Professional Documents
Culture Documents
Bio Process Engineering Principles Solutions Manual P Doran 1997 WW PDF
Bio Process Engineering Principles Solutions Manual P Doran 1997 WW PDF
tI !iI~'.!.~.!
oJ
if'
lit til
TEl:1032l88O-7518 F A I l _
E-mail: Ico.tnha.ao.ki. -~ -402751 Rll!laIlN
SOLUTIONS MANUAL
Bioprocess Engineering Principles
Pauline M. Doran
University of New South Wales, Sydney, Australia
Table of Contents
Solutions
Page
Chapter 2
Chapter 3
Chapter 4
Material Balances
17
ChapterS
Energy Balances
41
Chapter 6
54
Chapter 7
76
Chapter 8
Heat Transfer
86
Chapter 9
Mass Transfer
'98
Chapter 10
Unit Operations
106
122
139
151
NOTE
All equations, tables, figures, page numbers, etc., mentioned in this manual refer to the textbook,
Unit conversion
(a)
,1 10-
3 g
k ;-1
t
(b)
Therefore:
670mmHgft3
3
atml.19.604X
1O-2Btul.I.3048m
1 mmHg
llatm
1 it
I I= ,
1 100 em 1
1m
2.2
Unit conversion
Case 1
Convert to units of kg, m, s.
11
lOOOcm3
I.
Solutions: Chapter 2
2
From Table A.2 (Appendix A): 1 tt3 =: 2.832 x 10-2 m 3
From Table A.9 (Appendix A): 1 cP::: 10-3 kg m- l sl
1 rn= tOOcm= lOOOmm
Therefore, using Eq. (2.1):
n(3cms-l.l~n(251bfC3I0.4536kgl.1
Ift
~
l00cmU
lIb
2.832 x 10 2 m 3U _
3
Dup
Re::: - p -
(2mm.1
1m
l000mmU
-6 P
10
10
c .
-3
kgm
1 cP
-11
s
- 2.4 x 10
ease 2
Convert to units of kg, m, s.
From Table Al (Appendix A): 1 in.::: 2.54 x 10-2 m
From Table A.9 (Appendix A): 1 Ibm ft-I h- 1 ::: 4.134 x 10-4 kg m-t st
Ih=3600s
Therefore, usingEq. (2.1):
13~sl
= 1.5 x 104
2.3
From the Chemical Engineers' Handbook, the diffusivity of oxygen in water at 2S"C is 2.5 x 10- 5 cm2 sl. Assuming
this is the same at 28"C, !lJ= 2.5 x 10-5 cm1 st, Also, from the Chemical Engineers' Handbook, the density of water
at 28"e is PL ::: 0.9962652 g cm-3, and the viscosity of water at 28"C is JlL::: 0.87 cPo The density of oxygen at 28C
and 1 atm pressure can be calculated using the ideal gas law. As molar density is the same as n,V, from Eq. (2.32):
Temperature in the ideal gas equation is absolute temperature; therefore, from Eq. (2.24):
RT
""
latm
From the atomie weights in Table B.l (Appendix B), the molecular weight of oxygen is 32.0. Converting the result
for Pa to mass tenns:
Pa "" 4.05 x lO-5gmolem-
1 i~~~ll
3
3
"" l.30XlO- gcm-
From Table A.9 (Appendix A): 1 eP "" 10- 2 g cm~l s-l; from Table A.l (Appendix A): 1 ft "" 0.3048 m "" 30.48 cm.
The parameter values and conversion factors, together with Db "" 2 mm "" 0.2 em, can now be used to calculate the
dimensionless groups in the equation for the Sherwood number.
Solutions,' Chapter 2
0,87eP.
S_J1.L_
-1 s-11
1'0-2 gem
leP
-349
I) -
Therefore:
_Sh:lJ_(ll.21(2.5xl0-5cm2s-I)_IA 10-3
-I
02
-,<tUX
ems
kL - - - -
D1J
em
2.4
From the definition of density on p 16, mass is equal to volume multiplied by density, Therefore:
From p 16, weight is-the force with wrncha body is attracted to the centre of the earth by gravity. According to
Newton's law(p 15), this force is equal to the mass of the body multiplied by the gravitational acceleration.
(a)
From pIS, at sea level and 45 latitude. gravitational acceleration g = 32.174 it s-2. Therefore:
4
2
Weight = 2.008 x 10 lbmfts- ,
llbf
2 .= 6241b
32.174Ibm ft s
Answer: 624lbI When g :::: 32.174 ft s2, the number of lb mass is equal to the number of lb force,
(b)
From Table A.I (Appendix A): 1 m= 3.281 ft. Using the same procedure as in (a):
Weight = 624 Ibm (9.76 m s-Z .13.2~ft~ = 1.998 x 104 Ibm fts- Z
Converting to Ibf
4
2
llbf
Weight = 1.998 x 10 lbmfts- . -----''-~I
32.1741b m ft s-2
= 6211bf
Answer: 621lbf
2.5
Dimensionless numbers
First, evaluate the units of the groups cCP J.ll k) and (D G1p):
. (e
p ")
Umtsof - - ::::
k
I
(Bmlb- '1'1) Ibh- I ft- I
BIUh-1 ft-2('Pft-1tl
1
Ibh1ft1
= 1
Solutions: Chapter 2
Therefore, these groups are dimensionless. For the equation to be dimensionally homogeneous, (hICp G) must also be
dimensionless; the units of h must therefore cancel the units of Cp G.
Unitsofh "'" unitsofCpG "'" (Btulb- 1 "p-l)(1bh- 1 fr 2) "'" Btu "F-l h- 1 ft- 2
The dimensions of h can be deduced from its units. From Table A.7 (Appendix A), Btu is a unit of energy with
dimensions "'" L2Ml2. OF is a unit of temperature which, from Table 2.1, has the dimensional symbol E>. h is a unit
of time with dimension"'" T; ft is a unit of length with dimension"'" L. Therefore:
Dimensions of h = L2M'l2 a-I 1'"1 L-2 = MT" 3e- 1
2.6
As Np is a dimensionless number, equation (i) is not dimensionally homogeneous and therefore cannot be correct.
Answer: (li)
2.7
Molar units
From the atomic weights in Table Rl (Appendix B), the molecular weight of NaOH is 40.0.
(a)
FromEq. (2.19):
lb moles NaOH
20.0 lb
= 050 lbmol
4O.0lblbmol 1
=453.6 g.
20.01b
Therefore:
453.6gl = 9072 g
= 20.0Ib. 1-lib
9072g
4O.0g gmol-
= 227 grool
.-----
Solutions: Chapter 2
kg molesNaOR
1 kgmol
= 227 gmol. 11000
gmol I = 0.227 kgmol
2.8
(a)
From p 16, the density of water at 4C can be taken as exactly 1 g cm-3. Therefore, for a substance with specific
gravity L5129i~, the density at 20C is 1.5129 g cm*3,
(I)
lkg=l000g
1 m: 100cm
Therefore:
Answer: 1512.9 kg m- 3
(il)
From the atomic weights in Table 8.1 (Appendix B), the molecular weight of nitric acid (RN03) is 63.0. In 1 cm3
RNO" from Eq. (2.18)0
gram moles :
LS129g
1 : 0.0240 gmot
63.0ggmor
Therefore, the molar density is 0.0240 gmol cm-3 . From the definition of specific volume on p 16:
Molar specific volume :
1
1 d . : .,-_ _,,-1-:--:::;- : 41.67cm3 gmor 1
mo ar enslty
0.0240 gmol em 3
From p 16, as density is defined as the mass per unit volume, the mass flow rate is equal to the volumetric flow rate
multiplied by the density:
Answer: 80 g min- l
(ii)
From the atomic weights in Table B.l (Appendix B), the molecular weight of carbon tetrachloride, CC14, is 153.8.
Using the mass flow rate from (a):
Molar flow rate : 80 g min-
.l :5~0~1 =
0.52gmolmin- 1
2.9
Molecular weight
From p 17, the composition of air is close to 21 % oxygen and 79% nitrogen. For gases at low pressures, this means
21 mol% 02 and 79 mol% NZ. Therefore, in 1 gmol air, there are 0.21 gmot Oz and 0.79 gmol NZ From the atomic
weights in Table B.l (Appendix B), the molecular weights of Oz and NZ are 3Z.0 and 28.0, respectively. The
molecular weight of air is equal to the number of grams in 1 gmol:
1 gmolair
Answer. 28.8
2.10
Solutions.' Chapter 2
Mole fraction
The molecular weights can be obtained from Table B.7 (Appendix B): water 18.0; ethanol 46.1; methanol 32.0;
glycerol 92.1; acetic acid 60.1; benzaldehyde 106.1. In 100 g solution, there are 30 g water, 25 g ethanol. 15 g
methanol, 12 g glycerol, 10 g acetic acid, 8 g benzaldehyde, and no other components. Therefore:
Moles water = 30 g _I
Moles ethanol:: 25
Molesmethanol:: 15 g _I
Molesglycerol
= 12g. IIgmaII
92.1g = O.13gmol
= 10g.1 ~~~II
Moles benzaldehyde: 8 g _I
= 0.17 gmol
The total number of moles is 1.67 + 0.54 + 0.47 + 0.13 + 0.17 + 0.08:: 3.06 gmal. From Eq. (2.20):
;:~~ = 0.55
= ~:~ = 0.18
~:~~
~:~ = 0.04
= 0.15
= ~:~ : : : 0.06
~::
::::: 0.03
Answer: 0.55 water; 0.18 ethanol; 0.15 methanol; 0.04 glycerol; 0.06 acetic acid; 0.03 benzaldehyde
2.11
Temperature scales
2.12
Pressure scales
(a)
Assume that the atmospheric pressure is 14.7 psi. From Eq. (2.28):
Absolute pressure ::::: 15 psi + 14.7 psi::::: 29,7 psi
Solutions: Chapter 2
From Table A.5 (Appendix A): 1 psi = 6.805 x Hy2 atm. Therefore:
2
. 16.805 x 10- atm 1
Absolutepressure = 29.7psl.
1 psi
= 2.02atm
2.13
(a)
The molecular weights are calculated from TableB.l (Appendix B): penicillin 334.;4; glucose
180.2. The
maximum theoretical yield from the stoichiometric equation is 1 gruol of penicillin for every 1.67 gruol of glucose.
'This is equivalent to 334.4 g penicillin per 1.67 x 180.2 = 300.9 g glucose. or 1.1 g g-l.
The maximum theoretical yield in (a) is obtained when all the glucose consumed is directed into penicillin production
according to the stoichiometric equation. If only 6% of the glucose is used in this way, the actual yield of penicillin
from glucose is much lower, at 334.4 g penicillin per (300.9 x 100/6) g glucose, or 0.067 g g~l.
Answer: 0.067 g g-1
(c)
From the atomic weights in Table B.I (Appendix B), the molecular weight of phenylacetic acid is 136.2.
(I)
The only possible limiting substrates are glucose and phenylacetic acid. Using a basis of II medium, if (50 - 5.5) =
44.5 g glucose are consumed but only 6% is available for penicillin synthesis, the mass of glucose used in the
penicillin reaction is 44.5 x 6/ 100 2.67 g. 'This is equivalent to 2.67 g/180.2 g gmol-1 1.48 K 10- 2 gmol glucose
available for penicillin synthesis. At the same time, 4 g or 4 g/136.2 g gmol-1 2.94 x 10~2 gruol phenylacetic acid is
available which, according to the stoichiometric equation, requires 1.67 x 2.94 x 10- 2 4.91 x 10-2 gruol glucose for
complete reaction. As the gmol glucose required is greater than the gmol glucose available after growth and
maintenance activities, glucose is the limiting substrate.
Answer: Glucose
(il)
Of the 44.5 g I-I glucose consumed, 24% or 10.7 g I-I is used for growth. In a H~)-litre tank. the total mass of glucose
consumed for growth is therefore 1070 g or 1.07 kg.
Answer: 1.07 kg
(iii)
From (i), 1.48 x 10- 2 gmol glucose is used in the penicillin reaction per litre. According to the stoichiometry, this
produces 1.48 x 10-2/1.67 = 8.86 x 1O~3 gmol penicillin per litre. Therefore, in a l00-litre tank, 0.886 gmol or 0.886
gmol x 334.4 g gmol-1 296 g penicillin are formed.
Answer: 296 g
(iv)
IT, from (i), 1.48 x 10-2 gmol [1 glucose is used in the penicillin reaction, 1.48 x 10-2/1.67 = 8.86 x 10- 3 gmoll-l
phenylacetic acid must also be used. This is equivalent to 8.86 x 10- 3 gmoll-l x 136.2 g gmol-1 = 1.21 g t I
phenylacetic acid. As 4 g I-I are provided, (4 - 1.21) = 2.79 g I~I phenylacetic acid must remain.
Answer: 2.79 g I-I
Solutions: Chapter 2
2.14
(a)
Adding up the numbers of C, H, 0 and N atoms on both sides of the equation shows that the equation is balanced.
Answer: Yes
(b)
The molecular weights are calculated from Table B.I (Appendix B).
Cells: 91.5
Hexadecane: 226.4
From the stoichiometry, as 1 gmol of hexadecane is required to produce 1.65 gmol of cells, the maximum yield is 1.65
gmol x 91.5 g gmol-l =: 151 g cells per 226A g hexadecane, or 0.67 g g-I,
Answer: 0.67 g g-1
(e)
From the atomic weights in Table RI (Appendix B), the molecular weight of oxygen is 32.0. From the
stoichiometry, 16.28 gmol of oxygen is required to produce 1.65 gmal of cells which, from (b), is equal to 151 g cells.
The maximum yield is therefore 151 g cells per (16.28 groal x 32.0 g groot-I) =: 521 g oxygen, or 0.29 g g-1.
Answer: 3.74 kg
(il)
From the answer in (d)(i), the concentration ofhexadecane required is 3.74 kg in 3 m3, or 1.25 kg m- 3.
Answer: 1.25 kg m- 3
(ill)
According to the stoichiometric equation, production of 27.3 gmol cells requires 27.3 x 16.28/1.65 269.4 gmol
oxygen. As air at low pressure contains close to 21 mol% oxygen (p 11), the total moles of air required is 269.410.21
= 1282.9 gmot The volume of air required can be calculated using the ideal gas law. From Eq. (2.32):
V = nRT
p
Temperature in the ideal gas equation is absolute temperature; from Eq. (2.24):
v=
Answer: 31 m 3
1-.!.."'...1
3
1
3 = 31 3
(1282.9gmolj(82.057cm atmK- gmol-l)(293.15Kj
1 atm
. l00cm
m
c~
Combination of errors
""
=:
=:
o.OllmOlm-3~-1
O.Q67molm
Answer~
31 %. This example illustrates how a combination of small measurement errors can result in a relatively
large uncertainty in the final result.
3.2
(a)
The best estimate is the mean,
X.
FromEq. (3.1):
x = 5.15+5.45+5.50+5.35 = 5.36
Answer: 5.36
(b)
Calculate the standard deviation from Eq. (3.2):
x= 5.15+5.45+5.50+5.35+5.15+5.45+5.50+5.35 = 5.36
Solutions: Chapter 3
10
Answer: The best estimate of optimal pH is unchanged at 5.36, but the standard deviation is slightly lower at 0.14.
This example illustrates that although the standard deviation decreases as the number ofmeasurements is increased,
(j is not strongly dependent on n. The best way to improve the reliability of the mean is to ensure that the individual
measurements are as intrinsically accurate as possible, rather thanrepeat the measurement many times.
3.3
(a)
Xl = 1; Yl =10
X2=8;Y2=0.5
A straight line plot of y versus x on linear coordinates means that the data can be represented using Eq. (3.6). From
8-1
Xl)
Y=Axlh+B
with A and B given by the equations:
A =
X2= l;Y2=3
A straight line plot of Ity versus xl on linear coordinates means that the data can be represented using the equation:
lly = Ax2 +B
with A and B given by the equations:
A =
lin - Ity}
2
x2-xl
B = 1/y1
1/3 -lI6
2
-3
2 =-6.9xlO
1 -5
Xl=0.5;Yl=25
x2 550; Y2 2600
A straight line plot of y versus x on log-log coordinates means that the data can be represented using Eq, (3.10).
11
Solutions: Chapter 3
lnB
ln550-1nO.5
X2
= 1.5; YI = 2.5
= 10; Y2 = 0.036
on semilog coordinates means that the data can be represented using Eq. (3.15).
10 - 1.5
B = el.666 = 5.29
Answer: Y= 5.29 e-o.sOx
3.4
(aJ
The results determined using Eqs (3.1) and (3.2) are listed below.
Standard deviation
6.0
12.0
18.0
56.84
112.82
170.63
232.74
302.04
1.21
2.06
24.0
30.0
2.54
1.80
2.21
(bJ
35
--.
30
.9 25
~
g
8
20
15
~g
10
"'
5
0
50
100
150
200
Peak area
250
300
350
Solutions: Chapter 3
12
(e)
+ 0,83
Answer: y "'" 0.098 x + 0.83, where y is sucrose concentration in g 1-1 and x is peak area.
(d)
For x::: 209,86, the equation in (c) gives a sucrose concentration oi2IA g I-I.
Answer: 21.4 g I-I
3.5
(a)
The proposed model equation has the general form of Eq. (3.15); therefore, if the model is suitable, a plot of a versus
lIT on semi-logarithmic coordinates will give a straight line. As T in the equation is absolute temperature, "'c must
first be converted to degrees Kelvin using Eq. (2.24). The data are listed and plotted below.
Temperature (0C)
Temperature (K)
IIT(K-l)
15
20
25
30
35
288.15
293.15
298.15
303.15
308.15
3.47 x 10-3
4.4 x 10- 15
2.0x 10- 14
8.6x 10.. 14
3.5 x Jer I3
3.41 x lO w3
3.35 x leT3
3.30 x lfr3
3.25 x 10-3
lAx }0"'12
10- 11 r---~--.,...--~----r--~---.
["
"
fc
.Q
10- 12
10- 13
lii
"E
~
-lllJ:
10. 14
3.4x 10-3
3.3x 10-3
3.5 x 10-3
1ITemperature (K-1)
As the data give a straight line on semi~logarithmiccoordinates, the model can be considered to fit the data well.
(b)
The equation for the straight line in (a) is:
=:
where y is relative mutation frequency and x is reciprocal temperature in units of K~l. For dimensional homogeneity
the exponent must be dimensionless (p 12), so that -26,121 has units of K, and EIR in the model equation is equal to
26,121 K From Table 2.5, R =: 8.3144 J gmol-l K1; therefore:
E
=:
=:
217,180.4 J gmol-1
=:
217.2 kJ gmot 1
13
Solutions: Chapter 3
Answer: 217.2 kJ gmol-l
(c)
From the equation in (b) for the straight line,
3.6
(aJ
--
16
,
14
!'!l
c
i'!
12
10
C
0
0
m
~
.i1
4
2
0
0
12345
=:
1.58 + 2.10x
where yis increase in biomass concentration in g r 1 and xis decrease in medium conductivity in mS cm~l.
(b)
The residuals are calculated as the difference between the measured values for increase in biomass concentration and
the values for y obtained from the equation in (a).
Residual
-1.58
0.12
0.31
0.41
0.82
1.03
0.57
-!l.23
0.36
1.20
1.36
1.28
0041
0.19
-0.46
-!l.50
-!l.73
-1.69
-1.99
lAO
1.91
2.11
2.42
2.44
2.74
2.91
3.53
4.39
5.21
5.24
5.55
-1.00
1.48
0.02
1.37
Solutions: Chapter 3
14
2
3 ' - _ - ' -_ _-'-_---'_ _......_ _' - _ - '
The residuals are not randomly distributed: they are mainly positive at low values of decrease in medium
conductivity, then negative, then positive again. Therefore, the straight line fit of the data cannot be considered a very
good one.
3.7
(aJ
The results are plotted using linear coordinates below.
0.11
~
'"
0.10
os'
0.09
..
.~
.""
0.08
0.07
'E
,1l.
0.06
0.05
::J
0.04
0.00
0.02
0.04
0.06
0.08
Gas superficial velocity, uG (m s-1)
0.10
The data are reasonably well fitted using a linear model. The linear least squares equation for the straight line fit is:
= 0.054 + 0.466 x
where y is liquid superficial velocity in m s-l andx is gas superficial velocity in m sl. The sum of the squares of the
residuals between the measured values for liquid superficial velocity and the values for y obtained from the above
equation is 8.4 x 10-5,
15
Solutions: Chapter 3
(b)
The proposed power law equation has the same form as Eq. (3.10). Therefore, if the power law model is suitable. the
data should give a straight line when plotted on log-log coordinates.
0.01
om
0.1
The data are reasonably well fitted using a power law- modeL The equation for the straight line in the plot is:
y = 0.199 x O.309
where y is liquid superficial velocity in m sl andx is gas superficial velocity in m sl. The sum of the squares of the
residuals between the measured values for liquid superficial velocity and the values obtained from the above equation
is 4.2 x 10-5.
)
The nonlinear model is better because the sum of squares of the residuals is smaller.
3.8
(a), (b)
The proposed model equation has the same form as Eq; (3.15). Therefore, if the model is suitable, the data should
give a straight line when plotted on semi-logarithmic coordinates.
10' . , . - - . , . . . - . . . . , - - , - - - - , - - - - , , - -. . .- - - .
103
101
100 '--_.1-_-'-_-'-_-'-_-L_----'-_---'
10
15
20
Time (min)
25
30
35
Solutions: Chapter 3
16
(c), (d)
=.
where y is the number of viable cells and x is time in min. As the exponent must be dimensionless to preserve
dimensional homogeneity (p 12), the dimensions of kd are T-t; therefore k(! =. 0353 min-I, The dimensions of No are
the same as N, i.e, No is dimensionless and equal to 2.13 x 104.
Answer: kd =. 0.353 min-I. No =. 2.13 x 104; the dimensions of ka. are T"l, No is dimensionless
Material Balances
4.1
L
(i)
Assemble
Flow sheet
Buffer solution in
80 kg min- 1
Cell concentrate
6% bacteria
(li)
Hollow-fibre membranes
Fennentation broth
350 kg min- 1
1% bacteria
99% water
System boundary
No reaction occurs.
2.
Analyse
(i)
Assumptions
- steady state
-no leaks
- only water passes across the membrane
(ii)
Extra data
No extra data are required.
(ill)
Basis
1 min, or 350 kg fennentation broth
(iv)
Calculate
(i)
Calculation table
The calculation table below shows all given quantities in kg. The total mass of cell concentrate is denoted c; the total
mass of buffer out is denoted B. The columns for water refer to water originating in the fermentation broth.
18
Solutions: Chapter 4
Out
In
Stream
Fermentation
broth
Water
346.5
Buffer solution in
Cell concentrate
Bacteria
3.5
Buffer
0
80
Total
350
Water
Bacteria
Buffer
Total
?
?
O.06C
0
0
80
0.06C
80
C+B
Out
Buffer
Total
80
Buffer solution
out
Total
346.5
3.5
80
430
(li)
Mass-balance calculations
Bacteria balance
= 58.3 kg
B "'" 371.7 kg
Water balance
In
Stream
Fennentation
Water
346.5
broth
Buffer solution in
Bacteria
3.5
814fer
0
80
Total
350
Water
Bacteria
80
Cell concentrate
54.8
Buffer solution
out
291.7
3.50
0
0
80
58.3
371.7
346.5
3.50
80
430
346.5
Total
(iii)
3.5
80
430
4.
Finalise
(a)
After rounding to three significant figures, the total flow rate of buffer solution out of the annulus is 372 kg min-I.
The total flow rate of cell concentrate from the membrane tubes is 58.3 kg min-I.
Answer. 58.3 kg min I
Solutions: Chapter 4
19
4.2
Membrane reactor
t.
Assemble
Flow sheet
(i)
system boundary~
- -- - --
Feed
40 kg h- 1
10% glucose
90% water
I
Solvent
40 kg h- 1
- 1
Membrane system
Aqueous residue
0.2% glucose
0.5% ethanol
Product
System boundary
The system boundary is shown on the flow sheet.
(li)
(iii)
Reaction equation
2.
Analyse
Assumptions
- steady state
-no leaks
- yeast cells do not grow or dislodge from the membrane
- no evaporation
- all C02 produced leaves in the off~gas
- no side reactions
(li)
Extra data
Molecular weights (Table B.t, Appendix B): glucose = 180.2
ethanol =. 46.1
(i)
CO, =44.0
Basis
1 h, or 40 kg feed solution
(iv)
Compounds involved in reaction
Glucose, ethanol and carbon dioxide are involved in the reaction.
(v)
Mass~balanceequations
For glucose, ethanol and carbon dioxide, the appropriate mass-balance equation is Eq. (4.2):
(iii)
=.
For water, solvent and total mass, the appropriate mass-balance equation is Eq. (4.3):
mass in
3.
=.
mass out
Calculate
Calculation table
The calculation table below shows all given quantities in kg. The total mass of aqueous residue is denoted R; the total
mass of product out is denoted p; the total mass of carbon dioxide out is denoted G.
(i)
20
Solutions: Chapter 4
Stream
------Feed
Solvent
Glucose Ethanol
4
0
0
0
In
CO, Solvent H,O Total
40
0
0
36
0
0
40
40
Aqueous
Out
0
0
residue
Product
Off-gas
Total
40
36
80
?
0
0
?
?
0
0
0
P
G
0.002 R ?
R+P
(ii)
Mass-balance calculations
Solvent balance
R = 36.254 kg
Therefore, the residual glucose in the aqueous residue stream.::::: 0.002 R ::::: 0.073 kg; the ethanol in the aqueous residue
stream::::: 0.005 R::::: 0.181 kg.
Glucose balance
From the reaction stoichiometry, conversion of this amount of glucose generates 2 X 0.0218 = 0.0436 kgmol ethanol
and 2 x 0.0218 = 0.0436 kgmol COZ. Converting these molar quantities to mass:
0.0436kgmolethanol
0.0436kgmo1CO z = OJM36kgmOLI
~:~ll
= 1.92kg
C02 balance
= 2.010 kg
Ethanol leaves the system only in the product and aqueous residue streams. Therefore:
21
Solutions: Chapter 4
In
Stream
Feed
Solvent
Aqueous
residue
Product
Off-gas
Total
Out
Glucose Ethanol
0.073
0.181
0
0
1.829
0
0.073
2.010
40
36
80
36
36.254
0
1.92
40
0
0
0
41.829
1.92
1.92
40
36
80.00
(iii)
Check the results
All columns and rows of the completed table add up correctly.
4.
Finalise
(0)
1.829 kg ethanol are contained in 41.829 kg of product stream. The ethanol concentration is therefore 1.829/41.829 x
100%:::: 4.4%.
Answer: 4.4%
(h)
4.3
Ethanol distillation
1.
(i)
Assemble
Flow sheet
System
Feed
50,000 kg h-l
10%ethanal
90%watar
boUnda'l'\.
r
-t---,
I
I
I
I
I
I
I
I
I
I
I
I
I
Distillation
column
I
I
I
I
-+- -
Distillate
5,000 kg h- 1
45% ethanol
55% water
Bottoms
SolutilJns: Chapter 4
22
(li)
System boundary
Analyse
(i)
Assumptions
- steady state
-no leaks
(ll)
Extra data
(v)
3.
Calculate
(i)
Calculation table
The calculation table shows all given quantities in kg.
In
Stream
Ethanol
Feed
5,000
Water
45,000
Out
Total
50,000
Distillate
Bottoms
Total
5,000
45,000
50,000
Ethanol
Water
Total
2,250
?
2,750
?
5,000
?
(li)
Mass-balance calculations
Total mass balance
50,000 kg total mass in ::::: total mass out
:=
(5,000..,... 2,250) kg
:=
2,750 kg
Water balance
45,000 kg water in
Water out
:=
:=
water out
45,000 kg
Solutions: Chapter4
23
In
Stream
Out
Ethanol
Water
Total
Feed
Distillate
Bottoms
5,000
45,000
50,000
Total
5,000
45,000
50,000
Ethanol
Water
Total
2,250
2,750
2,750
42,250
5,000
45,000
5,000
45,000
50,000
(ill)
Check the results
All columns and rows of the completed table add up correctly.
4.
Finalise
(a)
The bottoms contains 2,750 kg ctha,")l and 42,250 kg water in a total of 45,000 kg. Therefore, the composition is
2,750/45,000 x 100% = 6.1 % ethanol. and 42,250/45,000 x 100% = 93.9% water.
Answer: 2,750 kg h- I
4.4
1.
(i)
Assemble
Flow sheet
Off-gas
System boundary
r\. -------,
I
I
1
-----L.o-l
3000 kg h1
I
Egg slurry
2% glucose
20% water
78% egg solids
I
I
1
I
Enzyme reactor
(n)
System boundary
The system boundary is shown on the flow sheet
(ill)
Reaction equation
2.
Analyse
(i)
Assumptions
- steady state
-no leaks
- air and off-gas are dry
- gases are at low pressure so vol% = mol%
I--.L
1 - - - _ - Product
I
1
I
0.2% glucose
24
Solutions: Chapter 4
(ti)
Extra data
Molecular weights (Table B.I, A.ppendix B): glucose::::: 180.2
02=32.0
NZ::::: 28.0
H20
= IS.0
Calculate
(i)
Calculation table
The mass of NZ accompanying 18 kg 02 in air can be calculated from the known composition of air. Converting 18
kg 02 to molar units:
ISkg02
kgmOll
= ISkg02 1 132.0kg
= 0.563kgmo102
Therefore, 79/21 x 0563 kgmol = 2.118 kgmol NZ enter in the air stream. Converting this to mass units:
2S.0kg I = 59.30kg N2
2,118kgmo1N2 = 2.118kgmoIN2 lkgmol
The calculation tables below show all known quantities in kg. The total mass of off-gas is denoted G; the total mass
of product is denoted P. The In side of the mass-balance table is complete,
Solutions: Chapter 4
25
59.30 kg NZ in ::::: NZ out
NZ out::::: 59,30 kg
Glucose balance
60 kg glucose in + 0 kg glucose generated ::::: 0.002 P kg glucose out + glucose consumed
Glucose consumed ::::: (60 - 0.002 P) kg
Converting the glucose consumed to molar tenus:
p) kgmol
From the reaction stoichiometry, conversion of this amount of glucose requires the same number of kgmol OZ.
Converting this molar quantity to mass of Oz:
5
(0.333 -1.11 x 10-
p) kgmo102
;~~~11
02 balam.:e
18 kg Oz in +0 kg Ozgenerated :::::{)Z out + (10.656 - 3.552 x 10-4 P) kg Oz consumed
02 out
= (18 -
(10.656 - 3.552 x
10"" P) kg
301O.7kg = I.0004Pkg
P
= 3009.6kg
x 10,4 x 3009.6) kg
Oz out::::: 8.41 kg
The mass of glucose out is 0.002 x 3009.6::::: 6.02 kg. The moles of glucose consumed is:
Glucose consumed::::: (0.333 - 1.11 x 10-5 x 3009.6) kgmol ::::: 0.300 kgmol
Therefore, from stoichiometry and the molecular weights:
Water consumed ::::: 0.300kgm01.1
:~:~il::::: 5.40kg
Solutions: Chapter 4
26
i9:~~ I = 58.86 kg
Water balance
600 kg water in + 0 kg water generated = water out + 5.40 kg water consumed
Water out
=594.6 kg
= 10.20 kg
Out
Glucose
Egg slurry
AllOff-gas
Water
Egg solids
02
N2
Gluconic acid
H2O,
Total
Product
0
6.02
0
594.6
0
2340
8.41
0
59.30
0
0
58.86
0
10.20
67.71
3009.6
Total
6.02
594.6
2340
8.41
59.30
58.86
10.20
3077.3
(iii)
All columns and rows of the completed table add up correctly to within round-off error.
4.
Finalise
(a)
To determine which is the limiting substrate, the number ofmoles available of each substrate involved in the reaction
must be determined. From the mass-balance table for streams in:
1 kg mOll
Moles glucose = 60 kg. 180.2 kg = 0.333 kgmol
1kgmOIl
Moleswater = 600 kg . 18.0kg = 33.3kgmol
1kgmOIl
Moles 02 = 18 kg. 32.0 kg = 0.563 kgmol
As the substrates are required in the molar stoichiometric ratio of 1: 1: 1 and glucose is available in the smallest molar
quantity, the extent of the reaction must be limited by glucose.
Answer: Glucose
(b)
Water and 02 are available in excess. As only 0.333 kgmol of each will be used if the reaction proceeds to
completion, from Eq, (2.34);
% excess water =
Solutions: Chapter 4
27
(c)
From the completed mass~balance table. the reactor off-gas contains 8.41 kg Oz and 59.30 kg N2. As gas
compositions are normally expressed in molar or volumetric terms (p 17), these mass values must be converted to
moles:
8.41 kg 02
kgmOll
= 8.4lkg02 132.0kg
1
= 0.263kgmo102
As the number of kgmol N2 was determined in the preliminary calculations to be 2.118, the total number of moles of
off-gas is (0.263 + 2.118) 2.381 kgmoJ. Therefore, the composition of the off-gas is 0.263/2.381 0.11 02, and
2.118/2.381 = 0.89 N,.
Answer: 0.11
Oz, 0.89 Nz
(d)
From the completed mass-balance table, the product stream has a total mass of 3009.6 kg and contains 6.02 kg
glucose, 594.6 kg water, 2340 kg egg solids, 58.86 kg gluconic acid and 10.20 kg H202. Therefore, the composition
is:
6.02
0002 1
3009,6 =.
g ucose
594.6
3009.6
= 0.198 water
2340
.
3009.6 = 0.778 egg solids
58.86 =.
0020 gIUCONC
. actd
3009.6
10.20
3009.6
= 0.003 H20 ,
Answer. 0.002 glucose. 0.198 water. 0.778 egg solids. 0.020 gluconic acid, 0.003 H202
4.5
Azeotropic distillation
1.
Assemble
Flow sheet
(0
,...-----------------..,
"rSystem boundary
--j-
1
1
Feed
95% ethanol
5% water
-----r-~
(ii)
Distillation
tower
------'-1-ol
1
1
1
System boundary
7.4"1" H20
Overhead
74.1% benzene
18.5% ethanol
1
Benzene feed
.,
--1---
Product
100% ethanol
Solutions: Chapter 4
28
(iii)
Reaction equation
No reaction occurs.
2.
Analyse
(i)
Assumptions
- steady state
-no leaks
(li)
Extra data
lOOOcm3 =11
l000g=lkg
(iii)
Basis
.ll~~m31.ll~gl
"'"
196.25kg
The calculation table shows all given quantities in kg. The total mass of feed in is denoted F; the total mass of
benzene feed in is denoted B; the total mass of overhead out is denoted v.
In
Stream
Ethanol
Water
Feed
Benzene feed
Product
Overhead
0.95 F
0.05F
Total
0.95F
Out
Benzene
o
B
0.05F
Ethanol
Total
F
B
F+B
Water
0.741 V
0.074 V
= (206.58 + 0.195 V) kg
Benzene balance
B kg benzene in
=.
=.
0.741 V
=.
= (196.25 + V) kg
0.064 V
V=. 161.4kg
196.25
V
196.25 +
Mass-balance calculations
=.
0
0.741 V
Ethanol balance
0.95 F kg ethanol in
Total
196.25
0
0.185 V 0.074 V
0.185 V
(ii)
Benzene
196.25 +
V
Solutions: Chapter 4
29
B = 119.6kg
These calculations allow completion of the mass-balance table with all quantities in kg.
In
Stream
Ethanol
226.2
F,ed
Benzene feed
Product
Overhead
Total
Water
11.9
226.2
11.9
Benzene
Total
238.1
119.6
0
119.6
119.6
357.7
Out
Benzene
Ethanol
Water
Total
196.25
29.9
11.9
119.6
196.25
161.4
226.2
11.9
119.6
357.7
(ill)
Check the results
All columns audrows of the completed table add up correctly to within round-off error.
4.
Finalise
Prom the completed mass-balance table, the mass of benzene required is 119.6 kg. Using the definition of density on
p 16, volume is equal to mass divided by density:
1000g
11 3 1 "'" 1371
119.6 kg-3' 1l k li
.
O.872gcm
g
l000cm
Volumeofbenzene"'"
4.6
1.
Assemble
Flow sheet
(i)
Off-gas
47 1m-as 02
15 litres CO2
----l
Medium
1425 9
3% glucose
1.75% ammonia
95.25% water
-----'-1_-I
1
I
I
I
Air-driven
reactor
I
1
1
1
1
Air
22 cm 3 milr 1 10r 10 d
25C, 1 atm
(n)
System boundary
The system boundary is shown on the flow sheet.
Drained liquid
1110g
0.063% glucose
1.7% ammonia
30
(iii)
Solutions: Chapter 4
Reaction equation
From Table B.2 (Appendix B), the molecular formula for glucose is C6H1206. The reaction equation is based on the
general stoichiometric equation for aerobic growth, Eq. (4.4):
C6H1206+aOZ+bNH3 ~ cCHaOpNo+dCOz+eHzO
2.
Analyse
(i)
Assumptions
- steady state
-no leaks
- air and off~gas are dry
- all the COz produced leaves in the off~gas
- gases are at low pressure so vol% = mol%
(li)
Extra data
11= lOOOcm3
Molecular weights (Table B.1, Appendix B): glucose = 180.2
02 = 32.0
NZ = 28.0
NH3 = 17.0
cOz 44.0
HzO= 18.0
Composition of air (p 17): 21% OZ, 79% NZ by volume
Ideal gas constant (Table 2.5): R = 82.057 cm3 atm K~l gmol~ I
(iii)
Basis
10 d. or 1425 g nutrient medium
(iv)
Compounds involved in reaction
Glucose, OZ' NH3. biomass, COZ and HZO are involved in the reaction.
(v)
Mass-balance equations
For glucose. 02, NH3, biomass, C02 and HzO, the appropriate mass-balance equation is Eq. (4.2):
3.
Calculate
(i)
Calculation table
Over 10 d. the volume of air sparged into the fennenter is:
Volumeofairin =
22cm3min-Ix10d.16~~nl.12:dhl
= 3.168x105 cm3
Converting tbis gas volume to moles using the ideal gas law, Eq. (2.32), with the temperature converted from <>C to
degrees Kelvin using Eq. (2.24):
Moles of air in = n = p V =
RT
5
3
= 12.95gmol
1 atm.(3.168 x 10 cm )
3
1
1
82.057cm atmK- gmor (25 +273.15) K
From the known composition of air, the moles ofOZ in the incoming air is 0.21 X 12.95 = 2.72 gmol, and the moles of
NZ is 0.79 x 12.95 = 10.23 gmo!. Converting these values to masses:
MassofOZin = 2.72gmOI.I
MassofNZin
{~;ll
= 87.04g
= 1O.23gmOI.I~~;11 =
286.4g
31
Solutions: Chapter 4
.
11000em31
1 atm(47litres).
11
L:::
RT
( . )I
=n =L =
RT
82.057em'.tmK Igmoll(25+273.15)K
:::
1.92gmol
= O.613gmol
MassofCOzout:::
0.613gmOl.l~~;11 = 26.97g
The calculation tables below show all known quantities in g. The In side of the mass~balance table is complete. The
total mass of off~gas out is denoted G; the total biomassbarvested is denoted R As the ratio of biomass fresh weight
to dry weight is 14:1, dry biomass comprises l!IS ::: 0.0667 of the total biomass. Because this problem requires an
integral mass balance, the biomass remaining in the fermenter after 10 d culture must also be included in the table
even though it is not contained in any of the streams flowing into or out of the vesseL
Using this result and adding up the row for the off*gas in the out table:
G
1798.44gtotalmassin::: (1110+G+B)gtotalmassout
Using the result for G:
32
Solutions: Chapter 4
=:
313.63 g
These calculations allow completion of the Out side of the massbalance table with all quantities in g.
Further mass-balance calculations allow evaluation of the masses of components consumed 'or generated in the
reaction.
Glucose balance
42.75 g glucose in + 0 g glucose generated = 0.699 g glucose out + glucose consumed
02; consumed
NH3 balance
24.94 g NH3 in + 0 g NH3 generated
= 25.60 g
C02 generated
= 26.97 g
H20 balance
1357.31 g H20 in + H20 generated = (1090.43 + 0.9333 B) g H20 out + 0 g H20 consumed
4.
Finalise
(a)
Rounding to three significant figures from the completed mass~balance table, the mass of dry roots produced is 20.9 g.
Answer: 20.9 g
(b)
To determine the stoichiometry, the calculated masses of components consumed or generated in the reaction must be
converted to molar quantities:
33
Solutions: Chapter 4
MolesofNH3consumed = 6.07 g
MolesofCOzgenerated=
.1 ~~~ll
= 0.357gmol
26.97g.I~~I! =
0.6l3gmol
~0:2 g
10mass
The moles of biomass generated is not yet known explicitly because the molecular formula for the dry biomass is
unknown. The above molar quantities can be used as coefficients in the reaction equation:
20.92
0.233 Coli1206 + 0.800 0, + 0.357 NH3 -+ MW b'
lomass
CH"OoN
+ 0.613 CO, + 1.435 H,O
P'" S
Dividing each coefficient by 0.233 to obtain the stoichiometry per gmol glucose:
89.79
CoH1206+3.430,+1.53NH3 -+ MWb'lOmass CH"OoNS+2.63CO,+6.16H,O
fJ
The values of a, /3 and 8 and the molecular formula for the biomass can obtained using elemental balances.
Cbalance:6
89.79
= MWb'
+2.63
lomass
Therefore:
89:79
MWblomass
= 3.37
This result can be used in the remaining elemental balances for completion of the stoichiometric equation.
Hbalance: 12 + 3 x 1.53 = 3.37 a+ 2 x 6.16 --) a = 1.27
Obalance:6+2x3.43
3.37/3+2x2.63+6.l6 --) /3 = 0.43
3.37 8 --) 8 0.45
N balance: 1.53
Converting to moles the mass quantities of glucose, 0z and NH3 available for reaction on the In side of the massbalance table:
Moles of glucose in
= 42.75g.1:8~o~1 = O.24gmol
Moles of 0z in = 8704g.1
MoiesofNH3in =
;~~11 = 2.72gmol
24.93g.111'~~-~11
= 1.47gmol
From the stoichiometric equation, reaction of 0.24 gmol glucose requires 0.24 x 3.43 = 0.82 gmol 0z and 0.24 x 1.53
= 0.37 gmol NH3' As the molar quantities of Oz and NH3 available for reaction are in excess of these values, glucose
must be the limiting substrate.
Answer: Glucose
34
Solutions: Chapter 4
(d)
The mass of glucose consumed is 42.05 g; the mass of dry biomass produced is 20.92 g. Therefore, the biomass yield
from glucose is 20.92/42.05 = 0.50 g g-1 dry weight.
Answer: 0.50 g g-1 dry weight
4.7
From TableB.2 (Appendix B), the molecular formula for glycerol is C3Hg03. From Table 4.3, the chemical formula
for Klebsiella aerogenes can be taken as CH 1. 7S00.43NO.22. Substituting these formulae into the general
stoichiometric equation for growth. Eq. (4.4), gives:
Biomassmolecularweight =
zg;:
= 25.8
rs = 4.67.
The degree of
1B = 1x4+1.75xl-0.43x2-0.22x3 = 4.23
which is also listed in Table 4.3. The theoretical oxygen demand can be determined from Eq. (4.16) with/= 0; from
Eq. (4.13). w = 3 for glycerol:
a = 1.99gmolgmol-1 =
L99gmOlgmOI-I.I::~II.I~~~11 =
0.69gg-
4.8
From Eq. (4.13), the stoichiometric equation for anaerobic growth and product fonnation by methane bacteria can be
written as:
0I3COOH+ b NH3
--j.
From Table B.8 (Appendix B), the molecular weight of acetic acid is 60.1. From Table B.l (Appendix B), the
molecular weight of CO2 is 44.0. The value of the stoichiometric coefficient d can be determined based on Eq. (4.14)
with carbon dioxide as the product and the yield YpS = 0.67 kg kg- 1 = 0.67 g g-l:
d =
Yps(MWsubstral~ =
MWC02
I
1
0.67gg- (60.1ggmor j = 0.915 gmol gmol-l
44.0ggmol I
The other coefficients can be determined using this result and elemental balances.
Cbalance:2 = c+d+/= c+0.915+f--j.f= L085-c
Hbalance:4+3b = 1.4c+2e+4f
balance: 2 = 0.40c+2d+e = OAOc+2xO.915+e = OAOc+L83+e --j. e = O.17-0.40c
N balance: b = 0.20 c
35
Solutions: Chapter 4
Substituting the expressions fort, e and b from the C, 0 and N balances, respectively, into the H balance:
4+3x0.20c
= l.4c+2x(0.17-0.40c)+4x(l.085-c)
4 c = 0.680
C :
0.170
Substituting this value for c into the expressions for the other coefficients gives b = 0,034, e = 0.102 and/: 0.915.
The yield of methane is therefore 0.915 gmol per gmol acetic acid
The maximum possible methane yield can be calculated using Eq. (4.20). From Eq. (4.13), w 2 for acetic acid and)
1 for methane. From TableB.2 (Appendix B); the degree of reduction of acetic acid relative to NH3 is it 4.00,
and the degree of reduction of methane relative to NH3 is lP = 8.00. Substituting these values into Eq. (4.20) gives:
WYs
fmax = )IP =
:i 1.00)
-1
1(8.00) = 1.0gmolgmol
The actual methane yield of 0.915 gmol gmol-l therefore represents 91:S%of the theoretical maximum.
4.9
(aJ
From Table B.2 (Appendix B), the .molecular formula for glucose isC6H1206. If all carbon in the substrate is
converted into biomass, production of carbon dioxide is zero. Therefore, from Eq. (4.4), the stoichiometric equation
for anaerobic growth of Cellulomonas is:
C~1206 + b NH 3 -+ c CH1.5iPO.~O.16 + e H20
C balance: 6 = c
Hbalance:12+3b: 1.56c+2e
o balance: 6 0.54 c + e
N balance: b : 0.16 c
Substituting the value for c from the C balance ,into the and N balances gives e = 2.76 and b = 0.96. respectively.
The yield of biomass from substrate in molar terms is therefore 6 gmol gmol-l.
Using the atomic weights in Table B.l (Appendix B), the molecular weight of glucose is 180.2. The biomass formula
weight calculated from Table B.l (Appendix B) is 24.46. Taking into account the 5% ash:
Biomass molecularweight =
2;9~6
= 25.75
Therefore, in mass terms, the molar biomass yield of 6 gmol gmol-l= (6 x 25.75) g biomass per 180.2 g substrate:
0.86 g g-l.
The maximum possible biomass yield is calculated using Eq. (4.19). From Eq. (4.13), W = 6 for glucose. From Table
B.2 (Appendix B). the degree ofreduclion of glucose relative to NH3 isrs = 4.00. The degree of reduction of the
biomass relative to NH3 is:
JB =
= 4.
00
wYs
1i3 =
6(4.00)
-1
4.00 = 6.0 gmol gmol
The theoretical maximum biomass yield is therefore the same as the actual biomass yield.
Solutions: Chapter 4
36
Answer: The biomass yield from substrate of 0.86 g g-t is 100% of the theoretical maximum. When there is no
product formo.tion and no oxygen for electron transfer, all the available electrons from the substrate must go to the
biomass.
(b)
(I)
From Table B.2 (Appendix B), the molecular formula for methanol is CH40 and the degree of reduction relative to
NH3 is 1S =6.00. The degree ofreduction of Methylophilus methylotrophus biomass relative to NH3 is:
_ lx4+1.68xl-0.36x2-0.22x3 -430
""
-.
emu""
W JS
Jh"
""
1 (6.00)
4.30
""
140
.
1
1-1
gIno gmo
From Table B.g (Appendix B). the molecular weight of methanol is 32.0. The biomass formula weight calculated
from the atomic weights in Table B.I (Appendix B) is 22.55. With 6% ash:
Biomassmolecularweight =
~:: = 23.99
In mass terms, the maximum possible molar biomass yield of lAO gmol gmoll is equal to (1.40 x 23.99) g biomass
per 32,0 g substrate = 1.05 g g-l,
Answer: 1he maximum possible biomass yield from methanol is 1.05 g g-}, In terms of Catoms,.the biomass yield is
1.40 grool grool-l as both biomass and substrate have 1 C atom each. In comparison, the C*atQm biomass yield from
glucose in (a) is 1 grool grool}. The main reason for the increased yield in (b) is the high degree of reduction of
methanol compared with glucose.
(il)
The actual yield of biomass from methanol is c = OA2 x lAO gmol gmol} = 0.59. The ox.ygen demand can be
determined from Eq. (4.16) if biomass remains the only major product so thatf= O. Using the parameter values
determined in (b) (i):
Therefore, 0.87 gruol ox.ygen is required r:.r gmol methanol. As the molecular weights of methanol and oxygen are
the same, the oxygen demand is 0.87 g g. methanol.
4.10
(a)
From Table B.2 (Appendix B), the molecular formula for glucose is C6H1206 and the molecular formula for ethanol
is C2H60. From Eq> (4.13), the stoichiometric equation for anaerobic growth and product formation is:
CJI}P6+bNH3 -+ cCHl.sO05NO.2+dC02+eH20+fC2H60
From Table B.8 (Appendix B), the molecular weight of ethanol is 46.1. Using the atomic weights in Table B.l
(Appendix B), the molecular weight of glucose is 180.2 and the biomass molecular weight is 24.6. The values of the
stoichiometric coefficients c can be determined from Eq. (4.12) and the yields Yxs -= O.ll g g.1 for yeast and Yxs
0.05 g g.1 for bacteria.
.
Yxs(MWsubstrate)
For bactena, c =
MW II
ce s
(I80.2ggmor )
= 0.05 g g-'
, = 037
. gmo1gmo1-'
24.6 g gmol-
37
Solutions: Chapter 4
Yeast
Cbalance:6 = c+d+2j= 0.81+d+2j~ d = 5.19-2j
Hbalance: l2+3b = 1.8c+2e+6j= 1.8xO.81+2e+6j~ 1O.54+3b = 2e+6j
o balance: 6 = 0.sc+2d+e+f= 0.5xO.81+2d+e+f~5.595 = 2d+e+j
Nbalance:b = 0.2e = O.2xO.81 = 0.16
Substituting the expression for b from the N balance into the H balances gives:
10.54+3xO.16 = 2e+6f
e=5.51-3f
Substituting this and the expression
for d" from the C balance into the 0 balance gives:
......
\
5.595 =2x(5.19-2j)+(5.51-3j)+f
6f
= 10.295
f= 1.72
Therefore, for yeast, the yield of ethanol from glucose is 1.72 grool grool,l.
Bacteria
C balance: 6 = c+d+2f= 0.37+d+2f~ d = 5.63-2f
Hbalance:12+3b = 1.8c+2e+6f= 1.8x037+2e+6f~ 11.33+3b = 2e+6f
o balance: 6 = 0.5c+2d+e+f= O.sxO.37+2d+e+f~5.815 = 2d+e+!
N balance: b = 0.2 c = 0.2 x 0.37 = 0.074
Using the same solution procedure as for yeast, substituting the expression for b from the N balance into the H
balances gives:
11.33 +3xO.074
= 2e+6j
e=5.78-3f
Substituting this and the expression for d from the C balance into the 0 balance gives:
5.815 = 2x(5.63-2j)+(5.78-3j)+f
6f= 11.225
= 1.87
Therefore, for bacteria. the yield of ethanol from glucose is 1.87 grool grool'}.
Answer~ 1.72 grool grool"} for yeast; 1.87 grool grool,l for bacteria
(b)
The maximum possible ethanol yield can be calculated using Eq. (4.20). From Eq. (4.13), w 6 for glucose andj 2
for ethanol. From Table B.2(Appendix B), the degree of reduction of glucose relative toNH3 is rs 4.00, and the
degree of reduction of ethanol relative to NH3 is
6.00. Using these values in Eq. (4.20) gives:
f max =
W JS
6 (4.00)
1P = 2(6.00) = 2.0gmolgmor
There:ore, the actu~ ethanol yield of 1.72 ~Ol gmol'} for yeast represe.nts 86%. of the theoretical maximum; for
bactena, the actual yield of 1.87 grool grool' represents 94% of the theoretical maxunum.
Answer: 86% of the theoretical maximum for yeast; 94% of the theoretical maximum for bacteria
4.11
From Table B.2 (Appendix B), the molecular formula for glucose is C6H 1206. Assuming that no products other than
biomass are formed, from Eq. (4.4), the stoichiometric equation for growth is~
Solutions: Chapter 4
38
C~1206+a02+bNH3 ~ cCHl.7~0.56NO.l7+dC02+eH:f)
Using the atomic weights in Table B.l (Appendix B), the molecular weight of glucose is 180.2. the molecular weight
of oxygen is 32.0, and the biomass molecular weight is 25.16. The value of the stoichiometric coefficient c can be
determined from the yield Yxs
Yxs(MWsubstrat~
MW
II
ce s
0.37gg- 1(180.2ggmor
1
25.16ggmor
-1
' = 2.65gmolgmol
Therefore, 2.65 groat cells are produced per gmol glucose consumed. Converting the oxygen demand to a molar
basis:
O.88g02125.16gcellslllgmOlOZI
0.88 g 02 per g cells =~. 1 g ce!J.s . 19mol cells . 32.0 g 02
Combining this with the result for c, the observed oxygen demand a is:
a=
1 gmol glucose
=183
.
From Table B.2 (Appendix B), the degree of reduction of glucose relative to NH31srS'='4;00. The degree of
reduction of the biomass relative to NH3 is:
_ lx4+1.79xl-0.56x2-0.17x3 -416
- .
~-
If no products are formed other than biomass, the theoretical oxygen demand can be determined from Eq. (4.16) with!
0; from Eq. (4.13), w = 6 for glucose:
As the theoretical oxygen demand is significantly higher than that observed, formation of other products acting as
electron acceptors is likely to have occurred in the culture.
Answer: Yes
4.12
Medium formulation
Using the atomic weights'in Table B.l (Appendix B), the molecular weight of (N14)zS04 is 132,1 and the biomass
molecular weight is 26.16. Using a basis of 1 litre, production of 25 g cells corresponds to 25/26,16 = 0.956 grool
cells. As each gmolcells contains O.25gmol N, (0.956x0.25) = 0.239gmol Nare-neededfrom the'medium for
biomass synthesis, As (NH4)zS04 is the sole N source and each gmol (Nl4)zS04contains 2gmol N, 0.239/2= 0.120
gmol (N14)zS04 is required. Multiplying this by the molecular weight, 0.120 x 132.-1 = 15.9 g (N14)zS04 are
required. The minimum concentration of (N}4)zS04 is therefore 15.9 g 1*1.
4.13
(a)
Recombinant protein can be considered as a product of cell cuItureeven though it is not excreted from the cells;
assume that recombinant protein is synthesised in addition to the normal E.- coli biomass composition. From Table
4.3, the chemical formula for E. coli can be taken as CH1.7700.49N0.24; from Table B.2 (Appendix B), the molecular
formula for glucose is C6H1206' Substituting these formulae into the general stoichiometric equation for growth and
product formation, Eq. (4.13), gives:
C~1206 +a02 +bNH3
-lo
cCHL7,o0.4~O.24+dC02 +e H20+fCHl.s.sO0.3INO,2S
Using the atomic weights in Table B.l (Appendix B), the molecular weight of glucose is 180.2, the biomass molecular
weight is 25.00, and the recombinant protein molecular weight is 22.03.
Solutions: Chapter 4
39
Assume that the biomass yield refers to the cell mass without recombinant protein. The value of the stoichiometric
coefficient c can be determined from the yield Yxs = 0.48 g g-l and Eq, (4,12):
c=
Yxs(MWsubs"ate)
MWcells
The value of the stoichiometric coefficientfcan be determined from the yield Yps
(4.14)'
1
_ 079
I
I-I
_- Yps(MWsubstrate) __ 0.096gg- (180.2ggmol-l) -,gmogmo
MW product
22.03 g gmol 1
The ammonia requirement can be, detemPneq. using an elemental balance for N.
N balance: b = 0.24 c + 0,25 f
.'
Substituting the above valoesforc and/into the N balance gives b = 0,24 x 3.46 + 0.25 x 0,79 = 1.03,
The oxygen demand can be determined using an .electron balance. From Table B,2 (Appendix B), the degree of
reduction of glucose relative to NH3 is -ns 4.00; from Table 4.3," the degree of reduction 'Of E. coli relative to NH3 is
JB 4.07. The degree of reduction of the recombinant protein relative to NH3 is:
_ lx4+1.55xl-0.31x2-0.25x3 _ 418
- .
~-
Iff in the stoichiometric equation is zero but c remains equal to 3.46, the ammonia requirement can be determined
using an elemental balance for N as follows:
N balance: b = 0.24 c = 0.24 x 3.46 = 0.83
Therefore, in wild-type E. coli the ammonia requirement is reduced from 1.03 to 0.83 grool gmol-1 glucose, a
decrease of 19%, Eq. (4.16) for the oxygen requirement becomes:
Therefore, the oxygen demand is increased from 1.65 to 2.48 gmol gmol-l glucose, a rise of 50%.
Answer. The ammonia and oxygen requirements for wild-type E. coli are 0.83 grool and 2.48 gmol per gmol glucose,
respectively. These values represent a 19% reduction and a 50% increase, respectively, compared with the genetically
engineered strain.
4.14
The stoichiometric equation for acetic acid production using cell culture must include terms for growth. Based on Eq.
(4.13), the stoichiometric equation for growth and product formation is:
C2H4>+a02+bNH3 ~ cCHLSOo.sNo.2+dC02+eH20+jC2f402
From Table 8.8 (Appendix B), the molecular weights of ethanol and acetic acid are 46.1 and 60.1, respectively. From
the atomic weights in Table B.1 (Appendix B), the biomass molecular weight is 24.63. The value of the
stoichiometric coefficient c can be determined from the yield Yxs 0.14 g g~l and Eq. (4.12):
c =
_Yx",s"(MW"","S::U,,bs::"_at-,-e)
MW cells
40
Solutions: Chapter 4
The value of the stoichiometric coefficient!can be determined from the yield Yps = 0,92 g g-1 and Eq. (4.14):
Yps(MWsubstrate)
MW odu
pr ct
=.
O.92gg- t (46.1ggmol-l)
1
6O.1ggmor
=.
-I
From Table B.2 (Appendix B), the degree of reduction of ethanol relative to NH3 is rs =. 6.00, and the degree of
reduction of acetic acid relative to NH3 is 'no =. 4.00. The degree of reduction of the biomass relative to NH3 is :
_ lx4+1.8xl-0.5x2-0.2x3 _ 420
1ll-
=.
-.
2 for acetic acid. Substituting these values into Eq. (4.16) for the
= 1/4(2x6.00-0.26x4.20-0.71x2x4.00)
=.
1.31
Therefore, with growth, 1.31 groat oxygen are required per gmol glucose consumed, compared with 1 gmoloxygen
per gmol glucose without groWth. Therefore, with growth, the oxygen demand for acetic acid production is increased
by31%.
Answer. The oxygen demand is increased by 31 %.
Energy Balances
5.1
(a)
From Table B.5 (Appendix B), Cp for m~cresol between 25"'C andlOO"C is 0.551 calg- I oC-t.Thespecific enthalpy
change calculated using Eq. (SIB) is:
6h
(0248T+0~153r2)[ calg-l
M
(d)
From Table B3 (Appendix B), the heat capacity of air between 65"C and 150"C is given by the equation:
= J,'~ Cp dT = J,~~ (28.94 + 0.4147x 10-2 T+ 0.3191 x 10-5 f2 - 1.965 x 10-9 rJ) dT J gmor1
15O"C
l5O"C
Souaions: Chapter 5
42
5.2
Heat of vaporisation
-The latent heat of vaporisation of water at BOC is obtained from Table C.l (Appendix C). Taking the average of the
values at nee and 34C~ Ah v = 2423.55 kJ kg~l at 33C From Eq. (5.16);
Mf = M!>h v = 20 gb- I (2423.55 kJ kg-Ij .11~gl
Mf = 48.5 kJ h- I
Answer: 48.5 kJ h- l
5.3
Steam tables
(aJ
The heat of vaporisation of water at 85"C is obtained from Table C.I (Appendix C). Taking the average of the values
at 84"C and 86"C, !:J.hy = 2296.05 kJ kg-! at 85C.
Answer: 2296.05 kJ kg- l
(bJ
From Table C.l (Appendix C), the enthalpy of liquid water at IOce relative to the triple point is 42.0 kJ kg- t , The
enthalpy of liquid water at 3S"C relative to the triple point can be estimated as the average of the values in Table Col
for 34<>C and 36C = 146.55 k:J kg-t. Using the relationship on p 89, the enthalpy of water at 35C relative to 1000e is
therefore (146.55 - 42.0) kJ kg-I"" 104.55 kJ kg-I.
2.5 atm
From Table C.3, the enthalpy at 100 kPa and 275C is 3024 kJ kg-I; the enthalpy at 500 kPa and 275"'C is 3013 kJ
kif 1. Interpolating between these values gives an enthalpy of 3019.8 kJ kg- l at 253.3 kPa.
5.4
1.
Assemble
(i)
Units
kg, h, kJ, C
(ii)
FkJw sheet
43
Solutions: Chapter 5
System boundar; \ .
Q (loss)
r
Medium in
..l.-_~
Heating vessel
=0.22 kW
1
I
I
1--'----_ Medium out
3250 kg h-1
3250 kg h-1
15C
44C
(ill)
System boundary
The system boundary is shown on the flow sbeet.
2.
Analyse
(i)
Assumptions
- steady state
-no leaks
- system is homogenous
- condensate temperature is 150C
- no shaft work
(li)
Basis
1 h, or 3250 kg medium in
(ill)
Reference state
H = 0 for water (steam) at its triple point
H 0 for medium at 15C
Extra data
(iv)
C medium 0.9 cal g-l 0(;-1 0.9 kca1 kg-I C- 1
1
v waterat 150C = 2113.1 kJ kg- (fable C.2, Appendix C)
1 kcal = 4.187 x 103 J (fable A.7, Appendix A)
1 W = 1 J s-1 (fable A.S, Appendix A); therefore, 1 kW =1 kJ s~l
6h
(v)
Mass balance
output
"""""
"""""
3.
Calculate
ldmtify ta"" in the 'nagy-balan" ,quatian
Ws =O. There are two components for the beat term, Q: Qross and Q from the condensing steam. With symbol MD =
medium. the energy-balance equation becomes:
(i)
=0
(M h)MD out at 44C is calculated as a sensible energy change from H = 0 at 15C using Eq. (5.13):
(M h)MDuut
Converting to kJ:
= M Cp aT = 3250 kg (0.9 keal kg-l 0c- l )(44 -15loe = 8.483 x 104 keal
Solutions: Chapter 5
44
(M h)MD out
4
8.483 x 10 kcaL
14.187X103J111kJ
1 kcal
'1000 1 I"" 3.55 x 105 kJ
= O.22kW. [lkJ,-1113600'1
1kW l h =792kJh-1
Therefore, on the basis of 1 h, {hess "" 792 kJ. Substituting values into the energy~balance equation gives:
Q = -3.56 x 105
kJ
Q has a negative value which is consistent with the sign conventions outlined on pp 87-88: heat must be supplied to
the system from the surroundings. This heat is provided as the latent heat of vaporisation as saturated steam at 150<>C
condenses. The enthalpy change from this change ofphase is calculated using Eq. (5.16) and must be equal to -Q.
3.56xloSkJ "" Msteam!JJl v
= Msteam(21l3,lkJkg- 1)
4.
Finalise
Answer: 168 kg
5.5
(a)
L
Assemble
(i)
Units
kg, b, kJ; C
(ii)
Flow sheet
Off-gas
System boundary
,~ - -- -
--
I
I
Feed
2000 kg h- 1
4% glucose
96% water
25C
I
I
r--t-
Q (cooling)
Inlet gas
100,000 litres min- 1
1 atm, 15"C
88% air
12%NHs
(ill)
System boundary
Reactor
(25,000 lltres)
1
I
I
--
I
I
I
Product
0.5% glucose
45
Solutions: Chapter 5
(iv)
Reaction equation
2.
Analyse
(i)
Assumptions
- steady state
-no leaks
- system is homogenous
- solutions are ideal
- inlet air and off-gas are dry
- all excess NH3 is dissolved in the aqueous phase
- all COz produced leaves in the off-gas
- negligible sensible heat change
- no evaporation
- no shaft work
(ii)
Basis
I h, or 2000 kg feed
(ill)
Reference state
H = 0 for water at its triple point
H = 0 for feed at 25C
(iv)
Extra data
Molecular'weights (Table B.t, Appendix B): glucose = 180.2
NH3 = 17.0
02=32.0
Nz = 28.0
glutamic acid = 147.1
C02 =44.0
H20 = 18.0
air = 28.8 (see Problem 2.9, Chapter 2)
Ideal gas constant (fable 2.5): R = 0.0820571 atm K-l gmol-l
Composition of air (p 17): 21% Oz, 79% Nz by volume
Heats of combustion (Table B.8, Appendix B):
Ah~ glucose = -2805.0kJ gmol-l
Ah~NH3 =-382.6kJ gmol- 1
-MIrxn-MyAhv-Q+ Ws
3.
=0
Calculate
(i)
Mass balance
As gas compositions are normally given in Yol%, 88,000 litres air and 12,000 litres NH3 enter the reactor every min.
On a basis ofl h, the volume of air in is 88,000 x 60 = 5.28 x 106 litres; the volume ofNE3 in is 12,000 x 60 = 7.20
x 105 litres. Using the known composition of air, the volume of Oz in = 0.21 x 5.28 x 106 = 1.11 x 106 Utres; the
volume ofNZ in = 0.79 x 5.28 x 106 = 4.17 x l06litres. Converting these gas volumes to moles using the ideal gas
law, Eq. (2.32), with the temperature converted from C to degrees Kelvin using Eq. (2.24):
Solutions: Chapter 5
46
Moles of 02 in = pV =
1 atm(l.l1 x 1Q6t)
= 4.69xI04gmol
0.0820571alm r' gmor 1 (15 + 273.15) K
RT
_pV -_
laJln(4.17XI0'1)
-176
10' gmoI
MI
o esofN 2m - - . x
RT 0.0820'71aJlnK 19moll(I'+273.I5)K
MolesofNH in=pV =
3
RT
latm(7.20xt051)
=3.05x10 4 g.mol
0.0820571aJlnK 'gmol-'(15+273.I5)K
.
These molar quantities can now be converted to masses using the molecular weights:
4
Mass of02 in = 4.69 x 10
4
MassofNH3 in = 3.05 x 10 gmol.!
;~;II.ll~gl = 5185 kg
Therefore, the total mass of inlet gas is 1500.8 + 4928.0 + 518.5 = 6947.3 kg.
The calculation tables below show all known quantities in kg. The total mass of off~gas is denoted G; the total mass
of product is denoted P.
In
Gluconic acid C02
Stream
Glucose
Peed
Inlet gas
Off-gas
80
518.5
02
1500.8
4928.0
0
0
HZO
1920
Total
2000
6947.3
Product
518.5
1500.8
4928.0
0
-=__~=",-_-",="-_==,--,,--
Total _ _ 80
-==,-_
0
1920
-,,,-_
_--,,=_
_ 8947.3
Out
Stream
Glucose
NHS
NZ
HZO
Total
Product
0
0.005P
0
?
?
0
?
0
0
?
?
0
0
?
G
P
Total
0.005P
G+P
Peed
Inlet gas
Off~gas
N2 balance
N2 is a tie component.
4928.0 kg N2 in = N2 out
N2 out = 4928.0 kg
Glucose balance
80 kg glucose in + 0 kg glucose generated = 0.005 P kg glucose out + glucose consumed
Glucose consumed :::: (80 - 0.005 P) kg
Converting the glucose consumed to molar terms:
Olucoseconsumed = (80-0.005 P) kg 1
From the reaction stoichiometry, conversion of this number of kgmol glucose requires the same number of kgmol
NH3 and 1.5 x the number of kgmo1 02. Converting these molar quantities to masses:
47
Solutions: Chapter 5
NH, consumed
02 consumed
= (21.312-1.332 x 10-3 P) kg
Similarly, expressions for the masses of glutamic acid, C02 and water generated can be determined ,from the
stoichiometry:
~:~ll
Water generated
= (23.976 -
1.499 x 10-3 P) kg
02 balance
1500.8 kg02 in + 0 kg 02 generated
= 02 out + (21.312 -
C02 balance
1.221
x 10-3 P) kg
Adding together ,the masses ofN2, 02 and C02 out gives the total mass of off-gas,O:
Substituting the above expression for a into the total mass balance:
8947.3kg = (6427.0+ 1.11 x 10-4 P+ P)kg
2520.3 kg = 1.000 P kg
P = 2520.3 kg
Therefore, from the total mass balance:
= (8947.3 - 2520.3) kg
G = 6427.0kg
Substituting the result for P into the glucose, 02 and C02 balances gives:
Solutions: Chapter 5
48
= 0.005 P kg =
12.60 kg
1.221 x 10-3 P) kg
=:
16.46 kg
Using the result for P to evaluate the masses of the other reactants and products involved in the reaction:
NH3consumed = (7.548-4.718 x 104 P) kg
= 6.36 kg
Water balance
1920 kg water in + 20.20 kg water generated = water out + 0 kg water consumed
Water out::: 1940.20 kg
Glutamic acid balance
kg glutamic acid in
+ 55.02 kg glutamic acid generated ::: glutamic acid out + 0 kg glutamic acid consumed
Glutamic acid out::: 55.02 kg
The Out side of the mass-balance table can now be completed with all quantities in kg.
Out
Stream
NZ
0
512.14
1482.9
0
4928.0
0
0
55.02
512.14
1482.9
4928.0
55.02
Glucose
NHl
Inlet gas
Off-gas
Product
0
12.60
Total
12.60
Feed
HZO
Total
16.46
0
0
1940.20
6427.4
2520
16.46
1940.20
8947.3
All columns and rows of the completed table add up correctly to within round-off error.
(ii)
Ws
Energy balance
Therefore, the energy*balance equation becomes:
=0; Mv =O.
-AHrxn-Q::: 0
The heat of reaction is evaluated using Eq. (5.20). As the heat of combustion ofCOZ and H20 is zero:
involved in the reaction. Converting the masses of reactants and products consumed or generated to moles:
Glucoseconsumed::: 67.40kg ::: 67AOkg ll~gl1 :8~o~
I::: 374gmol
49
Solutions: Chapter 5
As NH3 and glutamic acid are involved in the reaction in stoichiometric quantities. 374 gmol NH3 are consumed and
374 gmol glutamic acid are produced. Substituting these quantities into the heat of reaction equation gives:
MI"" : 374 gmol (-2805.0kJ gmol-lj + 374 gmol(-382.6kJ gmOl-lj_ 374 gmol(-2244.1 kJ gmol-lj
M:lrxn
= -353 x lOS kJ
3.53 x loS kJ -Q : 0
Q : 3.53 x loS kJ
From the sign conventions outlined on W 87-88. Q positive indicates that,heat must be removed from the system.
Answer: 353 x 105 kJ h- 1
(b)
If cooling were not provided, the heat of reaction would be absorbed as sensible heat by the streams passing through
the reactor. For a rough calculation of the effect of this heat on the temperature of the reactor, assume that the 353 x
105 kJ h- 1 is absorbed by 2000 kg h- 1 aqueous medium and 6947-3 kg l:r 1 gas. ,Assume that the heat capacity of the
aqueous medium is close to that of water:: 75.4 J gmol-l C-l (Table B-3, Appendix B) 75.4 kJ kgmol-l C-l, and
that the heat capacity of the gas stream is equal to that of air :: approx. 29 J gmol-l 0C- 1 (Table B.3, Appendix B):: 29
kJ kgmol-l C-l. From Eq. (5.12):
6T:
MI
(M Cplliquid + (M Cpl..,
5
1
353 x 10 kJ h-
T ::
1
(2000 kg h-1)(75.4kJ kgmor oc-1j.1
:: 23"C
;~~~ll
As a temperature rise of 23C in the reactor would not be well tolerated by most commercial organisms, provision of
adequate cooling for this reaction is an important consideration. Assuming that the usual temperature for the reaction
is 25C, the temperature without cooling woulJ,i increase to (25 + 23)OC 48C.
5.6
5 kgh-1
: 1.25kgOZh-1
4kgkg 1
Converting this quantity to gInol using the molecular weight of 02
1
0zrequired:: 1.25kgh-
0: 1.1 ~~~ll
.1 1
:: 39.06gmolh-
The heat of reaction for aerobic metabolism is approximately -460 kJ gmol- 1 Oz (p 100). Therefore, the heat of
reaction for alginate production is:
'This result can be used in the modified energy-balance equation, Eq. (5.26):
-6Hrxn -Mv tih v -Q+ Ws :: 0
:=
0 (no evaporation). From Table A.8 (Appendix A), 1 W:: 1 J s-1; therefore 1 kW:: 1 kJ
Solutions: Chapter 5
50
Q = 2.3 x 10" kJ h- I
From the sign conventions outlined on pp 87-88, Q positive indicates that heat must be removed from the system.
Answer: 2.3 x 104kJh 1
5.7
Acid fermentation
From Tables B.S andB,l(Appendix B), the molecular fannulae and molecular weights are:
sucrose = C12H2Z011: MW:: 342.3
The reaction equation can be obtained by modifying Eq. (4.13) for anaerobic growth andproo.uct-fonnation:
C 12HZZ0 11 +bNH3 -+ cCHl.gOo.sNo.2 +dCOZ +eHZO+!I C3~02
+h C2H 40 2 +Jj C4H ,02 +14 C,H60 3
The biomass yield from substrate Yxs = 0.12 g gol, This value can be used to determine the stoichiometric coefficient
c using Eq. (4.l2):
_ Yxs (MW substraJe)) _ 0.12 gg-l (342.3) _
MW cells
25.9
- 1.59
c -
The coefficientsh ,/2./3 and/4 can be determined similarly using the product yields and Eq. (4.14):
11
Jj = MW butyric acid
60.1
/4 -
Of the remaining coefficients b, d and e, because CO2 and H20 do not figure in heat of reaction calculations as their
heat of combustion = 0, only b need be determined. nus can be done using an elemental balance on N.
N balance: b = 0.2 c = 0.2 x 1.59 = 0.32.
To calculate the heat of reaction, the heats of combustion of the reactants and.products are required from Table E.8
(Appendix B):
M~ sucrose=-5644.9kJ gulOr l
M~biomass=-552kJ gmor 1
M~ propionic acid = -l527.3kJ gmol-l
M~ acetic acid=-874.2kJ gulOr l
51
Solutions.' Chapter 5
The heat of reaction is determined using Eq. (5.20). As the heat of combustion of C02 and H20 is zero:
Mlrxn = (n 6.h~)s +(nah~)A -(n M~)B -(n M~)PA -(nM~)AA -(nah~)BA -(nM~tA
=
where S sucrose, A = NH3, B = biomass, PA propionic acid, AA acetic acid, BA butyric acid, and LA = lactic
acid. Using a basis of I gmol sucrose, the n in this equation are the stoichiometric coefficients, Substituting values:
Iili""
= -474.8 kJ
This M rxn was determined on the basis of I gmol sucrose. For 30 kg sucrose consumed over a period of 10 d:
M rxn
=30kg.
llkg .
IOOOgll,gmOll(
342.3g -474.8 kJ gmol-I)
=-4.16x 104 kJ
The cooling requirements are determined using the modified energy~balanceequation,Eq. (5.26). For no evaporation
and no shaft work, M v = Ws = 0, so that:
Q = -Mfrxn
= 4.16 x 104 kJ
From the sign conventions outlined on pp 87-88. Q positive means that heat must be removed from the system.
Answer:4.16x 104 kJ
5.8
Ethanol fermentation
From Table B2 (Appendix B), the molecular formula for glucose is C6H1206 and the molecular fonnula for ethanol
is C2H60. From Eq. (4.13), the stoichiometric equation under anaerobic conditions is:
C6H1206+bNH3 ~ CCH1.7.s00.5SNO.lS+dC02+eH20+fC2H60
From Table B.8 (Appendix B), the molecular weight of ethanol is 46,1. From the atomic weights in Table B.I
(Appendix B), the molecular weight of glucose is 180.2 and the biomass fonnula weight is 25.58. Taking into
account the 8% ash:
Biomassmolecularweight = 2;':::
= 27.80
The value of the stoichiometric coefficient/can be determined from the yield Yps= 0.45-g g-1 and Eq. (4.14):
f =
Yps(MWsubstrate)
MW product
0.45gg- 1 (180.2ggmol-l)
-1
= 1.76gmolgmol
46.1 g gmol I
Substituting this and the results from the C and N balances ioto the H balance:
L44+ 3 (0.45-0.18d) = 1.75 (2.48-d) + 2e
1.21d-L55
= 2e
e = 0.61 d-0.78
Solutions: Chapter 5
52
Substituting the expressions for c, b and e into the 0 balance:
4.24
Substituting this value for d into the expressions for the other coefficients gives c "" 0.72, b = 0.13 and e "" 0.29. The
~~11
"
8.68gmol
From stoichiometry:
1
Moles glucose consumed "" 8.68gmolx 1.76
= 4.93gmol
Moles NH3 consumed "" 8.68 gmol x ~:~~ "" 0.64 gmal
Moles biomass produced "" 8.68 gmol x ~:;~ "" 3.55 gmat
Mlrxn
= (nAh~)G+(nAh~)A -(nah~)B-(nAh~)E
where G glucose, A = NH3' B biomass and E = ethanol. The n in this equation are the actual moles of reactants
and products consumed or produced. Substituting values gives:
/lH= = 4.93 gmol (-2805.0kJgmor1) + O.64gmol (-382.6kJ gmol-1)_3.55 gmol(c21.2kJ g-l)1 ~7:o~
= -1175 kJ
Using the modified energy~balance equation, Eq. (5.26), with M v =0 and Ws =0:
Mlrx,n
Q=-Mlrx,n= 117.5kJ
From the sign conventions outlined on ,pp87-88, Q positive means that heat must be removed from the system; in this
case, 117.5 kJ h- I is used to raise the temperature' of 25 I h- I water from lOoC. The sensible heat change of the water
can be calculated from Eq. (5.12). Using a value of 1 kg I-I for the density of water, Cp for water = 75.4 J gmol-I
C*I (Table B-3, Appendix B), and the molecular weight of water 18.0 (Table B.l, Appendix B):
lJ.T
= ~_
Mep
117.5 kJ h-
Answer: 21.2C
_ 112"<:
(25Ih-1 Ilkg~(754J
1-1oC- 1 11gmOllllOOOgll~fi .
. 11 U . gmo
. 18.0g lkg . lOOOJU
Solutions: Chapter 5
5.9
53
From Table B,8 (Appendix B), the molecular formula for sucrose is C12HZ2011' Therefore, from Eq. (4.4), the
stoichiometric equation for aerobic cell growth is:
CIZH22011 +a02+bNH3
-?
cCHl.8300.5sNo.17+dCOZ+eHZO
Using the atomic weights in Table R1 (Appendix B), the molecular weight of sucrose is 342.3 and the biomass
formula weight is 25.04. Taking into account the 5% ash:
Biomass molecularweight
= ~~ : 26.36
ni:::h ~,X4+J.83X1-0.55X2-0.17x3:
. ....
4.22
..
rs _-
12x4+22x1-11x2 _ 400
- .
The value of the stoichiometric coefficient c can be determined from the yield Yxs: 0.5 g g~l and Eq. (4.12):
C
26.36 g gmol 1
The oxygen requirements can be determined from Eq. (4.16) with/: 0; from Eq (4.13), w: 12 for sucrose:
Therefore, 5.15 gmol Oz are required for each 6.49 gmol biomass produced; this corresponds to 0.79 gmol Oz per
gmol biomass. Converting this oxygen demand to mass terms using the molecular weight of oxygen: 32.0 from
Table B.I (Appendix B):
1_
.
_ 0.79 gmolOz 132.0 g Ozlll gmol biomass
-1
0.79 gmol 0Zper gmol blOmasS - 1 gmol biomass' 1 gmol0 . 26.36 g biomass - 0.96 g g
z
The specific growth rate represents a rate of growth of 0.45 g biomass produced per g biomass per h. As 0.96 g 02
are required per g biomass produced, the specific rate of Oz consumption is 0.45 x 0.96: 0.43 g Oz.r,r g biomass per
h. When the biomass concentration is 10 g 1~1 in a 50,000 litre fermenter, the mass of cells is 10 g 1- x 50/}00 1: 5 x
105 g. Therefore, the total rate of 02 consumption is 0.43 g g-1 h- 1 x 5 x 105 g: 2.15 x loS g Oz h 1. Converting
this to moles:
5
Rate of 0 1 consumption : 2.15x 10 gh-1 .l
;~~ll :
6.72x 10 3 gmolh- 1
From p 100, the heat of reaction for aerobic growth is approximately -460 kJ gmol-l 02 consumed. Therefore:
The rate of heat removal from the fermenter is determined using the modified energybalance equation, Eq. (5.26),
withWs:Mv:O:
From the sign conventions outlined on pp 87-88, Q positive confrrms that heat is removed from the system.
Dilution of sewage
(i)
System
boUndary\
Water
F::::: 40,000 I h 1
r
I
I
I
I
I
I
I
"
- 1---
CA
I
I
I
I
I
I
I
Outlet stream
F=40,OOO I h- 1
CA
(Ii)
Define variables
V
volume of material in the tank; F ::::: volumetric flow rate into and out of the vessel::::: 40,000 1 h I ; CA :::::
kg
0022k 1-1
CAO::::: 10,000
450,ooof:::::'
g
(v)
d(VCA)
dt
As V is constant, it can be taken outside of the differential:
= -FCA
55
Solutions: Chapter 6
As F is also constant, the differential equation contains only two variables, CA and t. Separating variables gives:
dCA
-F
-=-dt
CA
V
Integrating:
J-FV
dCA
CA
dt
Using integration rules (D'.27) td(D.24) from Appendix D and combining the constants of integration:
-F
InCA = -yl+K
From the initial condition for CA, at t = 0, In CAO = K, Substituting this value of K into the equation gives:
-F
InCA = -yt+InCAO
CA
InCAO
C~
-F
=-1
= CAOe (-FIV; t
where CA has units of kg I-I and t has units of b. From this equation, at t= 5 h, CA
=0,014 kg I-I,
6.2
(i)
System
The system is the whole gutted fish placed in the batch drier at time zero. During drying, the mass of the system
decreases as water is removed.
(li)
Assumptions
No additional assumptions are required,
(iii)
Boundary conditions
At t = 0, the mass of water in the fish in the drier is equal to M()
(iv)
Water mass balance
The general unsteady-state mass-balance equation is Eq. (6.5), As there is no reaction, RO = RC = O. No water is
added during drying; the~fore Mi = 0, At any time during drying, as the rate of water removal Me is proportional to
the moisture contentM, Me k M where k is a constant, Substituting into Eq, (6.5) gives:
dM
Cit
=-kM
where M and t are the only variables. Separating variables and integrating:
Using integration rules (D.27) and (0,24) from Appendix. D and combining the constants of integration:
lnM=-kt+K
At I"'" 0, M = Mo; therefore. K"'" In Mo- Substituting this value of K into the equation gives:
Solutions: Chapter 6
56
InM = -kt+1nMo
M
In M
= -let
O.5M
Therefore:
M
In Mo
= -0.0347 t
where t has units of min. When 95% of the water has been removed, M =0.05 Mo_ Therefore:
In
O.05MO
M
= -0.0347 t
In 0.05
t
:=
-0.0347 t
l.44h
Answer. 1.44 h
6.3
System boUndary\
Inlet stream
Cod-liver oil drum
F;
P
- -
r
I
I
I
I
I
I
I
\.
- -
I
I
I
I
I
I
I
V
p
</
- - -
Oil tank
- - -
Outlet stream
Fo
</
(li)
Define variables
V = volume of oil in the tank; Fi "'" volumetric flow rate of cod~liver oil into the oil tank; F 0 volumetric flow rate of
mixed oil out of the oil tank; = mass fraction of vegetable oil; p"'" density of vegetable and cod-liver oils
(ill)
Assumptions
- no leaks
- oil tank: is well mixed; therefore in the outlet stream inside the tank
- densities of each oil and the oil mixture are the same
57
Solutions: Chapter 6
(iv)
Boundary conditions
At t= 0 when cod-liver oil first enters the oil tank, V = Vo = 60 litres. At t= 0,4>= o = 1.
(a)
d(VP)=Fp_Fp
dt
'
0
As P is constant it can be taken outside of the differential and cancelled:
dV
Pdt
= (Fi-FdJp
dV
dt = (Fi-FdJ
The differential equation contains only two variables, V and t. Separating variables and integrating:
dV
(Fi-FdJdt
Using integration rule (0.24) from Appendix D and combining the constants of integration:
From the initial condition for V, at t = 0, K = Vo. Substituting this value of K into the equation gives:
V= (i-Fo)t+ Vo
The time between 8 p.m. and 9 a.m. the next morning is 13 h. From the above equation for V,- for t 13 h, Fi 7.5 1
h- 1 ,Fo =4.81h- 1 and Vo=60l,V""'95.11. As this volume is less than the tank capacity of 1001, the tank will not
overflow.
'
Answer: No
(b)
Total mass balance
As the volumetric flow rates of oils into and out of the tank are the same and the density of the inlet and outlet streams
are assumed to be equal, the volume of oil in the tank is constant (see Example 6.2)-s0 that V = Vo;:::; 60 1 at all times.
Vegetable oil mass balance
The general unsteady~state mass-balance equation is Eq. (6.5). As there is no reaction, RG "'" RC O. No vegetable oil
enters the tank; therefore Mi "'" O. The mass flow rate of vegetable oil out is Mo "'" F o P 4>. The mass of vegetable oil
in the tank at any time is M"", V p 4>. Substituting these expressions into Eq. (6.5) gives:
d(V;:)
= -Fop
As both V and p are constants, they can be taken outside of the differential and p can be cancelled:
VP~ = -Fop
V~
= -Fo
As F0 is also constant, the differential equation contains only two variables, 4> and t. Separating variables and
integrating:
Solutions: Chapter 6
58
Using integration rules (D.27) and (D.24) from Appendix D and combining the constants of integration:
-Fo
In::::: yt+K
From the initial condition for 41, at t
=0, In <Po::::: K.. Substituting this value of K into the equation gives:
ln~
-Fo
= y'+lnib
~
-Fo
lnib=y'
~ =
In this problem. F0
:::::
ib e(-F,II'J'
II : : :
1 e....(l080 t
is dimensionless and t has units of h. The time between 8 p.m. and midnight is 4 h. From the above
4'= 0.73. Therefore, at midnight, the composition of oil in the tank is 73% vegetable oil and 27%
cod-liver oil.
where
<P
equation, at t= 4 h,
6.4
The general unsteady-state mass-balance equation is Eq. (6.5). For a batch culture, Mj ::::: Mo : : : O. For a mass balance
on cells. assuming there is no loss of cells from the system, e.g. by lysis, RC::::: O. The rate of generation of cells RG is
proportional to the concentration of cells present: RO = J.t x V where jJ is a constant, xis the cell concentration and V
is the culture volume. The total mass of cells M is equal to the culture volume V multiplied by the cell concentration
x: M = V x, Substituting these results into Eq. (6.5) gives:
d(Vx)
= J.txV
dt
Assuming that V is constant throughout the batch culture, it can be taken outside of the differential:
dx
V dt
dx
dt
= J.tx V
= J.tx
The differential equation contains only two variables, x and t. Separating variables and integrating:
-dxx = I'dt
Using integration rules (0.27) and (0.24) from Appendix. D and combining the constants of integration:
lnx = j1.t+K
=xo.
Therefore, at t
=0, In Xo =K.
59
Solutions: Chapter 6
lnx =
j.tt+lnxo
x
In- =
XO
j1,t
2XO
I n - = ,u(45 min)
XO
ln2 =
j.t
j.t
(45 min)
= 0.0154 min'l
Therefore:
In''::' =
0.0154t
x =
eO.Ol54 t
XO
XQ
After 12 h, the cell concentration is 6.54 x 104 times the cell concentration at the beginning of exponential growth. If
there is a lag phase, the cell concentration at the beginning of exponential growth is usually very close to that at
inoculation; therefore, the cell concentration is about 6.54 x 104 times the inoculum level.
6.S
Radioactive decay
The general unsteady~state m.ass~ba1ance equation is Eq. (6.5). In this problem, M j = Mo = O. For a mass balance on
isotope, RO O. The rate of isotope decay RC is proportional to the concentration of isotope present: RC -/q C V,
where kl is a constant, C is the isotope concentration and V is the solution volume. The total mass of isotope M is
equal to the solution volume V multiplied by the isotope concentration C: M = V C. Substituting these results into Eq.
(6.5) gives:
d(:CJ =-k,CV
If we assume that the density of the solution is constant during isotope decay, V is constant and can be taken outside
of the differential and cancelled:
dC
V(if =-k 1 CV
dC
(if
= -k1 C
The differential equation contains only two variables, C and t, Separating variables and integrating:
dC
= -k 1 dt
Jdg = f
-k) dt
Using integration rules (D27) and (D.24) from Appendix D and combining the constants of integration:
lnC=-k1 t + K
60
Solutions: Chapter 6
Assume an initial condition: at t "'" 0, C "'" CO, Therefore, at t "'" 0, In Co = K, Substituting this value of K into the
equation:
InC = -ktt+lnCo
C
In-=-k i t
Co
(a)
Co.
0.5 Co
I n - - = -kIth
Co
In 0.5 = -ki !h
_ -tn0.5
th - - -
k,
Therefore:
In2
th
= kl
Answer. Q.E.D.
(b)
From the equation derived in (a):
For t:h
=14.3 days:
kl
= 4.85 x 10-2 d- I
Substituting this value of kl into the general equation for isotope concentration:
In
go = -4.85 x 10-2
In
0.01 Co
Co
In 0.01
t
Answer. 95 days
-2
= -4.85 x 10
= -4.85 x 10.2 t
= 95 days
61
Solutions: Chapter 6
6.6
Continuous fermentation
(i)
System
Feed
F
xI =0
"
(li)
....
boUndary\
"
- - r- - - -
r
I
I
I
I
I
I
I
V
x
I
I
I
I
I
I
I
Product
F
Define variables
=volume of broth in the fennenter; F = volumetric flow rate into and out of the vessel; x = concentration of cells; s
= concentration of substrate; Xi. =concentration of cells in the feed; Si =concentration of substrate in the feed
V
(iii)
Assumptions
-no leaks
- fermenter is well mixed; therefore x and s in the outlet stream =x and s, respectively, inside the fermenter
- density of the fermentation broth is the same as that of the feed
Boundary condition
(iv)
Att=O,x=XO
(v)
Total mass balance
As the volumetric flow rates into and out of the fermenter are the same and the density of the inlet and outlet streams
are assumed equal, the volume of broth in the fermenter is constant (see Example 6.2) 8..Iid equal to Vat all times.
(aj
Cell mass balance
The general unsteady-state mass-balance equation is Eq, (6.5). As no cells enter in the feed stream, Mi =O. The mass
flow rate of cells out Mo = F x. The rate of cell generation RG = rx V = kl x V. Assuming that cell lysis is negligible,
RC = O. The mass of cells in the fermenter M is equal to V x. Substituting these terms into Eq. (6.5) gives:
d(Vx)
-_.= -Fx+k1xV
d'
dx
V dt = -Fx+k1xV
Dividing through by V and grouping terms:
dx
F
- = x(kt--)
d'
dx
Answer: dt = x (k I - V)
(b)
At steady state, dxldt = O. Therefore, from the equation derived in (a), at steady state kl must be equal to FIV.
Answer: kl
=f.<iv
62
Solutions: Chapter 6
(e)
As F, V and kl are constants, the differential equation derived in (a) contains only two variables, x and t. Separating
variables and integrating:
<Ix
F
-;- = (k'-l1)dt
J~ = f(k,-~)dt
Using integration rules (D.27) and (D.24) from Appendix D and combining the constants of integration:
lux:::: (k1-V)t+K
From the initial condition for x,at t= 0, In Xo = K. Substituting this value of K into the equation gives:
Inx:::: (k1-y)t+1nXO
'0
x=.xoe(kl--)t
,v
F
(k --) ,
Answer: x:::: XOe 1 V
(d)
22001h-1
4 = 0.5 eO.II t
inS = 0.11 t
t::::
18,9h
Answer: 18.9 h
(e)
The general unsteady-state mass-balance equation is Eq. (6.5). For substrate, the mass flow rates in and out are
Mj = F si and Mo = F s. The rate of substrate generation RG =0; the rate of substrate consumption RC =IS V = k2 x
V.The mass of substrate in the fermenter M is equal to V s. Substituting these terms into Eq. (6.5) gives:
d(Vs)
( i t = Fs i -Fs-k 2 xV
63
Solutions: Chapter 6
In this equation, F, V, kl and X{) are constants and there are only two variables, s and t. However, the variables cannot
be easily separated as in the previous problems, making algebraic solution difficult.
&
Answer. dt
(f)
An equation for &/dt in terms of x was dt;:rived in (e) as:
F
V
(si -s) = k 2 x
Vk Z
si- s = F'x
Answer. s
6.7
Vk
Z
= si -Tx
Fed-batch fermentation
System bOUndary\
Feed
F
s;
r
I
I
I
I
I
I
I
L
\.
'"- -
I
I
I
I
x
s
p
1
I
I
(ll)
Define variables
V = volume of broth in the fermenter; F = volumetric flow rate into the fermenter; x = concentration of cells in the
fermenter; s = concentration of substrate in the fermenter; Si = concentration of substrate in the feed; p = density of the
64
Solutions: Chapter 6
(iv)
Boundary condition
Att=O, V=Vo.
(a)
dV
Pdi
= pF
dV = F
dt
As F is constant, the differential equation contains only two variables, V and t. Separating variables and integrating:
dV = Fdt
Using integration rule (D.24) from Appendix D and combining the constants of integration:
v=
From the initial condition for V, at t
=0, Vo =K.
Ft+K
Answer: V=Ft+Vo
(b)
Substrate mass balance
The general unsteady-state mass-balance equation is Eq. (6.5). The mass flow rates of substrate in and out are
Mj F si and Mo = o. The rate of substrate generation RO 0; the rate of substrate consumption RC rs V kl S V.
The mass of substrate in the fermenter M is equal to V s. Substituting these terms into Eq. (6.5) gives:
d(V,)
-at
=Fsi-klsV
As neither V nor S is constant, both must be kept in the differential as a product. Expanding the differential using the
product rule (D.22) from Appendix D:
=F derived in (a) :
<is
Answer: dt
F
s
= V(Si-S)-kt
65
Solutions: Chapter 6
6.8
Plug-flow reactor
(i)
Flow sheet and system boundary
These are shown for a plug-flow reactor in the figure below.
System bOUndary,
...
~_ _!..I
Fee~--"""-II
~
- - - " ' - - -_ _~
-=-.,.....,.:..
z
S-.......- ~rOduct
~Ml
(ii)
Define variables
u := fluid linear velocity; z distance along the reactor; CA
reactant in the feed stream; A = reactor cross-sectional area
(iii)
Assumptions
-no leaks
-plug flow
:=
= concentration of
(a)
Reactant balance
Consider the system to be a small section of the reactor located between z and z + &. The general unsteady-state
mass-balance equation is Eq. (6.5). The rate ofentry of reactant into the system is:
Mj
= CAuAl
where
means that the parameter values are those at distance
which reactant leaves the system is:
Mo =
CAuAI
,+<\,
Reactant is not generated; therefore RO = O. The rate of consumption of reactant is given by the equation:
Rc=rcV:=rc A &
where A ilz is the volume of the system and rc is the volumetric rate of reaction. At steady state there is no
accumulation in the system and dM/dt = O. Substituting these expressions into Eq. (6.5) gives:
0= CAuAlz-CAuAlz+hz-rcA&;
As A is constant and does notdepend on z, it can be cancelled from each of the terms:
0= CAulz-CAulz+&-rcAz
Dividing through by A.<;:
Taking the limit as Llz approaches zero and applying the definition of the derivative (0.13) in Appendix D:
-d(eA u)
0= '"--az--rC
or
d(CA u)
dz
= -rC
As the fluid velocity is constant throughout the reactor, u can be taken outside of the differential:
Solutions: Chapter 6
66
dCA
Answer: u liZ
"" -rC
(b)
As
u and kl are constants, the differential equation contains only two variables, CA and z. Separating variables and
integrating:
dCA
CA
= -k) dz
U
f
f
dCA ""
CA
-k) dz
U
Using integration rules (D.2?) and (D.24) from Appendix D and combining the constants of integration:
InCA
-k)
= -z+K
U
From the initial condition in (b), at z = 0, In CAi =: K. Substituting this value of K into the equation gives:
CA
-kl
1n-=-z
CN
CA
=:
CAi e(-k,lu) z
(d)
The equation derived in (c) is directly analogous to the equation for change. in reactant concentration in a batch
reactor. As z "" u t where t is the time taken for the fluid to travel distance z. the above equation can be written as:
CA "" CAie""*lt
which is the same as the equation for reactant concentration in a batch reactor where CAi is the concentration at time
zero.
Answer: Essentially identical
6.9
Boiling water
67
Solutions: Chapter 6
(ii)
Extra data
Density of water = 1 kg I-I
Cp water = 75.4 J gmol-1 "'C-l (fable B.3, Appendix B) = 75.4 kJ kgmol-l "'C-l
Molecular weight of water (fable B.l, Appendix B) 18.0
1 W = 1 J s-l (fable A.8, Appendix A); therefore, 1 kW = 1 kJ sl
(iii)
Boundary conditions
Att=O,T=TO=18C
(a)
The general unsteady-state energy-balance equation is Eq. (6.10). For a batch system, Mi = Mo =0; also Ws = O.
Energy is accumulated by the system in the fonn of sensible beat only; therefore:
dE
<IT
(jJ=MCpdt
where M is the mass of water in the beaker and T is its temperature. Substituting these expressions into Eq. (6.10)
gives:
dT
MC
=-Q
Pdt
dT
Answer: M Cp dt = -Q
(b)
If Q, Cp and M are constant, T and t are the only variables in the differential equation. Separating variables and
integrating:
Using integration rule (D,24) from Appendix D and combining the constants of integration:
T=
From the initial condition for T, at t= 0, To
=K.
-Q
MCp
t+K
-12
T= MC t+To
p
t- 1, the mass of 2 litres of water M= 2 kg. Converting the Cp for water to mass
1
1
Cp = 75.4kJ kgmor "'C- .1
T
-Q
2kg 4.189kJkg
1=
Q = -62.45kJmin-
~::~11
-62.45kJmin-
"'e-
From the sign conventions outlined on pp 87-88, the negative value for
Answer: L04 kW
68
6.10
Solutions: Chapter 6
The system is the stirred tank containing the solution of glycerol in water.
(i)
Assumptions
-no leaks
- no evaporation
- tank is well mixed
- no shaft work
- heat capacities are independent of temperature between 15<>C and 90"C
- ideal solution
- system is adiabatic; therefore heat losses are negligible
(ii)
Extra data
Cp glycerol = 0.576 cal g-t C- l (Table B.s, Appendix B) = 0.576 keal kg-I "C- 1
Cp water = 75.4 J gmol-l C- l (Table B.3, Appendix B) = 75.4 kJ kgmol-l C- 1
Molecular weight of water (Table B.I, Appendix B) "" 18.0
1 kcal "" 4.187 x 103 J (Table A.7, Appendix A) = 4.187 k1
1 W =1 J s-1 (Table A.S, Appendix A); therefore, 1 kW = 1 kJ 5- 1
(iii)
Boundary conditions
Att=O,T=To=15"C
(a)
The general unsteady-state energy-balance equation is Eq. (6.10). For a batch system, Mj =Mo 0; also Ws = O.
Energy is accumulated by the system in the form of sensible heat only; therefore:
dE=MC dT
dt
Pdt
where M is the mass of glycerol solution in the tank and T is its temperature, Substituting these expressions into Eq,
(6.10) gives:
M has two components, glycerol and water, which have different heat capacities. Therefore, this equation can be
written:
where Mw is the mass of water in the tank, MO is the mass of glycerol, CpW is the heat capacity of water, and CpO is
the heat capacity of glyceroL
<IT
Answero(MWCpW+MOCpG)"dI =-Q
(b)
If
ii,
Mo are constant, T and t are the only variables in the differential equation. Separating
Using integration rule (0.24) from Appendix D and combining the constants of integration:
T=
-0.
t+K
(MwCpW+MGCpG)
From the initial condition for T, at t= 0, To:: K. Substituting this value of K into the equation gives:
69
Solutions: Chapter 6
Answer: T
-12
= (MwCpw+MOCpG) t+ To
(c)
The mass of glycerol in the tank MO = 4S kg; the mass of water Mw
terms:
Cpw = 7SAkJkgmor l
<)c-l',111~~~11
=55 kg.
The rate of heat input to the system is 0.88 x 2.5 kW "'" 2.2 kW "'" 2,2 kJ s-l.From the sign conventions outlined on pp
87-88, Q must be negative as heat is added to the system; therefore, Q"'" -2.2 kJ s-l. Substituting the parameter
values into the equation for Twith To 15<)C and T= 90<)C:
9O"C "'"
1
2.2kJst+ 15"C
55kg(4.189kJkg loC l)+45kg(2.412kJkg loe 1)
t
Answer: 3.2 h
6.11
Heating molasses
(i)
Flow sheet and system boundary
These are shown in the figure below.
System boundary~
- - -
-- -
I
I
Molasses solution in
1020 kg h- 1
20'C
1
I
I
Heating tank
I
I
I
/
- --
M
T
- - -
I
I
I
- -
-Q (from steam)
(ii)
Assumptions
- no leaks
- no evaporation
- tank is well mixed; therefore the temperature of the molasses solution out is the same as in the tank
- no shaft work
- beat capacity is independent of temperature
- negligible heat losses
70
Solutions: Chapter 6
(iii)
40psi
= 40PSi.16.8;;~al
= 275.8kPa
The temperature of saturated steam at 275.8 kPa interpolated from Table C.2 (Appendix C) "" l30.7e.
(v)
Boundary conditions
"
Att=O, T=To=20C
(vi)
'Total mass balance
As the mass flow rates into and out of the tank are the same, the mass of molasses solution in the tank M is constant
The general unsteady-state energy-balance equation is Eq~ (6.10). From the reference state, hi = 0; The value of h o
relative to the reference state is equal to the sensible heat-absorbed by the molasses'solution between Tref and the exit
temperature T. From Eq. (5.13):
ho
Ws = O.
= ~ = Cp(T-Tref)
The rate at which the molasses solution is heated is given by the equation:
Q = -U A (Tsteam -1)
From the sign conventions outlined on pp 87-88, Q must be negative as heat is added to the system. Energy is
accumulated in the form of sensible heat only; therefore:
dE=MC dT
<It
P <It
dT
dT
Answer: dt
(b)
As U, A, Tsteam, Mo. Cp Tref and M are all constant, Tand t are the only variables in the differential equation derived
in (a). Substituting the known numerical values for the parameters:
dT _ 190kcal m-2 .-1 0C- (1.5 m2) (130.7'C) + 1020 kg .-1 (0.85 kCalkg-1 oC- ) (20"C)
'
'
<It 5000kg(0.85kcalkg lo C 1)
_(1020 kg .-1 (0.85 kcal kg- 1 oC- ) + 190 kcalm-2 .-1 oC' (l.5 m 2)) T
'
5000kg(0.85kcalkg loC 1)
dT
dt
= 12.84-0.271 T
where T has units C and t has units h. Separating variables and integrating:
71
Solutions: Chapter 6
= eIt
dT
12.84-0.271 T
dT
-felt
12.84-0.271 T -
Using integration rules (D.28) and (D.24) from Appendix D and combining the constants of integration:
-1
0.271 In (12.84-0.2711)
= t+ K
-I
0.271In(l2.84-0.2711)+7.395
-I
Answer: 0.271 In (12.84- 0.2711) + 7.395 =
=t
(c)
Values of t corresponding to various temperatures in the tank can be calculated from the equation derived in (b).
Time, t
Temperature, T
CC)
(h)
20
0.00
25
0.74
1.68
2.93
4.84
9.01
11.0
15.8
21.5
30
35
40
45
46
47
47.3
r----,----,----,,----,-----,
10
15
Time (h)
20
25
Solutions: Chapter 6
72
(d)
From the equation derived in (b), as the logarithm of zero and negative numbers is not defined (p 413), the theoretical
maximum temperature that can be achieved in the tank occurs when 12.84 - 0.271 T= 0; Le. when T= 47.4C.
(e)
'The temperature cbanges constantly with time; therefore, strictly speaking, there is no steady state. For practical
purposes, however, the temperature approaches a constant value after about 16 h.
Answer. About 16 b
(f)
From the calculation table in (c), the temperature reaches 40C after 4.84 h.
Answer: 4.84 h-
6.12
(li)
Extra data
Cp glass vessel"" 0.20 cal g-l 0C- l "" 0.20 keal kg-I oct
Cp medium"" 0,92 cal g-l C l "" 0.92 keal kg-loCi
(ill)
Boundary conditions
Att=O,T=To=15C
(iv)
Energy balance
The general unsteady-state energybalance equation is Eq. (6.10). For a batch system., Mi = Mo = 0; also Ws =0.
Energy is accumulated by the system in the form of sensible heat only; therefore:
dE
dT
dt =MCpdt
M has two components, the glass vessel and the medium, which have different heat capacities. Therefore, this
equation can be written:
where My is the mass of the glass vessel, MM is the mass of the medium, Cpy is the heat capacity of the vessel, and
CpM is the heat capacity of the medium. Substituting into Eq. (6.10) gives:
dT
(MyCpy+MMCpM) dt =-Q
As (i, Cpy, CpM, My and MM are constant, T and t are the only variables in the differential equation. Separating
variables and integrating:
dT=
-Q
dt
f dT-f
-
-Q
dt
Using integration rule (D.24) from Appendix D and combining the constants of integration:
73
Solutions: Chapter 6
-Q
T=
From the initial condition for T, at t= 0, To
=K.
t+K
T=
-Q
t+To
The rate of heat input to the system is 450 W. Converting this to kcaI min-l:
Q = -450W
Co
From the sign conventions outlined on pp 87-88, Q must be negative as heat is added to the system. Substituting this'
and the other parameter values into the equation for Twith To = 15C and T= 36C:
36'C
l
6.45 kcal mint+ 150C
12.75 kg (0.20 kcal kg-I 'C- I) + 7.5 kg (O.92kcal kg-I 'C- I)
t
= 30.8 min
6.13
Water heater
dE
dt
dT
= MCPdt
where Mis the mass of water in the tank and Tis its temperature. Substituting these expressions into Eq. (6.10) gives:
dT
MCpdi=-Q
(aj
There are two components to
Q: the rate of heating from the steam, and the rate of heat loss to the surrounding air:
Q = UtAt (T-Tair)-UZAz(Tsteam -1)
This equation reflects the sign conventions outlined on pp 87-88: the term for the heat loss to the atmosphere is
positive to indicate heat removal from the system, while the term for heat input from the steam is negative.
Substituting into Eq. (6.10) gives:
Solutions: Chapter 6
74
MC dT
Pdt
dT
Cit
MCp
As Vt. A 1> Uz. AZ, T steam, Yair, Cp and M are all constant, T and t are the only variables in the differential equation.
Substituting the known parameter values:
dT
220 kcal m-2 h- I 0c- l (03 m 2)(130-1)C _ 25 kcal m-2 h- I 0C-l (O.9m 2) (T - 20Y'C
( - 1 "'C-1 . 1118.0kg
kgmOllllkCai
. 4.187k:JU
dt
lOOOkg 75.4kJkgmol
dT
dt = 9.026-0.088 T
where T has units of"C and t has units of h. Separating variables and integrating:
dT
9.026 - 0.088 T
f 9.026~.088T
=dt
dt
Using integration rules (0.28) and (D.24) from Appendix D and combining the constants of integration:
0~81n(9.026-0.0881) = '+K
From the initial condition for T. at t= 0:
-I
Applying the numerical value of To =24"C, K = -21.97. Substituting this value for K into the equation gives:
-1
dT
Cit
dt
= -1-000-'k=g7(7'=S=.4"'kJ=-k-'gm=-OI--I"'o-c--"'1'11'i~';;;=~=k0:i;TI'I"',/':/i::8~::C~"-;;:~
dT
dt
= 8.576 - 0.066 T
where Thas units of "C and t has units ofh. Separating variables and integrating:
75
Solutions: Chapter 6
dT
= <It
8.576- 0.066 T
8.576
~.066 T = f <It
Using integration rules (0.28) and (D.24) from Appendix D and combining the constants of integration:
-1
0.066 In (8.576-0.0661)
= t+K
-1
Applying the numerical value of To =24C, K =-29.47. Substituting this value for K into the equation gives:
-1
0.066 In (8.576-0.0661) + 29.47
=t
From this equation, for T = 80C, t "'" 11.4 h, Therefore, from (a), the time saved is (14,2..:,- 11.4) h"'" 2.& h, which
corresponds to 20% of the time required when heat losses occur.
Answer:
(a)
...---r---,---,,--,.----r---,
600
600
400
300
200
100
ol-_...L_......l._---''-_-'-_....L_--'
o
200
400
600
800
1000
1200
The rheogram in (a) is similar to those for pseudoplastic and Casson plastic fluids in Figure 7.7. It is not clear from
0 or not; therefore. both non-Newtonian models are worth
the rheogram whether the fluid exhibits a yield stress at
checking. From the equation in Figure 7.7 for pseudoplastic fluids, a plot of shear stress versus shear rate on log-log
r=
coordinates would be expected to give a straight line. This plot is shown below.
100
1000
10000
Solutions: Chapter 7
77
'1:=
The equation for the straight line in the plot is liZ =. 5.93 + 0.648 ytl2.. From the equation in Figure 7.7, this means that
K p = 0.648 dyn 11z Sllz cm- l and the yield stress 't{) = 35.2 dyn cm- 2. The sum of squares of the residuals for this data
fit is 8986.
Comparison of the residuals from the two models suggests that the equation for a pseudoplastic fluid is the better fit
Answer. Pseudoplastic fluid: n = 0.587; K = 11.43 dyn sn cm- 2
(e)
The apparent viscosity for a pseudoplastic fluid is given by Eq. (7.8) and can be calculated using the parameter values
determined in (b).
(I)
J1a
7.2
From Eq. (7.8), for pseudoplastic fluids, a plot of apparent viscosity versus shear rate on log-log coordinates can be
expected to give a straight line. Log-log plots for the different cell concentrations are shown below.
78
Solutions: Chapter 7
10
Cen concentrations:
.1.5%
03%
D 6%
0::-
..
10.5%
t3-
"
1
1
10
100
100
Cell concentration: 12%
0::-
..
!l
10
1
10
100
1000
Cell concentration: 18%
0::-
..
~
.~ 100 ~
E
....
...
10
1
10
Shear rate (sl)
100
Solutions: Chapter 7
79
10
Shear rate (5- 1)
100
The equations and parameter values for the straight lines in each plot are listed below.
Cell concentration (%)
Equation
I', = 1.5
1.5
Consistency index, K
(cp sn-l)
r0 = 1.5
1.5
1',=2.0r =2.0
Pa = 2.91 r-:O,050
2.0
0.95
2.9
10.5
I', = 5.38
<>.07.
0.92
5.4
12
0.61
18
21
0.75
3
6
r..
50
0.69
1.4,--,.---..--....--"..---.....
index, n
Flow behaviour
~. -"
5
!
!
Consistency, index, K
1.2
1.0
0.8
10
0.6
0.4 '--_ _..J....._ _.....J.._ _- ' ' -_ _- ' -_ _.....Il
10
15
Cell concentration ('Yo)
20
25
Solutions: Chapter 7
80
The cell broth is Newtonian up to a cell concentration of about 2%, then becomes pseudoplastic. The flow behaviour
index continues to decrease until a cell concentration of about 12% is reached. The consistency index rises
!broughout the culture with increasing cell concentration.
7.3
Impeller viscometer
(a)
If the rheology can be described using a power~law model, a plot of shear stress versus shear rate on log-log
coordinates can be expected to give a straight line. Values of shear stress and shear rate can be determined from
torque and stirrer speed data using Eqs (7.11) and (7.12) with k =10,1 and Dj, "'" 4 em "'" 4 x 1<r2 m. The results are
Torque (Nm)
Shear stress (N m- 2)
0.185
0.163
0.126
0.111
3.57 x
3.45 x 10-6
3.31 x 10-6
3.20 x 10.6
0.0559
0.0540
0.0518
0.0501
1.89
1.66
1.29
1.13
0.07
0.06
0.05
11~
"m"
0.04
<J)
0.03'1
..L...
1.5
-'
The equation for the straight line on the log-log plot is 1'=O,049jr20. From Eq. (7.7), this means that the flow
behaviour index n is 0.20 and the consistency index K is 0.049 N sn m- 2.
N'~ D' P
Rei
= ~1 ~ = -->=="(r'---"==-"IC"':""-"'-:"O,,, = 10,0
10.20.20-1 0.049NsO.20m-2. lk~~S-
This value for Rei is at the upper limit of the laminar range (p 137); therefore, we can conclude that flow at this and
lower stirrer speeds is laminar.
Solutions: Chapter 7
81
(oj
From Table 7.4, k = 30 for a helical-ribbon impeller. From Figure 7.25, flow with this type of impeller is laminar up
to about Rei = 103. These conditions allow use of higher stirrer speeds within the laminar region than is possible
using a turbine impeller. Solving for Ni from Eq. (7.23) and substituting values of n and Kfor the fluid from (a), the
maximwn stirrer speed at Rej = 30 can be calculated as:
N?--n
= Rei ~1 K
!if..".20 =
vf P
-21
1 kgms-2 ~
1N
II
(0.04m)21000kgm 3
Nl- 8= 2.02s-1.8
Ni = 1.48 s-l
r=
7.4
The Zwietering equation is an equation in numerics (p 12); therefore, the parameter values used in the equation must
have the units specified. V p =10 J.llll =10 xlo-6 m; g =9.8 m s~2 (p 16); Vj =30 em =0.3 m; PL =density of water =
1000 kg m- 3 . The dynamic viscosity of water J4... at 20"C is about 1 cP (p 133); from Table A.9 (Appendix A), this is
the same as J4... = 1O~3 kg m- I s~I. Using the definition of .kinematic viscosity from p 133:
VL
f.lL
10-3 kgm- 1 8-1
=-=
=10-u m2 s-1
PI.
lOOOkgm-3
This minimum stirrer speed for suspension of the cells can be compared with the minimum stirrer speed for dispersion
of air bubbles. Taking the average minimum tip speed of 2.0 m s-1 for bubble dispersion:
N
1
1t (0.3
m)
The stirrer speed for air dispersion is 3.7 times higher than for ceIl suspension. As power in the turbulent regime is
proportional to the stirrer speed cubed, about 50 times more power is required to disperse the air bubbles than to keep
the cells in suspension.
Answer: Bubble dispersion requires significantly more power than cell suspension.
Solutions: Chapter 7
82
7.s
(aJ
The Reynolds number for a Newtonian fluid in a stirred vessel is defined in Eq. (7.2). Using this equation to evaluate
the maximum viscosity jJ. under turbulent conditions with the density of water p= 1000 kg m- 3:
I.t
D~ P
1 I
.1
Rei
) 1000 kg m-3
.11001m1
em
104
-1 s
-1.
33 10-3kg m
J.l=.x
3
10 cP
l l = '33
cP
1kgm- s-
Answer: 3.3 cP
(bJ
The tip speed in the laboratory equipment is:
Tipspeed = 7tNj Di
= 1 (800min-1 -I 16:
sD
8-
In the large-scale vessel. Di =15 x 5 em =75 em. If the tip speed is kept the same after scale-up:
M.
tip speed _
_
1tDj
'" _
(
1t
75cm.l lOocm
_ 089 -1
) _ .
JJ.=
Rei
.em
10
=O,05kgm- l s- 1
Converting to cP:
= 50cP
Answer: Scale-up increases the maximum viscosity for turbulent conditions to 50 cP.
7.6
(aJ
Dj
(1)
The viscosity Of water at 20"C is about 1 cP (p 133); from Table A.9 (Appendix A), this is the same as lO-3 kg m- 1
s-l. Substituting parameter values into Eq.(7.2):
NiDrp
Rei
Ji
(90min-I116~sn~(lm)21000kgm-3
lO
11
kgm- C
6
1.5 x 10
From Figure 7.24 for a Rushton turbine, this value of Rei corresponds to turbulent flow and
The power required is evaluated using Eq. (720):
P =
NppNf Dr = 5.8 (lOOOkg m-3)(90 min- I .II:sn~3 (l m)5 = 1.96x 104 kg m2 s-3
83
Solutions: Chapter 7
From Table A8 (Appendix A), 1 W =I kg m 2 s-3; therefore:
P = L96xl04w
= 19.6kW
Answer: 19.6 kW
(ti)
Ret' =
(90min-
.11~n~(1 m)21000kgm-3
0.1 kgm- s-
4
= 1.5 x 10
From Figure 7.24 for a Rushton turbine, this value of Rei is still within theturbulent regime so that Np isagain5.8.
Therefore, the power required is the same as that calculated in (i): P =19.6 kW.
Answer: 19.6 kW
(iii)
J.l
(90 min=
=1~
From Figure 7.24 for a Rushton turbine, this value of Rei is within the transition regime. Np read from Figure 7,24 is,
about 3.5. The power required is evaluated using Eq. (7.18):
.! 16~n~3
Answer: 11.8 kW
(b)
From Figure 7.24 for a Rushton turbine, turbulence with Np =5.8 is achieved at a minimum Reynolds number of
about 104. For a viscosity of 1000 x 10-3 kg m- 1 s-1 = 1kg m- 1 s-l, the stirrer speed required can be detennined from
Eq. (7.2),
84
7.7
Solutions: Chapter 7
Di =- 7 em =- 0.07 m; p =- 1000 kg m~3. The viscosity of water at 20C is about I cP (p 133); from Table A.9
(Appendix A), this is the same as 10.3 kg m- 1 8. 1, Substituting parameter values into Eq. (7.2):
Rei =
2
NiDi P
--'-cC:-C- =
J.l.
From Figure 7.24 for a Rushton turbine, this value of Rei corresponds to turbulent flow and N~ can be taken as 5.8.
The power required is evaluated using Eq. (7.20):
p
= 32.9kgm2 s-3
Answer: 32.9 W; a significant fraction of the electrical power is dissipated as beat within the motor housing
7.8
Di = 0,67 m; p = density of water = 1000 kg m- 3. From TableA.9 (Appendix A). I cP = 10.3 kg mol s-l; therefore. Jl
= 4 cP = 4 x 10,3 kg m~I s'l. For a cylindrical tank of diameter Dr= 2 m and height H= 2m. the volume Vis:
(aJ
If the maximum specific power consumption is 1.5 kW m'3. the maximum power Pis:
P = (L5kWm-3)6.28m3 = 9.42kW
From Table A.8 (Appendix A), I W = I kg m 2 s'3; therefore 1 kW = 1000 kg m2 s-3. ConvertingP to kg m 2 s3:
P = 9.42kW =
Assume for now that the fluid flow is turbulent and Np = 5.8. The stirrer speed can be evaluated using Eq. (7.20):
N:=
,
NppDi
=~42xI03kgm2s-3
=120s-3
.
Check that this stirrer speed provides turbulent mixing conditions by evaluating the Reynolds number. Rei for
Newtonian fluids in a stirred vessel is defined in Eq. (7.2):
Rei = NiDf P = (2.29s-l)(O.67m)21000kgm-3 = 2.6x 105
j.l
4 x 10 3 kg m- I s 1
From Figure 7.24 for a Rushton turbine. this value of Rei is well into the turbulent regime; therefore the value for ~
assumed above is valid.
For high Rei> the mixing time can be calculated using Eq. (7.16):
85
Solutions: Chapter 7
= 1.54 V = 1.54(6.28m')
Nj
(O.67m)3 2.29S-1
D;
= 14s
Answer: The maximum allowable stirrer speed is 2.29 s-1 or 137 rpm; the mixing time is 14 s.
(b)
The ungassed power number was 5.8; therefore, the power number with gassing (Np)g =0.5 x 5.8 = 2.9. The stirrer
speed which delivers the maximum power P= 9.42 x 103 kg m2 s-3 can be evaluated using Eq. (7.18):
Nt =
(Np) pD;
g
3
2 3
9,42x10 kgm s- 241 -3
2.9(lOOOkgm-'j(O.67m)5 . s
= !541' =
DfN
1.54(6.28m')
(O.67m)3 2 .89s-1
= II s
Answer: The maximum allowable stirrer speed is 2.89 s-1 or 173 rpm; the mixing time is 11 s.
Heat Transfer
8.1
Rate of condnction
(a)
B::::: 15 em "" 0.15 m; liT"", qoo -.80) ::::: 620"C. which is equal to 620 K as temperature differences are the same on the
Celsius and Kelvin scales (p 18). The rate of heat conduction can be calculated using Eq. (8.10):
a.15m
Answer: 1.86 kW
(b)
In this case there are two thermal resistances in series. Their magnitudes are calculated using Eq. (8.15). For the
firebrick:
a.04m
(o,tWm lK 1)1.5m2
k2A
::::: O.27KW-1
~ Therefore, the total wall resistance RW= RI + RZ ::::: (0.33 + 0.27) K W~ I ::::: 0.60 K W~l, For thennal resistances in
series, the rate of heat conduction is calculated using Eq. (8.14):
Q=
I1T =
Rw
620K
= 1033W= 1.03kW
O.60KVI
Answer: 1.03 kW
8.2
The overall heaNransfer coefficient is calculated using Eq. (8.24) with hfh::::: 830 W m~2 K-I, hh::::: 1.2 kW m 2 K-I, B
=6mm::::: 0.006 m, k= 19 Wm,l K-l, he"" 1.7 kWm w2 K-l and hfc= O.
1
lIB
1
1
- = -+-+-+-+U
1. =
U
1
830Wm 2r-
hfh
hh
1.2kWm-2r-1.ll~:1
he
hfc
O.OO6m
19Wm IK-
1.7kwm-2K'"1.11~:1
+0
87
Solutions: Chapter 8
8.3
(a)
The mean temperature difference between the fermentation fluid and the cooling water is calculated from Eq. (8.35):
/iTA:
2 Tp-(Tct+Tco)
(2 x 35)OC-(S + 151'C
2
:
2
: 23.5OC
Answer. 23.5"C
(c)
U A is evaluated using Eq. (8.19) with /iT: /iTA:
UA
ATA
kJ s-l
= 14.6
23.5"<:
(d)
Applying Eq. (8.19) to determine /iT: /iTA for the new coil:
!iTA :
-iL
:
U A'
1
14.6 kJ s1
0.93 kJ s-l C
= 15.7"<:
The new cooling water outlet temperature Tco is determined using Eq. (8.35):
Answer: 30.6"C
(f)
M -
-I
14.6kJ,
_ 015k -I
c - C",(Tco-Tct) - 4.18kJkg-IoC I(30.6- Sl'C - .
gs
Therefore, installation of the new coil allows a 70% reduction in cooling-water requirements;
Answer: 70%
8.4
Ni: 80 rpm 80'60 1.33 sl. Cp culture fluid 4.2 kJ kg l c l : 4.2 x 1()3 J kg'} "c l . Cpc Cp water 75.4 J
gmol'} "C- I (Table B.3, Appendix B) 75.4 kJ kgmol-l "C- l . Converting Cpc ta a mass basis using the molecular
weight af water 18.0 (Table B.I. Appendix B):
Cpc
: 75.4kJkgmor l
"c-I.1 ~~~ll
10.3 N s m 2; from Table A.9 (Appendix A), I N sm2 =} kg m l s-l; therefore Jlb = 10-3 kgm- l sl. ktb = 0.6
W mol "e l ; from Table A.8 (Appendix A), 1 W = 1 J sl; therefore k fb 0.6 J 8"1 m- l "C-l. B: 6 mm;:: 0.006 m.
,llb;::
Solutions: Chapter 8
88
From p 97, as the heat of reaction for an exothermic reaction is negative, Aiirxn =-2500kW. From the modified
energy-balance equation, Eq. (8.33), when evaporation and shaft work can be neglected. Q=-Mrxn =2500 kW =2.5
x 106 W, According to the sign conventions on pp 88-89, Q positive is consistent with heat being removed from the
system. From Table A.8 (Appendix A), 1 W
(a)
The fermenter-side heat-transfer coefficient can be evaluated using the empirical correlation, Eq. (8A5). The
dimensionless nwnbers in this equation are Rei, Pr and Nu. Rei is given by Eq. (8.39):
Nu
h=--=
D
Therefore, as the fennenter fluid is the hot fluid, hh = 2.4 x 103 W m-2 e 1.
1- = .!.+~ =
V
hh
1
2AxI03Wm 20(;"1
U = L40x
O.OO6m
= 7.17xlO-4W-1mZoC
20Wm-1OC 1
103 wm-Zoe 1 =
1.40kWm-20e l
From Eqs (8.21) and (8.22), the beat-transfer resistance due to the pipe wall is B/k A; from Eq. (8.20), the total
resistance to beat transfer is l/Vk Therefore, the proportion of tbetotalresistance,duetothe-pipe wallis:
Answer: lAO kW m- 2 C- 1. The pipe wall contributes 42% of the total resistance to heat transfer.
(c)
The energy-balance equation for the cooling water, Eq. (8.32), relates the cooling water flow rate, the inlet and outlet
temperatures and the rate of heat transfer. From this equation, an expression for the outlet cooling-water temperature
is:
89
Solutions: Chapter8
where Tco has units of C and Me has units of kg b 1. An expression for the mean temperature difference between the
fermentation fluid and the cooling water can be determined from Eq. (8.35);
_ 2 Tp-(Tci + Teo} _ (lx30)OC-(1O+Tco}OC _ 6O"C-10"C-Tco _
Teo
ATA 2
2
2
- 25- 2
where !!TA and Teo have units of C. Substituting this expression into Eq. (8.19) for evaluation of A with AT= ATA
and the value of Ufrom (b);
=~ =
U!1TA
2500kW
1.40kWm-Zoc-1(25_
T;'fe
= 1.8x 103
25-
T~
where A has units of mZand .Teo has units of C. The above equations for Teo and A allow evaluation of these
parameters as a function of Me' The results for several values of Me between 1.2 x loS kg b 1 and 2 x 106 kg b 1 are
listed and plotted below.
M,(kgb- I )
Tco (0C)
A (m 2)
1.2 x loS
2.0xloS
3.0x loS
4.0x loS
8.0x loS
1.0 x 106
2.0 x J(j6
27.9
20.8
17.2
15.4
12.7
12.2
ILl
163
123
1I0
104
97
95
93
30,.....---..,.,.....---.,..-----.,..-.----,200
41
Temperature
o Area
o'o
J-
-'-
10
...J''--_ _--' 50
15
Me
20
x 1Q-5 (kg h 1)
(d)
From the,equations developed in (c), at a cooling.water flow rate of 5 x loS kg h*l, Teo 14.3C and A = 101 .tn.2.
The area A of a cylindrical coolingcoil is equal to 2 1t r L, where r is the cylinder radius and L is its length. For a
radius of 5 em 0.05 m:
101 m 2
= 21tr = 21t(0.05m)
= 321 m
Answer: 321 m. This is a long coolingcoil, representing a considerable expeme whenfabricatedfrom stainless steel.
90
Solutions: Chapter 8
8.5
(a)
Cpc Cp water = 75.4 J groat-! 0C"l (Table B.3, Appendix B):o 75.4 kJ kgmo}l C~l, Converting to mass terms
using the molecular weight of water = 18.0 (Table B.I. Appendix B):
Cpc
'c-ll i~~11 =
l
I
4,19kJ kg- 'C-
From Eq. (8.32), the rate of heat removal to the cooling water before cleaning is:
Q = McCpc(Tco-Tci)
The meantemperatute difference between the fennentation fluid and the cooling water can be calculated from Eq.
(835),
LiTA
2 Tp-(Tci + Tco)
2
(2 x 37)'C-(12 + 2S)'C
2
= 17'C
The area A ofthe cylindrical cooling~coi1 is equal to 2 1t r L, where r is the cylinder radius and L is its length, For r=
= 2 1t (0.06 m) (150 m)
:0
56.5 m 2
Evaluating the overall heat-transfer coefficient U from Eq. (8.19) with aT aTA:
-
- 1340.8kJs- -140kJ
-1 -Z'C-1
- -Q- U sm
ALiTA
(565m2)I7'C
'
(b)
If the fermentation temperature is maintained the same after cleaning the cooling-coil, the rates of heat removal Q
before and after cleaning must be equal. The new outlet cooling~water temperature can be calculated from Eq. (8.32):
+ 120C = 36.6OC
1340.8kJ s-1
13kgs-I(4,19kJkg-l,C I)
(e)
.The mean temperature difference between the fermentation fluid and the cooling water after cleaning is detennined
from Eq, (835),
1J.TA
2 TF-(Tci + Too)
2
= _.
= 12.7OC
The beat-transfer area is the same as before cleaning: A = 56.5 m2 . Evaluating Ufrom Eq. (8.19) with AT= tiTA:
=~ =
ALiTA
1340.8kJs-
= 1.87kJs-1m-20c-1
RT = _1_
UA
= 9.46 X 10..,3.k]""1 s 0C
This is the beat-transfer resistance after cleaning the cooling coil. 'The resistance before cleaning is calculated from
Eg. (8.20) using the value of U from (a):
91
Solutions: Chapter 8
The resistance due to the fouling deposits is equal to the difference between these two overall resistances
10-2 _ 9.46 x 10"3) = 3.14 x 10-3 kJ- I s 0c. Therefore, fouling contributes:
3.14x 1O-3 kr 1 soC
==~=:T'-:'::
L26x 10 2 kri soC
=:
(1.26 x
= 0.25
Answer. 0.25
8.6
Cph =: Cpc =: Cp water =: 75.4 J gmol"l C l (Table 8,3, Appendix B) 75.4 kJkgmot l C l . Converting to mass
terms using the molecular weight of water = IS.O(Table B.I, Appendix B):
Cph
=:
75.4kJkgmorl OC-1
.1 ;;~~ll
= 4.19kJkg- 1 C-1
P medium =: p water =: 1000 kg m"3. The viscosity of water at 20C is about 1 cP (p 133); from Table A.9 (Appendix
A), this is the same as 10"3 kgm- I s-l; therefore,,u medium =:,u water =: H}"'"3 kg m-I s-l. kfb medium = 0.54 W m- 1
C-1; from Table A.S (Appendix A), this is the same as 0.541 5""1 m~l 0C- 1.;tberefore, kfb medium =: 0.54 x 10-3 kJ
s-l m- 1 C l . From Table S.l, kfb water at 303 K= 0.62 Wm- 1 C-l;from Table AS-{A-ppendix A), this is the same
as 0.62 J s-l mol C-1; therefore, ktb water =0.62 x 10-3 kJ 5- 1 ar 1 0C- I . From Eq. (2.24), 303 K =: approx. 30C,
which is close enough to the conditions in the heat exchanger for evaluation of thermal conductivity. k pipe wall = 50
W mol C-I; from Table A.8 (Appendix A), this is the same as 50 J s-l mol C-l; therefore, k = 50 x 10..3 kJ s-l m- l
C l . B =: 5 mID =: 0.005 m.
(al
From the definition of density (P-16), the mass flow rate of the medium is equal to the volumetric flow rate multiplied
by the density:
The steady-state energy-balance equation for medium in the tubes of the heat exchanger is Eq. (8.32); therefore:
The heat-transfer coefficient for the medium in the tubes of the heat exchanger can be calculated using the empirical
correlation, Eq. (8.42). The parameters in this equation are Re, Pr and Nu. Re is given by Eq. (8.38). The linear
velocity of the fluid u is equal to the volumetric fIowrate per tube divided bythecross.sectional area of the tube. The
cross-sectional area ofa cylindrical tube =: 1,.z where ris the tube radius = 25 cm =: 0.025m. Therefore:
=:
50
volumetricflowrate
=:
numberoftube,(n?)
3 h-1
I~I
. 3600s
=:
0.236ms-1
=5 cm =0.05 m:
3
Re = Dup = 0.05m(0.236m,-I)IOOOkgm- = 1.18 x 104
Substituting parameter values into Eq. (8.38) with the tube diameter D
JIb
1O-3 kgm Is 1
This value of Re is within the range of validity of Eq. (8.42). Pr is given by Eq. (8.40):
0.54x1O-3kJs-1m-1oC I
This value of Pris also within the range of validity ofEq. (S.42). From Eq. (8.42):
Solutions: Chapter 8
92
= 94.6
The heat-transfer coefficient for the water flowing in the shell of the heat exchanger can be calculated using the
empirical correlation, Eq. (8.44). The parameters in this equation are C, Remax, Prand Nu. As the tubes of the heat
exchanger are arranged in line, from p 183. C 0.26. Remax is given by Eq. (8.38) with D equal to the outer tube
diameterdetennined as the sum of the inner tube. diameter and the pipe wall thicknesses: D = 0.05 m + 2 x 0.005 m
0.06 m. Substituting parameter values into Eq. (8.38):
Re
max
10-3 kg m- l s-1
fib
As this value is > 6 x UP, Remax is within the range of validity of Eq. (8.44). Prior theshellside water is given by
Eq. (8.40):
From the definition of Nu in Eq. (8.37) with D the outside tube diameter:
Nukfb
=-D- =
O.06m
= 1.19kJs-
m- "C-
As water is the hot fluid in this heat exchange system, hb = 1.19 kJ 5- 1 m- 2 "C-l.
(e)
The overall heat-transfer coefficient without fouling factors is calculated using Eq. (8.23);
~ = 1.92kJ1 sm 2 C
U
(d)
The outlet temperature of the water from the shell is detennined from Eq. (8.31):
- ~.
.Lho - .Lbl -
.....
MhCph
-- 60~
~
1048.3kJs-
3x
= 30~
104kgh-l.13~sl{4.19kJkg-loc-l)
The fluid flow directions and the inlet and outlet temperatures for a single~pass countercurrent shell-and-tube heat
exchanger are represented graphically below.
Solutions: Chapter 8
93
j60 C
0
Tei
=- 10"C
Teo
/'
=- 28<>C
Heat exchanger
Tho=-30"C
The temperature differences at the two ends of the exchanger are fl.Tl =- (30 - to) ::::: 20"C and /1T2 ::::: (60 - 28) ::::: 32"C.
Substituting these values into Eq. (8.34) for the log-mean temperature difference:
<IT. = LlTZ-LlTI
In(LlT2I<lTd
= (32- 20 e = 25.5OC
In (32120)
Answer: 25.5"C
(e)
The heat-transfer area is determined from Eq. (8.19) with AT::::: /1TV
A ::::: ~ :::::
U LlTL
1048.3k1s-
::::: 79m2
Answer: 79 m 2
(f)
The total area A of the tubes in a shall-and-tube heat exchanger is equal to 2 1t r L N, where r is the tube radius, L is
the length of the tubes and N is the number of tubes. For r::::: 2.5 cm::::: 0.025 m and N::::: 30:
A
79m2
L::::: 21trN::::: 21t(0.025m)30 ::::: 16.8m
From these results, LID::::: 16.8/0.05 ::::: 336, where D is the tube diameter. As this value is > 60, application of Eq.
(8.42) used.to detennine the tube-side heat-transfer coefficient is valid.
Answer: 16.8 m
8.7
Ni =- 50 rpm::::: 50/60::::: 0.83 s-l. Cph::::: Cpc::::: Cp water::::: 75.4 J gmol-l C-l (Table B.3, Appendix B)::::: 75.4 k1
kgmoll C- 1. Converting to mass tenns using the molecular weight of water::::: 18.0 (Table B.l, Appendix B);
Cph =- Cpc =-75.4kJkgmor l C- 1 =- 75.4kJkgmor 1 "'c- l
.! ~::~1! : :
4.19kJkg-1 "'C-l
kfb fennentation fluid =-ktb water. From Table 8.1, kfb water at 303 K =- 0.62 W urI "'C-l; from Table A.8 (Appendix
A), this is the same as 0.62 J s-l m- l oCl; therefore, kfb::::: 0.62 x 10-3 kJ sol m- 1 C 1. From Eq. (2.24), 303 K =approx. 30C, which is close enough to the conditions in the fennentation system for evaluation of thennal
conductivity. p fennentation fluid::::: p water =- 103 kg m'3. # fennentation fluid =- # water. The viscosity of water at
20"'C is about 1 cP (p 133); from Table A.9 (Appendix A), this is the same as to- 3 kg m- l sol. Assume that this value
applies under the conditions in this system, and that the fluid viscosity at the wall J1w is equal to the bulk viscosity J.I.b.
The fennenter-side heat-transfer coefficient can be evaluated using the empirical correlation, Eq. (8.45). The
dimensionless numbers in this equation are Rei, Pr and Nu. Rei is given by Eq. (8.39):
Solutions: ChapterS
94
From the definition of Nu in Eg. (8.37) with D::::: the tank diameter:= 3 m:
Nu k
7.7 X 103 (0.62 x 10-3 kJ s-1 m- I oc- l )
h =~ =
,;", 1.59kJ 8- 1 m-2 C- 1
D
3m
Therefore. as the fermentation fluid is the bot fluid, hh i:::: 1.59 .kJ sl m- 2 oe!. The overall heat-transfer coefficient in
the absence of fouling layers is .calculatedusing Eq. (8.23). Assuniingthat the beat-transfer coefficient for the cooling
water he and the tube wall resistance O'kean be neglected (p 185), from Eq. (8.23), U:= klJ = 1.59 kJ s-1 m- 2oC- I.
To maintain thefennentation temperature constant, tbecooling-coil must be capable of removing heat from the
,fermenter attbe rate at which it isprodu.ced. From p100,the heatof reaction for aerobic cultures is -460 kJ pergmol
~ygen consumed, Therefore. if the maximum oxygen demand = 90 gmol m- 3 b- l and the fennenter volume = 20
From the modified energy-balance equation, Eq, (8.33), when evaporation and sbaft work can be neglected,
Q= -AHrxn = 230 kJ sl. According to the sign conventions on pp 88-89, Qpositive is consistent with beat being
removed from the system, From the definition of density(p 16), the mass flow rate of-the- cooling water is equal to
the volumetric flow rate multiplied by the density:
Xl,
20m3h-I(103kgm-3)'13i~sl
= 5.56kgs- 1
Tco =
---- + Tei =
Mc Cpc
230kJs-I
(
)- + 12"C = 21.9"C
5.56 kg s-1 4.19 kJ kg-I oc;l
The mean temperature difference between the fermentation fluid and the cooling water can be determined from Eq.
(8.35):
tli'A =
2 Tp-(Tci + T,o)
(2 x 28)'C-(12 +21.9)"C
2
=
2
= 11.1"C
Substituting the results into Eq. (8.19) for evaluation of A with aT= !lTA:
The area A of a cylindrical cooling-coil is equal to 2 1t r L, where r is the cylinder radius and L is its length. For r =
7.5/2 = 3.75 em = 0.0375 m:
A
L=--=
21tr
13m2
_ =55m
21t(0.0375m)
95
Solutions: Chapter 8
As the required length of cooling-coil is considerably longer than the 45 m available in the offered fermenter, the
secondhand fermenter without modification is unsuitable for the proposed culture.
Answer: No
8.8
J.tb = 10,000 cPo From Table A.9 (Appendix A), 1 cP = 10-3 kg m- I s-l; therefore, JJb = 10,000 x 1O~3 .kg m- I s~I = 10
kgm- I sol. kfu = 2 W m- l C- l . From Table A.8 (Appendix A), this is the same as 2 J gol mol C- l ; therefore,ktb =
2 J s -1 m- 1 C = 2 x 1O~3 kJ s-l mol C- 1.
The fermenter-side beat-transfer coefficient can be evaluated using the empirical correlation, Eq. (8.45). The
dimensionless numbers in this equation are Rei, Pr and Nu. The dependence of Rejon stirrer speed is given by Eq.
(8.39),
2kJkg-Ioc-l(lOkgm-ls-I)
ktb
2 x 10 3 k1 C l m- l 0C-l
Pr=-P-=
=10
From Eq. (8.45), assuming that the viscosity at the wall is equal to the viscosity of the bulk-fluid:
Nu = 0.87 Rep62
From the definition of Nu in Eq. (8.37) with D = the tank diameter = 2.3 m:
Nukfb
= -V =
232NP62(2XlO-3kJs-lm-loc-l)
203m
.11.62
=0.20Ni
-1
kJs
-2
-1
Assuming that the heat~transfer coefficient for the cooling water he and he tube wall resistance Blk can be neglected
(p 185), from Eq. (8.23),
U = hh = 0.20N?62 kJs -I m-2 C- 1
Substituting the known parameters into Eq. (8.19) with liT = liTA = WOC:
Q = UA6TA =
W,
= P = NpgPN;
where the value of Np depends onRej, and Nj has units of s~l. From Table A.8 (Appendix A), 1 J sl = I kg m 2 s3;
therefore, 1 kJ s~l = 103 kg m2 s3 and:
Ws =
173NpN[ kg m2 s-3
.1
kJS-~
1
lOOOkgm s
From the modified steady-state energy-balance equation, Eq. (8.33), assuming evaporation is negligible:
Solutions: Chapter 8
96
Therefore:
-Mrxn
Q- WS = (S6.0,vp62_0.173NPNf)kJS-l
Values of Q, W
and -tJirxn calculated using the equations derived above are listed below as a function of Ni.
S
Values of Np as a function of Rei were obtained from the original reference (I.H. Rushton, E.W. Costich and H.I.
Everett, 1950, Power characteristics of mixing impellers. Chern. Eng. Prog.46. 467-476) for more accurate
interpolation of the power curve in Figure 7.24,
Nj
(s~l)
0.5
0.8
l.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
10.0
The values of
Rei
Q(1<1 ,.1)
Np
30.4
48.6
60.8
122
182
243
304
365
426
486
608
36.4
48.8
56.0
86.1
111
132
152
170
187
203
233
4.5
4.1
4.0
3.7
3.7
3.6
3.6
3.8
3.8
4.0
4.0
Ws
(kJ s-l)
0.10
0.36
0.69
5.12
17.3
39.9
77.9
142
225
354
692
36.3
48.4
55.3
80.9
93.4
92.4
74.0
28.1
-38
-151
-459
10
Stirrerspeed, Nj (s1)
(d)
'h
=3 8. 1,
Answer: About 3 s1
(e)
From p 100, the heat of reaction for aerobic cultures is -460.kJ per groal oxygen consumed. Therefore, if the rate of
oxygen consumption per g cells is 6 rnmol g.I h I = 6 x IO~3 gmol g.I h I, when the stirrer speed is 3 sl and 6Hrxn
=-93AkJs I :
Solutions: Chdpter 8
Biomass =
97
1
-93.4k:Js=L22XIIYg
I
6 10-' gmolg-I h- .I'6~sl (-460kJ gmol-I)
The cell concentration is equal to the biomass divided by the fermenter volume:
.
CeII concentration =
L22xl0 g
22 I-I
3 11000 11 = 1 . g
10m . --,1m
From the graph, as the stirrer speed is raised, the overall heat-transfer coefficient increases as beat transfer through the
boundary layer in the fermentation broth is improved. Therefore, the rate at which heat can be removed from the
system Qis increased. However, the rate at which heat is dissipated by the stirrer W
s also increases with stirrer
speed.. When the curves for Qand W
intersect,
the
entire
heat-transfer
capacity
of
the
fennenter cooling system is
s
being used just to remove the heat from stirring; the system in unable to remove any of the heat generated from
reaction. Accordingly, at high stirrer speeds, the system bas limited capacity to handle exothermic reactions.
Mass Transfer
9.1
Converting the units of the maximum specific ox.ygen uptake rate using the molecular weigbt of oxygen =32.0 (Table
B.I, Appendix B):
444
I
I gmol 1. 11gmol
32.0g II~I
qo = 5 mmo1g-I b- . 1lOOOmmol
. 3600s = '
x 10-5 g g-1-1
s
qox
The rate of oxygen transfer is given by Eq. (9.37); NAis maximum when CAL "" 0:
kLaC~ ""
As the maximum oxygen demand of the culture is greater than the maximum oxygen transfer rate in the fennenter, the
system will be limited by mass transfer.
9.2
Converting the units of the oxygen uptake rate using the molecular weight of oxygen"" 32.0 (Table B.I. Appendix B):
gmol
11~IIIOOOIII~1
1m3 ' 36008 =
1 I
1
1. 119mol
32.0g . l000g'
qox = 80 mmo11- h- . 1lOOOmmol
711
. x 10-4 kgm-3-1
s
IlgmOI I
lI...'!LI
g
1
= t0004mM=
0004
Ce n
'
, m m11o , l000mmol ' 1-,2.0
19mol . l000g' 1100011-128
1m3 - . x 10-4 kgm-3
(aJ
From Table 9.2. the solubility of oxygen in water at 30"C under 1 atm air pressure is 8,05 x 10-3 kg m 3 . If the
solubility in medium is 10% lower;
(kLa). =
ent
qox
(C~ -Cerit)
= O.10 s-1
x 10"2 kg m-3.
Solutions: Chapter 9
99
= . . qox
(kLa) .
(CAL -Cerlt)
ent
= 0.021s-1
(0.0346kgm-3-1.28XI0-4kgm-3)
9.3
(a)
The oxygen transfer rate for kLa determination by the oxygen~balance method is given as Eq. (9.48). From p 17, the
partial pressure of oxygen in the inlet air at 1 atm is (0.21 x 1 atm) = 0.21 atm; assuming that the exit gas leaves the
fermenter at the fermentation conditions (l atm pressure and 28C), the partial pressure of oxygen in the exit gas is
(0.201 x 1 atm) 0.201 atm. Using R 0.000082057 m3 atm K-1 gmol- 1 from Table 2.5 and converting the
temperatures to degrees Kelvin using Eq. (2.24):
N = _ I [(FgPAG) _(FgPAG) 1
A
RVL
TiT
[(200lmin-lI~10.2Iatm) (1891min-II~10.20Iatm)1
1
NA = 0.OOOO82057m3 attn K-1 gmol 1(200 I)
(20+ 273.15) K
NA
= 0.0174gmolm-3 s 1
(28 + 273.15)K
From Eq. (9,37) with the units of NA from (a) converted to mass terms using the molecular weight of oxygen = 32.0
(Table B.t, Appendix B):
If the measured exit gas composition of 20.1% 02 is an overestimation, the actual value is (l/Ll x 20,1)% 18.3%
02. Therefore, the partial pressure of oxygen in the exit gas is (0.183 x 1 atm) = 0.183 atm. From Eq, (9.48):
NA = _
I [(FgPAG) _(FgPAG) 1
RVL
TiT
0
[(200lmin-lI~10.2Iatm) (189Imin-II~10.183atm)1
(20+273.15)K
NA
(28 + 273.15)K
kLa
=...
NA
(CAL - CAL)
II...I.!>LI
1 -3 s-I . 132.08
0.0289 groom
1 01'1000
g
3
3
3
kg
(7.8 x 10- kg m- -0.52x 7.8 x 10m-3)
gIn
= 0,25s
_
1
The kr.,a value obtained in (b) using the incorrectly calibrated oxygen analyser is 60% of the actual leLa value; the
error is therefore 40%.
Solutions: Chapter 9
100
Answer: 40%. This calculation illustrates the sensitivity of the oxygen balance method to the accuracy ofall of the
measured parameters used in Eq. (9.48). This sensitivity arises from the subtraction of two similar numbers for the
moles of oxygen in and out of the system. When similar errors in both Fg terms are taken into consideration. the
error in the final kIft value can be very large,
9.4
leLa measurement
(a)
From p 16, g "" 9.8 m 8.2 . Assuming the density of the culture broth to be the same as warer, p "" 1000 kg m- 3. The
static pressure at the sparger is:
Ps = P g h "" 1000 kg m- 3 (9.8 m s2) (3.5 m) "" 3.43 x t()4 kg mwl sl
,From Table A.S (Appendix A), 1 kg m- l s2 = 9.869 x 10"6 aim; therefore:
Ps -_ 343
. x
-_ 343
. x
Ps is the pressure due to_the head of liquid above the sparger; oThctotal pressure at the'llparger iSh + atmospheric
pressure "" 1.34 atm.
From Tables B.8 and B.l (Appendix B), the molecular formulae for glucose and sucrose and the molecular weights of
the medium components are: glucose (C6H1206) = 180.2, sucrose (C12H22011) = 342.3, CaC03 = 100.1,
(NH4)2S04 = 132.1, Na2HP04 = 142.0 and KH2P04 = 136.1.
The parameter values for application in Eq. (9.45) are listed below. Values of Hi and Kj are taken from Table 95.
Medium component
Hi or Kj(m 3 mo1l)
Glucose
0.119 x 10.3
Sucrose
0.149 x 10.3
Zi
20g1-111mOllfoooll
180.2g 1m3 = 11l
1mol 11100011
8.5g1-I . 342.3g
1m3 =24.8
-0.303 x 10.3
1.3g1-1.11~~~~I'111~11 =
C032-
0.485 x 1<r3
l.3gl-I.ll~~~I'II~311 = 13.0
NR,+
-0.720 x 1<r3
2x13
. gr
S04 2-
0.453 x 10.3
11 1m3 1= 9.8
1.3g1-I . lImo]
132.1g
-0.550 x 10-3
1mol 11100011
2xO.09g1-I . 142.0g
1m3 = 1.3
0.485 x 10.3
0.09g1-1.11~;~~I'111~'1 = 0.63
-0596 x 10-3
0,12g1-I . 11mol
136.1g' 1 1 m 3 1 = 0.88
1.037x 10-3
1 1 1 m3 1 = 0.88
0.12 g 1-I , 11mol
136.1 g'
Ca2+
Na+
HP042K+
H2P04-
13.0
10001
1molg'
I 1 1m3 1 = 197
. 132.1
.
10001
I 10001
10001
101
Solutions: Chapter 9
10g1O(C~)
= O.5~HiZ?CiL + ~KjCJL
CAL
j
10-') (2)213.0+(0.485 x 10-') (2)2 13.0 + (-o.720x 10-') (1)2 19.7 +(0.453 x 10-') (2)2 9.8 +]
(-o.550X 10-') (1)2 1.3 + (0.485 X 10-') (2)2 0.63 + (-0.596 x 1O-')cl)2 0 .88 + (1.037 x 10-') (1)2 0.88
+ [(0.119X 10-') 111 + (0.149 x 10-') 24.8J
_ 05 [(-0.303 x
-.
CAL = 0.95CAIJ)
Solutes in the medium reduce the oxygen solubility by about 5%. From Table 9.2, the solubility of oxygen in water at
35C and 1 attn air pressure is 7.52 x 10-3 kg m~3. Using this value for C~, C~ = 0,95 x 7,52 x 10-3 kg m*3 =
7,14x 1O~3kgm~3.
From Henry's law, Eq, (9.43), the solubility of a gas is directly proportional to the total pressure. From (a), the total
pressure at the bottom of the tank is 1.34 attn rather than 1 attn; therefore:
C~
(c'"
AL
-CAL)
(C~-CAL)o-(C~-CAL)i
[(c:u.-CALlo
In
(C~L -CALli
The oxygen transfer rate for !La determination by the oxygen-balance method is given in Eq. (9A8). Assume that the
volumetric flow rates of gas into and out of the fermenter are measured under ambient pressure, Le. at I attn. From p
17, the partial pressure of oxygen in the inlet air at 1 attn is (0.21 x I attn) = 0.21 attn; the partial pressure of oxygen
in the outlet gas is (0.2015 x 1 aim) = 0.2015 atm. Assuming that the exit gas leaves the fermenter at the fermentation
temperature (35C), using R = 0.000082057 m3 attn K-l gmol-l from Table 2.5 and converting the temperatures to
degrees Kelvin using Eq. (2.24):
Solutions: Chapter 9
102
Y~lo.2latm) (4071S-11~10.2015atm)1
1
3
I
[(25 m minNA - 0.OOOO8Z057m3atmK 1gmor1(ZOm3)
(25+273.15)K
_
NA
=-
(35 + 273.I5)K
From Eq. (9.37) with (CAL - CAL) = (CAL - CAL)L from (d) and units of NA converted to mass terms using the
molecular weight of oxygen = 32.0 (fable B.t, Appendix B):
kLa
=-
'"
NA
=-
3Z 0g
00167
. Illkg
.
gIno1m-3 s-1 - 1lOf
. 1000 I
g
gIll
=- 0.15 s 1
3.46 x 10 3kgm 3
(CAL -CALt
Answer: 0.15 s-1
(g)
The maximum cell concentration supported by the fennenter can be calculated using Eq. (9.40) with C~equal to the
average solubility of oxygen between the top and bottom of the fermenter:
_ kLa(c~) _
max
x
-
qo
0I5s-I[C14;9.s7)XIO-3]kgm-31~1
-1
-74
l_lh_lllgmOII132.0gll~II~I-19g1
. mmo g
. lOOOmmol . 1gmol . looog . 36008
Answer: 19 g I-I
9.5
Dynamic kLa measurement
kLa is determined using Eq. (9.52) and the method described in Section 9.10.2. Take!} =- 10 s and CALI =- 43.5% air
saturation. The steady-state dissolved oxygen tension CAL = 73.5%. Calculated values of
In
(.,~p.:::,,-=-;;~p.~"'1 )
0.00
OAI
0.80
1.6
2.3
3.0
4.1
o
5
10
20
30
40
60
Solutions: Chapter 9
103
fq,a is equal to the slope of the straight line in the plot"'" 0.069 s-l.
9.6
Measurement of kLa as a function of stirrer speed: the oxygen-balance metbod of
Mukhopadhyay and Ghose
From p 17, the mole fraction of oxygen in the inlet air CYAoh "'" 0210. Convert the data for CAL to units of gmol m- 3
using the molecular weight of oxygen"'" 32 (Table B.l, Appendix B) and assuming that the density of the fermentation
broth is the same as that of water = 1000 kg m~3;
ppm =
1:
109
(lOookgm-J) .11O~XJgl.1
g .;~Oll
g
= 3.125x 10-2
gmol m-J
Values of CAL and fCYAO)i - CYAO)oJ for each stirrer speed are listed below.
Agitator speed
Fermentation time
(h)
300 rpm
0
4
5
6
7
8
9
10
11
500 rpm
700 rpm
CAL
[(YAGJi - (YAG)o]
(gmol m 3)
CAL
[(YAG); -(YAG)o)
(gmol m- 3)
[(YAG); - (YAG)o]
CAL
(gmol m- 3)
0.184
0.184
0.175
0
0.001
0.184
0.178
0
0.001
0.166
0.001
0.147
0.128
0.106
0.106
0.109
0.002
0.003
0.004
0.004
0.003
0.163
0.153
0.138
0.125
0.125
0.131
0.002
0.003
0.004
0.005
0.005
0.004
0.169
0.159
0.147
0.128
0.128
0.131
0.002
0.003
0.004
0.006
0.006
0.005
The tabulated values of CAL and [(y AO)i - (y AO)oJ for 0-10 b are plotted below. As CAL increases at 11 b after
being constant at 9 and 10 b, the final values in the table for each stirrer speed most likely reflect the decline phase of
culture growth and are therefore not included in the lqp analysis.
104
Soluticns: Chapter 9
0.20.---,,.---,,.----,----,---,-----.
300 rpm
o 500 rpm
700 rpm
0.15
<o~
0.001
0.002
0.005
0.004
0.003
0.006
(a)
The slopes of the straight lines in the plot for 300, 500 and 700 rpm are -19.58, -12.04 and -9.68 groot m-3,
respectively. These values can be used to determine,qa using R = 0.000082057 m3 atm gmol-l K~l from Table 2.5
and converting the temperature to degrees Kelvin using Eg. (224):
' -1
-J1TF.
kLa =
liminfi
66SV
RTVLX~ope = O,OOOO82057m3atmgmor1r1(29+273.15)K{31)xs}ope -
stope
For SOOrpm:
At 700 rpm'
k La =
-2.02gmolm-3s-1
-9.68 gmol m-3
= 0.21 s-
Answer: 0.10 sl at 300 rpm; 0.17 sl at 500 rpm; 0.21 s1 at 700 rpm
(b)
The intercepts of the straight lines in the plot for 300, 500 and 700 rpm are 0.185, 0.186 and 0.187 gmat m-3,
respectively. Taking the average, C~ is 0.186 gmol m- 3. Converting to mass terms using the molecular weight of
oxygen = 32.0 (Table B.t, Appendix B):
Solutions: Chapter 9
105
qo x
qox
PTFg
3atm(3Imin-lr~~[(YAG)i-(YAG)oj
O'{)OOO82057m3atmgmolIrI(29+273.15)K(31)
__
= 2.02[(YAG)-(YAG) jgmolm 3, I
I
The maximum rate of oxygen uptake occurs when [(yAO:>i - (yAO)oJ is maximum. At 300 rpm. the maximum value
of [(YAo)i - (YAeVo] is 0.004; therefore, .(qO x)max = 2.02 x 0.004 = 8.1 x 10- 3 gmol nr 3 s-l. At 500 rpm, the
maximum value of [(YAo)i - (YAO)o] is 0.005; therefore, (qoxhnax = 2.02x 0.005 = 1.0 x 1O~2 gmol m-3 s-l. At 700
rpm, the maximum value of [(YAo)i - (YAo)oJ is 0.006; therefore. (qO x)max = 2.02 x 0.006=1.2 x 10-2 gmoJ m- 3
s-1.
Answer: 8.1 x 10-3 gmoJ m-3 sl at 300 rpm; 1.0 x 10-2 gmol m-3 8- 1 at 500 rpm; 1.2 x 10- 2 grool m 3 sl at 700 rpm
Unit Operations
10.1
Bacterial filtration
(aJ
According to Eqs (10.12)-(10.14), a plot of fl Vf versus Vf should yield a straight,line for determination of the
filtration parameters. The data after converting the units to s and m3 are listed and plotted below.
Time, t (8)
120
180
360
600
900
1200
tlVr(s rn*3)
0.0108
0.0l2l
0.0180
0.0218
0.0284
0.0320
1.11 x 104
1.49 x 104
2.00 x 104
2.75 x 104
3.17x 104
3.75 x 104
4.0
1
.,
.!!.
3.0
x
....1:::.- 2.0
~
~
g
~~
1.0
Il:
0.0
0.00
0.01
0.02
0.03
0.04
The slope of the 'Straight line in the plot KI = 1.18 x 106 s m- 6 ; the intercept K2 = -363 s m o3 . From Eq. (10.13),
using the conversion factors 1 mmHg = 1.333 x 102 kg m- I s2 (Table AS, Appendix A) and 1 cP = 10- 3 kg m-I g-l
(Table A.9, Appendix A), the specific cake resistance a is:
2(0.25m2)'36OmmHg.I1.333\1~:-1
= ----,c=c---':i-~=-=""-:-----.l:-:-----:-
4.00p.110 3kgm Is Ij(22g1-111OO1j.I~~
lcP
1m3
lOOOglJ
= 8.0 x lO lO m kg-!
The intercept K2 is a relatively small negative number, which may practically be taken as zero. Therefore, from
Solutions: Chapter 10
107
tl yr = 7.5 x 10-3 min 1~1. From(a), K2 =0; therefore, from Eq. (10.12):
3
The filter area is obtained fromEq. (10.13) using the result for a from (a):
I'tac
4.0cP
.1 10-
3
\g:;:-I '-'I&ox 10
1O
1
1
mkg- (22 g l-
A = 2Kt6p =
2(1.13X 10' 'm-6) 360mmHg.
ff;;;II~I)
I1.333Xi~:-1 I
= 649m
,-'
A = 25.5m2
10.2
(a)
After converting units using the conversion factor 1 m3 = 106 mI, the data for tlyfand Yr are listed and plotted below.
Pressure drop (mmHg)
100
250
350
10.5
10.5
10.5
10-5
2.2 x 106
3.5 x 106
4.5 x 106
5.8 x 106
1O~5
6.7 x
8.1 x
9.2 x
l.0 x
10.5
10.5
10.5
750
7.0 x lOS
9.3x1OS
1.4 x 1()6
1.7 x 1()6
2.1 x 1()6
2.4 x 1()6
2.& x 1()6
3.1 x 1()6
3.5 x 106
5.0 x lOS
&.0 x lOS
1.1 x 106
1.4 x 1()6
1.7xl()6
2.0 x 1()6
2.3 x 1()6
25 x 1()6
2.& x 1()6
550
750
IfYr(S m 3)
Vf(m 3) pelleted
1.0 x
1.5 x
2.0 x
2.5 x
3.0x
3.5 x
4.0x
4.5 x
5.0 x
550
106
106
106
107
H,.5
12 x
1.7 x
2.5 x
3.0x
3.7 x
4.3 x
4.& x
5.3 x
6.0 x
1()6
1()6
106
106
1()6
106
1()6
1()6
1()6
9.0 x
1.3 x
1.& x
2.4 x
2.9 x
3.4 x
3.9 x
4.3 x
4.8 x
lOS
1()6
1()6
1()6
106
1()6
106
106
106
1.0 x
1.5 x
2.0 x
2.5 x
3.0 x
3.5 x
250
350
t/Vr(s m 3)
filamentous
1(T5
1(T5
10".5
1(T5
1(T5
10-5
4.0 x 10"5
4.5 x 10"5
5.0x lOwS
3.6 x 1()6
55 x 1()6
72x106
9.0 x 106
1J x 107
1.3 x 107
2.2 x
3.1 x
4.3 x
5.3 x
65 x
7.5 x
8.5 x
9.6 x
1()6
1()6
1()6
1()6
I1J6
106
106
106
1.7 x 1()6
2.7 x 1()6
3.6 x 1()6
4.4 x 1()6
52 x I1J6
6.IXI1J6
7.1 x I1J6
7.& x 11J6
&.& X11J6
1.3 x
2.1 x
2.7 x
3.4 x
106
106
106
106
4.0 x 106
4.7 x 106
5.6x 106
6.2 x 1()6
6.& x 1()6
1.1 x
1.7 x
2.3 x
2.& x
3.3 x
106
1()6
1()6
1()6
I1J6
4.0 x 106
45 x 1()6
5.1 x 106
5.7 x 106
Solutions: Chapter 10
108
12
Pressure drops:
10
o 250mmHg
.350mmHg
550mmHg
.. 750mmHg
-1"'-
PaUeted
100mmHg
~g
~I
2
0
2
3
Filtrate volume,
V; x 105 (m3)
,.
Filamentous
Pressure drops:
12
..
100mmHg
o 250mmHg
10
f
$
.350mmHg
550mmHg
.. 750mmHg
_1:::.,0
E
~
~g
F
2
0
0
Filtrate volume,
V;
x 105 (m3)
From Eq. (10.12), the slopes of the straight lines in the plots are equal to Kl for each pressure drop. 'These values are
listed below.
100
250
550
750
2.26 x 1011
L20x lOll
9.93
x lO lD
7.07 x 1010
5.77 x 10 10
3.73 x lOll
2.13 X 1011
1.75 x 1011
1.38 X lOll
Ll4 x 1011
Pelleted
Slope::: Kl (s m 6)
Filamentous
Slope:::: KI (8 rn6)
From Eq. (10.13), using the conversion factors 1 mmHg 1.333 x 102 kg m- I 8.2 (Table A.S, Appendix A) and 1 cP
::::: 1O~3 kg m- I s1 (Table A.9, Appendix A), the specific cake resistance aofthe pelleted cells is:
Solutions: Chapter 10
109
2AZ .6pK
3k;;-l I
Jl{c
.1 10-
l . 1~~~1'11::~1
s- I(0.25 gml-
where tip has units ofmmHg andKl has units of s m-6. Similarly for the filamentous cells:
2A2
_
a-
K
/;p
Jl{c
1_
2(1.8cmZ.I~P)2 /;p11.333xlOZkgm-ls-ZjKl
1.4cP.
loocml
I10-3kf;
1 lit
s-
ImmHg
6I
1.Il~mU:
0.lgml-
1~5A.K
-617
)- .
.ll::gl
k-l
Im g
The results for specific cake resistance obtained after substituting the values for tJ.p and K 1 into the equations are
listed below.
250
558 x 108
7.41 x
loB
2.30 x 109
3.29 x 10'
Pelleted
a(mkg~l)
100
550
750
8.58 x 108
9.60 x 108
1.07 x 109
3.78 x 109
4.68 xla'
5.28
Filamentous
a(mkg- I )
X109
(b)
From Eq. (10.2), the compressibility can be obtained by plotting the specific cake resistance a versus lip on log-log
coordinates. Using the conversion factor 1 mmHg:::: 1.333 x 102 kg m- 1 sZ (Table A.5, Appendix A) to convert the
units of lip, the data are listed and plotted below.
1.33 x 1()4
1.00 x lOS
5.58 x loB
7.41 x 108
8.58 X 108
9.60 x 108
l.07 X 109
2.30x109
3.29 X 109
3.78 X 109
4.68 x 10'
5.28 x 109
Pelleted
arm kg-I)
Filamentous
a(mkg- I )
_ 100 . -
,,-
!if
~--~-_~-~_~...,
o Pelfeted
Filamentous
"
10
Solutions: Chapter 10
110
From Eq. (ID.2), the equations for the two lines in tJ:e figure have the form, a= a' 1,s. For the pelleted suspension.
a= 2.60 x 107 ApO.323; for the filamentous suspenSIon, a= 4.42 x 107 Ap0.415, where lip has umts kg m l s2, a has
units m kg-I, and a' bas units kg-(l +s) m 1+3 sZs. Therefore. the compressibility is 0.323 for the pelleted suspension
and 0.415 for the fIlamentous suspension.
Answer: 0.323 for the pelleted suspension; OA15 for the filamentous suspension
(0)
The filtration equation for a compressible filter cake is Eq. (10.11) with a= a' ti[l. Assuming that the filter medium
resistance rm is negligible:
(Ap)J'-l :: _I ~
Substituting the parameter values for the filamentous suspension using consistent units, including the results ex':: 4.42
x 107 kg..(l+s) m 1+s s2f and s= 0.415 from (b):
(Ap)0.415-1 ::
Ih .
Ih1
13600'
2 x
(20m 3)
IAcP
.1 10- 3 klgc~-l ,-114.42X 107 kg-{I+O.415)m l +O.415 ,2x 0.415 ( 0.1 g ml-1 .
6
10
3
1 mm]
'I~I)
Iooog
Answer: 2086 mmHg. An assumption associated with this answer is that the filter cake characteristics measured at
pressures between 100 and 750 mmHg apply at the much higher pressure of2086 mmHg.
10.3
(a)
For negligible filter medium resistance, the filtration equation for a compressible fdter cake is Eq. (lO.lI) with rm
and a= c !Js:
t
Vf
=0
J1{a'c
t 2A
=----
Vi t>p>-1
Substituting the parameter values for the laboratory filter and using the conversion factor I psi
s2 (fable A.5, Appendix A):
Solutions: Chapter 10
lI..,tXc ""
r,
Answer: 3.67 x
111
2
1m 2
21 lOOcm 1)
2 ( Scm.
. -1-'
60s
23.5mm.
1 nun I
(Sooml. ~ )2 ( 12 si.16.89sxI03k~m-l
106 m1
P
1 pst
e21~0.57-1
(h)
The cycle time is lIN hours per revolution.
(el
As 30% of the rotating filter cloth is submerged at any time, each cm2 of cloth is submerged for 0.3 x the cycle time ""
O.3/N h.
(d)
The volume filtered per revolution is 20 m3 h~1 x liN h "" 20INm3.
(el
Eq. (10.11) with rm "" 0 and a",, !J.ps is:
I I
0.3 h 3600s
N'lh
-'-'-~';--c:.=.
20 m3
N
3kg -1 _2~0.57-1
367 105kg0.43 -2.430.14 45 . . 95 xlO
m s
.x
m
s
. pSt.
Ii
(20)
3
168
2(2n(0:75m)(1.2ml)'
ps
where N is the number of revolutions per hour. Calculating both sides of the equation gives:
54sm-3 "" 134~.9 sm-3
N = 24.9rph
Answer: 24.9 revolutions per hour
(I)
The ftltration time is increased from O.3IN h to O,SIN h. Substituting this value for t into the left-hand-side of the
equation in (e):
h
O.5
N
.
13600
Ih '1 _ 1343.9
20
_m3
N
-3
- -,;;-sm
Solutio1lS: Chapter 10
112
= 14.9 rph
10.4
Centrifugation of yeast
(a)
Convert the parameter values to units of kg, m, s:
Pr
=:
3
3
1.06gcm- = L06gcm-
3
0.997 gene
=:
1
Q = SOOlh- =
:=
'lli.:gl.ll~:r = l060kgm-3
3
O.997gcm-
.Ili.:g1ll~~m
3
1
= 997kgm-3
From Table A.9 (Appendix A), INs m- 2 = 1 kg mol g-1; 'therefore J.I. 1.36 x 10- 3 kgm- I 8- 1. D p = 5 MlD= 5 x
10-6 m. From Eq. (10.15) with g =: 9.8 m s-2 (p 16), the sedimentation velocity is:
u
g
= Pp -PfD 2g =
18p
3
(l060-997)kgm-
(SXI0-6m)29.8ms-Z_=6.31XIO-7ms-l
I: =
JL
=:
lUg
Answer: 110 m 2
(b)
From the relationship between specific gravity and density (p 16), as the density of water is close to 1.0000 g em-3 (p
16),
Pp
Dp
1kg
1. 11m
100 em 1
= 20. gem-3 = 20. gem-31. l000g
=:
2000kgm-3
From Eq. (10.15), the sedimentation velocity for the quartz particles is:
3
2 _
_ Pp -Pf
(2000-997) kg m)2 98
(01 10-3 m
ug _
-D g _
(
) . x
. ms-2 -_ 402
. x 10-3 ms -1
3
18,u
p
18 1.36x 10- kgm 1 s:-1
From Eq. (10.18), the sigma factor is:
r = -lL =
lUg
From the result in (a),
r for the yeast cells is 110/0.017 =6470 times that for the quartz particles.
10.5
= 0.017m2
Z(4.02xlo-3ms-l)
Solutions: Chapter 10
113
Pr = 1.00gcm- = 1.00gcm-
ll~glll~~mr = l000kgm-3
From Table A.9 (Appendix A), I Pa s = I kg m~l s~l; therefore /.l = 1.25 x 10"3 kg m~1 8"1. D p = 10--2 mm = 10--5 m;
b = 70 cm = 0.70 m; r= 11.5 cm = 0.115 m. As one revolution = 2ft radians where radians in a non~dimensional unit
(p 11), converting the centrifuge speed to radians s~1:
(J)
.!
=9.8 m s~2 (p 16), the sigma factor for the tubular~bowl centrifuge is:
"
1: = 21t~J:!:
= 21t ( 1.047x1O3 s_1)2 0.70m(0.115m)2 = 6.506 x 103 m2
g
9.8ms 2
Pp -P'D2
ug __ g _
_
18,u
)2 98
_ .
1307 x 10-6 ms -1
((l030-1000)1Qlm- ) (10-5 m
. ms-2 18 1.25 x Io-3 kgm-1 s-1
10.6
The sigma factor for the pilot~scale disc~stack bowl centrifuge 1:1 is calculated using Eq. (10.20) withg 9.8 m s2 (p
16), and (J) converted to rad sl using the conversion factor I revolution = 2 1t radians where radians is a non~
dimensional unit (p 11). For the pilot-scale device, '2 = 5 cm = 0.05 m and rl = I cm =
m:
om
:!: = 2noJ-(N-ll(,3_,1j =
1
3gIanO
2 1
1 . ~2 (25-1)
21t (21tx3000min- l . ~
1 60s
3(9.8ms 2)clan35')
(0.05m)3_(0.0Im)3) = 89.6m2
From Eq. (10.19), the sigma factor:rz for the bigger centrifuge is therefore:
I
:!: = Q2:!:I = 801min- (89.6m2) = 200m2
2
3.5 1OOn-1
Q1
From Eq. (10.20), for the bigger centrifuge with 1"2 = 75 cm = 0.075 m and rt = 2.35 cm = 0.0235 m:
oJ-
3glanO:!:,
2 n(N - IlH -
,1)
2
3 (9.8 m s-2)clan 45') 2048m
= 4 34x 10' s-2
2 n (55 -1) (0.075 m)3 - (0.0235m)3)
.
_ 659 r ad s-1 .
(J)-
II
10.7
and
II 1-
revolution
60 s - 6290 rpm
21trad
. lmin
Solutions: Chapter 10
114
where subscript 1 refers to the centrifugation conditions for the yeast suspension, and subscript 2 refers to the
centrifugation conditions for the cell debris. As the same centrifuge operated at the same speed is used in both
applications, ,1;1 =1:2 and:
Assuming that the particle and fluid densities are the same in both applications, cancelling terms gives:
~1 Ql
!'2 Q2
- 2 - =-2D pl
Dp2
or
10.8
Cen disruption
The relationship between pressure and protein release for a Manton-Gaulin homogeniser is given by Eq. (10.23). At
constant pressure, a semi-lagplat ofRm/(RnrR) versusN should yield a straight line, so thatthe value of k pa can be
determined from the slope.
The data for % protein release represent values of RIR m x 100. These data can be converted to Rm/(Rm_R) as
follows:
Rm
Rm-R
100
100
300
3
4
5
6
500
550
Rm
N
1
2
400
Rm-R
1.05
1.10
1.16
1.22
1.28
1.35
1.16
1.31
1.50
1.75
1.90
2.22
1.30
1.67
2.11
2.99
3.70
4.88
1.56
2.41
4.00
5.71
8.70
11.5
1.72
2.94
6.13
8.70
18.2
Solutions: Chapter 10
liS
30...--,---,----,---,--,--....---,
10
o
..
200 kg f an-2
300kg f an"2
400 kg f an"2
500 kg,an'2
550 kg,an'2
3
4
Number of passes, N
The values of k pa obtained from the slopes of the straight lines for each pressure are listed below.
200
300
0.050
0.129
0.267
500
550
0.406
0.580
A log-log plot of these values versus p can be expected to give a straight line with the value of a obtained from the
slope.
'l,.
0.1
'"
0.01 L100
---._ _~ _ ~ ~ _ ~ ~ ~ _ '
1000
Pressure, p (kgfcm- 2 )
As the equation to the straight line in the plot is k pa = 1.71 x 10-7 p2.37, a = 2.37. Therefore, for this system, Eq.
(10.23) becomes:
116
Solutions: Chapter 10
(a)
For 80% protein release, Rm/(Rm_R) "" 5.0. Rearranging the above empirical equation for the homogeniser and
substituting p "" 460 kgfcnc 2 gives:
N=
In(R=~R)
ln5.0
= 4.6
=
1.71 x 10-7 p2.37
1.71 x 10-7 (460)2.37
Therefore, 80% protein release is achieved within 5 passes through the homogeniser.
Answer: 5
(b)
For 70% protein release, Rm/(Rm_R) "" 3.33. Rearranging the empirical equation for the homogeniser and substituting
N=2 gives:
In(R=~R)
p2.37 = -"-'''--,fln3.33
"" 3.S2x 106
7
7
L71xlO- N-1.71xlO- (2)
p
:=
578 kgjcm 2
Answer: 578 kgjcm 2.An assumption associated with this answer is that the homogenisation characteristics
measured at pressures between 200 and 550 kgfcm2 apply at the higher pressure of578 klJfcm2,
10.9
(a)
From Eq. (10.24), for K"", 3.5, the product partitions into the upper phase. Eq. (10.27) withK:= 3.5 and Yu "" 0.8 is:
Vu
0.8 =
v.
Vu + 3.5
Rearranging gives:
0,8 Vu + 0,23 VI = Vu
0,23 VI
= 0,2 Vu
v,
YJ = LI5
Answer: US
(b)
The mass of enzyme in the two phases must be equal to the mass of enzyme in the original homogenate, The mass~
balance equation is:
From Eq. (10,24), for K = 3.5, CAu = 3.5 CAl. If VJ = 100 I, from (a) for 80% recovery, Vu = 115 l. Substituting
these values into the mass~balance equation with Vo = 150 I and CAD = 3.2 u ml- J = 3.2 x 103 u 1-1:
where CAl has units ofu 1~1. Solving the equation fOTCM
502.5 CAl = 4.8 x loS
CAl = 955 u 1~1
Solutions: Chapter 10
117
x 103 u I~I. From Eq. (10.29), the concentration factor for product partitioning into
Answer: 1.04
From Eq. (10.24), for K,= 10..2 CAn m2 CAl and the product partitions into the lower phase. If51 culture volume
is added to 2 I polymer solution and, after phase separation, the volume of the lower phase is 1 1, the volume of the
upper phase must be (5 + 2) - 1 6 L
(a)
The yield of virus in the lower phase is given by Eq. (10.28) with VI
Vr
11
(e)
From Eq. (10.24):
Rearranging the mass-balance equation in (b) and substituting for CAI gives:
CAu
CAuVu+CAIVi
CAO
Vo
CAuVu+KVI
The concentration factor for product partitioning into the lower phase is given by Eq. (10.29). Substituting for CAl
and CAO in this equation gives:
(d)
Using the equation for
Answer: 4.7
118
Solutions: Chapter 10
The elution volume for the toxoid is lower than for the impurity. Therefore, as the toxoid stays in the column for the
shorter time. it must be the larger molecule.
Answer: Toxoid
(b)
The internal pore volume in the gel in the laboratory reactor can be calculated using Eq. (10,42):
171
Taxoid Kp
ImpuntyKp
o) = (45-23)m! = 0629
= (V,-V
Vi
35m1
.
VTl ::::.
1t
(2DI)2 HI::::'
C
1&
(OoOISm)2
2
OAm::::.
VTI
=-
1t
7.07 x 10-5 m3
3
~ O.6m =- 0.118m
(TD02)2 HZ =- 1t (osm)2
If the void fraction in the large column is the same as in the small column, Vo2 in the large column is:
3
23m!.
V02
= rVol
TI
VTI =
~
6
10 5 m!3 (
3)
3
0.118m = 0.0384m
7.07 x 10
ViZ
= r!'itT1 VTI =
3
35m!. 1:
10 m!
( 3 ) = 0.0584m3
5 3 0.118m
7.07 x 10- m
If the largescale column is operated with the same packing and flow conditions, the partition coefficients can be
assumed to be the same-as those in the laboratory column. Therefore, from Eq. (10.41), for toxoid in the large column
with the value of K p from (b):
Ve2 = Kp Va + Vo2 = 0.171 (0.0584 m 3) + 0.0384 m 3 = 0.0484 m3
Answer: Toxoid
Solutions: Chapter 10
119
(d)
The liquid flow rate is scaled up in proportion to the column cross-sectional area. As the cross-sectional area ""
1&
D2)2
(
n 20
v2 "" VI
n(D;I)
1m
0.5 m 2
3
(D)2 "" 14mlmm. -1 . 131
(0015 ) "" 0.0156m
c2
2 "" VI -D
cl
-6-'
10 ml
,-1
IDlD
The retention time t'R is equal to the elution volume divided by the volumetric flow rate. For the toxoid in the large
column, using the results from (c) and (d):
Ve2
IR=-=
v2
0.0484 m 3
= 3.1 min
0.0156m3 min 1
HETP,H
(m s-l)
(m)
0,1 x 104
0.2 x 104
0.3 x 10-4
0.5 x 10-4
0,8 x 10-4
1.0 x 10-4
1.2 x 10-4
1.5 x 104
1.8 x 10.4
2.0 x 10.4
2.72 x 10.4
1.87 x 10-4
1.69 x 10-4
1.72 x 10-4
2.02 x 10-4
2.27 x 10-4
2.54 x 10-4
2,95 x 10-4
3.38 x 10.4
3.67 x 10-4
4,----,--...,---,---,----,
0.5
1.0
1.5
2.0
Unear rrquid velcoity, u x 1()4 (m $"1)
2.5
120
Solutions: Chapter 10
(h)
From the graph in (a), the minimum HETP is around 1.7 X H;4 m. This can be confirmed by differentiating the
equation for H and solving for dH/du = 0:
dB --A
- = -+8 = 0
du
.2
Therefore:
A
2xlO"""m2 ,-1
(
)
H=-+Bu+C=
5
1 +1.5s 3.65x1O-5 ms- 1 +5,7x1O-5 m= 1.67xl0-4 m
u
3.65x1O ms
Answer: The minimum HETP is 1.67 X 10-4 m, obtained at a liquid velocity of 3.65 X 10-5 m s~1.
(c)
The column diameter Dc = 25 em = 0.25 m~ The --volumetric flow ,.rate v is 0.311 min"1, ,The-linear ,flow-rate u is
obtained by dividing the volumetric flow rate by the column cross-sectional area:
u =
K(~'r
I mini
'm3
0311
. -I I60s . 110001 I
.
mm.
K(02gmr
_
= L05x 1O-4 ms 1
A
2x 1O"""m2 ,-1
(
)
H=-+Bu+C=
-4
1+1.5s 1.05xl0-4 ms-l +5.7xlO-5 m= 2.34xlO-4 m
u
1.05xlO ms
The capacity factors for the A and B chains are kA= 0.85 andkn = 1.05, respectively. From Eq. (l0.38):
o= kkB
= 1.05 = 1.235
0.85
Substituting these parameter values into Eq. (10.51) with L = 1 m for the larger column and k2 = k]J:
R
N,
=!
fT(O-I)(~)=\/
1m
0
kB+l
4
2.34xI0-4
4Vli
1.235
1.05+1
From p 248, as RN> 1.5. the two peaks are completely separated.
Answer: Yes
(d)
'.Por L = 0.7 m for the smaller column, the value of H corresponding to RN= 1.5 or virtual complete separation can be
detennined using Eq. 00.51):
kB+I
41.5
1.235
1.05 ) = 0.0136Jiil
1.05+1
H= 1.85xlO-4 m
The linear liquid velocity at which this value of H is obtained can be determined by rearranging the expression for H
121
Solutions: Chapter 10
2B
H-C,!<C-H)2_ 4BA
2B
= (1.85X 104
-5.7 x 1O-5)m
u
Therefore:
u
= 6.48 x 10-5 m sl
or
= 2.06xlO-S ms 1
1be maximum flow rate for complete separation-is-u =6.48wlO-5 m s-l. 'Betweenu = 2.06 x IO-S m sl and u = 6.48
x Io-S m sI,H < 1.85 x 104 m SO tbatRN> 1.5 and-eomplete:separationismaintained. The volumetric flow rate v is
equal to u multiplied by the column cross--sectional area:
v
Converting units:
10001
60s 1 = 0191
-1
v _
- 3. 18 x 10-6 m3 s-I . 1 1m3 1 ' 1lmin
.
nun
Homogeneous Reactions
11.1
Reaction eqnilibrium
From p 258. take the standard conditions to be 25C and 1 attn pressure. The temperature is converted to degrees
Kelvin using Eq. (224); from Table 2.5, R =8.3144 J K-l gmol-l = 8.3144x 10-3 kJ K-I gmol-l.
(a)
FromEq. (11.3):
inK
-t1GO
=~
=
RT
14.1klmol= 5.69
8.3144xlO-3kJr1gmoll(25+273.15K)
K = 295
The large magnitude of K indicates that the reaction can be considered .irreversible.
FromEq. (11.3):
_AGO
In K
=~ =
RT
-32kJ mor
= -1.29
8.3144xlO 3 kJK Igmoll(25+273.15K)
K
= 0.275
11.2
Eqnilibrium yicld
(a)
From Eq. (11.2) with G6P and GIP representing glucose 6-phosphate and glucose I-phosphate, respectively:
K =
CGtiP at equilibrium
0,038 M
=
= 19
C01patequilibrium
O.OO2M
Answer: 19
(b)
..
Theorettcal yIeld =
molesG6Pfonned
1mol
-1
mo = I mol mol
mo1es GlP us ed to orm G6P = -1-1
(c)
123
Solutions: Chapter 11
11.3
Reaction rate
(a)
Answer. The volumetric productivity is doubled, the specific productivity is unaffected. and the total productivity is
doubled.
(e)
(I)
RA
= RA =
rA
= 52081
08gl-lb-ll~:III~gl
lookgd-
Answer: 5208 I
(ij)
FromEq, (11.67):
11.4
Enzyme kinetics
Evaluate the enzyme kinetic parameters by plotting slv versus s as a Langmuir plot(p 272), The values are listed and
plotted below,
s(moll- 1)
Slv (min)
0.0250
12.89
0.0227
11.88
0.0184
0.0135
9.95
750
7.02
5.00
3.93
2.62
0.0125
0.00730
0.00460
0.00204
Solutions: Chapter 11
124
15,----,-----,.----...,
10
-I>
5
0.Q1
0.02
0.03
s (mol 1-1)
The equation for the straight line in the plot is slv = 1.70 + 445 s,wheres has units ofmoll-} and Slv bas units aiulin,
Therefore, from Eq. (11.39), I/vmax = 445 mOlll min, so that Vmax = 2.25 x 10"3 moII-} min-I. Also from Eq.
(11.39), Ktn/ vmax 1.70. Multiplying this value by the result for Vmax. K m = 3.83 x 10-3 moll- t ,
Answer: Vmax =2.25 X 10-3 mol 1-1 min'I; K m = 3.83 x 10-3 mol 1-1
11.5
(a)
The activation energy is determined from the Arrhenius equation, Eq. (11.21), with k equal to the initial fate of
glucose production. According to the Arrhenius equation, a plot of k versus liT on semi-logarithmic coordinates
should give a straight line.. 'The parameter values are listed and plotted below; Tis converted to degrees Kelvin using
Eq. (2.24).
T('C)
T(K)
liT (K'I)
20
30
40
60
293.15
303.15
313.15
333.15
3,41 x 10.3
3.30 x 10-3
0.31
0.66
1.20
6.33
3.19 x Icy3
3.00 x Icy3
Solutions: Chapter II
125
"1
10
."
E
"g
'g
'5
0.1
2.9
3.1
3.0
3.2
1/Temperature
3.3
X
3.4
3.5
103 (K 1)
o
The equation for the straight line in the plot is k 1.87 x lO lD c 73OO/ T, where k has units ofmmol m-3 5"1 and T has
units ofK. Therefore, from Eq. (11.21), EIR = 7300K From Table 2.5,R = 8.3144 J K~1 gmol- l = 8.3144 x 10-3 kJ
Kw l gmol-l; therefore, E= 7300 K x 8.3144 x 10-3 kJ K-I gmol-l = 60.7 kJ grool-l.
=328.15 K.
Answer: The reaction rateat55"C is 4.08 mmol m- 3 st or 9.5 times faster than the rate of 0.43 rnmol ro 3 sl at25"C.
(e)
From Table 2.5, the value of R in the appropriate units.is 1.9872 cal K-l gmol- 1, At 55"C = 328.15 K:
k
Therefore, from Eq. (11.45), the half-life of the enzyme at 55"C is:
t = In2 = In2
= 1.65h
h
kd
0.42b 1
At 25"C
=298.15 K:
kd = 2.25x 1027 e-41,63O!RT = 2.25x 1027 e-4I,630;(1.9872 x 298. 15)
= l009h
126
Solutions: Chapter II
Although the reaction rate is 9.5 times faster at 55 C than at 25C, the rate of deactivation is 0.42/(6.87 x 104) =: 611
times greater. Therefore, unless there are other considerations. 25C would probably be the more practical
temperature for processing operations.
Q
Answer: The enzyme halflife at 25C is 1009 h or 611 times longer than the
practical operating temperature is probably 2jl'C.
n.6
half~life
K m = 5 roM = 5 x 10-3 gmol t 1 = 5 x Hy6 gmol m- 3. The concentration offat is reduced from 45 gmol m~3 to 0.2 x
45 gmol m- 3 = 9,0 groat m-3: As this concentration range is well above the value of .&tn. s K m and. from p 269. v
"" vmax ' As v= -ds1dt. combining Eqs (11.35) and (11.44) gives:
J--<Is = f vmaxOe-kdtdt
Applying calculus rules (D.24) and (0.17) from AppendixD and combining the oonstants-ofintegration:
=0, s= sO.
Therefore:
-Vmaxfl
-$0=
id+ K
= $ 0vmoxO
- - - ( 1-e-<d I)
kd
At the beginning of the reaction, SO = 45 gmol m-3. Converting the units of VrnaxO:
10001
60
-1. 1lOOOnunol'
1 gmol 11 1 m 11
'1 42 1 -3 -1
vmaxO = 007
. nuno11-1 s-1 = 007
. mmo11-1 s
3 . min = . gmo m nun
From Eq. (11.45):
8nun
Substituting parameter values into the equation for $, when 80% of the fat is hydrolysed:
0.2 x 45 gmolm-3
= 48.276 e-O087 t
e-o087 t = 0.254
-0.087 t = -1.369
12.276
Solutions: Chapter 11
127
=-
15.7 min
11.7
(a)
The average rate-equal area construction is used to determine growth rates from the concentration data. The data and
calculations are tabulated below.
Time, t(h)
x (kg m-3)
<it (h)
0.0
0.20
0.01
0.33
0.03
0.33
0.21
0.17
0.06
0.22
om
0.5
0.10
0.25
0.40
0.75
0.32
0.15
0.25
0.60
1.0
0.47
0.53
0.50
1.06
1.5
1.00
1.10
0.50
2.20
2.0
2.10
2.32
0.50
4.64
2.5
4.42
2.48
0.30
8.27
2.8
6.9
2.50
0.20
12.50
3.0
9.4
1.50
0.10
15.00
3.1
10.9
3.2
11.6
3.5
11.7
3.7
11.6
0.70
0.10
7.00
0.10
0.30
0.33
-0.10
0.20
-0.50
The values of luIfit are plotted as a function of time below according to the method described on p 263.
16
14
rf
12
10
if
8
6
1/
.--r-
I:".
o
-2
0.0
0.5
1.0
1.5
2.0
2.5
3.0
Time (h)
:l
3.5
4.0
128
Solutions: Chapter 11
Results for <ix/dt read from the average rate-equal area curve and the calculated specific growth rates are listed below.
Time, t(h)
0.0
0.33
0.5
0.75
1.0
1.5
2.0
0.05
0.20
0.45
0.70
1.5
3.3
6.5
10.4
14.5
11.0
3.5
2.5
2.8
3.0
3.1
32
024
0.91
1.41
1.49
1.50
1.57
1.47
1.51
1.54
1.01
0.30
-0.03
-0.07
-0.3
-0.8
3.5
3.7
2.0
i:.
1.5
1.0
..
1'"
0.5
t'" /
0.0
-0.5
0
TIme (h)
(b)
As expected for most batch cell cultures, growth occurs at around the maximum specific growth rate for most of the
culture period. Taking the average of the values of J1. between times 0,75 hand 3 h .Ltmax = 1.50 0.05 h- l , where
0.05 is the standard deviation.
Answer: 1.50 h- I
(c)
From Eq. (11.49), the observed biomass yield Yxs at any point in time is equal to the ratio of the observed growth and
substrate consumption rates. The average rate-equal area construction is used to determine the substrate consumption
rates rs = -ds'dt from the concentration data, as shown below.
Solutions: Chapter 11
129
Time, t(h)
,(kg m-3)
0.0
25.0
0.33
0.5
24.8
24.8
0.75
24.6
1.0
Lv (h)
-0.2
0.0
0.33
0.17
0.0
-0.2
-0.3
0.25
0.25
0.80
1.20
24.3
-1.0
0.50
2.00
1.5
23.3
-2.6
0.50
5.20
2.0
20.7
-5.0
0.50
10.0
2.5
15.7
-5.5
2.8
10.2
-5.0
0.30
0.20
18.3
25.0
3.0
5.2
-3.55
0.10
35.5
3.1
-1.45
0.10
14.5
3.2
1.65
0.2
-0.2
0.30
0.67
3.5
0.0
0.0
0.20
0.0
3.7
0.0
0.61
The values of-As/tit are plotted as a function of time below according to the method described on p 263.
40
35
30
_
l-
25
1,
20
11~
15
10
I-
rf
I
l-
1/
/
.t>..
o
0.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
Time (h)
Results for -<is/ dt read from the average rate-equal area curve are listed below, together with the instantaneous
biomass yield coefficients calculated using Eq. (11.49) and the values of rx from (a).
Solutions: Chapter 11
130
Time. t(h)
0.0
0.33
0.5
0.75
1.0
1.5
2.0
2.5
2.8
3.0
3.1
3.2
3.5
3.7
0.'
0.5
0.6
1.0
1.6
3.0
0.10
0.33
0.45
0.44
0.50
0.45
0.47
0.47
7.'
13.9
22.2
33.0
27.5
7.0
0.4
0."
0.40
0.50
-{J.75
,
Values of the observed biomass yield from substrate Yxs are plotted as a function oftime below.
"x
D.
~
,
D.
0.4
;;
e-~
'll~
0.2
0.1
.il0
0.0
J
0
,
1
Time (h)
During the exponential growth phase between 0.75 b and 3 h when /.l = ,umax, Yxs is approximately constant with an
average value of 0.46 0.02 kg kg-I, where 0.02 is the standard deviation.
Answer:OA6 kg kg-I; ~s is approximately constant during exponential growth
U.S
(a)
The mid-point slope method is used to determine rates from the concentration data. The growth data are listed and
plotted below according to the method described on pp 264-265. Values of [(x)t+e- (x)t_el are read from the graph.
Time, ted)
0
5
10
15
0.64
1.95
4.21
5.5.
5
5
5
5
3.0
3.6
3.8
131
Solutions: Chapter 11
6.98
9.50
10.3
12.0
20
25
30
35
40
45
50
55
3.7
3.4
2.6
1.9
1.2
0.8
0.6
5
5
5
5
5
5
5
5
12.7
13.1
13.5
13.7
16
1.
"'"
12
10
j
0
0
8
6
2
0
0
10
20
30
Time (d)
40
50
60
The growth rate dxldt is determined using the central-difference formula. Eq. (11.23). These results and values of the
specific growth rate J.I. are listed and plotted below as a function of time.
Time, tId)
o
5
10
15
20
25
30
35
40
45
50
0.30
0.36
0.38
0.37
0.34
0.26
0.19
0.12
O.os
0.06
55
Values of the specific growth rate J.I. are plotted below,
0.154
0.086
0.069
0.053
0.036
0.025
0.016
0.009
0.006
0.004
132
Solutions: Chapter 11
0.15
:!?"-
,e
~
0,10
"'"
l"'l
;e
0.05
'"
0.00
L~,-~,-~,-::::b!:=L----J
10
ro
00
Time (d)
The mid~point slope method is used to determine the rate of substrate uptake as a function of time, The sugar
concentration data are plotted below according tathe method described onpp 264-265.
35
30
25
.$
c
0
20
~
~
c
15
,il,"
'"
I
I
I
I
I
I
I
I
10
<I
I
I
I
I
I
0
0
10
20
30
40
Time (d)
Values of[(s)t+e- (s}t-el read from the graph are listed in the table below.
50
60
Solutions: Chapter 11
133
Sugar concentration, s (g 1- 1)
Time, t (d)
30.0
30
35
40
45
50
27.4
23.6
21.0
18.4
14.8
13.3
9.7
8.0
6.8
5.7
55
5.1
10
15
20
25
-6.2
-6.1
5
5
5
5
5
5
5
5
5
5
-5.7
-5.4
-5.2
-4.6
-4.4
-3.9
-2.7
-1.9
The rate of substrate uptake -ds1dt is determined using the central-difference formula, Eq. (l1.23). These results and
values of the specific rate of substrate uptake qs are listed and plotted as a function of time below.
Time, t (d)
o
5
0.62
0.61
0.57
0.54
0.52
10
15
20
25
30
35
0.318
0.145
0.103
0.077
0.055
0.045
0.037
0.031
0.021
0.014
0.46
0.44
40
0.39
45
0.27
50
0.19
55
8'
i
!
"
l\!
Jl
0.35
0.30
0.25
0.20
"
0.15
0.10
7;
t
'"
0.05
0.00
0
10
20
30
40
50
60
TIme (d)
(c)
The instantaneous biomass yield coefficient is calculated using Eq. (11.49) and the values of rx and
(b). The results are listed and plotted below.
134
Solutions: Chapter 11
Time, t(h)
o
5
0.48
10
0.59
0.67
0.69
0.65
0.57
15
20
25
30
35
40
45
50
55
0.43
0.31
0.30
0.32
_ 0
0.8
1!i
e
jg
0.7
"x
0.6
~
E
,g
m-
3iZ~
'"
0.5
0.4
.S- '"
.Q
0.3
'"
0.2
0.1
<3
0.0
10
20
30
Time (d)
40
50
60
Answer: xs varies during the culture period within the range 0.30-0.69 g g~l dry weight.
11.9
(al
From Table B.8 (Appendix B), the molecular formulae for glucose and ethanol are C6H1206 and C2H{jO,
respectively. The reaction equation for fermentation of glucose to ethanol without cell growth is:
From the stoichiometry, the maximum theoretical yield of ethanol from glucose is 2 gmol gmol~l. From Table B.1
(Appendix B) the mol,ecular weights are: glucose:: 180.2; ethanol:: 46,1, Therefore:
Maximumtheoreticalyield =
;gmo:e~anol =
gmogucose
2 gmolethanol
,I ~.l~ll =
gm
11802g1
1 gmol glucose. 1 ~ol
In the absence of growth. fJ. in Eq. (11.83) is zero and the equation reduces to:
0.51gg 1
Solutions: Chapter 11
135
,
YpS
mp
=-
ms
= 051 ms
Foi S, cerevisiae, ms 0,18 kg kg-I h- I ; for Z mobiUs, mS 22 kg kg-I h- l . Applying these parameter values in the
above equation gives mp =0.092 h- l for S. cerevisiae and mp =1.12 h- l for Z rrwbilis.
Answer: 0.092 h- I for S. cerevisiae; 1.12 h- l forZ mobilis
(cJ
During batch culture at usual glucose concentrations, J1. = J1.rnax for most of the culture period (p 279). Eq. (11.83) can
therefore be written as:
Yps
_y,,;PXc:I'm~,,,,,-+_m-,,p
Jlmax
--+ms
Yxs
Substituting the parameter values for S. cerevisiae, including the result for mp from (b):
ips--
I
I
I
7.7 kg kg- (O.3h- ) + 1.12h- _ 048k kg-I
1
-.
g
O.3h+ 2.2 kg kg- I h- I
O.06kgkg 1
,
Yps
For Z mobilis:
,
Efficiency =
Yps
maximum theoretical yield
For Z. mobilis:
= 0.48kgkg-l = 094
0.51 g g-1
136
Solutions: Chapter 11
(f)
In Eq (11.70), the growth~associated term is Ypx ,umax, the nonwgrowthwassociated term is mp_ Therefore, using the
result from (e), the proportion of ethanol production from growth for S, cerevisiae is:
3.9 kg kg-I (0.4h- l )
Ypxl'max+mp - 3.9kgkg(OAh- 1)+0.092h 1 = 0.94
Ypxl'max
non~growth
I
7.7 kg kg-I (0.3 b- )
7.7kgkg-I(0.3h-I)+L12h 1
metabolism is 0.33.
= 0.67
Nongrowth~associated ethanol
production is more
Answer: For S. cerevisiae, 0.94 of the ethanol production is growth~~ociated and 0.06 is non-growthassociated. For
Z mobilis, 0.67 is growth~associatedand 0.33 is non-growth~associated. Z. mobilis produces a more substantial
proportion of its ethanol in non~growthassociated metabolism.
(g)
Fromp261;volumetric productivity is equal to specific productivity multiplied byceU concentration. From (e), as
the specific ethanol productivity qp for Z mobilis is 3.43/1.65 = 2.1 times that of S. cerevisiae, to achieve the same
volumetric productivity, the concentration of yeast must be 2.1 times that of bacteria.
(0
From Eq. (11.81) with,u= #max, for S. cerevisiae:
YXS
Pmax
l
1
+ 0.18 kg kg- h- l
0.11 kg kg-l
O.4h-l
,
Yxs = 0.105 kg kg
= 9.54 kg kg-l
-I
For Z mobilis:
~=_l_+_m_,_=
Yxs
Yxs J4nax
I
0.06 kg kg- l
,
Yx,
+ 2.2 kg kg- h-
= 24.0 kg kg-l
O.3h 1
= 0.042 kg kg-I
Answer: 0.105 kg kg.l for S. cerevisiae; 0.042 kg kg- l for2. mobilis. As Z mobilis produces less biomass per mass
of substrate consumed and per mass of ethanol produced than S, cerevisiae. biomass disposal is less of a problem with
the bacteria.
OJ
The ethanol yield from substrate is 12% higher using Z mobilis than S. cerevisiae. the specific productivity is 2.1
times higher so that a smaller and cheaper fermentation vessel is required to achieve the same rate of ethanol
production. and Z mobilis produces less than half the amount of biomass generated by S. cerevisiae per mass of
glucose consumed. All of these factors mean that Z. mobilis perfonns better than S. cerevisiae for ethanol production.
Solutions: Chapter 11
137
However, other aspects of the cultures and the ethanol production industry also need to be considered. Z mobilis
requires a higher pH (5.0) for growth than S. cerevisiae (3.5-4.0), and is therefore more susceptible to contamination.
Z mobilis also does not grow well on molasses, a common substrate material for fermentations, because of the high
salt content. The biomass produced in ethanol fermentation by yeast is often sold for use in animal feeds, whereas
application of bacteria for this purpose is not as well accepted in the industry. These are some of the reasons why Z
mobilis has not been widely adopted for industrial ethanol production, despite its superior ethanol production
characteristics.
O.025h 1
The number of generations of plasmid-containing cells over the 28..day period is, from Eq. (11.66):
I
l-a-p
=
l-L32-p
=
0.32+p
=
0.32+p
1_1.32_(224.2(1.32+p Il)p
l_a_2 n(a+p-lJ p
0.32+ (2 24.2 (0.32+Pl)p
0.32+214.38p(224.2")
141.49p(224.2 p)-0.109_p = 0
1bis equation can be solved for p by trial and error. Values of the left-band-side of the equation for various pare
listed below, starting withp = 0.001 as the first guess.
0.001
0.002
0.0007
0.00076
0.00077
0.000766
0.0339
0.1816
-0.0095
-0.0008
0.0006
0.000017
As the value of the expression wben p = 0.000766 is sufficiently close to zero, the solution can be taken as p =
0.000766.
Answer: 0.000766
1
3
kd = A e--EalR T = 10362 s-l e-283 kJ gmor /(8.3144x 10- kJK""1 gmo1-1 x 353.15K) = 2.20x 10--6 s-1
Solutions: Chapter 11
138
At 121C:
k
=.
A e-ErJ/RT
=.
0.04978-1
At 141C:
The relationship between the number of viable cells and time is given by Eq. (11.87). Converting the units of the
=.
108ceusl-l'111~11
=.
10
11
3
cellsm-
Therefore. per m 3, No =. 1011; N =. 10.3 . Substituting values into Eq. (11.87) gives:
10-3
1011 e-/cd t
=.
10-14
-32.24
=.
=.
e-kdt
-kd t
32.24
t=--
kd
Therefore, at 8We:
t =. 32.24 =.
kd
t =. 32.24
kd
3224
2.20 x 10-6 8-1
kd
=.
3600s
32.24
0.04978-1
= 32.24
.I~I = 4070h
32.24
60s
2.638- 1
= 12.3 s
Heterogeneous Reactious
12.1
(a)
A substrate shell mass~balance is perfonned around a thin slice of sludge of area A and thickness Llz located distance
Iu
Siudga
-----------------------------1------z
Bottom of lagoon
////
Substrate diffuses into the shell across the upper boundary at
Substrate consumption within the shell follows firstMorder kinetics. Following the procedure on p 301, from Pick's
law, the rate of substrate input by diffusion is:
where Vse is the effective diffusivity of substrate in the sludge. Similarly, the rate of substrate output by diffusion is:
The rate of substrate consumption in the shell is kl sA Az.Substituting these expressions into the mass-balance
equation, Eq. (4.1), with the rate of substrate generation = 0, at steady state:
Assuming that the substrate diffusivity and sludge area do not vary with distance ;::::
!t'soA(:!,.",-:l)-k1SA'" =
Taking the limit as A;::: --+ 0 and invoking the definition of the derivative as in Eq. (D. 12) in Appendix D:
~e:(:)-klS = 0
Solutions: Chapter 12
140
or
d 2s
Answer: 2JSe d? -k 1 S
:::::
(b)
At z::::: L, s::::: Sb. At Z "" O. we assume that the substrate concentration profile reaches a minimum so that ds/dz
Answer: At z::::: L, s::::: Jb; at z:::: O. cIs/dz::::: O.
(c)
(I)
If s:::: N efJz, using differentiation rule Eq. (0.17) in Appendix D:
= pNeP'
Wld
Substituting the expressions for s and d2s/dz2 into the differential equation in (a):
or
(H)
If s::::: N ePZ + M e-Pz, substituting the values for p from (I) above:
s;:; NezVk,/!Dse
+ Me-1:Jk,/Vse
Answer.N=M
(iii)
Substituting N for M in the equation for $ in (6):
=O.
Solutions: Chapter 12
141
, =
Applying the boundary condition at z
N(ezJk,l"s. +e-<Jk""s.)
=L:
'b =
Solving for N:
(Iv)
From the definition of cosh x, the numerator in the equation for s in (iii) is equal to 2 cosh (z
the denominator is equal to2 cosh (L kl/psc)' Therefore:
Jk1/.q.)
- 'b2Cosh(LJkl/.q.)
, _
2 cosh (Z
or
, _ cosh(zJk 11.q.)
'b - cosh(LJk 1/.q,l
Answer: QE.D.
(d)
Taking the derivative of s using the equation for s in (c) (iv);
=L:
(L Jk]I:lJ,
sinh
- ~ A-~ Jk I
Se ~o
1 !OSe COSh(L
A,obs -
Jk 1I!OSeSe )
Jkl/.27s )- Similarly,
e
Solutions.' Chapter 12
142
(e)
The internal effectiveness factor is defined in Eq. (12.26). For first-order reaction kinetics at substrate concentration
Sb everywhere in the sludge, the rate of reaction within the entire sludge volume is:
Substituting this and the expression for rA,obs from (d) into Eq. (12.26) for fIrSt-order kinetics:
rA,obs
1]il
= -.-
'A'
Cancelling and grouping terms and applying the definition of tanh x gives:
17i1
tanh(L
JkIffD,,)
LJ k1ffDs,
tanhj
~il
= -j-
Answer: Q.E.D,
(f)
For L = 2 em, the values of I. tanh <ftI and Tlil evaluated for the three sets of conditions are listed below.
Condition
(1)
0.50
2.0
10
(2)
(3)
1]il
0.46
0.96
1.0
0.92
0.48
0.10
The substrate concentration profiles are calculated using the equation for s as a ,function of z from (c) (iii) and
applying the definition of 1'1:
The results for Sb =10-5 grool em-] at various values of z are listed and plotted below.
Distance, z (em)
Condition (1)
0.0
0.3
0.7
1.0
1.2
8.87 x 10-<'
8.89x 10-6
9.00 x 10-6
9.15 x 10--6
9.27 x 10-6
9.50 x 10-6
9.78 x 10-6
1.00 x 10-5
I.S
1.8
2.0
Condition (3)
9.08 x 10- 10
2.14x 10-9
1.50 x 10- 8
6.74 x 10-8
1.83 x 10-7
8.21 x 10-7
3.68 x 10-<'
1.00 x 10-5
Solutions: Chapter 12
143
.,
1.2
E
0
"
1.0
Condition (1)
'& 0.8
4; = 0.50;
1111 = 0.92
0.6
0.4
~
I!,
'"
Condition (2)
0.2
Condition(3) ;1=10;1111=0.10
0.0
0.0
0.5
1.0
1.5
2.0
As tPi increases, 1Jil decreases. the concentration profile becomes steeper, and the minimum suhstrateconcentl'ation in
the sludge is reduced.
12.2
(aJ
From p 269, as CAs is O.5mM/0.015:tnM= 33 times the value of Km as a:frrst approximation we can consider the
kinetics to be effectively zero order with ko vmax. Converting the units of ~ to a per volume of gel basis:
k o = Vmax
= 0.12 mol s-1 kg- l (0.012kgm-3) .113;~11.11~gl = 4.61 x to-5 kgs- l m-3
III
-1 11000
= 0.5mM = 05x to-3 gmoH.
1m3
III I
g . looog
kg = 0.Ol6kgm-3
. 132
gmol
For zero-order reaction. the equation used to determine the substrate concentration inside the beads depends on
whether CA remains > 0 throughout the particle. The maximum particle radius for which this occurs can be
calculated using Eq. (12.17);
=
Therefore. the maximum particle diameter for CA >0 everywhere is 4.2 nun. Because the immobilised-enzyme beads
are smaller than this, CA > 0 and the oxygen concentration profile can be calculated using the equation for zero-order
reaction and spherical geometry in Table 12.1. Values for CA asa function of r areJisted and plotted below.
Radius, r (m)
2.0x
l.60x
1.7 x 10-3
1.5 x 10-3
1.19 x 10-2
1.2 x 1(J3
1.0 x 1(J3
0.8 x 10-3
05 x 10-3
0.2 x 10-3
0.0
9.60 x 10-3
6.63 x 10-3
5.02 x 10-3
3.71 x 10-3
2.28 x 10- 3
L51 x 10-3
1.37 x 10-3
Solutions: Chapter 12
144
20
0>
"- 15
M
0
<J
"
10
O'-_ _--''--_ _- l .
0.0
--'-
1.5
0.5
-'
2.0
As the minimum value ofCA atthe centre, of the bead is still about 2.9 timesKm the assumption of zeroorder
kinetics is reasonable.
(b)
As CA > 0 everywhere within the bead. for zero-order reaction tbismeans that the entire bead volume is active.
Answer: 1.0
(0)
FOf zeroorder reaction, the maximum conversion rate occurs when the oxygen concentration is greater than zero
everywhere in the particle. The largest bead size for this to occur was calculated in (a) is 4.2 rom.
Answer: 4.2 rom
12.3
(a)
k o = 10-3 mols- m-
The maximum particle radius for which oxygen concentration inside the beads remains greater than zero is calculated
usingEq. (12,17):
=
Therefore, the maximum particle diameter for aerobic conditions is 2 x 1 A5 = 2.9 mm.
145
Solutions: Chapter /2
Using this value, the minimum intraparticle oxygen concentration can be calculated from the equation in Table 12.5
for spherical geometry and f/) < 0.667:
CA,min
1)
3
3
6 LxI
4 0 9 m2 s8xlO
kgm
=3,24xlO-3 m=3.24mm
6.4 x 10-6 kg s 1 m 3
Therefore, the maximum particle diameter for aerobic conditions is 2 x 3.24 = 6.5 mm.
12.4
(a)
R = 1.5 mm = 1.5 x 10-3 m. Calculating the observable modulus Dfor spherical geometry from Table 12.6:
3
3
= 0.031
rA,obs = 1.5xlO- m
2.2 x 1O-5 kgs-l mS
6xlO- ms 1(6xIO-3kgm-3}
3 kSCAb
3
l2=!i
Answer: Insignificant; the surface oxygen concentration is only 3% lower than in the bulk medium.
(b)
From Table 12,7 for zero-order oxygen uptake kinetics, 1Jeo =1. The internal effectiveness factor l1io can be
determined from Figure 12.11 as a function of the observable Thiele modulus CPo Evaluating tP from the equation in
Table 12.4 for spherical geometry using the result for CAJ> from (a):
R)2
rA,obs
(I.5XlO-3 m)2
2.2XlO-5 kgs- 1 m-3
( 'vAe CAs =
fJ)='3
3
1.9XlO-9m2s-1(0.97X6xI03kgm3)=0.s0
From Figure 12.11, attP=0.50,1Jio= I. Using Eq,(12.46), 11T= 1Jio l1eo= I X I = I.
Answer: 1
(c)
Using the results from (a) and (b), the minimum intraparticle oxygen concentration can be calculated from the
equation in Table 12.5 for spherical geometry and tJ) < 0.667:
CA,min = CAS(l-itP)
= O,97X6XlO-3kgm-3(1-~(0.50)) =
Answer: Yes
Solutions: Chapter 12
146
12.5
D p "'" 120 JUD "'" 120 x 10.6 m. The external mass-transfer coefficient can be determined using the equations on p 322
for free~moving_spberes. The Grashof number is calculated from Eq. (12.51) with g "'" 9.8 m s2 from p 16 and the
uni{conversion factor 1 N s m- 2 = 1 kg m- l sl from Table A.9. Appendix A:
Gr= gD~PL(pp-PL)
= 9.8 m s-2 (I20X lO-6 mj' 103 kg m-3 (1.2 x Io'kgm-3 _1o'kgm-3) = 3.39
(10-3 N sm-2
.11 kg m- I ,-I h2
U
1 Nsm 2
Therefore, from Eq. (l2.S2).Rep =Gr/18:= 3.39'18 =0.188. The Schmidt number from Eq. (12.49) is:
10-3 Nsm-2 _II kgm$c
IlL
PL.vAL
8;11
IN.sm
103kgm-3(2.3xlO-9m2s
I)
= 435
Therefore, Rep Sc = 0.188 x 435 = 81.8. As this value is less than 104. the Sherwood number can be evaluated using
Eq. (12.55):
Sh =
J4 +
1.21(Rep Sc)"67 =
= 5.21
D = R TA,obs =
3 k s CAb
3
0.015 mol s-1 m-
::::: 0.015
Answer: Negligible
12.6
(3)
R =0.8 nun = 0.8 x 10-3 m. As external boundary~layers have been eliminated. CAs::::: CAb =0.85 kg m-3 and fie =1.
The value of Pas defined on p 313 is:
3
::::: 4.12
0.85kgm 3
From Figures 12.10-12.12, this value of p means that the reaction kinetics can be considered effectively f:trst-order.
Evaluating the observable Thiele modulus tP from the equation in Table 12.4 for spherical geometry:
4>
= (li)2
3
Answer: 0.12
Solutions: Chapter 12
147
(b)
From the definition of the effectiveness factor. Eq. (12.26):
3
L25xtO- .kgs-I m-3 =OOlO4k -I -3
0.12
.
gs m
Por first~order kinetics. r~s
rAJ;
= O.OI04kg s-1 m-
= 0.0122s-1
0.85kgm-3
CAs
kl (,-I)
'lit
0.01
0.05
0.10
0.20
050
0.80
1.0
1.3
0.0012
0.0061
0.0122
0.0244
0.0610
0.0976
0.122
0.159
0.183
0.220
0.244
2.6
5.8
8.2
11.6
18.3
23.1
25.8
295
31.6
34.7
365
0.34
0.16
0.12
0.086
0.055
0.043
0.039
0.034
0.032
0.029
0.027
0.0010
0.0052
0.0104
0.021
0.052
0.083
0.104
0.135
0.156
0.187
0.207
3.40x lO4
8.32 x lO4
1.25 x Ily3
1.81 X lO-3
2.86 x lO~3
3.57 x 10~3
4.06 x lO~3
4.59 X 10-3
4,99 x lO-3
5.42 x lO-3
5.59 x to- 3
1.5
1.8
2.0
The resultsfor 11i1 and rA.obs are plotted below as a function of enzyme loading.
0.4,----,,----,----,-----, 6
5
r-
I!
=w~
0.3
'A,obs
02
1"
"
~
'0
x
~
<!-
2
0.1
l!
c
II
~
~
0.5
-'-
1.0
Enzyme loading (1lffi01 g1)
1.5
...J
0
2.0
0:
148
Solutions: Chapter 12
As the enzyme loading is increased from 0.01 ~ol got, the effectiveness factor drops significantly. Although the
reaction rate continues to rise with increasing enzyme loading, at loadings above about 0.5 !J.mol g-t, less than 5% of
the potential activity of the enzyme is being utilised. Further increases in enzyme loading therefore represent an
effective waste of more than 95% of that enzyme,
12.7
(a)
Dp ::::: 1.5 nun =: 1.5 x 10-3 m. The particle Reynolds number is evaluated using Eq. (12.48) withPL =: density afwater
::::: 103 kg m- 3, andJiL =: viscosity afwater::::: 1 cP (p 133) = 10-3 kg mol 5. 1 (Table A.9. Appendix A):
10 3 kgm 1 8-1
As this value is within the range 10 < Rep < 104, the external mass-transfer coefficient can be determined using Eq.
(12.57) for spberical particles in a packed bed. Converting the diffusivity units to m 2 8. 1:
!lJ.
Ae
iJ)AL
::::: 9x 1O-Qcm 2 s- 1
= 9x 1O-10 m 2 s-1
= Sha/AL
s
Dp
'This value of ks can be used to-determine the observable modulus for external mass-transfer D from the equation in
Table 12.6 for spherical geometry. As the specific gravity of the wet cells is 1. from p 16, 1 g wet cells occupies a
volume of 1 cm3 and rA,obs = 0.28 mg cm-3 hoi. Converting these units to kg s~I m- 3:
rA,obs
= 0.28mgcm-3. h-I
= 0.28 mg cm- h-
Substituting this and the other parameter values into the equation for D:
1.5 X 10-3 m
2
_ 0075
3.24XlO-5ms-I(8mgl-I)I...!!'LjjlOOO11- .
1 m3
1Q6 mg
From Eqs (12.43) and (12.44):
As CAs is close to CAb. external mass-transfer effects are present but small.
Answer: The effect is small; the surface oxygen concentration is 7.5% lower than in the bulk medium.
(b)
Evaluating the observable Thiele modulus tP from the equation in Table 12.4 for spherical geometry Using the result
for CAs from (a):
149
Solutions: Chapter 12
<1>=(li)2
3
1.5X
rA,obs
=(
aJAeCAs
to-3m)2
1 3
7.78XlO'.." skgs- m-
-073
9X10-lOm2s-1(o.925X8mgl-I).!16kg !.!1~1!- .
10 mg
1m
From Figure 12.11 for zero-order reaction, at t1J = 0.73, 17io is very close to but slightly less than 1.0. Therefore,
internal mass-transfer effects can be considered negligible.
Answer: Negligible
(cJ
CAs = 0.925 x 8 mg 1" I = 7.4 mg I-I. As 1Jia is only very slightly less than 1.0, it is likely that oxygen is exhausted
just close to the centre of the clumps. Taking rA,obs to be essentially equal to the intrinsic zero-order rate constantko,
the maximum particle radius for the oxygen concentration to remain greater than zero throughout the clump can be
evaluated using Eq. (12.17):
_
-
(9xto-lOm2S-1)7.4mg'-11'6kQI'~11
F!-
Rmax
= 7.2 x 104
1Omgl'
1m
= 0.72 mm
Therefore, the maximum particle diameter for oxygen through to the centre of the clump is 2 x 0.72 = 1.4 mm, which
is only slightly less than the plant cell clump diameter of 1.5 mm.
Answer. The oxygen concentration falls from 7.4 mg I-I at the external surface to zero just near the centre of the
clumps.
12.8
(aJ
R = 2.5 mm = 2.5 x 10-3 m. The presence of external boundary-layers can be checked by calculating the observable
modulus for external mass-transfer, D. From Table 12.6 for spherical goomelry:
,Q=!!..
rA,obs
3 kSCAb
= 2.5x10-3 m
5
1 3
8.7XlO- kgs- m3.8x10 5 ms 1(8XlO-3 kgm-3)
=024
.
Answer: Yes
(bJ
As oxygen uptake is considered a zero-order reaction, for CAs> 0, l1eo = 1.
Answer: 1
(c)
In the absence of internal an;! external mass-transfer resistances, th~ reaction rate is r~b corresponding to CA = CAb
throughout the pellets. As rAb is related to rA,obs by Eq. (12.45), r b can be determined if we know 1JTo. Evaluating
the observable Thiele modulus <P using the equation in Table 12.4 tor spherical geometry and the result for CAs from
(a):
150
Solutions: Chapter 12
From Figure 12.11 for zero-order reaction. at <P = 5,66,1'/io = 0.30. Therefore, from Eq. (12.46), as TJeo "'" 1 from (b),
l7To "'" TJio TJeo "'" 0.30 x 1 = 0.30. Using Eq. (12.45):
r
'*
A,obs
rAb""'--"'"
~ro
87 10-'k -1 -3
,x
gs m
= 29
,x 10'""kgs -1 00-3
0.30
Answer. 2,9 x 10'4 kg lSI 00,3, or more than three times the rate actually observed
(d)
If external mass-transfer effects were eliminated, CAs = CAb = 8 x 10-3 kg 00,3, and the observed reaction rate would
be greater than 8,7 x-1O- 5 kg g-l.m- 3, Under these conditions. an-expression for the observable Thiele modulus ep
from the equation in Table 12.4 for spherical geometry is:
~ _(R)2
.... - -
where.rAObs has units of kgs- 1 00-3 .- Because the reaction is zero--order, r~s = r~b; therefore, from the result in (c),
r~s = 2,9'x 10-4 kg g-1 00,3, Using Eq. (12.26):
r A,obs
'ho
r A,obs
tP and TJio are related by the curve in Figure 12.11 for spheres and zero-order reaction. The value of rA,obs can be
determined
trial-and-error using Figure 12.11, and the equations derived above, As a ftrst guess, take r A,obs = 2.0
x 10-4 kg S' 00,3. Depending on the difference between the values of 1]io obtained from the figure and from the
equation with r ~s' adjust rA,obs as shown in the table below.
bl
11iO = r~Obs
<1>
9.92
4.96
0.19
0.34
rA,
2.0 x 10-4
1.0 x 10-4
0.69
0.34
Since the values for 11io in the last row are as close as practical, rA,obs "" 1.0 x 10-4 kg s-I 00-3. Therefore, compared
with the observed reaction rate of'8.7 x 10-5 kg Sol 00- 3 in the presence of both 'internal and external mass-transfer
resistances, eliminating the external boundary layers increases the reaction rate by about 15%.
00- 3
Reactor Engineering
13.1
For 75% conversion, sf = 0.25 so- TIle batch reaction time for enzyme processes is evaluated using Eq, (13.10):
Km I So sO-sf
tb = - - n-+-Vmax
sf
vmax
1.5 g 1-1
In
O.9gI 1 h 1
3g1-1
O.25X3g1 1
O.9gI 1 h 1
-I ~:~l
$4800 day-l
= $962
The mass of product formed is detennined from the mass of substrate consumed. which is equal to the change in
substrate concentration multiplied by the volume of the reactor V:
Mass of substrate consumed = (so-sf) V = (3-0.25x3)gl-1 (16001) = 3600g
As 1.2 g product are fonned per g substrate consumed:
= 6.84h
At 90% conversion, the operating cost is increased due to the longer reaction time~
Operatingcost = 6.84h.j
;:~I.$4800day-l = $1368
152
Solutions: Chapter 13
Mass of substrate consumed
=:
($0- Sf) V
=:
=:
4320 g
=:
5.18 kg
=:
=:
$649
=:
=:
revenue - operating cost- downstream processing cost "'" $3885 -$1368 - $649
The gain per batch from increasing the conversion from 75%:to90% is therefore $1868 -" $1715
=:
=:
$1868
$153.
Answer: There is a gain of $153 per batch; representing a 9% increase in the cost benefit at 75% conversion.
13.2
(0)
The initial concentration of substrate So =: 15% (w/v) =: 15 g per 100 ml =: 150 g 11. The final substrate concentration
Sf = 0.15 So = 0.15 x 150 g 1-1 = 22.5 g 1-1, Calculating the deactivation rate constant at 32"C using Eq, (11,45):
tb =-lln[l-k
Km In SfSo + SO-S,)]
d ( vmaxo
k
Vmaxo
d
l
1
1
In 1_2.75XIO-3h-l( 4.0gl- 10 lSOgl- +(150-22.5Jgr ) = 23.6h
2.75 x 10-3 h- 1
5.9 gl 1 h-1 22.5 g I-I
5.9 g I-I h- 1
-I
2.3d 24h
m In So + so-S,)]
( K
tb = -lln[l-k
d
k
vmaxo
Vmaxo
Sf
-I
L26xlO 2 h-l
1
1
In l-l.26XIO-Zh-l( 4.0gl- In 150gl- + (150-22.5j gl-I) = 17.7h
8.5gl- 1 h- 1
22.5g1 1
8.5g11h 1
As the batch reaction time is lower at 37"C, 37"C is the recommended operating temperature.
Answer: 37"C
(h)
From Eq. (13.33), the total batch reaction time at 37"C is:
153
Solutions: Chapter 13
tT =- 1b+tdn =- 17.7h+28h =- 45.7h
365d!W!
Numberofbatches =- 45.7 h per batch =- 192
In each batch, the mass of ammonium fumarate converted is 0.85 x 150 g r 1 =- 127.5 g 1-1 multiplied by the reactor
volume V. Therefore. the mass of substrates converted is 1275 V g =- 0.1275 V kg, where V has units of litres. From
the reaction stoichiometry, as the molecular weights of ammonium fumarate and aspartic acid are approximately
equal, the mass of aspartic acid produced is also 0.1275 Vkg. After one year or 192 batches. the mass of aspartic acid
produced is 0.1275 V x 192 =- 24.5 V kg. Using the conversion factor 1 tonne =- 103 kg (Table A.3, Appendix A), the
target level of aspartic acid production each year is 5000 x 103 =- 5 x 1()6 kg. To teach this target level:
24.5 Vkg = 5 x 106 kg
V= 2.04 x 1051
= 204m3
Answer: 204 m 3
13.3
(aJ
The initial cell concentration Xo =- 12 g/loo I =- 0.12 g 1-1. Assume that stationary phase is reached when Sf =- O. The
batch culture time can be determined using Eq. (l3.27):
l] =- 4.3h
gg- (
XS
] =- - -Il I n [0.575
tb =- - -I I n [Y
l+-(so-sr)
1+
I lOgl-I -0
Pmax
Xo
0.9 h0.12 g I
Answer: 4.3 h
(bJ
tb = _1_ln[1 + YXS
Pmax
Xo
Sf
0.12g'-
The biomass density at this time can be calculated from Eq. (13.19):
1
xf =- Xo ePmax iI =- 0.12 g.-I e(O.9h- x 3.9 h) =- 4.0 g I-I
13.4
Fed-batch schednling
(aJ
The initial substrate concentration So =- 3% (w/v) =-3 g per looml =- 30 g I-I. The batch culture time to achieveS{=- 0
. is determined using Eq. (13.27):
tb = _1_ln[l+ YXS(so-'d] =
I 1 1n[1+ 0.5 gg-I(30gl-I-Ol] = 13.3d
Jlmax
Xo
0.18d1.5g1-1
The biomass density at this time can be calculated using Eq. (13.19):
xf =- xoePmuft. =- 1.5 g 1-1
i0.18a' x 13.3 d) =-
16.4g1-1
Answer: The batch culture time is 13.3 days; the final biomass concentration is 16.4 g 1. 1.
154
Solutions: Chapter 13
(b)
The mass of cells at the start of fed-batch operation is equal to the fmal batch cell concentration multiplied by the
The fmal mass of cells after 40 d fed-batch culture can be determined using Eq. (13.50):
Answer, 4.04 kg
(c)
The mass of cells produced in each reactor run is equal to the final biomass minus the biomass used for inoculation:
Biomass produced per run
:=
where lb is the batcbreaction time and lfb is the fed-batch operation time. Substituting parameter values using the
result for 1b from (a):
IT
year:
Biomass produced per year = 3.89 kg x 5.06
:=
19.7 kg
Answer: 19.7 kg
13.5
(a)
An expression for the liquid volume as a function of time during fedbatch reactor operation can be derived from an
unsteady-state total mass balance as shown in the solution to Problem 6.7afrom Chapter 6. Using this expression:
Vo
=:
V-Ft
=:
Answer: 16 m3
(b)
From the definition of the dilution rate in Eq. (13.39), after 6 h cffed-batch operation when V"" 40 m 3 ;
D
=!:.. =
V
3 1
4m b40m3
=:
O,lOh-1
Substituting this value into Eq. (13.45) for the substrate concentration at quasi*steady state:
s=
DKS
Iimax-D
= O. 10 h- (0.I5kgm- ) = 0.06kgm-3
0.35h I_ O. lOb 1
Answer: 0.06 kg ro 3
(c)
Taking maintenance substrate requirements into account, for qp:: 0, Eq. (13.43) becomes:
Solutions: Chapter 13
155
Is
dt =
At quasi~steady state, dsld! '" 0, J1 '" D, ands
D(S.-S)-(.J!....+ms)x
1
Yxs
Sj.
o = DSi-(~s +ms)x
Solving for r.
1
Ds,
O.10h- (SOkgm- )
=,,-'=__~T'--""=':"-.1.= 14.0kgm-3
_D_+ ms
Yxs
x = xV =
At the start of fed-batch 0r.:ration when the liquid volume is 16 m3 , if operation is at quasi~steady state, the cell
concentration", 14.0 kg m- and:
x=xV=
Therefore, the mass of cells produced during fed~batch operation is (560 kg - 224 kg) = 336 kg.
Answer: 336 kg
13.6
Convert the parameter values to units of kg, m, s. Km. =0.54 g 1~1 =0.54 kg m- 3. During the reactor operation, s
0.02 g 1~1 = 0.02 kg m~3;si = 0.42 g 1~1 = 0.42 kg m~3. R = 1 mm = 10- 3 m. The active enzyme concentration per
unit volume of catalyst ea is:
ea = lO-4 g
250cm3
lO-4 g
250cm3
1m
Ae
7XI0-6cm2s-I'I~12
l00cm
= 7xlO- lO m 2 s-1
From Table B.l (Appendix B), the molecular weight of urea is 60.1 and the molecular weight of NH4+ is 18.0.
Therefore, from the stoichiometry, reaction of 60.1 g urea produces 2 x 18.0 =36.0 g Nf4+. Expressing the turnover
number k2 in terms of urea:
k2
ore: 1
36.0gNH4
k2
From Eq. (11.33), Vmax expressed on a'per volume gel basis is:
Vmax = k2 ea = 1.84 x 104 kg kg~l sl (4 x 10-4 kg m~3) = 7.36 kg m~3 s-l
As there are 250 em 3 gel per litre of liquid in the reactor, Vrnax expressed on a per volume liquid basis is:
156
Solutions: Chapter 13
1~131100011=
. 1m3
3
vrnax =736k
.
gm-3 s_1(2S0Cm
11 ) . lOOcm
184k
. gm-3-1
s
The rate of reaction can be determined after evaluating the effectiveness factor in the absence of external boundary
layers. From the definition of f30n p 313 with CAs = s:
p=
3
Km = O.54kgm- "'" 27
s
O.02kgm-3
From Figure 12.10, for this value of p the reaction kinetics can be considered first-order. Based on Eq. (11.36), the
effective first-order rate constant kl is:
-3-1
I .84kgills
"'" 3.418-1
3
0.54kgm-
_Calculating the Thiele modulus from the equation in Table 12.2 for first-order kinetics and spherical geometry:
~il = <Pi /
I
23.3 = 0.043
From Eq. (12.46), as TIe = 1, 1]T= 0.043. The flow rate of urea solution iDto and out of the reactor can be detennined
by evaluating the dilution rate D in the mass-balance equation, Eq. (13.54):
D =
7V~_T,;-V:;m7""';-'--:K
(Km + $) (si
$)
3
= -,0",.04=3"(I".8"4",kg"m"-,3-:o,-_IL)0",.0,,,2:.okg=mc.-_,, = 7.06 x 10-3 s-I
(0,54+ 0.02) kg m-3 (0.42-0.02) kg m-3
3
10- I s-I (30 min)
ll~n
= 12.71
Answer: 12.7litres
13.7
= 4% (w/v) = 4 gper 100ml =40 g 1-1 =40 kgm- 3 . Sf = s=0.02x40kg m-3 =0.8 kg m- 3. For the batch
reactor. X() = 0.01% (w/v) = 0.01 g per 100 ml = 0.1 g I-I = 0.1 kg m- 3.
SO= Si
' 3] = 11.6h
4I
- 3 (40-0.8) kg mtb = " In [Y
I +-('O-Sf) =
lin [10
+.
r-max
XO
O.44h
O.lkgm
xs
gg
Solutions: Chapter 13
157
_ 365dl*1 _
x 106 kg.
For continuous reactor operation, the steady'-state cell concentration is given by Eq. (13.62):
x = (Si-S)Yxs = (40-0.8)kgm- 3 (0.41gg- l ) = 16.1kgm-3
The dilution rate D corresponding to S = 0.8 kg m- 3 can be detennined using Eqs (13.57) and (lL6O):
1
3
M4h- {O.8kgm- j
D = p = I'm",,' =
Ks+s
07
. mg r
= O.44h-1
08kgm-3
. 11000111~1
3'
6
+.
1m
10 mg
Answer: The annual biomass production using continuous operation is 5.78 X 107 kg, which is 12.7 times the
production of 4.54 x 106 kg from batch culture.
13.8
So = Si = 10% (w/v) = 10 g per 100 ml = 100 g 1. 1 = 100 kg m- 3. Sf = S = 0.01 x 100 kg m-3 = 1 kg m- 3. Based on the
-unsteadystate mass-balance equation derived in Example 6.1 in Chapter 6 for first~order reaction, the equation for the
rate of change of substrate concentration in a batch reactor is:
d(V,) _ -Ie V
(itIS
where V is the reaction volume and k} is the reaction rate constant. As V can be considered constant in a batch
reactor, this term can be taken outside of the differential and cancelled from both sides of the equation:
ds
dt =-k 1 s
The differential equation contains only two variables, sand t. Separating variables and integrating:
ds
- = -kl dt
Using integration rules (D.27) and (D.24) from Appendix D and combining the constants of integration:
Ins=-klt+K
The initial condition is: at t = 0, S = so. From the equation, therefore, In So = K. Substituting this value of K into the
equation gives:
Solutions: Chapter 13
158
lns = -kl t+lnsQ
In-=-kt
'0
The batch culture time 1b is the time requited for the substrate concentration to reach Sf.
-l
sf
-10-
So
tb = - - =
k1
1kgm-3
3
lOOkgm
O.8XlO-4Cl13~sl
= 16.0h
tT = tb+tdn
= 16.0h+20h = 36h
lITl
24h
her 400
fh,onn "
num 0 atehesperyear
I=
3 g
400tonnes 1_l0__k_
=
o.ci--'-l"to"n"ne",
243
1.65 x 103 kg
Reactor volume
= I.65xl0
k:g
100 kg m-3
= 165m3
0:= FSi-Fs-1q sV
0:= FIV(Si-S)-kl sV
Solving for Fly.
F;
V----
The flow rate of penicillin G into the CSTR is 400 tonnes per year. Using the unit conversion factor 1 tonne:= 103 kg
(Table A.3, Appendix A) and the concentration of substrate in the feed stream Si := 100 kg m-3, the total volumetric
flow rate of the feed stream F is:
F:=
I I
i lId Illh
3
1Yeai
-1
10
kg . 1 365 d . 24 h . 3600 s
400 tonnes year . 1 tonne
100 kg m-3
159
SolutWns: Chapter 13
= 157m3
For the PFTR, if the density of enzyme beads is four times greater than in the other reactors. kl = 4 x 0.8 x 104 sl =
3.2 x 10-4 sl. By analogy with Eq. (13.83), the differential equation for change in substrate concentration with
position in the reactor for firstorder kinetics is:
<Is
Uctz=-k1s
The differential equation contains only two variables, s and z. Separating variables and integrating:
<Is
-k,
-=-dz
S
u
Using integration rules (D.27) and (0.24) from Appendix D and combining the<;onstants"of integration:
-k,
Ins = -z+K
u
= si. From the equation, therefore, In sf= K. Substituting this value of Kinto
-k,
Ins = -z+lnsj
u
Applying the defInition of the reactor residence time .. from Eq. (13.85):
sf
In- =-kl't'
si
Note that this is 1/4 the value obtained for the batch reaction time th. as expected from the analogous kinetic
characteristics ofbatch and PFTR reactors and the 4 x higher value ofk] in the PFTR.
As calculated for the CSTR, F = 1.27 X 10-4 m3 8. 1. Therefore. from the definition of .. in Eq. (13.51):
V
Solutions: Chapter 13
160
13.9
(a)
Sj:::::
10 g 1~1 ::::: 10 kg m- 3 , The dilution rate, which is the same for both reactors, is calculated using Eq. (13.39):
= f. =
1m3
501h-1 1
I
10001
a.5m3
= O.lOh-'
The cell and substrate concentrations entering the second reactor are the same as those leaving the first reactor. The
substrate concentration can be determined using Eq. (1358):
O.12h-1-O,lOh- 1
When maintenance requirements are significant, the cell concentration is calculated using Eq. (13.61):
x:::: D(sj -s)
.D. +ms
Yxs
= _O"'c.lO"b"-.'",(lcoO.-.cS".O",),,kg,.m=.
-3_ = 2.2 kgm-3
O.lOh-
O.5kgkg I
Answer: The cell concentration is 2,2 kg m-3; the substrate concentration is 5,0 kg ro- 3.
(b)
As growth is negligible in the second reactor,-x ::::; Xi ::::: 2.2 kg m- 3. The substrate concentration is determined by
rearranging Eq. (13.59)and solving for s with fJ::::: 0:
qp
Answer: 97%
(cj
As product is not formed in the first reactor, Pi = 0 for the second reactor. The product concentration is determined by
rearranging Eq. (13.64) and solving for p:
p
501h-lll~11
Answer: 3.5 kg m- 3
Solutions: Chapter 13
161
10
15
20
25
30
35
50
0.010
0.015
0.020
0.025
0.030
0.035
1740
17.4
25.1
39.8
1673
1990
1872
2313
2289
2000
46.8
69.4
80.1
100
O.OSO
SID OtM h)
2500
2000
:2
ore,
1500
1000
l-~_...L_~_L.~_...L_~_L._~....J
20
40
60
Substrate concentration,
80
S
100
(p.M)
The slope of the straight line in the plot is 10.48 h; the intercept is 1493 liM h. From Eq. (13.92), the slope = llPmax;
therefore, J.tmax =1/10.48 h = 0.095 h"l. The intercept = KS/p:max;thereforeKg = 1493 J.l,M hx 0.095 h"l = 142 J.l,M.
tlmaxSj
Calculating the flow rate from Eq. (13.39) with V = 1000 mI, F = D V"", 0.039 h"l x 1000 ml = 39 ml h~I.
Answer: 39 ml h"l
SID (g I-I h)
1.0
1.4
1.6
1.7
1.8
1.9
o.so
0.010
0.038
0.071
0.066
0.095
0.477
0.020
0.054
0.089
0.078
0.106
0.70
0.80
0.85
0.90
0.95
0.502
Solutions: Chapter 13
162
0.6
0.6
0.4
:2
.$
0.3
~ICl
0.2
0.1
0.0
0.0
0.1
0.2
0.3
Substrate concentration,
0.4
S
0.5
(g 1-1)
'The slope of the straight line in the plot is 1.027 h;the intercept is 0.0119 g I-I h. From Eq. (13.92), the slope:
Iftlmax; therefore, J.Lmax:::: 1/1.027 h "'" 0.97 hoi. The intercept:::: KS/J.I.max; therefore Ks =0.0119 g I-I h x 0.97 h- t =
0.012 g l-t,
From Eq. (13.93), Yxs and ms can be determined from the slope and intercept of a plot of 1I~ versus lID, where
Y~s is calculated using Eq. {13.94) '\II(ith Sj "" 10 g I~l. The relevantdata are listed and plotted
beISt,
Flow rate, F (l h- 1)
liD (h)
Y~s(g g-l)
Ill"
1.0
1.4
1.6
1.7
1.8
1.9
050
0.70
0.80
0.85
0.90
0.95
2.00
1.43
1.25
1.18
1.11
LOS
0.315
0.323
0.329
0.328
0.324
0.326
3.175
3.096
3.040
3.049
3.086
3.067
XS
3.20,---,---,-.,--,,--,---r--,
3.15
--'?:-X
b
.$
_ m 3.10
3.05
3.00
0.8
1.0
1.2
1.4
1.6
1.8
2.0
2.2
(g g-l)
Solutions: Chapter 13
163
The scatter in the plot is typical for measured values of l/Y~, The slope of the straight line in the plot is 0.12 g g.l
h- I ; the intercept is 2.93 g g-1. From Eq. (13.93), the slope =- ms; therefore ms =- 0.12 g g.l h- 1. The intercept =I/ yxs ; therefore Yxs =- 1/2 .93 h-I =- 0.34 g g-l.
,.z,
f. =-
=-
3 1
1.5m h1t (0.06 m)Z
=-
132.6mh-1
The value of the specific death constant is evaluated using Eq. (11.46) with R =- 8.3144 1. gruoll ,K~l from Table 2.5,
Ed =- 288.5 kJgmol-l =- 2.885 x loS J gruolI, A =- 7.5x 1039 h l , and the temperature convertedfromoC to degrees
Kelvin using Eq. (2.24):
kd
=A e-EdiR T == 7.5 x 1039 h-1 e-Z.885 x lOS J gmorlt[(8.3144J gmor1 K"1)(130+ Z73.15H(] = 313.1 h- 1
Within a period of 3 months "" 90 d, the number of cells Nl entering the steriliser is equal to the medium volumetric
flow rate Fmultiplied by the cell concentration and the time:
Nj
1~:~)90d.12::1 = 3.24 x 10 14
Within the same 3-month period, the acCeptable number of cells remaining at the end of the sterilisation treatment is
NZ =- L Therefore:
NZ
Nt
=-
1
3.24x 10 14
=-
3.09 x 10-15
(a)
For perfect plug flow .withno:axial dispersion, the sterilisation time can be determined using Eq. (13,97):
N1
In-
N2
thd
=-
kd =
1n 3.24XlO
14
1
313.1h 1
= O.107h
To allow the medium to remain for this period. of time in the.holding ,section,of:the steriliserpipe,.the length of pipe
required is equal to the linear velocity of the medium u multiplied by t'hd:
Answer: 14.2 m
(h)
Calculating the Reynolds number for pipe flow using Eq, (7.1) with pipe diameter D =- 12 cm =- 0,12 m:
Dup
0,12 m(132.6m h-1) lOOOkgm-3
Re=---=
=-3978
,u
4kgm-1 h 1
The value of !J)vu Dcorresponding to this Re is found from Figure 13.40. Using the experimental curve as this gives
a higher 2i than the theoretical curve and thus a more conservative design, 1Jzlu D "" 1.5. Therefore:
164
Solutions: Chapter 13
where L has units of m. Similarly, an expression for the Damkohler number Da from Eq. (13.102) is:
k L
Da
=- du "'"
(313.1 h- 1) L
132.6mb-1
"'" 2.36
The design problem can be solved from this point using tria1~andwerror methods and Figure 13.41. As a first guess, try
L = 20 ID. The values for Pe and Da are evaluated using the equations determined above, and the corresponding value
for N2/Nl read from Figure 13.41. Depending on how this value compares with the target of 3.09 x 10- 15 , the value
of L is adjusted until the results for N2/N} coincide. The calculations are shown in the table below.
L(m)
Pe
Da
20
110
18
19
99
47
42
105
45
4x
1 x 10- 14
1.5 x to- 15
The last value of N2/NI is as close as practicable to 3.09 x 10- 15 considering the resolution of Figure 13.4l.
Therefore. the required length of pipe in the holding section is about 19 m. or 34% longer than that detennined for
ideal plug flow.
Answer: About 19 m
(e)
For L =- 14,2 m, from the equations developed in (b), Pe :::: 78 and Va:::: 34, From Figure 13.41, N2/Nl is about 5 x
10- 12; therefore, NI/N2 :::: 2 X 1011. As N2 :::: 1, N} :::: 2 x 1011, i.e. one contaminant enters the fermentetfor every 2 x
lOll that enter the steriliser, For F:::: 1.5 m 3 h- l and an input contaminant concentration of lOS ml- l , the time
required for 2 x 1011 contaminants to enter the steriliser is:
2 x 1011