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Bio Process Engineering Principles
Bio Process Engineering Principles
Pauline M. Doran
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SOLUTIONS MANUAL
Bioprocess Engineering Principles
Pauline M. Doran
University of New South Wales, Sydney, Australia
Page
NOTE
All equations, tables, figures, page numbers, etc., mentioned in this manual refer to the textbook,
Bioprocess Engineering Principles.
Introduction to Engineering Calculations
1.5 x
10-6 cP ::::: 1.5 x 10-6 cP ,1 10-
3 g
k ;-1
t
s-ll.ll~~mI = 1.5 x 10-11 kg s-1 cm- 1
Answer: 1.5 x 10- 11 kg s-1 em- t
(b)
From Table A.S (Appendix A): 1 bp (British)::::: 42.41 Btu min-I
Therefore:
(e)
From Table A.S (Appendix. A): 1 mmHg:= 1.316 x 10-3 attn
From Table A.I (Appendix A): 1 ft = 0.3048 m
=
From Table A.7 (Appendix A): 11 atm 9.604 x 10-2 Btu
From Table A8 (Appendix A): 1 Btu min-I::::: 2.391 x to- 2 metric horsepower
Im=lOOcm
11= lOOOcm3
Ih=60min
Therefore:
(d)
=
From Table A.7 (Appendix A): 1 Btu 0.2520 kcal
From Table A.3 (Appendix A): Ilb = 453.6 g
Therefore:
1
345 Btu Ib- = 345 Btulb-
1
.1 o.2i~~Call·14;3~: g I = O.192kcal g-l
Answer: 0.192 kcal g-1
n(3cms-l.l~n(251bfC3I0.4536kgl.1 ~
3
(2mm.1 1m Ift
2.832 x 10 2 m 3U _
Dup
Re::: - p - =
l000mmU l00cmU
10
-6 P
I lIb
10
-3
kgm
1
s
-11 - 2.4 x 10
7
c . 1 cP
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 s·t
Ih=3600s
Therefore, usingEq. (2.1):
= 1.5 x 104
13~sl
Answer: 1.5 x 104
Temperature in the ideal gas equation is absolute temperature; therefore, from Eq. (2.24):
From Table 2.5, R "" 82.057 cm3 atm K-I gmol~l. Substituting parameter values into the density equation gives:
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 3
-1 s-11
S_J1.L_
0,87eP.
1'0-2 gem
leP -349
c - PrJ) - (0.9962652g cn,-3)(2.5 x 10 5em2 s I) -
Therefore:
_Sh:lJ_(ll.21(2.5xl0-5cm2s-I)_I·A 10-3 -I
kL - - - - 02 -,<tUX ems
D1J . em
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:
Converting these units to lbj' from Eq. (2.16), 1lbf= 32,174 Ibm it s·2; therefore:
4 2 llbf
Weight = 2.008 x 10 lbmfts- , 2 .= 6241b
32.174Ibm ft s
f
Answer: 624lbI When g :::: 32.174 ft s·2, 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 = 6211bf
32.1741b m ft s-2
Answer: 621lbf
. (e p ")
Umtsof - - ::::
I
(Bmlb- '1'1) Ibh- I ft- I
= 1
k BIUh-1 ft-2('Pft-1tl
1 2
UnilsOf(DG) = (ftllbh- ft- = 1
J1. Ibh1ft1
4 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:
As Np is a dimensionless number, equation (i) is not dimensionally homogeneous and therefore cannot be correct.
Answer: (li)
(a)
FromEq. (2.19):
(b)
From Table A.3 (Appendix A): lIb =453.6 g. Therefore:
9072g
gram moles NaOH = I = 227 grool
4O.0g gmol-
Answer: 227 gmol
(c)
From p 16, 1 kgmol::::: 1000 gmot. Therefore, from (b):
.-----
Solutions: Chapter 2 5
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
LS129g
gram moles : 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:
1
Molar specific volume : 1 d . : .,-_ _,,-1-:--:::;- : 41.67cm3 gmor 1
mo ar enslty 0.0240 gmol em 3
(b)
(I)
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):
Answer: 0.55 water; 0.18 ethanol; 0.15 methanol; 0.04 glycerol; 0.06 acetic acid; 0.03 benzaldehyde
T(K) = -40+273.15
T(K) = 233
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
(b)
From p 19, vacuum pressure is the pressure below atmospheric. If the atmospheric pressure is 14.7 psi:
(b)
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.
(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: 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,
(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.
(d)
Production of 2.5 kg cells is equivalent to 2500 g =: 2500 g/91.5 g gmoI-l = 27.3 gmol cells. The minimum amounts
of substrates are required when 100% of the hexadecane is converted according to the stoichiometric equation.
(I)
From the stoichiometry, production of 27.3 gmol cells requires 27.3/1.65 =16.5 gmol =16.5 gmol x 226.4 g gmol-I =
3736 g = 3.74 kg hexadecane.
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):
From Table 2.5, R "" 82.057 cm3 atm K-I gmol-I. Substituting these values into the equation for V gives:
v= 3 1
(1282.9gmolj(82.057cm atmK- gmol-l)(293.15Kj 1-.!.."'...1
3 = 31 3
1 atm . l00cm m
Answer: 31 m 3
Presentation and Analysis of Data
x = 5.15+5.45+5.50+5.35 = 5.36
Answer: 5.36
(b)
Calculate the standard deviation from Eq. (3.2):
(c)
(d)
x= 5.15+5.45+5.50+5.35+5.15+5.45+5.50+5.35 = 5.36
10 Solutions: Chapter 3
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.
(h)
=
Xl = 3.2; Yl 14.5
);2 = 8.9; Y2 = 38.5
A straight line plot of y versus x Ih on linear coordinates means that the data can be represented using the equation:
Y=Axlh+B
Answer:y=20.1x'k -21.5
(0)
Xl=5;Yl=6
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
(d)
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).
From Eqs (3.13) and (3.14),
Solutions: Chapter 3 11
(eJ
Xl = 1.5; YI = 2.5
X2 = 10; Y2 = 0.036
A straight line' plot of y,versus X on semi·log coordinates means that the data can be represented using Eq. (3.15).
From Eqs (3.17) and (3.18):
B = el.666 = 5.29
(bJ
35
30
--.
.9 25
••
0
~•
20
g 15
8
~g 10
"' 5
0
0 50 100 150 200 250 300 350
Peak area
12 Solutions: Chapter 3
(e)
The linear least squares fit of the data is:
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.
10- 11 r---~--.,...--~----r--~---.
[" 10- 12
•"
fc
.Q 10- 13
lii
"E
~
= 10. 14
-lllJ:
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 K·1; therefore:
(c)
From the equation in (b) for the straight line, ao is equal to 9.66 x 10Z4.
Answer: 9.66 X 1024
16
--,
!'!l
14 ••
c
••i'! 12
C
•g
0
10
•
0
8
~ • •• •
•• •
6
~
••m 4
•~ 2 •
.i1
0
0 12345 6
Decrease in medium conductivity (mS cm-1)
y =: 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).
o -1.58
0.12 0.57
0.31 -!l.23
0.41 0.36
0.82 1.20
1.03 1.36
lAO 1.28
1.91 0041
2.11 0.19
2.42 -0.46
2.44 -!l.50
2.74 -!l.73
2.91 -1.69
3.53 -1.99
4.39 -1.00
5.21 1.48
5.24 0.02
5.55 1.37
14 Solutions: Chapter 3
·2
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.
0.11
~
0.10
'"
.§.
os' 0.09
.~ • •
~
0.08
.""
'E
0.07
•
,1l. 0.06
•
•
~
~ 0.05
::J
0.04
0.00 0.02 0.04 0.06 0.08 0.10
Gas superficial velocity, uG (m s-1)
The data are reasonably well fitted using a linear model. The linear least squares equation for the straight line fit is:
y = 0.054 + 0.466 x
where y is liquid superficial velocity in m s-l andx is gas superficial velocity in m s·l. 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,
Solutions: Chapter 3 15
(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
Gas superficial velocity, uG (m s·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 s·l andx is gas superficial velocity in m s·l. 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 non·linear model is better because the sum of squares of the residuals is smaller.
10' . , . - - . , . . . - . . . . , - - , - - - - , - - - - , , - -. . .- - - .
103
101
100 '--_.1-_-'-_-'-_-'-_-L_----'-_---'
o 5 10 15 20 25 30 35
Time (min)
16 Solutions: Chapter 3
(c), (d)
The equation for the straight line in the figure is:
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
I I
I I
Buffer solution in Buffer solution out
80 kg min- 1 I Hollow-fibre membranes I
I I
Cell concentrate Fennentation broth
6% bacteria
I I 350 kg min- 1
1% bacteria
99% water
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) Compounds involved in reaction
No compounds are involved in reaction.
(v) Mass-balance equation
As there is no reaction, the appropriate mass-balance equation is Eq. (4.3):
In Out
Stream
Water Bacteria Buffer Total Water Bacteria Buffer Total
Fermentation 346.5 3.5 0 350
broth
Buffer solution in 0 0 80 80
Cell concentrate ? O.06C 0 C
Buffer solution ? 0 80 B
out
Total 346.5 3.5 80 430 ? 0.06C 80 C+B
C = 58.3 kg
Total mass balance
430 kg total mass in = (C + B) kg total mass out
Water balance
346.5 kg water in = water out
These calculations allow completion of the mass~balance table with all quantities in kg.
Stream In Out
Water Bacteria 814fer Total Water Bacteria Buffer Total
Fennentation 346.5 3.5 0 350
broth
Buffer solution in 0 0 80 80
Cell concentrate 54.8 3.50 0 58.3
Buffer solution 291.7 0 80 371.7
out
Total 346.5 3.5 80 430 346.5 3.50 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.
(b)
The total flow rate of cell concentrate from the membrane tubes is 58.3 kg min-I.
system boundary~
Feed
- -- - -- - 1
40 kg h- 1 I I Aqueous residue
10% glucose 0.2% glucose
I I
90% water 0.5% ethanol
I Membrane system I
I I
Solvent Product
40 kg h- 1 I I
2. Analyse
(i) 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
CO, =44.0
(iii) 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):
For water, solvent and total mass, the appropriate mass-balance equation is Eq. (4.3):
3. Calculate
(i) 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.
20 Solutions: Chapter 4
Stream In Out
------- Glucose Ethanol CO, Solvent H,O Total Glucose Ethotwl CO, Solvent H2 O Total
Feed 4 0 0 0 36 40
Solvent 0 0 0 40 0 40
Aqueous 0_002R 0.005 R 0 0 ? R
residue
Product 0 ? 0 ? 0 P
Off-gas 0 0 ? 0 0 G
Total 4 0 0 40 36 80 0.002 R ? ? ? ? R+P
Water balance
Water is a tie component.
36 kg water in ::::: water out
Water out::::: 36 kg
As water appears on the Out side of the table only in the aqueous residue stream:
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
4 kg glucose in + 0 kg glucose generated ::::: 0.073 kg glucose out + glucose consumed
C02 balance
okg COZ in + 1.92 kg C02 generated = C02 out + 0 kg C02 consumed
C02 out = 1.92 kg = G
Ethanol balance
o kg ethanol in + 2.010 kg ethanol generated = ethanol out + 0 kg ethanol consumed
These calculations allow completion of the mass~balance table with all quantities in kg.
Stream In Out
Glucose Ethanol CO, Solvent H,O Total Glucose Ethanol CO2 Solvent H,O Total
Feed 4 0 0 0 36 40
Solvent 0 0 0 40 0 40
Aqueous - 0.073 0.181 0 0 36 36.254
residue
Product 0 1.829 0 40 0 41.829·
Off-gas 0 0 1.92 0 0 1.92
Total 4 0 0 40 36 80 0.073 2.010 1.92 40 36 80.00
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)
The mass flow rate ofCOz is 1.92 kg b- 1.
System boUnda'l'\.
r -t---, Distillate
5,000 kg h- 1
45% ethanol
I I 55% water
I I
I I
I Distillation
I
Feed
I column I
50,000 kg h-l
10%ethanal I I
90%watar
I I
I I
I I
- - -+- - - Bottoms
22 SolutilJns: Chapter 4
2. Analyse
(i) Assumptions
- steady state
-no leaks
(ll) Extra data
No extra data are required.
(ill) Basis
1 h, or 50,000 kg feed
(Iv) Compounds involved in reaction
No compounds are involved in reaction.
(v) Mass¥balance equation
As there is no reaction, the appropriate mass-balance equation is Eq. (4.3):
3. Calculate
(i) Calculation table
The calculation table shows all given quantities in kg.
Stream In Out
Ethanol Water Total Ethanol Water Total
Feed 5,000 45,000 50,000
Distillate 2,250 2,750 5,000
Bottoms ? ? ?
Total 5,000 45,000 50,000 ? ? ?
Therefore, from the total column on the Out side of the table:
Ethanol balance
5,000 kg ethanol in ::::: ethanol out
Water balance
45,000 kg water in := water out
These calculations allow completion of the mass~balance table with all quantities in kg.
Solutions: Chapter4 23
Stream In Out
Ethanol Water Total Ethanol Water Total
Feed 5,000 45,000 50,000
Distillate 2,250 2,750 5,000
Bottoms 2,750 42,250 45,000
Total 5,000 45,000 50,000 5,000 45,000 50,000
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.
(b)
Directly from the table, the rate of alcohol loss in the bottoms is 2,750 kg h- I .
Answer: 2,750 kg h- I
Off-gas
System boundary
r\. -------,
I 1
I I
1
Egg slurry-----L.o-l Enzyme reactor I--.L
1 - - - _ - Product
3000 kg h·1 I I 0.2% glucose
2% glucose
20% water I 1
78% egg solids I
--t- - I
Inlet air
18 kg h-1 02
2. Analyse
(i) Assumptions
- steady state
-no leaks
- air and off-gas are dry
- gases are at low pressure so vol% = mol%
- H202 remains in the liquid phase
24 Solutions: Chapter 4
For egg solids. Nz and total mass, the appropriate mass-balance equation is Eq, (4.3):
2S.0kg I = 59.30kg N2
2,118kgmo1N2 = 2.118kgmoIN2· lkgmol
1
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
NZ out::::: 59,30 kg
Glucose balance
60 kg glucose in + 0 kg glucose generated ::::: 0.002 P kg glucose out + glucose consumed
02 balam.:e
18 kg Oz in +·0 kg Ozgenerated :::::{)Z out + (10.656 - 3.552 x 10-4 P) kg Oz consumed
301O.7kg = I.0004Pkg
P = 3009.6kg
Therefore, from the oxygen balance:
G ::::: (66.64 + 3.552 x 10-4 x 3009.6) kg
G = 67.71 kg
and:
Oz out::::: (7.344 + 3.552 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
Water balance
600 kg water in + 0 kg water generated = water out + 5.40 kg water consumed
Stream Out
Glucose Water Egg solids 02 N2 Gluconic acid H2O, Total
Egg slurry -
All-
Off-gas 0 0 0 8.41 59.30 0 0 67.71
Product 6.02 594.6 2340 0 0 58.86 10.20 3009.6
Total 6.02 594.6 2340 8.41 59.30 58.86 10.20 3077.3
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
I
1kgmOIl
Moleswater = 600 kg . 18.0kg = 33.3kgmol
1
1kgmOIl
Moles 02 = 18 kg. 32.0 kg = 0.563 kgmol
1
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);
(33.3 - 0.333) kgmol
% excess water = 0.333 kgmol x 100% = 9900%
(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 = 0.263kgmo102
1
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,.
6.02 0002 1
3009,6 =. g ucose
594.6
3009.6 = 0.198 water
2340 .
3009.6 = 0.778 egg solids
0020 gIUCONC
58.86 =.
3009.6
. act·d
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
2. Analyse
(i) Assumptions
- steady state
-no leaks
(li) Extra data
lOOOcm3 =11
l000g=lkg
(iii) Basis
2501 ethanol product
(iv) Compounds involved in reaction
No compounds are involved in reaction.
(v) Mass~balanceequation
As there is no reaction, the appropriate mass-balance equation is Eq. (4.3):
3. Calculate
(i) Calculation table
As all quantities in mass-balance calculations must be masses (rather-than vo!umes), 250 l-absolute ethanol must first
be converted to mass. From the deflnition of density on p 16, mass is equal to volume multiplied by density:
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.
Stream In Out
Ethanol Water Benzene Total Ethanol Water Benzene Total
Feed 0.95 F 0.05F o F
Benzene feed o o B B
Product 196.25 0 0 196.25
Overhead 0.185 V 0.074 V 0.741 V V
Total 0.95F 0.05F B F+B 196.25 + 0.074 V 0.741 V 196.25 +
0.185 V V
F = (206.58 + 0.195 V) kg
Benzene balance
B kg benzene in =. 0.741 Vkg benzene out
B =. 0.741 V
V=. 161.4kg
F = 238.1 kg
Solutions: Chapter 4 29
B = 119.6kg
These calculations allow completion of the mass-balance table with all quantities in kg.
Stream In Out
Ethanol Water Benzene Total Ethanol Water Benzene Total
F,ed 226.2 11.9 0 238.1
Benzene feed 0 0 119.6 119.6
Product 196.25 0 0 196.25
Overhead 29.9 11.9 119.6 161.4
Total 226.2 11.9 119.6 357.7 226.2 11.9 119.6 357.7
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
Volumeofbenzene"'" 119.6 kg-3' 1l k li. 11 3 1 "'" 1371
O.872gcm g l000cm
Off-gas
47 1m-as 02
15 litres CO2
----l
Medium -----'-1_-I 1
1425 9 1 1
3% glucose
1.75% ammonia I I
95.25% water I Air-driven 1
reactor
1 I
1 1
I 1
Drained liquid
1 1 1110g
L _ 0.063% glucose
J 1.7% ammonia
Air
22 cm 3 milr 1 10r 10 d
25°C, 1 atm
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):
For NZ and total mass, the appropriate mass-balance equation is Eq. (4.3):
3. Calculate
(i) Calculation table
Over 10 d. the volume of air sparged into the fennenter is:
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):
5 3
Moles of air in = n = p V = 1 atm.(3.168 x 10 cm ) = 12.95gmol
RT 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:
The gas volumes in the off-gas must also be converted to masses. First, convert the volumes of 02 and COZ 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 4 31
V .
1 atm(47litres). 11000em31
11
Mo1esofO z out::: n::: L::: ::: 1.92gmol
RT 82.057cm3 atmK- 1 gmor 1 (25+273.15) K
Using this result and adding up the row for the off*gas in the out table:
B =: 313.63 g
Therefore, the dry biomass produced is 0.0667 x 313.63 =20.92 g; the mass of water in the biomass is 0.9333 X
313.63 = 292.71 g.
These calculations allow completion of the Out side of the mass·balance 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 balance
87.04 g 02 in + 0 g 02 generated = 61.44 g 02 out + 02 consumed
C02 balance
og C02 in + C02 generated = 26.97 g C02 out + 0 g C02 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:
Solutions: Chapter 4 33
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' CH"OoN + 0.613 CO, + 1.435 H,O
lomass 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.
89.79
Cbalance:6 = MWb'lomass
+2.63
Therefore:
89:79 = 3.37
MWblomass
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
N balance: 1.53 = =
3.37 8 --) 8 0.45
(cj
Converting to moles the mass quantities of glucose, 0z and NH3 available for reaction on the In side of the mass-
balance table:
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.
From Table B:8 (Appendix B), the molecular weight of glycerol is"92.1. The biomass formula weight calculated from
the atomic weights in Table B.l (Appendix B) is 23.74. Taking into account the 8% ash:
The value of the stoichiometric coefficient c can be detennined from:the yield Yxs =0.4 g g-1 and Eq. (4.12):
l
c = Yxs(MWsubstrate) = 0.40 g g-l (92.lggmOr ) = 1.43gmolgmol-1
MW cells 25.8 g grool 1
From Table B.2 (Appendix B), the degree of reduction of glycerol relative to NH3 is rs = 4.67. The degree of
reduction of the biomass relative to NH3 is:
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:
Therefore. 1.99 gmo! oxygen are required per grool glycerol. From the atomic weights in Table B.l (Appendix B),
the molecular weight of oxygen is 32.0. Converting a to mass terms:
d = Yps(MWsubstral~ = I 1
0.67gg- (60.1ggmor j = 0.915 gmol gmol-l
MWC02 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
Solutions: Chapter 4 35
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 :i «1.00) -1
fmax = )IP = 1(8.00) = 1.0gmolgmol
The actual methane yield of 0.915 gmol gmol-l therefore represents 91:S%of the theoretical maximum.
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:
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:
I x4+ 1.56 x 1-0.54x2-0.16x3 00
JB = = 4.
wYs 6(4.00) -1
croax = 1i3 = 4.00 = 6.0 gmol gmol
The theoretical maximum biomass yield is therefore the same as the actual biomass yield.
36 Solutions: Chapter 4
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
JB- 1 -.
From Eq. (4.13), W "" 1 for methanol. Substituting'values into Eq. (4.19);
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:
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.
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.
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
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:
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
f = 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:
W JS 6 (4.00) 1
f max = 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
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 =0.37 g g-l andEq. (4.12):
Yxs(MWsubstrat~ 0.37gg- 1(180.2ggmor j -1
c = MW II
ce s
=
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 = 0.69 gmol 02 groot-1 cells
Combining this with the result for c, the observed oxygen demand a is:
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
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):
The value of the stoichiometric coefficientfcan be determined from the yield Yps =0.20 x 0.48 =0.096 g g-l and Eq,
(4.14)'
1
f _- Yps(MWsubstrate) __ 0.096gg- (180.2ggmol-l) -,gmogmo
_ 079 I I-I
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,
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.
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):
The value of the stoichiometric coefficient!can be determined from the yield Yps = 0,92 g g-1 and Eq. (4.14):
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- 1 -.
From Eq. (4.13), W = 2 for ethanol and j =. 2 for acetic acid. Substituting these values into Eq. (4.16) for the
theoretical oxygen demand gives:
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%.
(b)
From Table B.5 (Appendix B). Cp for ethylene glycol betweenlO"C and 20"C can be taken as 0.569 cal g-1 "C- 1.
The specific enthalpy change calculated using Eq. (5,13) is:
(c)
Prom Table B.6(Appendix B), Cp for succinic acid between 15"C-and 120°C is given by the expression 0.248 +
0.00153 T. where Tis in "c and Cp is in cal got °C~l. The sensible energy change is best determined from the integral
of this equation between the limits T:::: 15"C and T:::: 1200C:
6h
'''''' CpdT = J,,,,,"c (0.248+ 0.(01531) dT calg-l
= J.lS"C 1S"C
6h = (0248T+0~153r2)[ calg-l
M = 36.9 cal g.l
(d)
From Table B3 (Appendix B), the heat capacity of air between 65"C and 150"C is given by the equation:
where Cp is heat capacity in J gmol-l °C l and Tis temperature in °C. The sensible energy change can be determined
= =
by evaluating the integral of this expression between the limits T 150°C and T 65°C:
M = 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
42 Souaions: Chapter 5
Mf = 48.5 kJ h- I
Answer: 48.5 kJ h- 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 36°C = 146.55 k:J kg-t. Using the relationship on p 89, the enthalpy of water at 35°C relative to 1000e is
therefore (146.55 - 42.0) kJ kg-I"" 104.55 kJ kg-I.
(cJ
-The enthalpy of saturated water vapour at 40°C relative to the triple point can be read directly from Table C.I
(Appendix C) as 2574.4 kJ kg-I.
(dJ
The enthalpy of superheated steam at 2.5 atm and 275°C relative to the triple point can be obtained from Table C.3
(Appendix C). To convert the pressure to kPa, from Table A.S (Appendix A), 1 atm "" 1.013 x lOS Pa. Therefore:
System boundar; \ .
Q (loss) =0.22 kW
r 1
I
I
Medium in ..l.-_~
Heating vessel 1--'----_ Medium out
3250 kg h-1 3250 kg h-1
15°C 44°C
2. Analyse
(i) Assumptions
- steady state
-no leaks
- system is homogenous
- condensate temperature is 150°C
- 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 15°C
(iv) Extra data
= =
C medium 0.9 cal g-l 0(;-1 0.9 kca1 kg-I °C- 1
6h 1
v waterat 150°C = 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
(v) Mass balance
The mass balance is already complete.
(vi) Energy-balance equation
At steady state, Eq. (5.9) applies:
:E(Mh) - :E(Mh)- Q+ W, = 0
input output
""""" """""
3. Calculate
(i) 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:
(M h)MDuut = M Cp aT = 3250 kg (0.9 keal kg-l 0c- l )(44 -15loe = 8.483 x 104 keal
Converting to kJ:
44 Solutions: Chapter 5
(M h)MD out = 4
8.483 x 10 kcaL 1 kcal '1000 1 I"" 3.55 x 105 kJ
14.187X103J111kJ
The rate of heat loss is 0.22 kW. Converting to k:J hoi:
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.
4. Finalise
Answer: 168 kg
Off-gas
System boundary
,~ - -- - - -- 1
I I
I I
I Reactor I
Feed Product
(25,000 lltres)
2000 kg h- 1 I I 0.5% glucose
4% glucose
I / I
r--t-
96% water
25°C
I
- -- .
Q (cooling)
Inlet gas
100,000 litres min- 1
1 atm, 15"C
88% air
12%NHs
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 25°C
(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
Ah~ glutamic acid =-2244.1 kJ gmor 1
(v) Compounds involved in reaction
Glucose, ,ammonia, oxygen, glutamic acid, carbon dioxide and water are involved in the reaction.
(vi) Mass-balance equations
For,glucose, ammonia, oxygen; glutamic acid. carbon dioxide and water, the appropriate mass~balanceequation,is Eq.
(4.2),
For Nz and total mass, the appropriate mass-balance equation is Eq. (4.3):
-MIrxn-MyAhv-Q+ Ws =0
3. 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):
46 Solutions: Chapter 5
MI · _pV -_
o esofN 2m - -
laJln(4.17XI0'1) -176
- . x
10' gmoI
RT 0.0820'71aJlnK 19moll(I'+273.I5)K
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.
Stream In
Glucose 02 Gluconic acid C02 HZO Total
Peed 80 o o o o 0 1920 2000
Inlet gas o 518.5 1500.8 4928.0 o 0 o 6947.3
Off-gas
Product
Total _ _ 80-=__~=",-_-",="-_==,--,,--
518.5 1500.8 4928.0 0 -,,,-_
0 _--,,=_
1920 _ 8947.3 -==,-_
Stream Out
Glucose NHS °z NZ Gluconic acid COz HZO Total
Peed
Inlet gas
Off~gas 0 0 ? ? 0 ? 0 G
Product 0.005P ? 0 0 ? 0 ? P
Total 0.005P ? ? ? ? ? ? G+P
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
02 balance
1500.8 kg02 in + 0 kg 02 generated = 02 out + (21.312 - 1.332 x 10-3 P) kg 02 consumed
2520.3 kg = 1.000 P kg
P = 2520.3 kg
Substituting the result for P into the glucose, 02 and C02 balances gives:
48 Solutions: Chapter 5
Using the result for P to evaluate the masses of the other reactants and products involved in the reaction:
These results can be used directly in the energy balance for evaluation of the cooling requirements. However,
completion of the mass balance allows the calculations to be checked.
NH3 balance
518.5 kg NH3 in + 0 kg NB3 generated = NH3 out + 6.36 kg NB3 consumed
NH3 out =512.14kg
Water balance
1920 kg water in + 20.20 kg water generated = water out + 0 kg water consumed
The Out side of the mass-balance table can now be completed with all quantities in kg.
Stream Out
Feed
Glucose NHl °z NZ Gluconic acid CO2 HZO Total
Inlet gas
Off-gas 0 0 1482.9 4928.0 0 16.46 0 6427.4
Product 12.60 512.14 0 0 55.02 0 1940.20 2520
Total 12.60 512.14 1482.9 4928.0 55.02 16.46 1940.20 8947.3
All columns and rows of the completed table add up correctly to within round-off error.
-AHrxn-Q::: 0
The heat of reaction is evaluated using Eq. (5.20). As the heat of combustion ofCOZ and H20 is zero:
where G ::: glucose, A ::: NH3 and GA = glutamic add. The nin this equation are the moles of reactant or product
involved in the reaction. Converting the masses of reactants and products consumed or generated to moles:
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
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.
(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
T :: 353 x 10 kJ h- :: 23"C
1
(2000 kg h-1)(75.4kJ kgmor oc-1j.1 ~~~~ll +(6947.3 kg h- 1)(29 kJkgmor1 oc-1j .1 ;~~~ll
As a temperature rise of 23°C 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 25°C, the temperature without cooling woulJ,i increase to (25 + 23)OC 48°C.
5 kgh-1
: 1.25kgOZh-1
4kgkg 1
Converting this quantity to gInol using the molecular weight of 02 =32.0 (Table B.I, Appendix B):
0zrequired:: 1.25kgh-
1
0: 1.1 ~~~ll
.1 1 g
:: 39.06gmolh-
1
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
with Ws :: 1.5 kW andMv := 0 (no evaporation). From Table A.8 (Appendix A), 1 W:: 1 J s-1; therefore 1 kW:: 1 kJ
s·1 and:
50 Solutions: Chapter 5
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.
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):
The coefficientsh ,/2./3 and/4 can be determined similarly using the product yields and Eq. (4.14):
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~NH3 =-382.6kJ gmol-l
M~biomass=-552kJ gmor 1
M~ propionic acid = -l527.3kJ gmol-l
M~ acetic acid=-874.2kJ gulOr l
M~ butyric acid =-2183.6kJ gmor 1
M~ lactic acid = -1368.3 kJ gmol-l
Solutions.' Chapter 5 51
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:
t:Jirxn = -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:
Answer:4.16x 104 kJ
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:
1.21d-L55 = 2e
e = 0.61 d-0.78
52 Solutions: Chapter 5
d = 1.76
Substituting this value· for d into the expressions for the other coefficients gives c "" 0.72, b = 0.13 and e "" 0.29. The
completed stoichiometric equation is therefore:
C6H1206+0.13NH3 ~ O.72CH u sOO.SSNO. 18+ 1.76 CO2 + O.29HZO + 1.76CZH60
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
/lH= = 4.93 gmol (-2805.0kJgmor1) + O.64gmol (-382.6kJ gmol-1)_3.55 gmol(c21.2kJ g-l)·1 ~7:o~ I
- 8.68 gmol (-1366.8 kJ gmol-l)
= -1175 kJ
Mlrx,n
Using the modified energy~balance equation, Eq. (5.26), with M v =0 and Ws =0:
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):
1
lJ.T = ~_ = 117.5 kJ h- _ 112"<:
Mep (25Ih-1 Ilkg~(754J 1-1oC- 1 11gmOllllOOOgll~fi - .
. . 11 U . gmo . 18.0g· lkg . lOOOJU
Answer: 21.2°C
Solutions: Chapter 5 53
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:
12x4+22x1-11x2 _ 400
rs _- - .
The value of the stoichiometric coefficient c can be determined from the yield Yxs: 0.5 g g~l and Eq. (4.12):
The oxygen requirements can be determined from Eq. (4.16) with/: 0; from Eq (4.13), w: 12 for sucrose:
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 energy·balance 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.
,
System boUndary\
r - - 1---
" - 1
I I
I - I
Water
I I Outlet stream
F::::: 40,000 I h· 1 I I F=40,OOO I h- 1
CA
I I
I V I
CA
I I
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
f 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 -F
In- =-1
CAO V
C~ = CAOe (-FIV; t
Substituting the known values for CAo. F and V:
CA = 0.022 e-O·089 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,
Answer: 0.014 kg I-I
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:
56 Solutions: Chapter 6
InM = -kt+1nMo
M
In M
o
= -let
At t= 20 min, M = 0.5 MO. Substituting these values into the equation:
O.5M
In -:MOo = -k (20 min)
In 0.5 = -k (20 min)
k = 0.0347 min~l
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:
O.05MO
In M = -0.0347 t
o
In 0.05 := -0.0347 t
Answer. 1.44 h
System boUndary\ \. ;
r - - - - - 1
I I
I I
Inlet stream I I Outlet stream
Cod-liver oil drum F; I I Fo
P p
I V I
</
I p I
</
I I
Oil tank
L - - - - - - - J
(a)
Total mass balance
The general unsteady~state mass--balance equation is Eq. (6.5). As there is no reaction, RO = RC = O. The t2.ta1 mass
=
flow rate into the oil tank is equal to the volumetric flow rate multiplied by the density of the cod-liver oil: Mi Fi p.
Similarly, Mo = Fo p. The total mass of oil in the tank is equal to the volume of oil multiplied by its density: M = V p.
Substituting these expressions into Eq. (6.5) gives:
d(VP)=Fp_Fp
dt ' 0
I dV = I (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.
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:
58 Solutions: Chapter 6
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:
-Fo
ln~ = y'+lnib
~ -Fo
lnib=y'
~ = ib e(-F,II'J'
In this problem. F0 ::::: 4.8 I h-l. Substituting the known values for </Jo and V:
II : : : 1 e....(l·080 t
where <Pis dimensionless and t has units of h. The time between 8 p.m. and midnight is 4 h. From the above
equation, at t= 4 h,4'= 0.73. Therefore, at midnight, the composition of oil in the tank is 73% vegetable oil and 27%
cod-liver oil.
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 = J.tx V
dx
dt = 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
=
Assume an initial condition: at t 0 at the beginning of ex.ponential growth, x =xo. Therefore, at t =0, In Xo =K.
Substituting this value of K into the equation gives:
Solutions: Chapter 6 59
lnx = j.tt+lnxo
x
In- = j1,t
XO
When t = 45 min, x = 2 xo. Substituting these values into the equation:
2XO
I n - = ,u(45 min)
XO
ln2 = j.t (45 min)
Therefore:
In''::' = 0.0154t
XO
x = XQ eO.Ol54 t
x=6.54x 104 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.
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
C = -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)
When t= !h, the half-life of the isotope; C = 0.5 Co. Substituting these values into the equation:
0.5 Co
I n - - = -kIth
Co
In 0.5 = -ki !h
_ -tn0.5
th - - -
k,
Using mathematical rule (D. 10) in Appendix D, -In 0.5 =In 1/0.5 =In 2. Therefore:
In2
th = kl
Answer. Q.E.D.
(b)
From the equation derived in (a):
In go = -4.85 x 10-2 t
0.01 Co -2
In Co = -4.85 x 10 t
....
"
System boUndary\
Feed
r - - r- - - - 1
Product
F I I F
xI =0 x
I I
" I I
•
I I
I V
I
I x I
I • I
(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'
As V is constant, it can be taken outside of the differential.
dx
V dt = -Fx+k1xV
dx F
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:
F
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:
F
Inx:::: (k1-y)t+1nXO
• F
10- :::: (kl--)t
'0 V
F
x=.xoe(kl--)t
,v
F
(k --) ,
Answer: x:::: XOe 1 V
(d)
Substituting the parameter values into the equation derived in (c}
-1 22001h-1
x:::: (0.5gl-1)e(0.33h - 10,0001)/
where x has units of g 1-1 and thas units ofh. For x:::: 4.0 g I-I;
4 = 0.5 eO.II t
inS = 0.11 t
t:::: 18,9h
Answer: 18.9 h
(e)
Substrate mass balance
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
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 = VF (si -s)-k1X{)e ~l-~t
V
(f)
An equation for &/dt in terms of x was dt;:rived in (e) as:
,
Vk Z
si- s = F'x
VkZ
Answer. s = si -Tx
System bOUndary\
-
\.
-
'"- -
Feed
r 1
F I I
s;
p I
I
- I
I
I I
V
I x 1
I s I
p
I I
L J
(a)
Total mass balance
The general unsteady-state mass-balance equation is Eq. (6.5). As total mass cannot be generated or consumed, RO =
RC =O. No mass leaves the fennenter; therefore Mo =O. The mass flow rate in Mj = p F. The total mass in the
fermenter M is equal to V p. Substituting these terms into Eq. (6.5) gives:
d(VP)=pF
dt
As P is constant, it can be taken outside of the differential and cancelled:
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= Ft+K
From the initial condition for V, at t =0, Vo =K. Substituting this value of K into the equation gives:
v= Ft+Vo
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:
<is F
Answer: dt = V(Si-S)-kt s
Solutions: Chapter 6 65
(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
z
where k means that the parameter values are those at distance z from the front of the reactor. Similarly, the rate at
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
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:
66 Solutions: Chapter 6
dCA
Answer: u liZ "" -rC
(b)
Answer: at Z"" O. CA =CAi
(e)
If the reaction is first-order, rc =: kl CA where kt is the first-order rate constant. The differential equation becomes:
As u and kl are constants, the differential equation contains only two variables, CA and z. Separating variables and
integrating:
dCA = -k) dz
CA U
f fdCA ""
CA
-k) dz
U
Using integration rules (D.2?) and (D.24) from Appendix D and combining the constants of integration:
-k)
InCA = -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 U
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.
(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
Pdt
=-Q
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= -Q t+K
MCp
From the initial condition for T, at t= 0, To =K. Substituting this value of K into the equation gives:
-12
T= MC t+To
p
Using the density of water = 1 kg t- 1, the mass of 2 litres of water M= 2 kg. Converting the Cp for water to mass
terms:
1 1
Cp = 75.4kJ kgmor "'C- .1 ~::~11 = 4.189 kJ kg- 1 "'e- I
T =the boiling temperature of water =100°C; t =11 min. Substituting the parameter values into the equation for T:
(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,
Cpw, CpO, MW and Mo are constant, T and t are the only variables in the differential equation. Separating
variables and integrating:
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:
Solutions: Chapter 6 69
-12
Answer: T = (MwCpw+MOCpG) t+ To
(c)
The mass of glycerol in the tank MO = 4S kg; the mass of water Mw =55 kg. Converting the Cp for water to mass
terms:
System boundary~
- - - -- - - 1
I I
I I
I I
Molasses solution in Heating tank Molasses solution out
1020 kg h- 1 I I 1020 kg h- 1
20'C M T
I / 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
(a)
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 = ~ = Cp(T-Tref)
Ws = O. 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
Substituting these expressions into Eq. (6.10) gives:
dT -
M Cp dt = -Mo Cp (T - Tref) + U A (Tsteam - n
After rearranging, the differential equation is:
dT = UATsteam+MoCpTref _(fJoCp+UA)T
dt MCp MCp
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:
Solutions: Chapter 6 71
dT = eIt
12.84-0.271 T
-felt
f dT
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
From the initial condition for T, at t = 0:
-I
= 0.271
K In (12.84-0.271 To)
Applying the numerical value of To =20°C, K =-7.395. Substituting this value for K into the equation gives:
-I
0.271In(l2.84-0.2711)+7.395 =t
-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).
Temperature, T Time, t
CC) (h)
20 0.00
25 0.74
30 1.68
35 2.93
40 4.84
45 9.01
46 11.0
47 15.8
47.3 21.5
50 r----,----,----,,----,-----,
(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= 47.4°C.
(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 40°C after 4.84 h.
Answer: 4.84 h-
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
(My Cpy + MM CpM)
f dT-f-
-Q
(My Cpy+MM CpM)
dt
Using integration rule (D.24) from Appendix D and combining the constants of integration:
Solutions: Chapter 6 73
T= -Q t+K
(MV CpV + MM CpM)
From the initial condition for T, at t= 0, To =K. Substituting this value of K into the equation gives:
T= -Q t+To
(Mv CpV + MM CpM)
The rate of heat input to the system is 450 W. Converting this to kcaI min-l:
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 = 15¢C and T= 36¢C:
l
6.45 kcal min- t+ 150C
36'C =
12.75 kg (0.20 kcal kg-I 'C- I) + 7.5 kg (O.92kcal kg-I 'C- I)
t = 30.8 min
Answer: 30.8 min
(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:
74 Solutions: Chapter 6
MC dT
Pdt
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
=
dt ( - 1 "'C-1 . 1118.0kg
lOOOkg 75.4kJkgmol
kgmOllllkCai
. 4.187k:JU
n
dT
dt = 9.026-0.088 T
where T has units of"C and t has units of h. Separating variables and integrating:
dT =dt
9.026 - 0.088 T
f 9.026~.088T = f 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
K = 0.088 In (9.026-0.088 ToJ
Applying the numerical value of To =24"C, K = -21.97. Substituting this value for K into the equation gives:
-1
0.088 In (9.026-0.0881) + 21.97 = ,
Answer: 14.2 h
(b)
If beat losses can be neglected, Qhas only one component and Eq. (6.10) becomes:
dT
MCp <It
dT = <It
8.576- 0.066 T
Answer: 2.8 h, or 20% of the time required when heat losses occur
Fluid Flow and Mixing
700 ...---r---,---,,--,.----r---,
600
600
400
300
200
100
ol-_...L_......l._---''-_-'-_....L_--'
o 200 400 600 800 1000 1200
Shear rate (s·1)
(b)
The rheogram in (a) is similar to those for pseudoplastic and Casson plastic fluids in Figure 7.7. It is not clear from
the rheogram whether the fluid exhibits a yield stress at r=
0 or not; therefore. both non-Newtonian models are worth
checking. From the equation in Figure 7.7 for pseudoplastic fluids, a plot of shear stress versus shear rate on log-log
coordinates would be expected to give a straight line. This plot is shown below.
The equation for the straight line in the log-log plot is '1:=
11.43 ;-0587. Therefore, the flow behaviour index n =
0.587 and the consistency index K =. 11.43 dyn sit cm- 2. The sum of squares of the residuals for this data fit is' 1137.
From the equation in Figure 7.7 for Casson plastic fluids, a plot of the square root of shear stress versus the square
root of shear rate on linear coordinates would be expected to give a straight line. This plot is shown below.
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
(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)
(Ii)
10
Cen concentrations:
.1.5%
03%
0::- D 6%
.£. L
••t
• 10.5%
•
I
~
t3-
"
1
1 10 100
Shear rate (8- 1)
100
Cell concentration: 12%
0::-
.£.
t
••E
e
!l
~
10
1 10 100
Shear rate (sol)
1000 ,
Cell concentration: 18%
0::-
.£.
~
8 ....
.~ 100 ~
E
...
I
10
1 10 100
Shear rate (s·l)
Solutions: Chapter 7 79
•
f
I
10 100
Shear rate (5- 1)
The equations and parameter values for the straight lines in each plot are listed below.
1.4,--,.---..--....--"..---.....
index, n
• Flow behaviour
o Consistency, index, K
1.2
c
~. -" 1.0
5
!
! 0.8
10
£ 0.6
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.
Stirrer speed (s·l) Torque (Nm) Shear stress (N m- 2) Shear rate (gw 1)
0.07
0.06
i
0
~
0.05
11-
~
e
"m"
~
0.04
<J)
1 1.5 2
Shear rate (s-1)
The equation for the straight line on the log-log plot is 1'=O,049jr°·20. 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.
(b)
The impeller Reynolds number for pseudoplastic fluids is defined in Eq. (7.23). If Rei at the highest stirrer speed is in
the laminar range, conditions at the other stirrer speeds are also laminar. Therefore, for Ni = 0.185 s·1 and using the
=
unit conversion factor 1 N 1 kg m s·2 (Table A.4, Appendix A):
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.
(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
1 vf P
!if..".20 =
103 (30o.zo-1) (0.049 N sO.20 m -21 1 kgms-2 ~
1N II
I (0.04m)21000kgm 3
Nl- 8= 2.02s-1.8
Ni = 1.48 s-l
Answer: The shear rate range can be extended from 1.9 s-1 with a Rushton turbine impeller to 44 s-1 with a helical-
ribbon impeller.
Pp -_ 104 -3 Iloocml3
. gcm. m . I~I_
lOOOg - lO4Okg m-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:
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.
82 Solutions: Chapter 7
From Table A.9 (Appendix A), 1 .kg m- I s·1 = 103 cP; therefore:
3
33 10-3kg m
J.l=.x -1 s
-1. 10 cP
l l = '33
cP
1kgm- s-
Answer: 3.3 cP
(bJ
The tip speed in the laboratory equipment is:
In the large-scale vessel. Di =15 x 5 em =75 em. If the tip speed is kept the same after scale-up:
Converting to cP:
= 50cP
Answer: Scale-up increases the maximum viscosity for turbulent conditions to 50 cP.
NiDrp (90min-I·116~sn~(lm)21000kgm-3 6
Rei = Ji
= lO
3
kgm- C
11 = 1.5 x 10
From Figure 7.24 for a Rushton turbine, this value of Rei corresponds to turbulent flow and Np can be taken as 5.8,
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
Solutions: Chapter 7 83
P = L96xl04w = 19.6kW
Answer: 19.6 kW
(ti)
For a viscosity of 100 x 10-3 kg m- 1 s-1 =0.1 kg m- 1 s-l, Rei is:
NiDf p (90min-
1
.11~n~(1 m)21000kgm-3 4
Ret' = = 1 1 = 1.5 x 10
# 0.1 kgm- s-
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)
For a viscosity of 104 x 10-3 kg m- 1 s-l = 10 kg m- 1 s-l, RCi is:
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):
P = NppNf Dr = 3.5 {tOOOkg m-3) (90 min- 1 .! 16~n~3 (l m)5 = 1.18 x 104 kg m2 s-3
P = L18xl04W = 11.8kW
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),
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 = 32.9W
This value is considerably lower that the electrical power consumed by the stirrer motor.' Much of the remainder of
the electrical power is converted into heat within the motor bousing.
Answer: 32.9 W; a significant fraction of the electrical power is dissipated as beat within the motor housing
3
V = 7t{;Y H = 7t{2;t 2m = 6.28m
(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 s·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):
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):
Solutions: Chapter 7 85
t = 1.54 V = 1.54(6.28m')
m D; Nj (O.67m)3 2.29S-1
= 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 = P 5 = 3 2 3
9,42x10 kgm s- - 241 -3
(Np) pD; 2.9(lOOOkgm-'j(O.67m)5 - . s
g
t = !541' = 1.54(6.28m') = II s
m DfN 1
(O.67m)3 2 .89s-1
Answer: The maximum allowable stirrer speed is 2.89 s-1 or 173 rpm; the mixing time is 11 s.
Heat Transfer
(b)
In this case there are two thermal resistances in series. Their magnitudes are calculated using Eq. (8.15). For the
firebrick:
~ 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):
1. = 1 + 1 + O.OO6m + 1 +0
1 1
U 830Wm 2r- 1.2kWm-2r-1.ll~:1 19Wm IK- 1.7kwm-2K'"1.11~:1
(b)
The mean temperature difference between the fermentation fluid and the cooling water is calculated from Eq. (8.35):
Answer. 23.5"C
(c)
U A is evaluated using Eq. (8.19) with /iT: /iTA:
UA = Q = 14.6 kJ s-l
23.5"<:
ATA
(d)
(c)
Applying Eq. (8.19) to determine /iT: /iTA for the new coil:
- 1
!iTA : -iL : 14.6 kJ s-
1 = 15.7"<:
U A' 0.93 kJ s-l °C
The new cooling water outlet temperature Tco is determined using Eq. (8.35):
Answer: 30.6"C
(f)
From Eq. (8.32), for the new coil with Q: 14.6kJ s-l, Tci = goC and Teo =30.6"C:
- -I
M - Q - 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%
Cpc = 75.4 kJ kgmol-l "C- l : 75.4kJkgmor l "c-I.1 ~~~ll ;:: 4.19kJkg- 1 "C- l
10.3 N s m· 2; from Table A.9 (Appendix A), I N sm·2 =} kg m· l s-l; therefore Jlb = 10-3 kgm- l s·l. ktb = 0.6
,llb;::
=
W mol "e l ; from Table A.8 (Appendix A), 1 W = 1 J s·l; therefore k fb 0.6 J 8"1 m- l "C-l. B: 6 mm;:: 0.006 m.
88 Solutions: Chapter 8
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 =1 J 8. 1; therefore Q= 2.5 x 106 J s·1 =2500 kJ s-I,
(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):
(b)
The overall heat-transfer coefficient in the absence of fouling layers can be calculated using Eq. (8.23). Assuming
that the heat-transfer coefficient for the cooling water h c can be neglected (p 185):
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:
Solutions: Chapter8 89
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);
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);
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.
30,.....---..,.,.....---.,..-----.,..-.----,200
41 • Temperature
o Area
(d)
=
From the,equations developed in (c), at a cooling.water flow rate of 5 x loS kg h*l, Teo 14.3°C and A = 101 .tn.2.
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 a
=
radius of 5 em 0.05 m:
A 101 m 2
L = 21tr = 21t(0.05m) = 321 m
Answer: 321 m. This is a long cooling·coil, representing a considerable expeme whenfabricatedfrom stainless steel.
90 Solutions: Chapter 8
From Eq. (8.32), the rate of heat removal to the cooling water before cleaning is:
Evaluating the overall heat-transfer coefficient U from Eq. (8.19) with aT aTA: =
- 1
- -Q- -
U - - 1340.8kJs- -140kJ
-
-1 -Z'C-1
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):
(e)
.The mean temperature difference between the fermentation fluid and the cooling water after cleaning is detennined
from Eq, (835),
U =~ =
- 1340.8kJs-
, = 1.87kJs-1m-20c-1
ALiTA (565 m2) 12,7'C
The overall beat-transfer resistance is given by Eq. (8.20):
The resistance due to the fouling deposits is equal to the difference between these two overall resistances =: (1.26 x
10-2 _ 9.46 x 10"3) = 3.14 x 10-3 kJ- I s 0c. Therefore, fouling contributes:
Answer. 0.25
P medium =: p water =: 1000 kg m"3. The viscosity of water at 20°C 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. 30°C,
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:
(b)
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 3 h-1 I~I
u =: volumetricflowrate =: m . 3600s =: 0.236ms-1
numberoftube,(n?) (30) n (0.025 ml'
=5 cm =0.05 m:
Substituting parameter values into Eq. (8.38) with the tube diameter D
3
Re = Dup = 0.05m(0.236m,-I)IOOOkgm- = 1.18 x 104
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):
This value of Pris also within the range of validity ofEq. (S.42). From Eq. (8.42):
92 Solutions: Chapter 8
As the medium in the tubes is the cold fluid in this heat exchange system, he =1.02 kJ s·l m-2 0C- l ,
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):
As this value is > 6 x UP, Remax is within the range of validity of Eq. (8.44). Prior theshell·side water is given by
Eq. (8.40):
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 = 0.52 kJ s·l m~2 0C- 1
(d)
The outlet temperature of the water from the shell is detennined from Eq. (8.31):
- I
~ - ~. -- 60~
.Lho - .Lbl - .....
Q ~ -
1048.3kJs- = 30~ ~
MhCph 3x 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
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
L In(LlT2I<lTd
r
= (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
- I
A ::::: ~ ::::: 1048.3k1s- ::::: 79m2
U LlTL 0.52kJ s-I m-2 oc- I (25.5OC)
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
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. 30°C, 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):
94 Solutions: ChapterS
Nu = 0.87 Re?,62 Pr0.33 (::::)""14 = 0.87(8.3 x 1O~0,62 (6.8P·33 (1)0,14 = 7,7 x 103
From the definition of Nu in Eg. (8.37) with D::::: the tank diameter:= 3 m:
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 s·l. 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:
Q 230kJs-I
Tco = ---- + Tei = ( )- + 12"C = 21.9"C
Mc Cpc 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):
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 13m2
L=--= _ =55m
21tr 21t(0.0375m)
Solutions: Chapter 8 95
As the required length of cooling-coil is considerably longer than the 45 m available in the offered fermenter, the
second·hand fermenter without modification is unsuitable for the proposed culture.
Answer: No
8.8 Optimum stirring speed for removal of heat from viscous broth
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.
C.LIb 2kJkg-Ioc-l(lOkgm-ls-I) 4
Pr=-P-= =10
ktb 2 x 10 3 k1 C l m- l 0C-l
From Eq. (8.45), assuming that the viscosity at the wall is equal to the viscosity of the bulk-fluid:
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),
Substituting the known parameters into Eq. (8.19) with liT = liTA = WOC:
The power dissipated from the stirrer, Ws ' is equal to the power P calculated using Eq. (7.18), In this system, the
value of Np with gassing (Npg) is 40% lower or 0.6 x the value of Np read from Figure 7.24. Therefore:
Therefore:
-Mrxn = Q- WS = (S6.0,vp·62_0.173NPNf)kJS-l
Values of Q, W S
and -tJirxn calculated using the equations derived above are listed below as a function of Ni.
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,
00
a Ws
• -AHrxn
5 10
Stirrerspeed, Nj (s·1)
(d)
The rate of removal of metabolic heat (the -Aiirxn component of 'h reaches a tnaltimurn at aroundNj =3 8. 1,
Answer: About 3 s·1
(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 s·l and 6Hrxn
=-93AkJs· I :
Solutions: Chdpter 8 97
1
Biomass = -93.4k:Js- =L22XIIYg
x
6 10-' gmolg-I h- .I'6~sl (-460kJ gmol-I)
I
The cell concentration is equal to the biomass divided by the fermenter volume:
5
. L22xl0 g 22 I-I
CeII concentration = 3 11000 11 = 1 . g
10m . --,-
1m
Answer: 12.2 g l~l
(I)
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 s intersect, the entire heat-transfer capacity of the fennenter cooling system is
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
I
qo = 5 mmo1g-I b- . 1lOOOmmol 32.0g II~I
I gmol 1. 11gmol . 3600s = ' 444 x 10-5 g g-1-1
s
The rate of oxygen transfer is given by Eq. (9.37); NAis maximum when CAL "" 0:
kLaC~ "" O.15s- 1 (ax 1O-3 kgm-3) "" 1.20 x 10-3 kg m-3 s-l
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.
1 I
qox = 80 mmo11- h- . 1lOOOmmol
1 gmol
1. 119mol
32.0g . l000g' 11~IIIOOOIII~1
1m3 ' 36008 = 711
. x 10-4 kgm-3-1
s
Ce· n
= t0004mM=
' 0004
, m m11-
1 IlgmOI I
o , l000mmol ' 1-,2.0
g
lI...'!LI
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;
To maintain the oxygen concentration in the medium at the critical level, from Eq. (9.41):
(bJ
From Table 9.1, the solubility of oxygen in water at 30"C under 1 atln oxygen pressure is 3.84 x 10"2 kg m-3.
Therefore:
Solutions: Chapter 9 99
N = _ I [(FgPAG) _(FgPAG) 1
A RVL TiT 0
1 [(200lmin-l·I~10.2Iatm) (1891min-I·I~10.20Iatm)1
NA = 0.OOOO82057m3 attn K-1 gmol 1(200 I) (20+ 273.15) K - (28 + 273.15)K
NA = 0.0174gmolm-3 s· 1
Answer: 0,0174 gmol m~3 s~l
(b)
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):
(e)
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
_ 1 [(200lmin-l·I~10.2Iatm) (189Imin-I·I~10.183atm)1
NA - 0.OOOO82057m3 atmK-1 gmorl (2001) (20+273.15)K - (28 + 273.15)K
NA 1 -3 s-I . 132.08
0.0289 groom 1 01'1000II...I.!>LI _
kLa =... = gIn g = 0,25s 1
(CAL - CAL) 3 3
(7.8 x 10- kg m- -0.52x 7.8 x 10-3 kg m-3)
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%.
100 Solutions: Chapter 9
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,
Ps = P g h "" 1000 kg m- 3 (9.8 m s·2) (3.5 m) "" 3.43 x t()4 kg mwl s·l
,From Table A.S (Appendix A), 1 kg m- l s·2 = 9.869 x 10"6 aim; therefore:
Ps -_ 343
. x 104 kg m-1 8-1 -_ 343
. x 104 kgm-1 s-1 . 19.869Xlo-6atml_
1 I - 034
. atm
1 kgm- s-
Ps is the pressure due to_the head of liquid above the sparger; oThctotal pressure at the'llparger iSh + atmospheric
pressure "" 1.34 atm.
(b)
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.
10g1O(C~)
CAL
= O.5~HiZ?CiL + ~KjCJL
t j
_ 05 [(-0.303 x 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
• •
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
35°C 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.
(e)
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:
(d)
The logarithmic~meanconcentration difference is given by Eq. (9.53). From (b), the solubility of oxygen at the top or
outlet end of the vessel is 7.14 x 10-3 kg m~3; the dissolved oxygen concentration at this location is 50% air saturation
or 0.50 x 7.14 x 10-3 = 3.57 x 10- 3 kg m- 3. From (c), the solubility of oxygen at the bottom or inlet end of the vessel
is 9.57 x 10-3 kg m~3; the dissolved oxygen concentration at this location is 65% air saturation or 0.65 x 9.57 x 1O~3 =
6.22 x 10*3 kg m~3. Substituting these values into Eq. (9.53):
(e)
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 (35°C), 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):
102 Solutions: Chapter 9
_ I
3
[(25 m min-
1
Y~lo.2latm) (4071S-1·1~10.2015atm)1
NA - 0.OOOO8Z057m3atmK 1gmor1(ZOm3) (25+273.15)K - (35 + 273.I5)K
(f) .. •
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):
3Z 0g
NA 00167
. gIno1m-3 s-1 - 1lOf. Illkg
. 1000 I _
kLa =- '" =- gIll g =- 0.15 s 1
(CAL -CALt 3.46 x 10 3kgm 3
(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~) _ 0I5s-I[C·14;9.s7)XIO-3]kgm-31~1 _ -1
x
max
- qo -74 l_lh_lllgmOII132.0gll~II~I-19g1
. mmo g . lOOOmmol . 1gmol . looog . 36008
Answer: 19 g I-I
In (.,~p.:::,,-=-;;~p.~"'1 )
and (12 - (1) are listed and plotted below.
0.00 o
OAI 5
0.80 10
1.6 20
2.3 30
3.0 40
4.1 60
Solutions: Chapter 9 103
4 •
fq,a is equal to the slope of the straight line in the plot"'" 0.069 s-l.
1 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.
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
f
i 0.15
<o~
(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):
-J1TF.
' -1
- 3 atm (31 nun .
liminfi
66SV _ -2.02 gmol m-3 8-1
kLa = RTVLX~ope = O,OOOO82057m3atmgmor1r1(29+273.15)K{31)xs}ope - stope
For SOOrpm:
At 700 rpm'
-2.02gmolm-3s-1 1
k La = = 0.21 s-
-9.68 gmol m-3
Answer: 0.10 s·l at 300 rpm; 0.17 s·l at 500 rpm; 0.21 s·1 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):
(c)
Equating Eqs (9.39) and (9P6.2),
Solutions: Chapter 9 105
PTFg
qo x = R T II. [(YAG)i - (YAGlo]
3atm(3Imin-lr~~[(YAG)i-(YAG)oj __
qox = = 2.02[(YAG)-(YAG) jgmolm 3, I
O'{)OOO82057m3atmgmolIrI(29+273.15)K(31) I 0
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 s·l at 300 rpm; 1.0 x 10-2 gmol m-3 8- 1 at 500 rpm; 1.2 x 10- 2 grool m· 3 s·l at 700 rpm
Unit Operations
4.0
1 •
.,
.!!. 3.0
•
-
0
x
....1:::.- 2.0
~
~
g
~~ 1.0 •
~
Il:
0.0
0.00 0.01 0.02 0.03 0.04
Filtrate volume, ~ (m3)
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 s·2 (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:
(h)
tl yr = 7.5 x 10-3 min 1~1. From(a), K2 =0; therefore, from Eq. (10.12):
3 1
_ t/Vr = 7.5xl0- minl- 1100011'160' 1 = 113 10'
K 1- -6
Vf 40001' 1m3 'lmin . x sm
The filter area is obtained fromEq. (10.13) using the result for a from (a):
ff;;;¥I·I~I)
3
, I'tac 4.0cP .1 10- \g:;:-I '-'I&·ox 10
1O 1
mkg- (22 g l-
1
A = 2Kt6p =
2(1.13X 10' 'm-6) 360mmHg.
I1.333Xi~:-1 I ,-'
= 649m
4
A = 25.5m2
1.0 x 10.5 2.2 x 106 12 x 1()6 9.0 x lOS 7.0 x lOS 5.0 x lOS
1.5 x 10.5 3.5 x 106 1.7 x 1()6 1.3 x 1()6 9.3x1OS &.0 x lOS
2.0 x 10.5 4.5 x 106 2.5 x 106 1.& x 1()6 1.4 x 1()6 1.1 x 106
2.5 x 10-5 5.8 x 106 3.0x 106 2.4 x 1()6 1.7 x 1()6 1.4 x 1()6
3.0x 1O~5 6.7 x 106 3.7 x 1()6 2.9 x 106 2.1 x 1()6 1.7xl()6
3.5 x 10.5 8.1 x 106 4.3 x 106 3.4 x 1()6 2.4 x 1()6 2.0 x 1()6
4.0x 10.5 9.2 x 106 4.& x 1()6 3.9 x 106 2.& x 1()6 2.3 x 1()6
4.5 x 10.5 l.0 x 107 5.3 x 1()6 4.3 x 106 3.1 x 1()6 25 x 1()6
5.0 x H,.5 6.0 x 1()6 4.8 x 106 3.5 x 106 2.& x 1()6
Vf filamentous t/Vr(s m· 3)
1.0 x 1(T5 3.6 x 1()6 2.2 x 1()6 1.7 x 1()6 1.3 x 106 1.1 x 106
1.5 x 1(T5 55 x 1()6 3.1 x 1()6 2.7 x 1()6 2.1 x 106 1.7 x 1()6
2.0 x 10".5 72x106 4.3 x 1()6 3.6 x 1()6 2.7 x 106 2.3 x 1()6
2.5 x 1(T5 9.0 x 106 5.3 x 1()6 4.4 x 1()6 3.4 x 106 2.& x 1()6
3.0 x 1(T5 1J x 107 65 x I1J6 52 x I1J6 4.0 x 106 3.3 x I1J6
3.5 x 10-5 1.3 x 107 7.5 x 106 6.IXI1J6 4.7 x 106 4.0 x 106
4.0 x 10"5 8.5 x 106 7.1 x I1J6 5.6x 106 45 x 1()6
4.5 x 10"5 9.6 x 106 7.& x 11J6 6.2 x 1()6 5.1 x 106
5.0x lOwS &.& X11J6 6.& x 1()6 5.7 x 106
108 Solutions: Chapter 10
12
Pressure drops: PaUeted
• 100mmHg
f$
10
o 250mmHg
.350mmHg
~
6 8 o 550mmHg
~
.. 750mmHg
x
-1"'- 6
~
~g
~
•
~I 2
0
0 2 3
Filtrate volume,
•
V; x 105 (m3)
5 6
,.
Pressure drops: Filamentous
12 • 100mmHg
f o 250mmHg
..
$
0
10 .350mmHg
o 550mmHg
.. 750mmHg
x 8
_1:::.,-
0 6
E
~
~g
F •
i 2
0
0 1 2 3
Filtrate volume, V;
•
x 105 (m3)
6 6
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.
=
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 s·1 (Table A.9, Appendix A), the specific cake resistance aofthe pelleted cells is:
Solutions: Chapter 10 109
Jl{c
1_
-
1.4cP.
I10-3kf; 1 lit
s- 0.lgml-
ImmHg
1.Il~mU:
6I .ll::gl
-617
)- . x v ~ Im g
k-l
The results for specific cake resistance obtained after substituting the values for tJ.p and K 1 into the equations are
listed below.
Pelleted
a(mkg~l) 558 x 108 7.41 x loB 8.58 x 108 9.60 x 108 1.07 x 109
Filamentous
a(mkg- I ) 2.30 x 109 3.29 x 10' 3.78 x 109 4.68 xla' 5.28 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 s·Z (Table A.5, Appendix A) to convert the
units of lip, the data are listed and plotted below.
Pelleted
arm kg-I) 5.58 x loB 7.41 x 108 8.58 X 108 9.60 x 108 l.07 X 109
Filamentous
a(mkg- I ) 2.30x109 3.29 X 109 3.78 X 109 4.68 x 10' 5.28 x 109
_ 100 . - ~--~-_~-~_~...,
,,- o Pelfeted
!if • Filamentous
S
6
-x
"
10
Pressure drop, Apx 10'4 (kg m·1 s·2)
110 Solutions: Chapter 10
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 s·2, 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)0.415-1 ::
Ih .
13600'
Ih1
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 . 10
6
'I~I)
1 mm]
3 Iooog
Converting units using the conversion factor I mmHg = 1.333 x 102 kg mol s·2 (fable A.5, Appendix A):
!¥J = 2.78 x 105 kgm- 1 8-2 = 2.78x 105 kg m- l 8-2 .1 I mmHg I = 2086mmHg
1.333 x 102 kg m I s-2
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.
t
=
Vf
t 2A 2
J1{a'c =----
Vi t>p>-1
Substituting the parameter values for the laboratory filter and using the conversion factor I psi =6.895 x 103 kg mol
s·2 (fable A.5, Appendix A):
Solutions: Chapter 10 111
2
1m 2
. -1-'
23.5mm. 60s 21 lOOcm 1)
2 ( Scm.
lI..,tXc "" 1 nun I "" 367x 105 kg0.43 m-2.43 s0.l4
r, (Sooml. ~ )2 ( 12 si.16.89sxI03k~m-l
106 m1 P 1 pst
e21~0.57-1 .
(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:
3kg -1 _2~0.57-1
I I
0.3 h 3600s
N'lh
-'-'-~';--c:.=. -
.x m s . pSt.(
367 105kg0.43 -2.430.14 45 . . 95 xlO
Ii
168
m s
(20)
ps 3 m
20 m3 - 2(2n(0:75m)(1.2ml)' N
N
where N is the number of revolutions per hour. Calculating both sides of the equation gives:
N = 24.9rph
(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):
O.5
N
h
. 13600
Ih '1 _ 1343.9-3
20 - -,;;-sm
_m3
N
112 Solutio1lS: Chapter 10
N = 14.9 rph
Answer; 14.9 revolutions per hour
Pp =:
3
1.06gcm- = L06gcm-
3
'lli.:gl.ll~:r = l060kgm-3
Pr =: 0.997 gene
3
:= O.997gcm-
3
.Ili.:g1·ll~~m 3
1 = 997kgm-3
1
Q = SOOlh- = 500lh-l'!l~JbJ~sl = l.39xlO-4 m3 s-1
=
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:
3
u = Pp -PfD 2g = (l060-997)kgm- (SXI0-6m)29.8ms-Z_=6.31XIO-7ms-l
g 18p P 18 (1.36 x 10 3 kgm 1s-l)
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),
1kg 3
Pp = 20. gem-3 = 20. gem-31. l000g 100 em 1
1. 11m =: 2000kgm-3
Dp =0.1 nun = 0.1 x 10-3 m. From Eq. (10.15), the sedimentation velocity for the quartz particles is:
3
_ -
ug _ Pp -Pf 2 _
-D g _ (
(2000-997) kg m- (01 10-3 m
) . x . ms-2 -_ 402
)2 98 . x 10-3 ms -1
18,u p 3
18 1.36x 10- kgm 1 s:-1
From the result in (a), r for the yeast cells is 110/0.017 =6470 times that for the quartz particles.
Answer: By a factor of 6470.
3
Pr = 1.00gcm- = 1.00gcm-
3
·ll~gl·ll~~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:
From Eq. (10.22) withg =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
From Eq. (10.15),
3
ug __ -
Pp -P'D2
- g _
_ ((l030-1000)1Qlm- ) (10-5 m
)2 98
. ms-2 -
_ .
1307 x 10-6 ms -1
18,u p 18 1.25 x Io-3 kgm-1 s-1
From Eq. (10.19), the sigma factor·:rz for the bigger centrifuge is therefore:
I
:!: = Q2:!:I = 801min- (89.6m2) = 200m2
2 Q1 3.5 1OOn-1
From Eq. (10.20), for the bigger centrifuge with 1"2 = 75 cm = 0.075 m and rt = 2.35 cm = 0.0235 m:
2
oJ- = 3glanO:!:, = 3 (9.8 m s-2)clan 45') 2048m = 4 34x 10' s-2
2 n(N - IlH - ,1) 2 n (55 -1) (0.075 m)3 - (0.0235m)3) .
_ 659 r ad s-1 .
(J)-
II revolution
21trad II 1-
60 s - 6290 rpm
. lmin
and
114 Solutions: Chapter 10
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 - =-2-
D pl Dp2
or
The data for % protein release represent values of RIR m x 100. These data can be converted to Rm/(Rm_R) as
follows:
Rm 100 100
Rm-R = loo-RIRm x 100 = 100-% protein release
The results are listed and plotted below.
Rm
N
Rm-R
30...--,---,----,---,--,--....---,
• 200 kg f an-2
o 300kg f an"2
• 400 kg f an"2
10 o 500 kg,an'2
.. 550 kg,an'2
1 2 3 4 5 6 7
Number of passes, N
The values of k pa obtained from the slopes of the straight lines for each pressure are listed below.
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
'"
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:
(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 = -"-'''--,f- ln3.33
_"" 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 kgfcm·2 apply at the higher pressure of578 klJfcm·2,
Vu
0.8 = v.
I
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
=
As CAu 3.5 CAl> CAn = 3.34 x 103 u I~I. From Eq. (10.29), the concentration factor for product partitioning into
the upper phase is:
Answer: 1.04
(a)
The yield of virus in the lower phase is given by Eq. (10.28) with VI =11, Vu =61 and K = 10-2:
Vr 11
Y, = VuK + V, = 61(10-2)+ 11 = 0.94
Answer: 0.94
(b)
The mass of viral particles in the two phases must be equal to the mass of viral particles in the original culture broth.
The mass..balance equation is:
(e)
From Eq. (10.24):
Rearranging the mass-balance equation in (b) and substituting for CAI gives:
CAu
CAuVu+CAIVi CAuVu+KVI
CAO = Vo =
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 4: derived in (c) with Vo = 51, VI = I 1, Vu = 61 and K = 10,2:
51
Answer: 4.7
118 Solutions: Chapter 10
Answer: Toxoid
(b)
The internal pore volume in the gel in the laboratory reactor can be calculated using Eq. (10,42):
The total volume oitbe large~scale column of diameter D c2::::' 0.5 m and height HZ =- 0.6 m is:
3
23m!. ~
6
V02 = rVol VTI =
10 5 m!3 ( 3)
0.118m = 0.0384m
3
TI 7.07 x 10 m
If the large·scale 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):
(d)
The liquid flow rate is scaled up in proportion to the column cross-sectional area. As the cross-sectional area ""
1& (DC/2)2, the volumetric flow rate v2 in the large column is:
(D2)2
0
(e)
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 0.0484 m 3
IR=-= = 3.1 min
v2 0.0156m3 min 1
4,----,--...,---,---,----,
(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 =
v
=
0311
. mm. I mini
'm3
. -I I60s . 110001 I _
= L05x 1O-4 ms 1
K(~'r K(02gmr
Substituting this result into the equation for H:
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):
RN,
=!
4Vli
fT(O-I)(~)=\/
0 kB+l 4
1m
2.34xI0-4 m
(1.235-1)( 1.05 )=159
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):
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
as a function of u and solving for u:
Solutions: Chapter 10 121
u = (1.85X 104 -5.7 x 1O-5)m± V (5.7 x 10-5 m-1.85x 104 m)' -4 (1.5 s)(2X 10-9 m2 s-l)
2 (1.5 s)
(a)
FromEq. (11.3):
-t1GO 1
inK =~ = 14.1klmol- = 5.69
RT 8.3144xlO-3kJr1gmoll(25+273.15K)
K = 295
The large magnitude of K indicates that the reaction can be considered .irreversible.
(b)
FromEq. (11.3):
_AGO 1
In K =~ = -32kJ mor = -1.29
RT 8.3144xlO 3 kJK Igmoll(25+273.15K)
K = 0.275
The relatively small magnitude of K indicates that the reaction is reversible.
Answer: 19
(b)
From Eq. (11.9) and the reaction stoichiometry:
.. molesG6Pfonned 1mol -1
Theorettcal yIeld =
mo1es GlP us ed to £orm G6P = -1-1
mo = I mol mol
Answer:: I mol mol~l
(c)
From p 260 and using a basis of I litre:
(ij)
(iii)
(e)
(I)
RA =100 kg d~l; rA =0.8 g I-I h- I , From Eq. (1 1.16):
I
V = RA = = 52081
lookgd-
rA 08gl-lb-ll~:III~gl
Answer: 5208 I
(ij)
FromEq, (11.67):
0.0250 12.89
0.0227 11.88
0.0184 9.95
0.0135 750
0.0125 7.02
0.00730 5.00
0.00460 3.93
0.00204 2.62
124 Solutions: Chapter 11
15,----,-----,.----...,
10
!
-I>
5
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
- 10
"1
."
E
§.
"g
'g 1 •
I
~
~
'5
~ 0.1
2.9 3.0 3.1 3.2 3.3 3.4 3.5
1/Temperature X 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.
(b)
Converting 55<>C to degrees Kelvin using Eq. (2.24), T= 55 + 273.15 =328.15 K. Substituting this value into the
equation for k obtained in (a):
k = 1.87 x 1010 e-73001T = 1.87 x 1010 e-73001328.15 = 4.08 romol m-3 s·1
Similarly, for T= 25"C =25 + 273.15 = 298.15 K:
k = 1.87 x 1010 e-73OO/T = 1.87 x WiD e-73001298.15 = 0.43 mmol mw3 s·1
Therefore, the rate at 55"C is 4.08/0.43 = 9.5 times faster than at 25"C.
Answer: The reaction rateat55"C is 4.08 mmol m- 3 s·t or 9.5 times faster than the rate of 0.43 rnmol ro· 3 s·l 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
d
= 2.25 x 1027 e-4I,630IRT = 2.25x 1027 e-4l,630/(1.9872 x 328.15) = 0.42h-l
Therefore, from Eq. (11.45), the half-life of the enzyme at 55"C is:
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) = 6.87x lO-4 h-1
and the enzyme half-life is:
Although the reaction rate is 9.5 times faster at 55 C than at 25°C, the rate of deactivation is 0.42/(6.87 x 104) =: 611
Q
times greater. Therefore, unless there are other considerations. 25°C would probably be the more practical
temperature for processing operations.
Answer: The enzyme half·life at 25°C is 1009 h or 611 times longer than the half~life of 1.65 h at 55°C. The more
practical operating temperature is probably 2jl'C.
J--<Is = f vmaxOe-kdtdt
Applying calculus rules (D.24) and (0.17) from AppendixD and combining the oonstants-ofintegration:
-Vmaxfl
-$0= id+ K
S - - - ( 1-e-<d I)
= $ 0vmoxO
kd
At the beginning of the reaction, SO = 45 gmol m-3. Converting the units of VrnaxO:
60 10001
. nuno11-1 s-1 = 007
vmaxO = 007 -1. 1lOOOnunol'
. mmo11-1 s 1 gmol 11 1 m 11 '1 42 1 -3 ·-1
3 . min = . gmo m nun
Substituting parameter values into the equation for $, when 80% of the fat is hydrolysed:
-0.087 t = -1.369
Solutions: Chapter 11 127
t =- 15.7 min
Time, t(h) x (kg m-3) <!.x (kg m-3) <it (h) <!.xl<it (kg m-3 h- I )
The values of luIfit are plotted as a function of time below according to the method described on p 263.
16 , , , , , ,
14 -
12 rf
10
8 if -
6
/
4
1/
/
2
.--r-
o I:".
-2
,
0.5
, , , , , :l
0.0 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Time (h)
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 o o
0.33 0.05 024
0.5 0.20 0.91
0.75 0.45 1.41
1.0 0.70 1.49
1.5 1.5 1.50
2.0 3.3 1.57
2.5 6.5 1.47
2.8 10.4 1.51
3.0 14.5 1.54
3.1 11.0 1.01
32 3.5 0.30
3.5 -0.3 -0.03
3.7 -0.8 -0.07
2.0
- 1.5
..
i:.
~ 1.0
1'" 0.5
t'" / 0.0
-0.5 • •
0 1 2 3 4
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
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- ·
_
1,
25
J
1 20 I- ·
~
11~ 15 rf
10 l-
I ·
1/
/
5
Y
o • .t>..
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).
130 Solutions: Chapter 11
Time. t(h)
0.0 0.' o
0.33 0.5 0.10
0.5 0.6 0.33
0.75 1.0 0.45
1.0 1.6 0.44
1.5 3.0 0.50
2.0 7.' 0.45
2.5 13.9 0.47
2.8 22.2 0.47
3.0 33.0 0."
3.1 27.5 0.40
3.2 7.0 0.50
3.5 0.4 -{J.75
3.7 o
,
Values of the observed biomass yield from substrate Yxs are plotted as a function oftime below.
• 0 D.•
"x
~
;;
D.•
~
,
0
E
e-
0.4 -
-~
'll~
.'" '" 0.3
0"
~
E 0.2
~
~ 0.1 -
.il0
0.0
J , , ,
0 1 2
Time (h)
3
•
,
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.
0 0.64 5
5 1.95 5 3.0
10 4.21 5 3.6
15 5.5. 5 3.8
Solutions: Chapter 11 131
20 6.98 5 3.7
25 9.50 5 3.4
30 10.3 5 2.6
35 12.0 5 1.9
40 12.7 5 1.2
45 13.1 5 0.8
50 13.5 5 0.6
55 13.7 5
16
1.
f 12
~
"'"
~
10
~
j
0
0
8
~ • •
~
2
0
0 10 20 30 40 50 60
Time (d)
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 0.30 0.154
10 0.36 0.086
15 0.38 0.069
20 0.37 0.053
25 0.34 0.036
30 0.26 0.025
35 0.19 0.016
40 0.12 0.009
45 O.os 0.006
50 0.06 0.004
55
-
~
:!?- 0.15
"-
{
,e
~
0,10
"'"
;e
l"'l 0.05
'"
0.00 L~,-~,-~,-::::b!:=L----J
o 10 ro M ~ W 00
Time (d)
35
30
-
~
25
.$
c
0 20
~
~
~
c
8 15 ,
,il," I
I
'" 10 I
I
<I
I
I I
5 I I
I I
I I
0
0 10 20 30 40 50 60
Time (d)
Values of[(s)t+e- (s}t-el read from the graph are listed in the table below.
Solutions: Chapter 11 133
o 30.0 5
5 27.4 5 -6.2
10 23.6 5 -6.1
15 21.0 5 -5.7
20 18.4 5 -5.4
25 14.8 5 -5.2
30 13.3 5 -4.6
35 9.7 5 -4.4
40 8.0 5 -3.9
45 6.8 5 -2.7
50 5.7 5 -1.9
55 5.1 5
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 0.318
10 0.61 0.145
15 0.57 0.103
20 0.54 0.077
25 0.52 0.055
30 0.46 0.045
35 0.44 0.037
40 0.39 0.031
45 0.27 0.021
50 0.19 0.014
55
0.35
-
~ 0.30
8'
i 0.25
!
•"
l\!
0.20
Jl 0.15
"
0
7;
2 0.10
e
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 rs from (a) and
(b). The results are listed and plotted below.
134 Solutions: Chapter 11
Time, t(h)
o
5 0.48
10 0.59
15 0.67
20 0.69
25 0.65
30 0.57
35 0.43
40 0.31
45 0.30
50 0.32
55
_ 0 0.8
"x
1!i 0.7
e
jg 0.6
~
E 0.5
,g
·m-•
3iZ~
.S- '"
E
'"
0.4
0.3
.Q
0.2
'"
~
~ 0.1
•
<3 0.0
0 10 20 30 40 50 60
Time (d)
Y
Answer: xs varies during the culture period within the range 0.30-0.69 g g~l dry weight.
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 =
2 gmolethanol ,I ~.l~ll =
gm
_
0.51gg 1
gmogucose 11802g1
1 gmol glucose. 1 ~ol
(h)
In the absence of growth. fJ. in Eq. (11.83) is zero and the equation reduces to:
Solutions: Chapter 11 135
, mp
YpS =-
ms
Therefore, for Yr.s equal to the maximum theoretical yield:
mp = 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.
(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:
, _y,,;PXc:I'm~,,,,,-+_m-,,p
Yps = Jlmax
--+ms
Yxs
Substituting the parameter values for S. cerevisiae, including the result for mp from (b):
(dj
Using the results from (8) and (c), for S. cerevisiae:
,
Efficiency = Yps = 0.43 kg kg-I = 084
maximum theoretical yield 0.51 g g-1 .
For Z mobilis:
,
Efficiency = Yps = 0.48kgkg-l = 094
maximum theoretical yield 0.51 g g-1 .
(ej
From Eq. (11.70) withf.l = J.!max, for S. cerevisiae:
For Z. mobilis:
(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:
and the proportion from non~growth metabolism is 0.33. Non·growth~associated ethanol production is more
substantial for Z. mobilis.
Answer: For S. cerevisiae, 0.94 of the ethanol production is growth~~ociated and 0.06 is non-growth·associated. 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~growth·associated 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.
(h)
From p 261, total productivity is equal to specific productivity multiplied by cell concentration and fermenter volume.
At zero growth. ,u in Eq. (11.70) is zero and q~ = mp, Therefore, from (b), the s~cific productivity qp for S.
cerevisiae is 0.092 h· l , and for Z. mobilis, LI2 h' , As the value for Z. mobilis is LI /0.092 = 12.2 times that of S.
cerevisiae, to achieve the same total productivity at the same cell concentration, the fermenter volume for the yeast
culture must be 12.2 times that for the bacteria.
(0
From Eq. (11.81) with,u= #max, for S. cerevisiae:
l
-J- = _1_ + _m_,_ = 1 + 0.18 kg kg- h- l = 9.54 kg kg-l
Yxs YXS Pmax 0.11 kg kg-l O.4h-l
, -I
Yxs = 0.105 kg kg
For Z mobilis:
1 l
~=_l_+_m_,_= I + 2.2 kg kg- h- = 24.0 kg kg-l
Yxs Yxs J4nax 0.06 kg kg- l O.3h 1
,
Yx, = 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.
The number of generations of plasmid-containing cells over the 28..day period is, from Eq. (11.66):
I
_ ,,", _ (0.025h- )28d·12::I_
n- - ln2 _24.2
ln2
If the fraction of cells containing plasmid is F= 0.66, fromEq. (11.64):
066 = l-a-p = l-L32-p = 0.32+p = 0.32+p
. l_a_2 n(a+p-lJ p 1_1.32_(224.2(1.32+p Il)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 0.0339
0.002 0.1816
0.0007 -0.0095
0.00076 -0.0008
0.00077 0.0006
0.000766 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
At 121°C:
The relationship between the number of viable cells and time is given by Eq. (11.87). Converting the units of the
initial concentration of contaminants xo:
Therefore. per m 3, No =. 1011; N =. 10.3 . Substituting values into Eq. (11.87) gives:
10-14 =. e-kdt
-32.24 =. -kd t
32.24
t=--
kd
Therefore, at 8We:
Wastewater
Siudga
---------------------- -------
Iu
--1-------
z
Bottom of lagoon
////
Substrate diffuses into the shell across the upper boundary at z+.dz. and diffuses out across the lower boundary at z.
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'" = 0
Taking the limit as A;::: --+ 0 and invoking the definition of the derivative as in Eq. (D. 12) in Appendix D:
~e:(:)-klS = 0
140 Solutions: Chapter 12
or
d 2s
Answer: 2JSe d? -k 1 S ::::: 0
(b)
At z::::: L, s::::: Sb. At Z "" O. we assume that the substrate concentration profile reaches a minimum so that ds/dz =O.
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:
N=M
Answer.N=M
(iii)
Substituting N for M in the equation for $ in (6):
Solutions: Chapter 12 141
, = N(ezJk,l"s. +e-<Jk""s.)
Applying the boundary condition at z =L:
'b = N(,LJk, 12lo, +e-LJk,l"s.)
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 Jkl/.27s )- Similarly,
J
the denominator is equal to2 cosh (L kl/psc)' Therefore: e
, _ Jk1/.q.)
2 cosh (Z
- 'b2Cosh(LJkl/.q.)
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);
sinh (L Jk]I:lJ, )
- ~ A-~ Jk I
r
A,obs - Se ~o 1 !OSe COSh(L Jk 1I!OSeSe )
142 Solutions.' Chapter 12
(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:
tanh(L JkIffD,,)
17i1 =
LJ k1ffDs,
For L = 2 em, the values of ¢I. tanh <ftI and Tlil evaluated for the three sets of conditions are listed below.
Condition ¢I 1]il
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.
.,E
1.2
0
1.0
"
~
Condition (1)
-•
'& 0.8
x
4; = 0.50; 1111 = 0.92
0.6
f g
0.4 Condition (2)
~ 0.2
I!, Condition(3) ;1=10;1111=0.10
'" 0.0
0.0 0.5 1.0 1.5 2.0
Distance from the bottom of the lagoon, z (cm)
As tPi increases, 1Jil decreases. the concentration profile becomes steeper, and the minimum suhstrateconcentl'ation in
the sludge is reduced.
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
Converting CAs to units ofkg m- 3:
CAs -1 11000
= 0.5mM = 05x to-3 gmoH. 1m3 III . 132 III I
g . looog
gmol kg = 0.Ol6kgm-3
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.
2.0x l.60x
1.7 x 10-3 1.19 x 10-2
1.5 x 10-3 9.60 x 10-3
1.2 x 1(J3 6.63 x 10-3
1.0 x 1(J3 5.02 x 10-3
0.8 x 10-3 3.71 x 10-3
05 x 10-3 2.28 x 10- 3
0.2 x 10-3 L51 x 10-3
0.0 1.37 x 10-3
144 Solutions: Chapter 12
20
f
0>
"- 15
-
M
0
x
<J
"
~
10
~
§ 5
0
c
~
0 O'-_ _--''--_ _- l . --'- -'
As the minimum value ofCA at·the centre, of the bead is still about 2.9 timesKm• the assumption of zero·order
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 zero·order 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.
Therefore, the maximum particle diameter for aerobic conditions is 2 x 1 A5 = 2.9 mm.
(b)
The particle radius is 1.45/2 "'" 0.725 rom "'" 7.25 x 10-4 m. As this radius is less than Rmax determined in (a), oxygen
is present everywhere in the particle. Therefore, as the kinetics are zero-order, T1i "'" 1. From Eq. (12.26) with 1Ji "'" I:
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:
(c)
If the cell density is reduced bya factor of 5, ko is reduced to 1/5 its previous value, Therefore, ko = 115 (3.2 x 10-5 kg
s-1 m- 3) = 6.4 x 10-6 kg s-l m- 3 . From Eq, (12,17):
4 0 9 m2 s8xlO
6 LxI 1) 3
kgm
3
=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.
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
( 'vAe CAs = (I.5XlO-3 m)2 2.2XlO-5 kgs- 1 m-3
fJ)='3 3 1.9XlO-9m2s-1(0.97X6xI03kgm3)=0.s0
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:
Answer: Yes
146 Solutions: Chapter 12
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
K (10-3 N sm-2 .11 kg m- I ,-I h2
1 Nsm 2 U
Therefore, from Eq. (l2.S2).Rep =Gr/18:= 3.39'18 =0.188. The Schmidt number from Eq. (12.49) is:
1
10-3 Nsm-2 _II kgm- 8;11
$c = IlL = IN.sm = 435
PL.vAL 103kgm-3(2.3xlO-9m2s I)
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):
Using this value of ks to determine n from the equation in Table 12.6 for spherical geometry:
120xlO-6 m
3
D = R TA,obs = 2 0.015 mol s-1 m- ::::: 0.015
3 k s CAb 3 9.99 x 10 'ms I (0.2molm-3j
From Eqs (12.43) and (12.44);
External mass*transfer effects are insignificant as CAs ,., CAb. Because respiration is zero-order and the cells are
present only-on the surface of the beads. CAs> 0 is all that is required to ensure maximum reaction rate.
Answer: Negligible
3
jJ::::: Km ::::: 35kgm- ::::: 4.12
CAs 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:
3 .PAe CAs 3 2 3
1.3 x 1O-1l m s-1 (0.85 kg m- ) .
From Figure 12.11. at <1>= 8.0. flil =0.12. Therefore. from Eq. (12.46). TJT =11i 11e::::: 0.12 x I ::::: 0.12.
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
(e)
The value of 0.0122 s·1 for kt corresponds to an enzyme loading of 0.1 Ilmol got. The Thiele modulus 4't can be
evaluated as a function of enzyme loading usingothe equation ·for first-order reaction and spherical geometry from
Table 12.2. with kt·directly proportional to the' enzyme 10ad.ing,Por¢>I < 1O,.the-intemal effectiveness factor l1il is
determined using the equation in Table 12.3 and the' definition·of coth x; for tf1I > 10. from Eq. (12.30) 1]u II¢!. For =
each value of kJ, r~s kt CAs. and rA,obs can be determined from these results and the,definition of the effectiveness
=
factor in Eq. (12.26); Calculated values of these'parameters for several different enzyme loadings are listed below.
Enzyme loading (llJllol g~ 1) kl (,-I) ¢I 'lit r'"A, (kg s-t m-3) rA,obs (kg s-t m- 3)
The resultsfor 11i1 and rA.obs are plotted below as a function of enzyme loading.
0.4,----,,----,----,-----, 6
5 1"
r¥- 0.3
'A,obs
4 "~
I! 3
-
'0
x
02 ~
<!-
=w~ 0.1
2 ~
l!
c
0
1 II
~
~
0:
0.0 ' -_ _-..J'-_ _- l . -'- ...J
0
0.0 0.5 1.0 1.5 2.0
Enzyme loading (1lffi01 g·1)
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,
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:
iJ)AL =2 x iJ)Ae =2 x 9 x 10-10 m 2 s·1 =1.8 x 10-9 m 2 s-l. The Schmidt number from Eq; (12.49) is:
9 2 1
k
s
= Sha/AL = 27.0(1.8 X 1O- m s- ) = 3.24xlO-5 ms- I
Dp 1.5 x 10 3 m
'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:
1.5 X 10-3 m
2 7.78x 10-5 kg s-l m-3 _ 0075
3.24XlO-5ms-I(8mgl-I)·I...!!'Lj·jlOOO11- .
1Q6 mg 1 m3
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):
Solutions: Chapter 12 149
1.5X to-3m)2 1 3
<1>=(li)2 rA,obs =( 2 7.78XlO'.." skgs- m- -073
3 aJAeCAs 3 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):
F!-
(9xto-lOm2S-1)7.4mg'-1·1'6kQI'~11·
_ 1Omgl' 1m
- 7.78 x 10-5 kg s-1 m 3
Answer. The oxygen concentration falls from 7.4 mg I-I at the external surface to zero just near the centre of the
clumps.
As. CAs is significantly less than CAb, external mass-transfer effects are present.
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 87 10-'k -1 -3
'* A,obs
rAb""'--"'" ,x gs m = 29
,x 10'""kgs -1 00-3
~ro 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
.... - -
r A,obs _ (2.5 x 10- 00)2
-
3
r A,obs 4
( ) = 4.96x 10 rA,obs
3 :tJAeCAs 3 1.75xI0-9 m 2 s 1 8xlO-3kgm 3
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 r A,obs
'ho =-.-
rAs
= 2.9 x 10-4 kg C 1 00-3
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 bl 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.
rA.obs (kg s-I 00-3) 11iO = r~Obs <1> 1Ji.o (from Figure 12.11)
rA,
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%.
Therefore:
Cost benefit = revenue - operating cost-downstream processing cost = $3240- $962 - $563 = $1715
Carrying out the calculations for 90% conversion. the batch reaction time for Sf = 0.10 So is:
= 6.84h
At 90% conversion, the operating cost is increased due to the longer reaction time~
Cost benefit =: revenue - operating cost- downstream processing cost "'" $3885 -$1368 - $649 =: $1868
The gain per batch from increasing the conversion from 75%:to90% is therefore $1868 -" $1715 =: $153.
Answer: There is a gain of $153 per batch; representing a 9% increase in the cost benefit at 75% conversion.
For enzyme subject to deactivation, the batch reaction time is evaluated using Eq. (13.13);
tb =-lln[l-k
k
Km In SfSo + SO-S,)]
d ( vmaxo Vmaxo
d
1 1 l
= -I 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
tb = -lln[l-kd ( Km In So + so-S,)]
k d vmaxo VmaxoSf
1 1
= -I In l-l.26XIO-Zh-l( 4.0gl- In 150gl- + (150-22.5j gl-I) = 17.7h
L26xlO 2 h-l 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:
Solutions: Chapter 13 153
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:
(bJ
If only 70% of the substrate is consumed, Sf =- 0.3 So =- 0.3 x 10 g I-I =- 3 g I-I. From Eq. (13.27):
tb = _1_ln[1 + YXS ('o-'d] = _1_1 1n[1 + 0.575 g g~I flO g I-I _ 3 grIl] = 3.9 h
Pmax Xo 0.9h- 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
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
initial medium volume:
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 := 4040 g - 1.5 g j-l (100 I) = 3890 g = 3.89 kg
where lb is the batcbreaction time and lfb is the fed-batch operation time. Substituting parameter values using the
result for 1b from (a):
The total biomass produced annually is equal to the biomass produced per run multiplied by the number of runs per
year:
Answer: 19.7 kg
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 ;
3 1
D =!:.. = 4m b- =: O,lOh-1
V 40m3
Substituting this value into Eq. (13.45) for the substrate concentration at quasi*steady state:
I 3
s= DKS = O. 10 h- (0.I5kgm- ) = 0.06kgm-3
Iimax-D 0.35h I_ O. lOb 1
(c)
Taking maintenance substrate requirements into account, for qp:: 0, Eq. (13.43) becomes:
Solutions: Chapter 13 155
dt =
£Is D(S.-S)-(.J!....+ms)x
1 Yxs
At quasi~steady state, dsld! '" 0, J1 '" D, ands« Sj. Therefore, the equation reduces to:
o = DSi-(~s +ms)x
Solving for r.
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:
Therefore, the mass of cells produced during fed~batch operation is (560 kg - 224 kg) = 336 kg.
Answer: 336 kg
Ij)
Ae
= 7xlO-6 cm2 s-1 = 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:
From Eq. (11.33), Vmax expressed on a'per volume gel basis is:
Vmax = k2 ea = 1.84 x 104 kg kg~l s·l (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=
3
vrnax =736k
. gm-3 s_1(2S0Cm
11 ) . lOOcm . 1m3 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:
3
p= 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
0.54kgm-3
_Calculating the Thiele modulus from the equation in Table 12.2 for first-order kinetics and spherical geometry:
1 I
~il = <Pi / 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 3
= -,0",.04=3"(I".8"4",kg"m"-,3-:o,-_IL)0",.0,,,2:.okg=mc.-_,, = 7.06 x 10-3 s-I
(Km + $) (si $) (0,54+ 0.02) kg m-3 (0.42-0.02) kg m-3
Answer: 12.7litres
1 1 1 1 ' 3] = 11.6h
tb = " In [Y
xs gg
I +-('O-Sf) = lin [10
+.4I - 3 (40-0.8) kg m-
r-max XO O.44h O.lkgm
_ 365dl¥*1 _
Numberofbatches - 31.6bperbatcb - 277
The total annual.biomass.productionfrom batch culture is therefore 1.64 x 104 kg x 277 = 4.54 x 106 kg.
For continuous reactor operation, the steady'-state cell concentration is given by Eq. (13.62):
The dilution rate D corresponding to S = 0.8 kg m- 3 can be detennined using Eqs (13.57) and (lL6O):
1 3
D = p = I'm",,' = M4h- {O.8kgm- j = O.44h-1
. 11000111~1
1
Ks+s . mg r
07 3' 6 08kgm-3
+.
1m 10 mg
From the definition of the dilution rate. Eq. (13.39):
The rate of biomaSs production F x= 440 m3 h- I x 16.1 kgm~3 = 7084 kg b- 1. The number of days per year available
for continuous reactor operation is (365 - 25) = 340 d; this corresponds to 340 d x 24 h d-} = 8160 h. Therefore. the
total biomass produced per year is 7084 kgh-} x 8160 h =5.78 x 107 kg. This production level is 5.78 x 107/4.54 x
106 = 12.7 times the amount produced using batch culture.
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.
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:
158 Solutions: Chapter 13
The batch culture time 1b is the time requited for the substrate concentration to reach Sf.
sf -l 1kgm-3
-10- n 3
So lOOkgm
tb = - - = = 16.0h
k1 O.8XlO-4Cl·13~sl
If the downtime between batches too is 20 b, from Eq. (13.33):
365d'
Numberofbatches = 36hperbatcb = 243
lITl
24h
To treat 400 tonues penicillin G annually, using the unit conversion factor 1 tonne:= 103 kg (Table A.3, Appendix A):
For a CSTR operated under steady state conditions, Fi ::::: Fo = F, V is constant, and ds/dt = O. Therefore, themass~
balance equation for frrst·oro.er reaction derived in Example 6.1 in Chapter 6 becomes:
0:= FSi-Fs-1q sV
0:= FIV(Si-S)-kl sV
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:
I I i lId Illh I
3
1Yeai
-1 10 kg . 1 365 d . 24 h . 3600 s
400 tonnes year . 1 tonne
F:= := 1.27x 10-4 m3 s-1
100 kg m-3
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 s·l =
3.2 x 10-4 s·l. By analogy with Eq. (13.83), the differential equation for change in substrate concentration with
position in the reactor for first·order 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
The boundary condition is: atz= 0, S = si. From the equation, therefore, In sf= K. Substituting this value of Kinto
the equation gives:
-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):
1m3
501h-1 1 I
D = f. = 10001. = O.lOh-'
V a.5m3
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):
When maintenance requirements are significant, the cell concentration is calculated using Eq. (13.61):
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 ) V
s::::: $i- ( Y +mS x
ps p
Substituting the parameter values with Si ::= 5.0 kg m- 3;
Answer: 97%
(cj
As product is not formed in the first reactor, Pi = 0 for the second reactor. The product concentration is determined by
rearranging Eq. (13.64) and solving for p:
Flow rate, F (ml h"l) Dilution rate, D (h"l) Substrate concentration, S (J,lM) SID OtM h)
2500
• •
2000
•
:2
~
•
ore, • •
1500
1000 l-~_...L_~_L.~_...L_~_L._~....J
o 20 40 60 80 100
Substrate concentration, S (p.M)
The slope of the straight line in the plot is 10.48 h; the intercept is 1493 liM h. From Eq. (13.92), the slope = llPmax;
therefore, J.tmax =1/10.48 h = 0.095 h"l. The intercept = KS/p:max;thereforeKg = 1493 J.l,M hx· 0.095 h"l = 142 J.l,M.
tlmaxSj0.095h- 1 (100/lM) -1
Derit = KS+sj = 142Jl,M+lOOliM = 0.039h
Calculating the flow rate from Eq. (13.39) with V = 1000 mI, F = D V"", 0.039 h"l x 1000 ml = 39 ml h~I.
Answer: 39 ml h"l
Flow rate. F (I hoI) Dilution rate, D (h- 1) Substrate concentration, S (g 1"1) SID (g I-I h)
0.6
0.6
0.4
-
:2
~
.$
0.3
~ICl
0.2
0.1
0.0
0.0 0.1 0.2 0.3 0.4 0.5
Substrate concentration, S (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) Dilution rate, D (hw l ) liD (h) Y~s(g g-l) Ill" (g g-l)
XS
3.20,---,---,-.,--,,--,---r--,
3.15
•
--
b
.$
_ m 3.10
-'?:-X •
•
3.05
••
3.00
0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
YOilution rate (h)
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.
The value of the specific death constant is evaluated using Eq. (11.46) with R =- 8.3144 1. gruol·l ,K~l from Table 2.5,
Ed =- 288.5 kJgmol-l =- 2.885 x loS J gruol·I, 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:
NZ 1 =- 3.09 x 10-15
Nt =- 3.24x 10 14
(a)
For perfect plug flow .withno:axial dispersion, the sterilisation time can be determined using Eq. (13,97):
N1 14
In- 1n 3.24XlO
N2 1
thd =- kd = 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:
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:
where L has units of m. Similarly, an expression for the Damkohler number Da from Eq. (13.102) is:
k L (313.1 h- 1) L
Da =- du "'" 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.
20 110 47 4x
18 99 42 1 x 10- 14
19 105 45 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