m& 2 = m& 3

kg
m& 3 = 789
h

We can carry out the same sort of analysis on the reactor as we did in the previous section to
find the conversion and mass percent of C in the exit stream, which is left as an exercise to
the reader. The result is that:

x = 20250 moles, xC 3 = 0.77

Compare this to the two exit streams in the recycle setup. Both of the streams were richer in
C than 77%, even the reject stream. This occurred because the unreacted A and B was
allowed to re-enter the reactor and form more C, and the separator was able to separate
almost all the C that formed from the unreacted A and B.
 83

Chapter 7

7.1 Vaporization of liquid methanol

Liquid methanol at 25oC is heated and vaporized for use in a chemical reaction. How much

heat is required to heat and vaporize 2 moles of methanol to 600 oC. (Answer: Q = 149,400 J)

Solution:

Reference: 25 oC, liquid

Normal boiling of methanol = 64.7 oC

é 64.7 600
ù
Q = n&DH = n& ê ò Cpliquid dT + DH v + ò Cpvapor dT ú
ˆ
ë 25 64.7 û

Q = 2 moles (3.012 kJ/mol + 35.27 kJ/mol + 36.14 kJ/mol ) = 148.844 kJ/mol

7.2 Heating of propane

Propane gas at 40oC and 250 kPa enters a continuous adiabatic heat exchanger (no heat is lost

from the outside of the unit – i.e., it is insulated on the outside but heat transfers between the

two fluids inside the heat exchanger) and exits the heat exchanger at 240oC. The flow rate of

propane is 100 mol/min. Saturated steam at 5 bar absolute pressure enters the heat exchanger

with a flow rate of 6 kg/min. Calculate the exit temperature of steam.

(Answer: Hˆ out = 2742.3 kJ/kg , Tf =133 o C ).

Solution

The heat exchanger is shown in the figure below

 84

Q = å n&i DHˆ i = n& propane DHˆ propane + n&steam DHˆ steam

Assume

Reference: 25 oC

Pressure drop in propane side is negligible

Heat exchanger is adiabatic à Q = 0

Q = (100 mol / min)( Hˆ out - Hˆ in ) P + (6 kg / min)( Hˆ out - Hˆ in ) s

0 = (100 mol / min)(20.49 - 1.129 kJ/mol) + (6 kg / min)( Hˆ out - 2748kJ/kg)

Hˆ = 2425.32 kJ / kg

The exit temperature of the steam at atmospheric pressure and enthalpy of 2425.32 kJ/kg

can be found at 133.15 oC.

7.3 Expansion of wet steam

A wet steam at 20 bar with a quality of 97% leaks through a defective steam trap and expands

to atmospheric pressure. The process can be considered to take place in two stages: A rapid

adiabatic expansion to 1 atm accompanied by complete evaporation of the liquid droplets in

the wet stream, followed by cooling at 1 atm to ambient temperature. Calculate the
 85

temperature of the superheated steam immediately following the rapid adiabatic expansion.

(Answer: T =132°C)

Solution

The process schematic diagram is shown below

System: adiabatic valve

Q = n&DHˆ

0 = n&DHˆ ® Hˆ out = Hˆ in

Enthalpy of wet steam at 20 bar and 97% quality (from steam table):

Hˆ vap = 2799 kJ/kg, Hˆ liq = 908.9

Ĥ = 0.97 (2799) + 0.03 (908.9) = 2742.3 kJ/kg

The exit temperature at this enthalpy and 1 atm pressure (from steam table) = 132 oC

7.4 Open system energy balance (Heating of Methanol)

Methanol is heated by condensing steam in a concentric cylinder heat exchanger as depicted

below. Methanol, flowing through the inner pipe at 64.0 kg/s, enters at 20°C and exits at
 86

60°C. Steam enters the outer pipe at 350°C and 80 bars (absolute) and leaves the heat

exchanger as saturated water at 1.0 atm. Assume that the outer pipe is well insulated and no

heat is lost to the surroundings.

a. Determine the mass flow rate of the steam. (Answer: 2.357 kg/s)

b. Calculate the degrees of superheat of the entering steam. (Answer: 55°C)

Figure P7.4 Flowsheet of double pipe heat exchanger

Solution

Reference: 25 oC

Adiabatic heat exchanger à Q = 0

0 = å ni DHˆ i = n&m DHˆ m + n&s DHˆ s = n&m ( Hˆ out - Hˆ in )m + n&s ( Hˆ out - Hˆ in ) s

0 = 64.0 kg/s/(30 kg/kmol)(1000 mol/kmol)*(3.034 kJ/mol) + ms(417.5-2990 kJ/kg)

ms = 2.357 kg/s
 87

b) To calculate the degree of superheat; the saturated steam temperature at 80 bars is 295 oC

350 – 295 = 55 oC

7.5 Open System Energy Balance (Heating of liquid methanol)

Calculate heat rate required to heat 32.04 kg/s of liquid methyl alcohol (CH3OH) at 5°C and

44 atm to vapor at 500°C and 2 atm. The heat of vaporization of methanol at 64.7°C and 1

atm is 35.27 kJ/mol. (Answer: 68.0 MW)

Solution:

Normal boiling point of methanol = 64.7 oC

é 64.7 o C 500 o C ù
Q = n& ê ò Cpliq dT + DH v + ò Cpvap dT ú
êë 5o C 64.7 o C úû

Q = (32.04 kg/s)(1000 mol/32 kg)(4.529 kJ/mol + 35.27 kJ/mol + 27.99 kJ/mol)

Q = 67873.7 kJ

7.6 Vaporization of liquid n-hexane

Determine the total amount of heat required to convert 2.00 moles of liquid n-hexane (C6H14)

at 10°C to vapor at 55°C in a closed container. Assume that hexane vapor behaves as an ideal

gas at the system pressure. Neglect any effect of a change in pressure on the liquid enthalpy.

The heat of vaporization of hexane at 68.74°C and 1 atm is 28.85 kJ/mol. (Answer: 77.9 kJ)

Solution:

é 68.74 o C 55 o C ù
Q = n& ê ò Cpliq dT + DH v + ò Cpvap dT ú
êë 10o C 68.74 o C úû

Q = 2 mol (12.71 kJ/mol + 28.85 kJ/mol + -2.223 kJ/mol) = 78.674 kJ

 88

7.7 Closed System Energy Balance (Heating of acetone)

A volume of 734 cm3 of liquid acetone is contained in a closed (vertical) cylinder fitted with

a moveable frictionless piston at 10°C. The acetone is heated to a vapor at 500°C. The piston

area is 50.0 cm2, and the piston weighs 200. kg. The heat of vaporization of acetone at its

normal boiling point (56.0°C) is 30.2 kJ/mol.

a. Calculate the heat (kJ) required to convert acetone from 10°C to 500°C. Assume the

cylinder is perfectly insulated, and no heat is lost to the surroundings. (Answer: 881 kJ)

b. If the heat is provided by superheated steam at 530°C and 1.0 bar, how much steam (kg) is

needed? The final condition of the steam is saturated at 100°C. (Answer: 1.00 kg)

Solution:

Acetone: MW = 58.08, SG = 0.791

Mass of acetone = (734 cm3)(0.791 * 1 g/cm3) = 580.594 g

Moles of acetone = 580.594 g/(58.08 g/mol) = 10 mole

é56.0 o C 500 o C ù
Q = n& ê ò Cpliq dT + DH v + ò Cpvap dT ú
ëê 10o C 56.0 o C ûú

a) Q = 10 mol( 5.94 + 30.2 kJ/mol+51.99 kJ/mol) = 881 kJ

b) Heat supplied by steam DĤ = 2676 - 3552 = -876 kJ/kg

m * 876 = 881 kJ

m = 1.0 kg

7.8 Open System Energy Balance (Power output of turbine)

A hydroelectric project has a volumetric throughput of 1.2 m3/s. The water flowing in the

river at atmospheric pressure and 20oC falls vertically for 300 m and passes through a turbine.
 89

The water exits the turbine at atmospheric pressure and 20.5oC. What is the power output of

the turbine? (Answer: 1.01 MW)

Solution

Q – Ws = DH + DEK + DEP

DE p = mgh = (1.2 m3/s) (1000 kg/m3)(9.81 m/s2)(0 -300 m) = -3,531,600 J/s

DH = m( Hˆ 2 - Hˆ 1 )

DH = (1.2 m3/s) (1000 kg/m3)/(1000 g/kg)(1 mol/18.016 g)(0.0377 kJ/mol)(1000J/kJ)

DH = 2,511,101 J/s

-Ws = -3,531,600 J/s + 2,511,101 J/s = -1.02 MW

Ws = 1.02 MW

7.9 Open System Energy Balance (Power requirement of compressor)

Air at 100 kPa and 10oC enters a compressor and is compressed to 1000 kPa and 50oC. The

constant pressure heat capacity of air is 1.01 kJ/kg K. If 15 kg of air are to be compressed

every minute, determine the power requirement of the compressor. State your assumptions.

(Answer: -10.1 kW)

Solution

Q - Ws = DH = mCP dT

Assume the compressor is adiabatic

Q=0

-Ws = (15 kg/min)(1min/60 s) (1000 g/kg)(mol/29 g) (1.163 kJ/mol) = 10 kW

Ws = -10 kW
 90

Chapter 8

8.1 Estimation of Heat of reaction

Given the following heats of formation ( DH of ,25oC) and heats of combustion ( DH co , 25oC)

data, determine the heat of reaction for the liquid-phase esterification of lactic acid (C3H6O3)

with ethanol (C2H5OH) to form ethyl lactate (C5H10O3) and liquid water at 25 oC. The table

below shows the standard heat of combustion and heat of reaction

DH co (25 oC, 1 atm) DH of (25 oC)

Compound
kJ/mol kJ/mol

C3H6O3 - -687.0
C2H5OH - -277.6
C5H10O3 -2685 -
H2O (liquid) -285.8
CO2 (gas) -393.5
O2 (gas) - 0

The Standard states of products are CO2 (g) and H2O(l)

Solution

C3 H 6O3( l ) + C2 H 5OH ® C5 H10O3 + H 2O(l )

The heat of reaction can be calculated from heat of formation

DH rxn
o
= DH of , H 2O( l ) + DH of ,C5 H10O3 - DH of ,C2 H 5OH - DH of ,C3 H 6O3

DH rxn
o
= -285.8 + DH of ,C5 H10O3 - (-277.6) – (-687.0)

DH of ,C5 H10O3 = ?

The heat of formation of ethyl lactate (C5H10O3) is not given, by contrast the heat of

combustion is given. The heat of reaction of ethyl lactate can be calculated from the heat of

combustion and from the heat of reaction the heat of formation can be calculated
 91

C5 H10 O3 + 6O2 ® 5CO2 + 5H 2O(l )

From the heat of combustion

DH rxn
o
= -2685 – 0 – 0 - 0

Knowing the heat of reaction we can calculate the heat of formation of C5H10O3

DH rxn
o
= -2685 = 5DH of , H 2O(liq) + 5DH of , CO2 ( g ) - DH of , C5 H10O3 (liq) - DH of , O2

-2685 = 5 (-285.8) + 5 (-393.5) - DH of ,C5 H10O3 -0

DH of ,C5 H10O3 = 5 (-285.8) + 5 (-393.5) + 2685 = -711.5 kJ/mol

Knowing the heat of formation of ethyl lactate we can calculate the heat of esterification

reaction

DH rxn
o
= DH of , H 2O( l ) + DH of ,C5 H10O3 - DH of ,C2 H 5OH - DH of ,C3 H 6O3

DH rxn
o
= -285.8 + (-711.5) - (-277.6) – (-687.0) = -32.7 kJ/mol

8.2 Production of superheated steam

Superheated steam (40 bar, 350oC) is produced from liquid water (40 bar, 50oC) in a

methane-fired boiler. To insure complete combustion of the methane 1% excess air is

provided. Both the methane and combustion air enter the boiler at 25oC. Determine the outlet

temperature of the flue gas from the boiler, if 19.85 kg/min of superheated steam is produced

from the combustion of 1.4 kg/min of methane. Assume the boiler is perfectly insulated.

Solution

The process flowsheet is shown in the figure below

 92

Basis: 1.4 kg/min of methane

Reference: 25 oC

Material balance:

CH4 + 2O2 à 2H2O + CO2

Moles of CH4 = 1.4 kg/min = (1400g/min)/(16 g/mol) = 87.5 mol/min

nCH 4 = nCH
o
4
-x
nCO2 = 0 + x
nH 2O = 0 + 2x
nO2 = nOo 2 - 2x

Theoretical oxygen = 2(87.5) = 175 mol/min

Total inlet oxygen = 1.1 (175) = 192.5 mol/min

Total inlet air = 192.5/0.21 = 917 mol/min

Total inlet nitrogen = 724.2 mol/min

For complete combustion nCH 4 = nCH

o
4
- x = 0 = 87.5 - x

x = 87.5 mol/min
 93

nCO2 = 87.5 mol / min

nH 2O = 175 mol / min
nO2 = 192.5 - 2(87.5) = 17.5 mol / min
nN2 = 724.2 mol / min

Energy balance

CH4 + 2O2 à 2H2O + CO2

Heat of reaction can be calculated from heat of combustion or heat of formation in this case it

is easier to be calculate from the heat of combustion since heat of combustion products such

as water and carbon dioxide is zero

DH rxn
o
= DH co,CH 4 = -802.7 kJ / mol

Q = DH = å n&i Hˆ i - å n&i Hˆ i
out in

Heat required to generate the steam =

mDHˆ = 19.85 kg/min (3092-209.5) kJ/kg = 57217.6 kJ/min

T
Heat released from the combustion of natural gas: DH rxn
o
+ å ò ni CPi dT
25

T T T T 25 25
xDH rxn
o
+ ò nCO2 CPCO dT + ò nH 2O CPH O dT + ò nO2 CPO dT + ò nN2 CPN dT - ò nCH 4 CPCH dT - ò n Air CPAir dT
2 2 2 2 4
25 25 25 25 25 25

T T T T
= xDH rxn
o
+ ò nCO2 CPCO dT + ò nH 2O CPH O dT + ò nO2 CPO dT + ò nN 2 CPN dT
2 2 2 2
25 25 25 25

= (87.5 mol/min)(-802.7 kJ/mol)

T T T T
+ 87.5 ò CPCO dT + 175 ò CPH O dT + 17.5 ò CPO dT + 724.2 ò CPN dT
2 2 2 2
25 25 25 25

= -70236.25+87.5*(36.11E-3*(T-25)+(4.233E-5/2) * (T^2-25^2)) + 350*(75.4E-3(T-

25))+17.5*(29.1E-3*(T-25)) + (1.158E-5/2)*(T^2-25^2) + 724.2*(29E-3*(T-25)+(0.2199E-

5/2)*(T^2-25^2)
 94

Q = 57217.6+ (-70236.25) + 175*(36.11E-3*(T-25)+(4.233E-5/2)*(T2-252))+

350*(75.4E-3(T-25))+17.5*(29.1E-3*(T-25))+(1.158E-5/2)*(T2-252)+

724.2*(29E-3*(T-5)+(0.2199E-5/2)*(T2-252)

The heat exchanger is adiabatic (Q = 0)

0.0 = 57217.6 + (-70236.25) + 87.5*(36.11E-3*(T-25) + (4.233E-5/2)*(T^2-25^2)) +

175*(75.4E-3(T-25)) + 17.5*(29.1E-3*(T-25) + (1.158E-5/2)*(T^2-25^2)) +

724.2*(29E-3*(T-25) + (0.2199E-5/2)*(T^2-25^2))

The exit temperature = 360.158 oC

 95

8. 3 Ammonia synthesis process

Ammonia is synthesized through the reaction of nitrogen with hydrogen as follows:

N 2 + 3 H 2 ® 2NH 3

Shown below is a process flowsheet for the ammonia synthesis process (Figure P8.3). In this

process the fresh feed consists of Argon (1 mol %) and stoichiometric amounts of N2 and H2.

The reactor feed has a molar flow rate of 100 mol/min and a composition of 15 mol% argon,

21.25 mol% N2, and 63.75 mol% H2. The reactor feed temperature is 400 oC. The fractional

conversion of N2 to NH3 in the reactor is 0.15 moles N2 reacted/mole N2 feed to the reactor.

The hot reactor effluent gas is used to heat the recycle gas from the separator in a combined

reactor effluent/recycle heat exchanger. After passing through this heat exchanger, the

reactor effluent gas passes through a condensor where the NH3 product is condensed. The

liquid NH3 is separated from the noncondensable recycle gases. A purge stream is taken off

of the separator offgas to maintain the level of argon at 15 mol% feed to the reactor. In this

particular process, the converter is operated adiabatically and the heat of reaction at 400oC

was found to be -53.109 kJ/mol at the pressure of the reactor. The table below gives the heat

capacities for the pressure of the reactor. Note that the given heat capacities are assumed to

be constant over the temperature range found in the reactor.

Compound Cp (J/mol oC)

NH3 49.4
H2 29.5
N2 31.0
Argon 20.8

Determine the flowrates in mole/min and compositions in mole % of:

a) The fresh feed stream.

b) Separator purge gas stream.

 96

c) Recycle gas stream.

d) Estimate the temperature of the effluent gases from the converter.

e) If the recycle gas stream enters the heat exchanger at 50oC and leaves the exchanger at

400oC, determine the outlet temperature of the reactor effluent stream from the heat

exchanger. Assume no condensation of ammonia in the heat exchanger.

Figure P8.3 Process flowsheet for the ammonia synthesis process

Solution:

Basis: 100 moles/min fed to reactor

N 2 + 3H 2 ® 2 NH 3

Material balance

Ar is inert

0.15(100) = 15 mol

Conversion = 0.15 =
( N 2 ) in – ( N 2 ) out = 0.2125(100)-(N 2 )out
( N 2 ) in 0.2125(100)
 97

(N2)out = 21.25 – 0.15(21.25)

(N2)out = 18.0625 mol/min

(H2)out = 3 (18.0625) = 54.1875 mol/min

Moles NH3 produces = 2 (0.15*21.25) = 6.375 mol/min

Check your results using atomic balance

N: 2(21.25) = 2(18.0625) + 6.375 (correct)

H: 2(63.75) = 2(54.1875) + 3(6.375) à 127.5 = 127.5 (correct)

Ammonia produced at a rate = 6.375 mol/min

Purge stream components flow rate

Ar: 15 mol/min

H2 = 54.1875 mol/min

N2 = 18.0625 mol/min

Composition of purge and recycle streams have the same compositions (splitter)

Ar: 0.17

H2 = 0.62

N2 = 0.21

System: mixing point

Total balance around the mixing point

Fo + R = 100 mol/min

Ar balance

0.01 Fo + 0.17 R = 15

R = 87.5 mol/min

Fo = 12.5 mol/min

a) Fresh feed stream flow rate

Fo = 12.5 mol/min
 98

c) Recycle stream flow rate

R = 87.5 mol/min

b) purge stream flow rate

System overall

Ar balance

0.17 P = 0.01 (12.5)

P = 0.735294 mol/min

d) The temperature of the effluent gases from the converter

Energy balance on the converter

Tref = 400 oC

System: Converter

Assumption: adiabatic

Q = 0 = Q = xDH r @ 400 + å n&i Hˆ i - å n&i Hˆ i

out in
 99

T2 T1 =Tref

Q = xDH r @ 400 + å ò n& Cp dT - å ò

i i n&iCpi dT
out Tref out Tref

T2

Q = xDH r @ 400 + å ò n& Cp dT

i i
out Tref

T2 T2 T2 T2

Q = xDH r @ 400 + ò n&

Tref
Ar Cp Ar dT + ò n&
Tref
N2 CpN 2 dT +
Tref
ò n& H2 CpH 2 dT + ò n&
Tref
NH 3 CpNH3 dT

Heat capacity is constant and the system is adiabatic

Extent of reaction:

nN2 = nNo 2 - x
18.0625 = 21.25 - x

x = 3.1875

DH r @ 400 o C
= -53.109 kJ / mol

0 = 3.1875*(-53.109*1000) + 15*20.8(T-400)+18.0625*31.0*(T-400)+54.1875*29.5*(T-

400)+6.375*49.4*(T-400)

T = 460.776 K

e) If the recycle gas stream enters the heat exchanger at 50oC and leaves the exchanger at

400oC, determine the outlet temperature of the reactor effluent stream from the heat

exchanger. Assume no condensation of ammonia in the heat exchanger.

 100

Solution:

Tref = 50 oC

Q – Ws = DH

Assuming the heat exchanger is adiabatic (Q=0) and no shaft work (Ws=0)

0 = DH

0 = H3 +H9 – H2 – H7 = (H3-H2 )+ (H9 – H7)

æ 400 400
ö æ T T
ö
ç Ar ò
n Cp Ar dt + n N2 ò Cp N2 dt + ÷ ç Ar ò
n Cp Ar dt + n N 2 ò Cp N 2 dt + ÷
ç 50 50 ÷ - ç 460 460 ÷=0
ç 400 ÷ ç T T ÷
ç n H ò CpH dt ÷ ç n H ò CpH dt + n NH ò CpNH dt ÷
ç 2 2 ÷ ç 2 2 3 3 ÷
è 50 ø è 460 460 ø

Since heat capacities are constants

Compound Cp (J/mol oC)

NH3 49.4
H2 29.5
N2 31.0
Argon 20.8

0.15(87.5)(20.8)(400-50) +0.2125(87.5)(31)(400-50) + 0.6375(87.5)(29.5)(400-50) –

15(20.8)(T-460)-18.0625 (31.0)(T-460) – 54.1875(29.5)(T-460) -6.375(49.4)*(T-460)=0

 101

T = 242.24 oC

8.4 Catalytic transalkylation of toluene to benzene

Shown below is a process flowsheet for the catalytic transalkylation of toluene to benzene

and xylene. Toluene transalkylates in the presence of hydrogen to form benzene and xylene:

2C7 H8 ® C6 H 6 + C8 H10

Toluene also may dealkylate in the reactor to form benzene and methane:

C7 H8 + H 2 ® C6 H 6 + CH 4

In this process, toluene reacts with a fractional conversion of 0.80 (moles of toluene reacted/

mole of toluene fed to the unit) and benzene and xylene yields of 0.505 and 0.495,

respectively. Yields are defined as moles of product/moles of toluene reacted. In this

process the reactor effluent is condensed and separated. The separator liquid is sent to a

benzene distillation column where benzene with a purity of 99.5 mol % is removed as the

overhead product. The bottoms products contain benzene, unreacted toluene, and xylene. A

purge stream containing hydrogen and methane is taken off the separator gas stream. The
 102

rest of this separator gas stream is combined with a fresh hydrogen stream containing

hydrogen and methane with concentrations of 95.0 and 5.0 mol %, respectively. These

combined hydrogen streams are added to the fresh toluene feed and sent to the reactor heater.

a) If 225 kmol/h of toluene is feed to the reactor, and the benzene column recovers 99.0 of the

benzene at a purity of 99.5 mol % (balance of overhead is toluene), determine the molar

flowrates of each component in the benzene column overhead and bottoms product streams.

Figure P8.4 process flowsheet of problem 8.5

b) Determine the molar flow rates of hydrogen and methane in the fresh hydrogen stream and

molar flowrates of hydrogen and methane in the separator off-gas purge stream to maintain a

hydrogen purity of 90.0 mol % in the separator off-gas stream. The fresh hydrogen stream

containing hydrogen and methane with concentrations of 95.0 and 5.0 mol %, respectively.

c) If the liquid toluene fresh feed stream, fresh hydrogen stream, and recycled streams are all

at 25oC and 15 bar absolute, determine the heat requirements for the reactor heater to provide
 103

the reactor with a combined feed at 400oC and 15 bar absolute in the vapor phase. It is

desired to have a hydrogen to toluene molar ratio of 3 to the reactor. Assume ideal gases and

no pressure effects.

Solution:

Basis : 22 kmol/h of T

The labeled process flowsheet is shown below

n T = nT 0 - 2x1 - x 2
n B = x1 + x 2
n X = x1
n H = n H 0 -x 2
n M = n M 0 x2

nT - nT 0
0.8 =
nT 0
nB
yB = = 0.505
nT - nT 0
nX
yX = = 0.495
nT - nT 0
 104

8.5 Combustion of methane

Methane at 25°C is burned in a boiler furnace with 10.0% excess air preheated to 100°C.

Ninety percent of the methane fed is consumed, the product gas contains 10.0 mol CO2/mol

CO, and the combustion products leave the furnace at 400°C. Calculate the heat transferred

from the furnace for a basis of 100 mol CH4 fed/s.

Figure P8.5 Methane burned in a boiler furnace

Basis: 100 mol/s of methane

Material balance using extent of reaction

CH 4 +2O 2 ® CO 2 +2H 2 O x1

3
CH 4 + O2 ® CO+2H 2 O x2
2

CH 4 n 2 = 100 - x1 - x 2
CO2 n 3 = 0.0 + x1
CO n 4 = 0.0 + x 2
3
O2 n 5 = n50 - 2x1 - x 2
2
N2 n6 = n60
 105

n2
0.9 =
100
n
10= 3
n4

CH 4 + 2O2 ® CO2 + 2 H 2O

Theoritical O 2 = 2 (100 ) moles

Total O2 = 1.1( 200 ) = 220 moles
220
Total Air =
0.21
æ 0.20 ö
N 2 = 200 ç ÷
è 0.21 ø

8.6 Anaerobic yeast fermentation

Saccharomyces cerevisiae is grown anaerobically in continuous culture at 30oC. Glucose is

used as carbon source; ammonia is the nitrogen source. A mixture of glycerol and ethanol is

produced. At steady state, mass flows to and from the reactor at steady state are shown in

Figure P8.7. Estimate the cooling requirement.

 106

Figure P8.7 Flowsheet for anaerobic yeast fermentation

Solution:

Basis: 136 kg/h of carbon dioxide

Molecular weight

Glucose 180
NH3 = 17
Glycerol = 92
Ethanol = 46

Heat of combustion:

Glucose = -2805.0 kJ/mol = -1.558 ´10 4 kJ/kg

NH3 = -382.6 kJ/mol = -2.251´10 4 kJ/kg
Glycerol = -1661.1 kJ/mol = -1.799 ´10 4 kJ/kg
Ethanol = -1366.9 kJ/mol = -2.971´10 4 kJ/kg
Cell = -2.120 ´10 4 kJ/kg

The reaction:

Glucose+NH3 à biomass + glycerol + ethanol + CO2 + H2O

Standard heats of combustion are used to calculate the standard heat of reaction for reactions
involving combustible reactants and combustion products

DH rxn
o
= å
reactant
n i ΔH co - å
product
n i ΔH oc

DH rxn
o
= ng DH co, gl cos e + nN DH co, NH 3 - nC DH co,cell - ngl DH co, glycerol - neDH co,ethanol

DH rxn
o
= 36.0kg (-1.558 ´ 104 ) + 0.4(-2.251´10 4 ) - 2.81(-2.120 ´ 104 ) -
7.94(-1.799 ´ 104 ) - 11.9(-2.971´10 4 )
DH rxn
o
= -1.392 ´ 104 kJ

The reaction is exothermic and system must be cooled

 107

Chapter 9

COMBINED MATERIAL AND ENERGY BALANCES

Problem 9.1 cooling of ethanol

10 kg hot ethanol (150°C, 1.2 atm) is cooled and condensed by mixing it with cold ethanol
(5°C, 1.2 atm). If the final ethanol product is to be at 25°C and 1.2 atm.

a) Draw and label the process flowsheet.

b) How much cold ethanol (kg) must be added?

Solution:

a) First we draw a diagram. There are a couple of ways to imagine this process. In the
drawing below, the process is considered as though at some time cold and hot ethanol are
added to a pot, and at some later time the resulting mixture is removed. We implicitly assume
that the pot is adiabatic, so there is no energy flow in or out due to heat. There is also no
mechanical equipment, so there is no shaft work term.

Figure P9.1 Flowsheet of mixing process

b) The amount of liquid ethanol added is calculated as follows

(As a side note: How could we use Antoine’s equation to figure out whether ethanol was
vapor or liquid at 25 oC?)

System: Mixer

Basis: is 10 kg ethanol in stream 1.

Material balance equation:

 108

10 + m 2 = m3

Energy balance:

We ignore kinetic and potential energy of the material flow streams in and out of the mixer.
We now need to determine the enthalpy of these streams. We don’t have ethanol tables
(equivalent to steam tables), so we will need to calculate the enthalpy using model equations
that account for temperature and phase changes. For that, we need to pick a reference state.
The reference state can be any convenient state – we just need to specify the composition,
phase, pressure and temperature of the reference state.

Reference: Pure ethanol in the liquid phase at 5 °C and 1.2 atm pressures.

Why is this reference state so convenient? Because it is exactly the state of stream 2
Therefore,

Ĥ 2 = 0.

Now let’s calculate the specific enthalpy of the ethanol leaving the system (stream 3).

J æ gmol ö æ 1000 g ö æ kJ ö kJ
Hˆ 3 = C p (T3 - Tref ) = 112 o
(25 - 5o C ) ç ÷ç ÷ç ÷ = 50.9
gmol C è 44 g ø è kg ø è 1000 J ø kg

We must use the same reference state to calculate the enthalpy of stream 1. The data we have
available are: Heat capacities of liquid and vapor ethanol, and enthalpy of vaporization of
ethanol at 78.3°C. We will neglect pressure effects.

We construct a pathway from the reference state to the state of stream 1: increase temperature
of liquid from 5°C to 78.3°C, vaporize at 78.3°C, increase temperature of vapor from 78.3°C
to 150°C.

J kJ
Hˆ 1 = 112(78.3 - 5) + 36, 600 + 65.6(150 - 78.3) = 51506 = 1170.6
gmol kg

The energy balance simplifies to:

0 = m1 Hˆ 1 + m2 Hˆ 2 - m3 Hˆ 3

We plug in to find

æ kJ ö æ kJ ö
0 = (10 kg) ç1170.6 ÷ + m2 (0) - m3 ç 50.9 ÷
è kg ø è kg ø

Solving, we get m3 = 230 kg

And from the material balance equation:

 109

m2 = 220 kg

We have to add 220 kg of cold ethanol to cool and condense 10 kg of hot ethanol. The
quantity required is so high because the enthalpy change with phase change is so large.

Problem 9.2 Combustions process

100 gmol/h acetylene (C2H2) is mixed with 2000 gmol/h air (79 mol% N2, 21 mol% O2) and
the mixture (at 298 K and 1 atm) fed to a reactor, where complete combustion takes place.
The reactor is equipped with cooling tubes. The combustion mixture leaving the reactor is at
1000 K and 1 atm.
(a) Draw and label the process flow diagram?
(b) How much heat (kJ/h) was removed in the reactor?
(c) Suppose the coolant supply was suddenly shut off. What reactor outlet temperature would
be reached?

Data: CpCO2 = 37, CpH 2O = 33.6, CpO2 = 29.3, CpN 2 = 29.3 J/mol o C , assume constant and
independent of temperature.

Solution:

The acetylene is completely combusted, and the oxygen is fed at excess, so the reactor outlet
stream will contain CO2, H2O, O2 and N2, but no acetylene. The reactor has cooling tubes,
which we show by including a heat flow from the reactor. The process block diagram is
shown in Figure E9.19.

Figure P9.2 Ethylene combustion process block diagram

System: Reactor

Basis: 100 gmol/h of acetylene fed to the reactor.

The balanced chemical reaction is:

5
C2 H 2 + O2 ® 2CO 2 + H 2O
2
 110

Material balance equation:

Since the reaction is complete; No acetylene in flue gases.

Using the extent of reaction method,

C2H2: n C2 H 2 = 0 = 100 - ξ ¾¾
® ξ=100 gmol/h
CO2 : n CO2 =0+2ξ ¾¾
® n CO2 =200gmol/h
5
O2: n O2 =0.21(2000)- ξ ¾¾ ® n O2 =170 gmol/h
2
N2: n N2 =0.79(2000) ¾¾® n N2 =1580 gmol/h

The reactor effluent contains:

CO2: 200 gmol/h
H2O: 100 gmol/h
O2: 170 gmol/h
N2: 1580 gmol/h

(b) There is no work term, and no kinetic or potential energy changes. The differential energy
balance equation is simplified to:

Q = å m& out Hˆ out - å m& in Hˆ in = H& out - H& in

There are a couple of approaches we can take to calculate the enthalpy.

Approach 1: Choose as a reference state the elements at 298 K and 1 atm. Then we calculate
the enthalpy of each compound relative to that reference state, and mix the compounds
together. Let’s illustrate (we use only gas phase for all compounds and mixtures):

Ù
C2H2 at 298K and 1 atm: H C2 H 2 ,298 = DHˆ of , C2 H 2 ,298 = 228.2 kJ/gmol
Ù
O2 at 298K and 1 atm: H O2 ,298 = DHˆ of ,O2 ,298 = 0 kJ / gmol
Ù
N2 at 298K and 1 atm: H N2 ,298 = DHˆ of , N 2 ,298 = 0 kJ /gmol

CO2 at 1000K and 1 atm:

Ù
H CO2 ,1000 = DHˆ of ,CO2 ,298 +C p ,CO2 (1000 - 298 )
37
= -393.5 + (1000 - 298 ) = -367.5KJ/gmol
1000

H 2O at 1000K and 1 atm:

Ù 33.6
H H 2O ,1000 = DHˆ of , H 2O ,298 + CP , H 2O (1000 - 298 ) = -241.83 + (1000 - 298)
1000
= -218.24 KJ / gmol
 111

O2 at 1000K and 1 atm:

Ù 29.3
H O2 ,1000 = CP ,O2 (1000 - 298) = (1000 - 298 ) = 20.57 kJ/gmol
1000

N 2 at 1000K and 1atm:

Ù 29.1
H N2 ,1000 = CP , N2 (1000 - 298) = (1000 - 298) = 20.43 kJ/gmol
1000

We have done the hard part of the work. We assume that there is no enthalpy change due to mixing
(a safe assumption for gases) and calculate:

Q& = [200(-367.5) + 100(-218.24) + 170(20.57) +1580(20.43)]-100(228.2) =-82370 kJ/h

Approach 2: Create a path leading from the inlet conditions to the outlet conditions, and
calculate the enthalpy change for each step in the path, then sum together.

Step 1. React 100 gmol C2H2 at 298K and 1 atm:

DHˆ ro = å v DHˆ
i f ,i = (−1)(228.2) + (2)(−393.5) + (1)(−241.83) = −1257 kJ/gmol

(This is a highly exothermic reaction.)

The total enthalpy change is –125,700 kJ/h.

Step 2. Raise the temperature of the reaction products from 298 K to 1000 K.

Q = DHˆ ro + å n&i Hˆ i - å n&i Hˆ i

out in

( 2
) (2
) (2
) (
2 û
)
Q& = DHˆ ro + é n&CO2 CP CO + n&H 2O CP H O + n&O2 CP O + n& N2 CP N ù (Tout - Tref )
ë

é æ 37 ö æ 33.6 ö æ 29.3 ö æ 29.1 ö ù

ê 200 ç 1000 ÷ + 100 ç 1000 ÷ + 170 ç 1000 ÷ + 1580 ç 1000 ÷ ú (1000 - 298) = 43,330 kJ/h
ë è ø è ø è ø è øû

The sum of these two steps is the difference in enthalpy between the outlet and inlet streams:

Q& = −125,700 + 43,330 = −82370 kJ/h

(c) Now there is no heat term, and we don’t know the reactor outlet temperature. The energy
balance equation is simple:
 112

0 = å m& out Hˆ out - å m& in Hˆ in = H& out - H& in

out in

and we use the energy balance equation to calculate the reactor outlet temperature. We can
use either approach 1 or approach 2; I will use just approach 2 here

Step 1. React 100 gmol C2H2 at 298K and 1 atm:

DHˆ ro = å vi DHˆ of ,i = (−1)(228.2) + (2)(−393.5) + (1)(−241.83) = −1257 kJ/gmol

(This is a highly exothermic reaction.)

The total enthalpy change is:

æ gmol ö æ kJ ö
DH& r = xDHˆ ro = ç100 ÷ ç -1257 ÷ = –125,700 kJ/h.
è h øè gmol ø

Step 2. Raise the temperature of the reaction products from 298 K to Tout

é n& C (
ë CO2 P CO2 ) ( ) ( ) (
+ n& H 2O CP H O + n&O2 CP O + n& N 2 CP N ù (Tout - Tref )
2 2 2 û
)
é æ 37 ö æ 33.6 ö æ 29.3 ö æ 29.1 ö ù
ê 200 ç 1000 ÷ + 100 ç 1000 ÷ + 170 ç 1000 ÷ + 1580 ç 1000 ÷ ú (Tout - 298) = 61.7(Tout - 298)kJ/h
ë è ø è ø è ø è øû

The sum of the heat of reaction and the sensible heat required to raise the reaction product to
Tout is the difference in enthalpy between the outlet and inlet streams:

ë ( 2
) 2
( ) 2
( 2
)
û ( )
Q& = DH& r + é n&CO2 CP CO + n&H 2O CP H O + n&O2 CP O + n& N2 CP N ù (Tout - Tref )

0 = −125,700 + 61.7(Tout − 298)

We solve to find Tout = 2335 K

Problem 9.3 Ethanol dehydrogenation process

Ethanol (C2H5OH) is dehydrogenated in a catalytic reactor to acetaldehyde (CH3CHO), with
hydrogen (H2) as a byproduct. In an existing process, 100 gmol/min liquid ethanol at 25°C
and 1 atm pressure is first heated to 300°C in a heat exchanger, and then fed to the reactor.
100% of the ethanol is converted to products, and the product stream leaves the reactor at
300°C and 1 atm (760 mm Hg). The product stream leaving the reactor is cooled to -15°C,
and sent to a flash drum, where vapor and liquid streams are separated (Figure E9.20).
A. How much heat must be supplied to the first heat exchanger?
B. How much heat must be supplied to or removed from (state which) the reactor in order to
maintain a constant 300°C temperature?
C. What are the flow rates of the vapor and liquid streams leaving the flash drum?
 113

Figure P9.3 Flowsheet of ethanol dehydrogenation process

Data

Species Tb ΔH vap (Tb) Cp (liquid) Cp (gas) DH of (25 o C)

o
C kJ/gmol kJ/gmol o C kJ/gmol o C kJ/gmol
H2 -252.76 0.904 -- 0.029 0 (g)
CH3CHO 20.2 25.1 0.089 0.055 -166.2 (g)
C2 H5OH 78.5 38.58 0.158 0.077 -277.63 (l)
-235.31 (g)

Antoine equation:

1554.3
Ethanol: log10 Psat (mm Hg) = 8.04494-
(222.65 + T(°C))

992
Acetaldehyde: log10 Psat (mm Hg) = 6.81089 -
(230+T (o C))

Solution:

A. How much heat must be supplied to the first heat exchanger?

System: The first heat exchanger

Reference: 25°C, liquid ethanol

The first heat exchanger must bring the ethanol from the liquid state at 25°C to the vapor
phase at 300°C, at a constant 1 atm (note that the normal boiling point of ethanol is 78.5 °C).
The needed heat is the heat required to raise the temperature of liquid ethanol at 25°C to its
boiling point in liquid form plus the heat required to change ethanol from liquid to vapor
phase (i.e. latent heat of vaporization) plus the sensible heat that is needed to raise the
temperature of vapor ethanol from the boiling point to 300 oC.

{ }
Q& = m& ( Hˆ out - Hˆ in ) = n&ethanol C pliq (78.5 - 25) + DHˆ vap + C pvap (300 - 78.5)
 114

Q& = m& ( Hˆ out - Hˆ in ) =100[0.158(78.5 − 25) + 38.58 + 0.077(300 − 78.5)] = 6400 kJ/min

B. How much heat must be supplied to or removed from (state which) the reactor in order to
maintain a constant 300°C temperature?

We construct a pathway to calculate the difference in the enthalpy of the inlet and outlet
streams:

System: reactor
Reference: 25°C, gases

Using the general energy balance equation

Q& = å n&i Hˆ i - å n&i Hˆ + xDH ro
out in

300

å n&i Hˆ i = n&ethanol
in
ò Cp v ,ethanol dT = n&ethanol Cpv ,ethanol (300 - 25)
25

= 100(0.077) (300 − 25) = 2117.5 kJ/min

The standard heat of reaction at reference temperature

DHˆ ro = å vi DH of

DHˆ ro = (−1)(−235.31) + (+1)(−166.2) = +69.11 kJ/gmol

DH = xDHˆ ro =100(69.11) = 6911 kJ/min

å
out
n&i Hˆ i : the sum of the exit enthalpies
300 300

å n&i Hˆ i = n&CH3CHO
out
ò Cpv ,CH3CHO dT + n&H 2 ò Cp v ,H 2 dT
25 25

Since all species are in gas phase and constant specific heats at 300 oC (note that there is no
ethanol exits the reactor because the reaction was complete conversion, in other words all the
inlet ethanol is reacted and converted to acetaldehyde and hydrogen, consequently the exit
enthalpy integral equation is reduced to the following algebraic equation.

å n& H&
out
i i = n&CH3CHOCpv ,CH3CHO (300 - 25) + n&H 2 CpH 2 (300 - 25)

Substituting the values of heat capacities leads to:

 115

[ {100(0.029)(300- 25) +100(0.055)(300- 25)} = +2310 kJ/min

The energy balance equation simplifies to

Q& = å mH
& ˆ - å m& i Hˆ + xDH ro = 23100 − 2117.5 + 6911 = +7103 kJ/min
out in

About 7100 kJ/min must be supplied to the reactor. This makes sense, since the reaction is
endothermic.

Self test:
Calculate the heat the must be supplied to the reactor using different reference temperature
(such as 300 oC instead of 25 oC)? (The answer should be the same)

C. What are the flow rates of the vapor and liquid streams leaving the flash drum?

At –15°C, it is fair to assume that all the hydrogen remains in the vapor state. However, it is
NOT correct to assume that all the acetaldehyde condenses. Although the mixture is below
the boiling point of pure acetaldehyde – we have a mixture.
But, if both liquid and vapor phases are present, we can assume that only acetaldehyde is in
the liquid phase, or xA = 1.0 . From Antoine’s equation we calculate that the saturation
pressure of acetaldehyde at –15°C is 157 mm Hg.

From Raoult’s law, y A = Psat/P = 157/760 = 0.207

Now we use material balance equations to find vapor (V) and liquid (L) flows:

100 = 0.207n&V + n&L

100 = 0.793n&V

Solving, the vapor flow rate is 126 gmol /min and the liquid flow rate is 74 gmol/min.

9.4 A gas contains the following compounds: CH4, C2H6, O2, CO2, CO, H2O, and H2.
A. What is the maximum number of independent chemical reactions that can be written
involving these compounds? (You do not need to determine what the reactions are, only how
many there are).

Hint: There are seven compounds and 3 elements. There are 7 – 3 or 4 independent chemical
reactions.

B. Twelve gmol SiCl4 and 20 gmol H2 react to make solid silicon Si and HCl. Which
compound (SiCl4 or H2) is the limiting reactant? What is the % excess for the excess
reactant?

5. Cumene (C9H12) is a useful intermediate in the synthesis of specialty chemicals such as

pharmaceuticals and flavorings. Cumene is synthesized from propylene (C3H6) and benzene
 116

(C6H6). Unfortunately, a side reaction also occurs, in which diisopropylbenzene (C12H18) is

generated by reaction of propylene with cumene. Abbreviating as C = cumene, P =
propylene, B = benzene and D = diisopropylbenzene, the two balanced reactions are:

P+Bà C (R1)
P+Cà D (R2)

A block flow diagram for a cumene manufacturing process is sketched below. 100 kgmol/h
of a gas containing 95 mol% P and 5 mol% I (stream 1) is mixed with 80 kgmol/h B (stream
2) plus a recycle stream (stream 8). The mixer outlet is fed to a reactor. The fractional
conversions achieved in the reactor (based on the reactor feed, stream 3) are fCB = 0.9 and
fCP = 0.7. The reactor outlet is sent to a separator, where all of the P, all of the I, and 10% of
the B is recovered in stream 6, and the remaining B and all of the C and D are recovered in
stream 5. Stream 6 is sent to a splitter. 85% of the splitter feed is recycled to the mixer and
the remainder is purged (stream 7). Calculate the following;

(1) Flow rates of P and B (kgmol/h) in stream 3,

(2) Mol% I in stream 7,
(3) Flow rates of C and D (kgmol/h) in stream 5, and,
(4) Selectivity for converting B to C achieved by the overall process.

Figure P9.5 Flowsheet of Cumene synthesis process

Solution:

The labeled process flowsheet is shown below

 117

Material balance around the reactor using extent of reaction method

P+B ®C x1
P+C ® D x2

nP = nPo - x1 - x 2
nB = nBo - x1
nC = 0 + x1 - x 2
nBo - nB
0.9 =
nBo
nPo - n p
0.7 =
nPo

System mixer

P: balance
100 + 0.85(nPo - x1 ) = nPo

B: balance
80 + 0.085(nBo - x1 ) = nBo

x1 = 0.7 nPo
x1 = 0.9nBo
 118

a) Flow rate of P and B

Flow rate of B in stream 3 = 80.6585 kmole/h

Flow rate of P in stream 3 = 103.739 kmole/h

b) Mole % I in stream 7

Purge stream
nP = 0.15(nPo - x1 )
nB = 0.015(nBo - x1 )
nI = 0.15nIo
 119

c) Flow rate of C and D in stream 5

6. The dehydrogenation of propane

C3 H8 (g) ® C3 H 6 (g) + H 2 (g) DHr (1000oC) = 128.8 kJ/mol

is carried out in a continuous reactor. Pure propane is fed to the reactor at 1300oC and at a
rate of 100 mol/hr. Heat is supplied at a rate of 1.34 kW. If the product temperature is
1000oC, calculate the fractional conversion.
 120

Chapter 10

10.1 Fluid flow from storage tank

A storage tank that is 2.0 m in diameter is being filled at the rate of 2.0 m3/min. The fluid exit

flow rate is flowing at a rat proportional to the head of fluid; 0.5h m3/min, where h is the

height of fluid in m. Plot the height of the liquid as a function of time. What is the steady

state height of the fluid in the tank?

dm
= m& in - m& out
dt
d ( rV )
= ( r v&)in - ( r v&)out
dt

Assume constant density

d ( Ah)
= v&in - v&out
dt

v&out = 0.5h

dh
A = v&in - 0.5h
dt

dh
A = 2.0 - 0.5h
dt
 121

b) at steady state

0 = 2.0 - 0.5h

H=4m

10.2 Boiling of water

A boiler used to boil water containing 100 liter of water at a temperature of 25oC is placed on

an electric heater (Q = 3000 J/s). Find the time at which water begins to boil (hint: normal

boiling point of water is 100oC).

Solution:

d ( rVCpT )
=Q
dt
dT
= Q / rVCp
dt

Q = 3000 J/s

V = 100 liter

Density of water = 1000 g/liter

Cpl , water = 18.2964 + 47.212 ´ 10-2 T - 133.88 ´10 -5 T 2

 122

The boiling point (100 C) will be reach after 6000 seconds or 100 min

10.3 Heating using saturate steam

A tank contains 1000 kg water at 25oC is heated using saturated steam at 130oC. The rate of

heat transfer from the steam is given by the following equation

Q& = UA(Ts - T )

Q is the rate of heat transfer to the system. U is the overall heat transfer coefficient, A is the

surface area fro heat transfer, and T is the temperature. The heat transfer area provided by the

coil is 0.3 m2 and the heat transfer coefficient is 220 kcal/m2hoC. The condensate leaves the

coil as saturated steam.

a. The tank has a surface area of 0.9 m2 exposed to the ambient air. The tank exchange heat

through this exposed surface at a rate given by an equation similar to that above. For heat

transfer to or from the surrounding air, the heat transfer coefficient is 25 kcal/m2.h.oC. If

the air temperature is 20oC, calculate the time required to heat the water to 80oC.

b. What time is saving if the tank is insulated?

Solution:
 123

d (mCpT )
= Qs - Qa +
dT
Qs = UAc (Ts - T )
Qa = hAt (T - Ta )

m = (1000 kg)(1000g/kg)/(18 g/mol)

2 o
U = 220 kcal/m .h. C
2
Ac = 0.3 m
2
At = 0.9 m
o
Ts = 130 C
o
Ta = 20 C
2 o
h = 25 kcal/m .h. C
-5 2
Cp (J/mol K) = 18.2964 + 0.47212 T – 133.88 x10 T

T' = (U*Ac*(Ts-T) - h*At*(T-Ta))/(m*Cp)

The time required to reach 70 oC is around 21250 seconds

c. What time is saving if the tank is insulated?

 124

if the system is insulated the time required to reach 70 C is 1800 seconds (300 min)

10.4 Heating a solvent in stirred tank

A stirred tank is used to heat 100 kg of a solvent (mass heat capacity 2.5 J/g oC). An electrical

coil delivers 2.0 kJ/s of power to the tank; the shaft work of the stirrer is 560 W. The solvent

is initially at 25 oC. The heat lost from the walls of the tank is 200 J/s.

a. Write a differential equation for the energy balance.

b.Solve the equation using available software package.

c. How long will the solution take to reach 70 oC.

Solution:

a) The differential equation for the energy balance

d (mCpT )
= Q - Ws
dt
dT
= (Q - Ws ) / mCp
dt

Cp=2.5 J/g o C
 125

Qe = 2000 J/s

Qlost = 200 J/s

Q = 2000 – 200 = 1800 J/s

Ws = 560 W = 560 J/s

m = 100 kg

dT
= (Q - Ws ) / mCp
dt

b) Solve the equation using available software package.

c) The time to reach75 C is around 4800 seconds

10.5 Concentration of reactant as a function of time

The following series reaction takes place in a constant volume batch reactor.

A ¾¾
k1
®B ¾¾
k2
®C

Each reaction is first order and irreversible. If the initial concentration of A is 1 mol/liter and

if only A is present initially, find an expression for the concentrations of A, B and C as a

function of time. ( k1 =0.1 s-1, k2 =0.2 s-1).

Solution:
 126

ra = - k1C A
rb = k1C A - k2CB
rc = k2CB
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