MATERIAL REQUIREMENTS AND FLOWS 13
Note however that there is some redundancy here, as C was already
calculated from the overall balance, and
P2 = P - P, = 5.71 (1.18)
In this example the topology was not complex: the calculations were
straightforward, as it was possible to complete the solution by marching
forward from the inlet. However, an attempt to solve the problem 'back-
wards', by solving around separator 2 first, would be unsuccessful: it is often
found preferable for the directions of the material and information flows to
coincide. Note that the balances on the individual units must always be
consistent with the overall balance.
1.1.4 Recycles
Recycle streams are very common in process technology. They are used for
various reasons and, in particular, to conserve material and to increase
process efficiency. The carbon dioxide loop in Fig. 1.1 is a good example;
note, too, that the solvent may also recycle valuable extracted components.
In a similar way, the efficiency of a continuous fermenter (as used in ethanol
production, for example) can often be increased, for example by recycling
cells and unconsumed nutrients.
We illustrate the effects of recycling and the method of solving material
balance problems with recycle in the next example.
EXAMPLE 1.5
One important bioprocess where recycling allows significant improve-
ments in process efficiency is the enzymatic isomerization of glucose:
Glucose ~ Fructose
This reaction is reversible, and the equilibrium constant is close to 1. Thus
the best that can be achieved is a product stream containing 50% each of
glucose and fructose. However, fructose and glucose can be partially
separated (by using a chromatograph, for example), so that the process
flowsheet in Fig. 1.7 may aI/ow higher yields of fructose by recycling
unreacted glucose to the reactor.
In practice the glucose feed is always contaminated with a small
percentage of inert oligosaccharides, and this has an important bearing on
the recycle process.
As an example consider a simplified process in which the fresh feed
contains 98% glucose and 2% oligosaccharides; all percentages are on a
weight basis.
14 INTRODUCTION TO PROCESS DESIGN
Boundary for overall balance
r-----------------------------------------------,
r- - - - - - - - - - - - - - - - - - -, r- - - - - - - - - - - - - - - - -,t
I I I I I
Fresh , Enzyme ' ,
feed - .......-H reactor F(product)
, , , L.-_--.-__ ---A : :
'-- - -Reactor-bou-ndary - - -~ '-ciiromatograph -b-ouiida~ 1
Recycle, R i p
L _ _ ....
___ -_ _-_ _ _- -
___ _ _-.
____._- -
___ _ _- -
___ __-_ _ _-.....
_____ - -_-
__ _ _'
,
~.... (purge)
Fig. 1.7 Example 1.5: glucose isomerization process.
The reaction products are at equilibrium. The chromatograph is as-
sumed to achieve perfect separation of the fructose and glucose: that is,
the product stream is glucose-free; the recycle is fructose-free; al/ the
oligosaccharide leaves the separator in the glucose stream. We now
consider how the process yield varies with recycle, R.
Basis: 100 kg fresh feed
At steady state, there is no change in any composition or flow; then an
overall balance (see Fig. 1.7) where the system boundary is cut only by
the feed, product and purge streams, gives
100 = F + P (1.19)
and an overall balance on inerts yields
2 = (1 - x)P (1.20)
where x is the fraction of glucose in stream P.
Notice that, without the purge stream, inert oligosaccharides would build
up in the process.
Specifying x fixes P and F. Thus if x = 0.9 (i.e. the inerts comprise 10%
of the stream), P = 20 and F = 80 kg. If x = 0.95, P = 40 and F = 60 etc. In
order to see what this implies for the recycle we must consider what
happens inside the process.
First consider a balance over the reactor (Fig. 1.7). The flows of glu-
cose, fructose, and inerts (all in kg) are:
In Out
Glucose 98 + 0.9R 49 + 0.45R
Fructose o 49 + 0.45R
Inert 2 + 0.1R 2 + 0.1 R
Total 100 + R 100 + R
where the equilibrium condition (i.e. that the glucose and fructose concen-
trations are equal) has been used to calculate the glucose and fructose
MATERIAL REQUIREMENTS AND FLOWS 15
exit concentrations in column 3. Note that, as in the previous examples,
the overall total acts as a check on the calculation.
Although this balance doesn't itself yield the recycle (in fact it holds for
all possible values of R) we can follow through one or more of the
components to check that the internal and overall balances coincide, and
to complete the solution of the problem. That is, the solution must ensure
that the flows of all components in the outlet stream from the reactor
equate to their flows in the exit stream from the chromatograph, and thus
to the flows in the purge and recycle. The easiest component to use is
fructose, as the fructose leaving the reactor all ends up in stream F after
the separator. Thus a balance on fructose over the chromatograph (see
boundary illustrated in Fig. 1.7) gives
49 + 0.45R = F = 80 (1.21)
so that R = 68.9kg.
There is only one value of the recycle flow consistent with the predeter-
mined value of x. You can readily check that as x, the fraction of glucose
in the recycle stream, decreases so must R increase. The object of recycle
in this case was to increase the yield of fructose on glucose. In the
absence of recycle the fractional conversion of glucose would be 0.5. Here
the fractional conversion is
80
y=-=0.816
98
Again you can check that increasing the recycle rate (which must be
increasingly dilute in glucose) would give an increased conversion of
glucose. For example, at x = 0.2, R = 485 kg, and y = 0.995.
Of course, this increased conversion is not realized at zero cost: there
is an increasingly large volume of material to recirculate and the reactor
must be redesigned to achieve the chosen efficiency (which here is to
reach equilibrium).
Finally, return to the balance over the separator (Fig. 1.7). The glucose
and inerts entering from the reactor enter the recycle stream and a purge
split is then taken to maintain the inerts balance. The mass balance on
glucose and inerts over the split must satisfy the requirements imposed.
Thus:
Leaving Leaving in P Recycle
separator
Glucose 49 + O.4SR O.1P O.1R
Inerts 2 + O.9R O.9P O.9R
which, since F = 100 - P, are both consistent with equation (1.21).
16 INTRODUCTION TO PROCESS DESIGN
You should check that all the individual and total flows in and out of each
process unit balance.
1.1.5 Solving problems that include recycles
Invariably, the first step in trying to solve any problem should be to estab-
lish an overall balance, as was done in Example 1.5 by equations (1.19) and
(1.20). As the example shows, problems involving recycle loops are some-
times tractable analytically. Sometimes, however, it is then necessary to
resort to trial-and-error methods, and many computer-aided design pack-
ages incorporate efficient algorithms for this.
In Example 1.5 the recycle flow necessary to reconcile the component
balances could be arrived at by such a process: that is, by repeated trials
with different values of R. The method is illustrated below.
EXAMPLE 1.6: NUMERICAL SOLUTION OF RECYCLE PROBLEM
The same values of the feed flow (100kg) and glucose concentration in
the purge (x= 0.9) are assumed as in Example 1.5. Thus, from the overall
balance (equations (1.19) and (1.20)), P= 20 kg and F= 80.
The calculation procedure is as follows:
1. Guess R.
2. With x= 0.9, calculate glucose (g) and inerts (i) in recycle (= A in Table
1 .1).
3. Using feed content 98 kg glucose and 2 kg inerts, calculate 9 and i at
entry to reactor (= B in Table 1.1).
4. Using equilibrium condition, calculate 9 and f at reactor exit (= C in
Table 1.1).
5. Calculate fructose product, Fe' and compare with target stream F(= 80).
6. Calculate 9 and i leaving separator (= D).
7. Calculate 9 and i in recycle from 0 - P and compare with target (= A).
If the calculated values do not match with the design or assumed values
(Le. in steps 5 and 7) try a new R and repeat until answers converge.
The procedure is illustrated in Table 1.1 for two iterations. The correct
result can be converged on readily using a simple algorithm.
1.1.6 Reaction stoichiometries
Although Example 1.5 involves a reaction, it is relatively simple to handle
because of the simplicity of the reaction stoichiometry: one mole (or kg) of
glucose gives one mole (or kg) of fructose. Thus it is easy to keep track of
the flows.
MATERIAL REQUIREMENTS AND FLOWS 17
Table 1.1 Example 1.6
First iteration, R = 50
A B C Fe F 0 P D-P
g 45 143 71.5 0 0 71.5 18 53.5
f 0 0 71.5 71.5 80 0 0 0
i 5 7 7 0 0 7 2 5
T 50 150 150 71.5 80 78.5 20 58.5
Result: Calculated fructose product (Fe) < Design value
Calculated glucose in recycle (D-P) > Assumed value
:. Try higher R
Second iteration, R = 80
A B C Fe F 0 P D-P
g 72 170 85 0 0 85 18 67
f 0 0 85 85 80 0 0 0
i 8 10 10 0 0 10 2 8
T 80 180 180 85 80 95 20 75
Result: Calculated fructose product (Fe) > Design value
Calculated glucose in recycle (D-P) < Assumed value
:. R too high: try new value in range 50 < R < 80
Many situations, however, are more complex. In food and bioprocess
operations involving more than blending, the raw materials are transformed
(bio )chemically into new products, and these processes may be too compli-
cated to represent by a simple chemical equation. Consider for example the
processes involved in transforming milk into cheese and whey, or the set of
reactions involved in extrusion cooking. Nonetheless, however complex the
chemical processes, we can be sure that:
1. a total overall mass balance must close;
2. balances on the chemical elements (C, N etc.) must close;
3. a balance on inert components must also close.
For example, in a typical microbial process we have
C-, N-, H-, 0-, etc. sources + cells = more cells and products
The usual approach taken in attempting to describe these processes is to
write an overall pseudo-chemical equation. For example, the production of
single cell protein (SCP) from an n-alkane carbon source (assuming an
average composition ClOH 20 ) has been described by:
O.168ClOH 20 + 1.402 + O.18NH3
= CH1.8400.41NO.18 + O.674C0 2 + 1.039H20 (1.22)
Note that, while this equation does not pretend to give a mechanistic
description, it must satisfy various consistency requirements, as follows.
18 INTRODUCTION TO PROCESS DESIGN
Each element should balance on the left- and right-hand sides of the
equation. Thus:
LHS RHS
C 1.68 1.674
H 3.90 3.878
0 2.8 2.797
N 0.18 0.18
It will be seen that, to a fair degree of accuracy, the balance is achieved.
The total mass on the right- and left-hand sides of the equation must also
be equal. If the individual elemental balances are satisfied then the overall
balance must also be automatically satisfied. Thus:
LHS = 0.168 x 140 + 1.4 x 32 + 0.18 x 17 = 71.38
RHS = 22.92 + 0.674 x 44 + 1.039 x 18 = 71.28
Here the 'molecular mass' of the microbial cells is 22.92: to avoid ambiguity
it is conventional to define the molecular mass of a 'carbon mole' of
cells: that is, of cells defined with the number of C atoms set arbitrarily to 1.
Note that the overall cell composition simply represents the relative
proportions between the elements. Different organisms or the same
organism under different growth conditions will have (slightly) different
compositions.
In general, moles are not conserved, where (bio-)reactions occur. In
the example above there is an increase of almost one mole over the reac-
tion. Usually, therefore, in dealing with biological processes it is more
convenient to work in mass units. It must be emphasized that all com-
ponents that are not transformed in the process (i.e. elements or inerts) are
conserved.
It is noteworthy that the closure of the mass balance in this example is not
perfect. One reason is that the overall stoichiometry does not have the same
fundamental significance as a typical single chemical equation, such as Nz +
3Hz ~ 2NH3 • The equation quoted above is the net result of many simulta-
neous and parallel reactions, not just one; moreover, a C-mole of cells is a
very different concept from a mole of a chemical or biochemical compound,
and must be empirically determined. In practice, instrument errors
and inaccuracies, variations in flows and hold-ups in a process conspire to
make the accurate closure of material balances extremely difficult. Never-
theless, the use of experimental data to attempt to establish elemental or
overall material balances is a most important diagnostic tool for the process
engineer.
MATERIAL REQUIREMENTS AND FLOWS 19
1.1.7 Stoichiometric and yield coefficients
The premultipliers in the stoichiometric equation (1.22) (0.168, 1.4 etc.) are
the stoichiometric coefficients. They represent the molar proportions be-
tween the various components involved in the reaction. By convention
the coefficient of one of the reagents or products is set to 1: it is immaterial
which is chosen. Thus in section 1.1.6, 1.4 moles of oxygen are consumed
per C-mole of cells produced (and per 0.18 moles of ammonia consumed,
etc.). Given the molecular masses of the components these coefficients are
readily transformed into mass units. Consider equation (1.22):
0.168CIOH 2o + 1.402 + 0.18NH3 = CHl.8400.4INo.18 + 0.674C02 + 1.039H20
Mol mass:
140 32 17 22.92 44 18
The mass of cells per unit mass of C-source is
Y = 22.92 = 0.974 (1.23)
0.168 x 140
Y is known as a yield coefficient and has the units of kgkg-I (here, kg
cells kg-I n-alkane). Yield coefficients can be defined for each pair of prod-
ucts and substrates.
Thus for the reaction
A + bB + cC + ... = pP + qQ + rR + ...
we can write the yield coefficient between product P (molecular mass Mp)
and substrate B (molecular mass MB):
(1.24)
The stoichiometric and yield coefficients represent the ratios between com-
ponents consumed and produced; it is quite rare for all the components to
be fed in the same proportions as their coefficients (that is, in stoichiometric
proportions), and care must be taken in handling these real problems.
1.1.8 Use of stoichiometric and yield coefficients in design
Consider a complex process:
A + bB + cC + ... =pP + qQ + rR + ...
where A, B etc. represent the compounds participating as substrates in the
reaction. For convenience suppose that P is the primary product. Yield
coefficients are defined, for example:
YPA = kg P produced kg-I A consumed (= p.Mp/MA ),
YPB = kg P produced kg-I B consumed (= p.Mp/bMB ) etc.
20 INTRODUCTION TO PROCESS DESIGN
Table 1.2 Use of stoichiometric and yield coefficients in design
In In Out Out
(kg) (kmol) (kmol) (kg)
A WA wAIMA (1-x)w AIM A (1 - x)w A
B WB wBIMB wBIMB -xbwAIMA WB - xbwAMB/(M A)
p 0 0 xpwAIMA xpwAMp/(MA)
Q 0 0 xqwAIMA xqwAMd(MA)
:E W=W A + ... w
Now consider a process with feed comprising W A, W B , •.• kg of A,B etc.
Suppose a fraction x of A is converted by the reaction above: what are the
quantities of A,B, ... P,Q, ... leaving in the product streams?
We illustrate how an overall balance can be arrived at in terms of
the stoichiometric coefficients: from the reaction stoichiometry, W moles
of A react with (wb) moles of B (etc.) to produce wp moles of P, etc.;
similarly, y kg of A react with ybMBIMA kg of B. Thus we can construct
a table of inputs and output. In Table 1.2 the calculation sequence goes
from left to right across the columns. The totals of columns 1 and 4 must
balance.
The fractional conversions of the feed components are equal (i.e. to x)
only when their molar flows are in the same ratio as the stoichiometric
coefficients: that is, they are fed in stoichiometric proportions. This can be
seen by considering the entries for component B in the table above. The
fractional conversion z is defined by (1 - z)(column 2) = (column 3):
so that
(1 - z) = (1 - x)
when
wB = bW A
MB MA
In many processes of practical importance the feed components are not
fed in stoichiometric proportions; the substrate that would first disappear
if the process went to completion is called the limiting reagent. (This is
not necessarily the limiting substrate in the language of fermentation
technology.)
The same type of calculation as shown in Table 1.2 can be carried though
using yield rather than stoichiometric coefficients, as illustrated in the
following example.
MATERIAL REQUIREMENTS AND FLOWS 21
EXAMPLE 1.7
We take as an example the (ap) process for SCP production based on n-
alkanes. Details are summarized below. The aim is to establish a com-
plete mass balance over the whole process.
Basis: 100kg n-alkane
Data
C-source: C-10 (Le. C 10 H20)
O-source: air; supplied in 20% excess over stoichiometric requirement
N-source: ammonia; supplied in 5% excess over the stoichiometric
requirement
Salts: added in aqueous solution, neglect in balance
Cell concentration in product stream: 30 g 1-1
Yield: 90% of alkane converted
Yield coefficients
On the basis of the stoichiometry above (equation (1.22)):
0.168C lO H20 + 1.402 + 0. 18NH 3
= CH1.8400.41No.18 + 0.674C02 + 1.039H 20
the yield coefficients (Table 1.3) are readily calculated from equation
(1.24), which in its most general form is
Y;j = [ :: )[ ~: }k9 component i)(kg component jt
rII Off gas
Alkane
Salts
==::::>
> --jt--~ Product
broth
Water
Air and
ammonia
Fig. 1.8 Example 1.7: fermenter.
22 INTRODUCTION TO PROCESS DESIGN
Table 1.3 Example 1.7: Yield coefficients
Compound Molecular Stoichiometric Cell yield coefficient, Yxf
mass coefficient (kg cells) (kg compound 1)-1
n-Alkane 140 0.168 0.9745
Oxygen 32 1.40 0.5116
Ammonia 17 0.18 7.49
Carbon dioxide" 44 0.674 0.7729
Water" 18 1.039 1.226
Cells 22.92
aDenotes product
Table 1.4 Example 1.7: Calculation of mass balance
Component In: feed Consumed or Out in product
(kg) produced Stream
(kg) (kg)
Alkane 100 99 1
Oxygen 200 188.6 11.4
Nitrogena 658.4 658.4
Ammonia 13.66 12.87 0.79
Cells 96.48 96.48
Carbon 124.74 124.74
dioxide
Watert> 78.71 78.71
Total 972.06 0.54 971.52
aAssuming air to be 23.3 wt % oxygen
bExcluding water added to fermenter
where a;, M; and ai' ~ are the stoichiometric coefficients and molecular
masses associated with 'j' and 'j'.
The ratio of quantities consumed or produced between any pair of
substrates and products i and j is given in terms of the cell yield coeffi-
cients in Table 1.3 by
Yij YXi (kgl')(kg).)-1
=Y.
XI
For example, between oxygen and alkane:
Yoa = 0.9745 =1.905kg oxygen (kg alkanet
0.5116
On the basis of 100 kg n-alkane the theoretical requirements for oxygen
and ammonia can be calculated:
Theoretical oxygen requirement = 1.905 x 100 = 190.5 kg
Theoretical ammonia requirement = 0.130 x 100 = 13.0 kg
