Ind. Eng. Chem. Res.

2006, 45, 5287-5297 5287

PROCESS DESIGN AND CONTROL

Process Water Management

Santanu Bandyopadhyay* and Mandar D. Ghanekar
Energy Systems Engineering, Indian Institute of Technology, Bombay, Powai, Mumbai 400076, India

Harish K. Pillai
Department of Electrical Engineering,Indian Institute of Technology, Bombay, Powai, Mumbai 400076, India

Water management addresses the problem of optimal allocation of reusable water among different water-
using operations. Wastewater management deals with optimal design of effluent treatment units to respect
environmental norms. However, optimal design of effluent treatment units should be solved in conjunction
with the problem of optimal allocation of water among different processes that use water. A new methodology
for targeting minimum effluent treatment flow rate satisfying minimum freshwater requirement is proposed
in this paper. The proposed methodology can be applied to fixed-flow-rate as well as fixed-contaminant-load
problems having a single contaminant. A source composite curve is proposed for directly targeting generation
of wastewater. Freshwater can be indirectly targeted using overall mass balance. To target distributed generation
of wastewater, wastewater composite curve is proposed. On the basis of this wastewater composite curve,
targets for effluent systems can be set. All these targets can be set on a single concentration-contaminant
load diagram before designing the detailed water-allocation network. Analytical algorithms are proposed to
solve the integrated water and wastewater management problem. The minimum contaminant removal ratio of
the effluent treatment system and the minimum number of required effluent treatment units are also reported
in this paper.

1. Introduction network. Wang and Smith2 proposed a systematic graphical

Because of environmental regulations, water management has
become an important issue for process engineers. The cost of
treating wastewater streams is increasing steadily as environ-
mental regulations are becoming more and more stringent. This
issue can be effectively addressed by process-integration
techniques. One of the goals of process integration is to integrate
resources, such as energy, materials, etc., with technologies, to
minimize emission and wastes. Process water management can
be divided into two distinct activities. One activity deals with
optimum allocation of reusable water to different processes to
minimize freshwater requirement. The other activity aims at
optimal treatment of wastewater generated in different processes
to meet environmental regulations. The primary objective of
this paper is to address these two issues of process water
management simultaneously.
In literature, methods proposed for freshwater targeting use
either conceptual approaches of process integration or use
mathematical optimization techniques. Methodologies based on
conceptual approaches help in getting a physical insight of the
problem through its graphical representations and simplified
tableau-based calculation procedures. On the other hand,
mathematical-optimization-based methodologies are preferred
to address issues such as multiple contaminants, controllability,
flexibility, cost-optimality, etc.
El-Halwagi and Manousiouthiakis1 proposed systematic
composite representations to identify targets for mass exchange
* Corresponding author. Tel.: +91-22-25767894. Fax: +91-22-
25726875. E-mail: santanu@me.iitb.ac.in.
10.1021/ie060268k CCC: $33.50 © 2006 American Chemical Society
Published on Web 06/16/2006
method for freshwater targeting. These methods are applicable
for units, which can be modeled as mass transfer units (e.g.,
washing, scrubbing, etc.) with water being used as a mass-
separating agent. These operations have a fixed contaminant
load, and the maximum allowable inlet and outlet concentrations
are specified. The flow rate of water entering and leaving the
unit is the same and can be calculated using the following
expression,
∆m
f) (1)
Cout - Cin
where ∆m is the mass load of the contaminant and Cin and Cout
are inlet and outlet concentrations of the contaminant, respec-
tively. Cin and Cout are not allowed to exceed the specified
maximum values.
The targeting method proposed by Wang and Smith2 consists
of plotting the limiting water composite curve with contaminant
load as the horizontal axis and the contaminant concentration
as the vertical axis. Since the contaminant load and concentration
difference obeys a linear relationship (eq 1), the limiting
composite curve is a piecewise linear curve. The freshwater is
represented as a straight line in this concentration vs contaminant
load diagram, as per eq 1. The freshwater line is then rotated
with the freshwater inlet concentration as a pivot until it just
touches the limiting composite curve. The reciprocal of the slope
of this rotated line gives the required minimum freshwater flow
rate. The limiting water composite curve sets the lower limit
for freshwater utilization, because at no point can the freshwater
line cross the limiting composite curve. However, the freshwater
5288 Ind. Eng. Chem. Res., Vol. 45, No. 15, 2006
line is allowed to touch the limiting composite curve, as the
required driving forces (for mass transfer) are built-in in the
limiting curve. Since the inlet flow rate is identical to the outlet
flow rate for each unit, the wastewater flow rate for the network
equals the targeted freshwater flow rate.
This method cannot be applied for processes such as cooling
tower, boiler, etc., because these units cannot be modeled as
mass transfer operations.3 These operations have specified inlet
and outlet flow rates, which may not necessarily be equal and,
therefore, can account for water losses or gains. These units
may be modeled with outlet streams leaving at a specified
concentration, while the inlet streams have a maximum allow-
able concentration.4
Wang and Smith5 proposed a method for problems with fixed-
flow-rate operations through local recycling and splitting of
water-using operations to meet the flow-rate constraints. For
problems with water loss/gain, Wang and Smith5 obtained the
limiting composite curve by neglecting changes in water flow
rate (through water loss/gain) and then accounted for the changes
in the freshwater line. Here, the freshwater line becomes
piecewise linear, and the targeting procedure becomes tedious
and iterative. The targeting methodology proposed by Dhole et
al.3 involves separate plots for source and demand composites,
with flow rate as the horizontal axis and contaminant concentra-
tion as the vertical axis. The two composites are translated
horizontally till they touch each other (at the pinch), and the
nonoverlapping portions of the curves determine the targets for
minimum freshwater and wastewater flow rates. However, this
procedure does not give true targets.6 Mixing of two streams
relaxes the pinch and, therefore, increases the overlap of the
two composites. This, in turn, decreases the freshwater require-
ment.
Sorin and Bedard7 and Polley and Polley8 proposed a set of
rules for solving fixed-flow-rate problems with few water
utilization processes. Hallale6 developed a new graphical
approach (water surplus diagram) for freshwater targeting.
Though it can be considered for fixed-contaminant-load prob-
lems as well as fixed-flow-rate problems, it is a graphical
iterative procedure. Tan et al.9 developed a tabular iterative
approach to ease the exercise of graphical iterations. A rigorous
graphical technique, on the cumulative contaminant load-
cumulative flow rate diagram, has been developed recently to
target freshwater requirement involving separate source and sink
composite curves.4,10,11 The two composites are translated
horizontally till the source composite lies just below the sink
composite curve, and the nonoverlapping portions of the curves
determine the targets for minimum freshwater and wastewater
flow rates. Mathematical optimization techniques have also been
used to solve freshwater minimization problem.12-14 Water
targeting for batch processes has been developed by Foo et
al.15,16
All the above methods essentially describe the procedure for
targeting minimum freshwater requirement. Through the overall
mass balance, the amount of generated wastewater is determined.
Because of environmental norms, it becomes essential to treat
wastewater streams, containing contaminants in large quantities,
before discharge to the environment. It is an important part of
the process water management to design and target minimum
effluent treatment flow rate to guarantee environmental limits.
Wang and Smith17 have developed a systematic approach for
the design of distributed effluent treatment systems. This
procedure has been extended by Kuo and Smith18 for multiple
Figure 1. Water allocation network, as proposed by Polley and Polley,8
satisfying freshwater target for example 1. (The values show flow rate in
t/h with contaminant concentrations in ppm within braces.)
Table 1. Limiting Process Data for Example 1
inlet/demand outlet/source
contaminant contaminant
concentration flow rate concentration flow rate
processes (ppm) (t/h) (ppm) (t/h)
P1 20 50 50 50
P2 50 100 100 100
P3 100 80 150 70
P4 200 70 250 60
concentration of contaminant in freshwater, Cfw ) 0 ppm
environmental limit for discharge concentration, Ce ) 50 ppm
removal ratio of the treatment unit, r ) 0.95
treatment processes. Mathematical optimization techniques have
also been used to design distributed effluent treatment sys-
tem.19,20
Overall water management in a process industry is usually
performed sequentially. The designs of water-using processes
are addressed first, and subsequently, on the basis of the
designed water-reuse network, the distributed effluent treatment
system is designed. This sequential procedure may lead to
suboptimal solution for the distributed effluent treatment system.
To illustrate the point, let us consider example 1. The limiting
process data for example 1 is given in Table 18 with additional
assumptions that the environmental limit is 50 ppm and the
contaminant removal ratio of the treatment unit is 95%. If
freshwater is used to satisfy the demand for each of the
individual processes, the freshwater consumption may be
estimated to be 300 t/h. However, reusing water from other
processes, the minimum freshwater requirement can be calcu-
lated as 70 t/h with a corresponding effluent flow rate of 50
t/h. Polley and Polley8 proposed a water-allocation network
satisfying the minimum freshwater target (Figure 1). This
network produces an effluent stream of 50 t/h with a contami-
nant concentration of 250 ppm. To meet the environmental
regulation, 42.11 t/h of effluent has to be treated in the treatment
unit (not shown in Figure 1). However, this is not optimal. It is
possible to redesign the network (as demonstrated later in this
paper) such that only 35.96 t/h of effluent needs to be treated
to meet the environmental regulation (a reduction of 15%).
Therefore, it is essential to target effluent treatment simulta-
neously with the freshwater targeting.
In a seminal paper, Takama et al.21 solved the complete water
management problem using nonlinear optimization technique.
Kuo and Smith22 presented a methodology to discuss the
 Ind. Eng. Chem. Res., Vol. 45, No. 15, 2006 5289

interaction between operations that use water and effluent Table 2. Generation of Source Composite Curve and Targeting
treatment systems. In this method, they plotted limiting com- Wastewater for Example 1
posite curve, freshwater curve, and effluent treatment curve on contaminant net cum. mass cum. wastewater
a single concentration-contaminant load diagram. However, this concentration flow rate flow rate load mass load flow rate
(ppm) (t/h) (t/h) (kg/h) (kg/h) (t/h)
method is only applicable to fixed-contaminant-load operations.
In this paper, a novel methodology is developed for simul- 250 60 60 0 0 40
200 -70 -10 3 3 35
taneously targeting distributed effluent treatment system and 150 70 60 -0.5 2.5 50
minimum freshwater requirement. A source composite diagram 100 20 80 3 5.5 45
is introduced to target minimum wastewater production both 50 -50 30 4 9.5 10
for fixed-contaminated-load and fixed-flow-rate problems. In 20 -50 -20 0.9 10.4 -20
the proposed methodology, freshwater requirement is calculated 0 0 -20 -0.4 10 0
through the overall mass balance. The source composite diagram
is then used to develop the wastewater composite curve. The
Step 4. Calculate the entries of the fourth column by the
minimum effluent flow rate for treatment, minimum contaminant
formula Pi ) Qi-1(Ci-1 - Ci). Note that Q0 is assumed to be
removal ratio, and minimum number of treatment units required
zero.
for the overall effluent treatment process are also targeted in Step 5. The fifth column contains the cumulative contaminant
this paper. Graphical representations as well as analytical
mass load ∆mi ) ∑j)1 i
Pj.
algorithms are proposed to address integrated process water
Step 6. Calculate the corresponding wastewater flow rate fww,i
management issues. The conceptual approach presented in this
) (∆mT - ∆mi)/(Ci - Cfw) where Cfw is the concentration of
paper is restricted to a single contaminant.
the freshwater and ∆mT ()∆mn) is the total contaminant load
of the process. Note that wastewater flow rates are calculated
2. Wastewater Targets for concentrations such that Ci > Cfw.
Now the fifth column (cumulative mass load) may be plotted
In the following subsections, a new methodology is proposed against the first column (concentration) to obtain the source
to target simultaneously the minimum freshwater requirement, composite curve. The largest entry in the last column is the
maximum water reuse, minimum wastewater generation, and minimum wastewater flow-rate target.
minimum effluent to be treated to meet environmental norms. The last entry in the third column gives water loss/gain in
In the proposed method, minimum wastewater produced is the overall process. A negative entry suggests water loss, and
targeted directly. In this method, a novel limiting composite a positive entry indicates an overall water gain in the process.
curve, called source composite curve, is proposed. The source For a fixed-contaminant-load problem, the last entry should be
composite curve is plotted on a concentration (C) vs contaminant zero. This is expected because there is no water gain/loss in
load (∆m) diagram. any process.
2.1. Source Composite Curve and Targeting Wastewater. In step 6 of the previous algorithm, minimum wastewater is
Every fixed-contaminant-load problem may be converted to a targeted from the source composite diagram. This is similar to
fixed-flow-rate problem at the targeting stage with the limiting the freshwater targeting approach of Wang and Smith.2 Similar
water flow rate being the specified flow rate for each process.4 to eq 1, the equation for the wastewater line is given as
Therefore, a water allocation problem may be modeled with
outlet streams leaving at a specified concentration and flow rate ∆m ) ∆mT - fww(C - Cfw) (2)
(sources of wastewater), while the inlet streams have a
maximum allowable concentration and a specified flow rate. At any concentration, the wastewater line cannot pickup more
The outlet of any process may be viewed as a source of contaminant load than what is available (given by the source
wastewater, while the inlet to any process represents the scope composite curve). The minimum wastewater can be targeted
of reusing wastewater or demands of wastewater. The source by rotating the wastewater line with (∆mT, Cfw) as the pivot
composite curve represents the maximum contaminant load at point such that it just touches the source composite curve. Note
different contaminant concentrations. Physically, the source that the wastewater line has a negative slope (eq 2), and the
composite curve is equivalent to the grand composite curve in slope is inversely proportional to the wastewater flow rate. This
heat-exchanger network synthesis23 and invariant rectifying and is equivalent to targeting nonpoint utilities in a heat-exchanger
stripping curves in distillation.24 An algebraic procedure for the network. Step 6 represents the analytical procedure equivalent
generation of source composite curve and targeting minimum to this graphical targeting of wastewater on the concentration
wastewater production is given below. (C) vs contaminant load (∆m) diagram.
2.1.a. Minimum Wastewater Targeting Algorithm. Minimum wastewater targeting algorithm is applied on
example 1. The limiting process data for example 1 is given in
Step 1. Arrange all the distinct concentrations (of freshwater,
Table 1.8 Values calculated by applying this proposed algorithm
demands, and sources together) in descending order in the first
are shown in Table 2. In Table 2, the last entry in the third
column. Without loss of generality, the entries of the first
column is -20. It suggests that there is an overall water loss of
column are C1 > C2 > C3 > ... > Cn.
20 t/h. The bottom entry in the fifth column signifies the total
Step 2. For each concentration Ci (in the first column), put contaminant load of the process, and the same has to be picked
the corresponding net flow Fi in the second column. The net up by the wastewater (∆mT ) 10 kg/h). The maximum entry in
flow Fi is calculated by taking the algebraic sum of flow rates the sixth column sets the minimum wastewater targets as 50
corresponding to a concentration Ci. We adopt the convention t/h.
of positive flow rates for sources and negative flow rates for The source composite curve and wastewater line for example
demands. 1 are shown in Figure 2. The maximum slope of the wastewater
Step 3. The corresponding entries in the third column are line corresponds to the minimum wastewater flow rate, since
cumulative flow rates given by the formula Qi ) ∑j)1 i
Fj. they have an inverse relationship (eq 2). So the minimum
5290 Ind. Eng. Chem. Res., Vol. 45, No. 15, 2006

Figure 2. Source composite curve and wastewater line for example 1. Figure 3. Source composite curve, wastewater line, and wastewater
composite curve for example 1.

wastewater flow rate target comes out to be 50 t/h, and the Table 3. Generation of Wastewater Composite Curve for Example 1
corresponding pinch composition (CP) is 150 ppm. Total water wastewater cum.
demand for this example is 300 t/h, and total available water cum. flow rate, mass
flow rate is 280 t/h. Therefore, there is a net loss of 20 t/h of contaminant mass wastewater after first cum. load
conc load flow rate pinch wastewater removed
water (last entry of third column in Table 2). Thus, the minimum (ppm) (kg/h) (t/h) (t/h) (t/h) (kg/h)
freshwater target comes out to be 70 t/h. It may be noted that,
250 0 40 25 25 0
for a fixed-contaminant-load problem, the minimum wastewater 200 3 35 -10 25 1.25
target is equal to the minimum freshwater target, as there is no 150 2.5 50 50 2.5
water loss/gain. 100 5.5 45 50 5
2.2. Wastewater Composite Curve. Wastewater line rep- 50 9.5 10 50 7.5
20 10.4 -20 50 9
resented by eq 2 gives the total wastewater available from the 0 10 0 50 10
unit. This information is sufficient for designing a centralized
effluent treatment plant and end-of-the-pipe solution. However, 2.2.a. Algorithm for Wastewater Composite Curve.
for the most efficient effluent treatment plants, the optimal Step 1. Determine overall wastewater flow rate, corresponding
design of treatment units must be solved in conjunction with pinch point (CP), and contaminant load removed up to pinch
the optimal freshwater allocation problem.18 It has been observed point (∆mTP) using minimum wastewater targeting algorithm.
that, for optimum design of the effluent treatment unit, Step 2. Repeat step 6 of previous algorithm considering ∆mT
wastewater streams should not be merged together to form a ) ∆mTP and Cfw ) CP. Therefore, wastewater flow rate is
single wastewater stream.17,18 Therefore, it is of utmost impor- calculated using the formula fww,1,i ) (∆mTP - ∆mi)/(Ci - CP)
tance to identify wastewater sources at different concentrations. for concentrations such that Ci > CP. The maximum of this
To identify wastewater streams at different concentration, Kuo column is the wastewater that can be generated (fww,1) that
and Smith18 suggested a simple procedure. First, the minimum corresponds to a new pinch point (CP,1).
freshwater requirement is determined. Since they have addressed Step 3. Repeat step 2 until the pinch concentration coincides
problems with fixed contaminant load, the freshwater line and with the top concentration (C1). Every repetition produces a
the wastewater line are identical. Up to the pinch point, the wastewater flow rate (fww,k) that corresponds to a pinch point
minimum freshwater targeted cannot be reduced further. After (CP,k).
the pinch point, the limiting composite curve and the freshwater Step 4. Cumulative wastewater flow rates are tabulated in
line diverge from each other. Considering the pinch point as a the next column using the formula Ri ) fww,k for Cp,k g Ci >
pivot, the freshwater line can be further rotated to minimize Cp,k-1.
the freshwater requirement. This procedure is equivalent to the Step 5. The last column contains the cumulative contaminant
removal of pockets for the grand composite curve in the context mass load removed by wastewater ∆mww,i ) ∑j)1 i
Rj-1(Cj-1 -
of heat-exchanger network design.23 Cj). Note that R0 is assumed to be zero.
The previous methodology can be followed on the source Similar to the source composite curve, plotting the last column
composite curve to obtain the wastewater composite curve. This against the concentration gives the wastewater composite curve.
procedure, in essence, removes all local concavities or pockets Results obtained by using the algorithm for the wastewater
and produces an outer convex curve. For a problem having only composite curve for example 1 are given in Table 3. For better
wastewater sources and no demand, the outer convex curve or readability, the first, fifth, and sixth columns of Table 2 are
the wastewater composite curve coincides with the source reproduced in the first three columns of Table 3. As indicated
composite curve. before, for example 1, minimum wastewater generated is 50
The wastewater composite curve divides the source composite t/h, which corresponds to a pinch concentration of 150 ppm
curve into different regions. Each region, in the order of (CP ) 150 ppm), and load removed up to pinch concentration
decreasing concentrations, cumulatively produces more waste- is 2.5 kg/h (∆mTP ) 2.5 kg/h). In example 1, only one step is
water than the previous one. Whenever there is an addition of sufficient for removing all pockets. Step 2 produces a pinch
wastewater at a particular concentration, the slope of the point that coincides with the top concentration of the first
wastewater composite curve decreases. This is essentially due column, i.e., 250 ppm. Both the wastewater line and the
to the convexity of the wastewater composite curve. This wastewater composite curve, for example 1, are plotted in Figure
property may be used to prove optimality of effluent treatment 3.
targets. From Table 3, it can be interpreted that wastewater is
Similar to the wastewater targeting approach, to avoid a generated at two different concentration levels (corresponding
tedious graphical targeting, an analytical algorithm is developed. to two pinch points): 25 t/h of wastewater is generated at 250
 Ind. Eng. Chem. Res., Vol. 45, No. 15, 2006 5291

Table 4. Generation of Source Composite Curve, Targeting Wastewater, and Generation of Wastewater Composite Curve for Example 1 with
Cfw ) 20 ppm
wastewater wastewater cum.
cum. flow rate, flow rate, mass
contaminant net cum. mas mass wastewater after first after cum. load
conc flow rate flow rate load load flow rate pinch second wastewater removed
(ppm) (t/h) (t/h) (kg/h) (kg/h) (t/h) (t/h) pinch (t/h) (t/h) (kg/h)
250 60 60 0 0 45.22 36.67 25 25 0
200 -70 -10 3 3 41.11 25 -10 25 1.25
150 70 60 -0.5 2.5 60.77 60 60 2.5
100 20 80 3 5.5 61.25 61.25 5.5
50 -50 30 4 9.5 30 61.25 8.56
20 -50 -20 0.9 10.4 0 61.25 10.4

ppm (second pinch point) and (50 - 25) t/h, i.e., 25 t/h, of
wastewater is generated at 150 ppm (first pinch point).
A network satisfying fresh and wastewater targets for example
1 may be obtained using the nearest-neighbor algorithm,4 and
it is shown in Figure 4. It may be noted that the concept of
water mains, introduced by Kuo and Smith,22 is not necessary
to design a water-allocation network satisfying distributed
wastewater targets.
Example 1 is slightly modified to observe the applicability
of the proposed methodology and algorithm for contaminated
freshwater (Cfw > 0). Freshwater is assumed to have a
concentration of 20 ppm (Cfw ) 20). Note that 20 ppm is the
maximum limit for concentration up to which freshwater can
be supplied. Beyond this, example 1 will become unsolvable,
as the maximum allowable concentration limit for the purest
demand (P1 in Table 1) is 20 ppm. Results related to source
composite curve, wastewater line, and wastewater composite
curve are tabulated in Table 4. The minimum wastewater flow
rate target comes out to be 61.25 t/h, and the corresponding
pinch composition is 100 ppm. Through the overall mass
balance, this corresponds to a freshwater target of 81.25 t/h.
Note that, because of an increase in the contaminant level in
the freshwater, the freshwater requirement increases by 16%.
In this case, wastewater is generated at three different concen-
tration levels (corresponding to three pinch points): 25 t/h of
wastewater is generated at 250 ppm (third pinch point); (60 -
25) t/h, i.e., 35 t/h, of wastewater is generated at 150 ppm
(second pinch point); and (61.25 - 60) t/h, i.e., 1.25 t/h, of
wastewater is generated at 100 ppm (first pinch point).
2.3. Targeting Effluent System. After targeting the waste-
water, the next step is to find out the effluent treatment flow
rate for a given set of operations. As discussed in previous
subsections, the source composite and wastewater composite
curves can be obtained simultaneously before designing the
water-allocation network.
Let us denote Ce as the concentration below which wastewater
may be discharged from the treatment plant (as the environ-
mental regulations imposed on the overall plant). The contami-
nant load has to be treated and removed in the effluent treatment
plant. This can be explained better through Figure 5. We then
draw a vertical line on the concentration vs contaminant load
diagram that meets the wastewater composite curve at Ce. The
vertical line divides the wastewater composite curve and, hence,
the total contaminant load into two parts. Let us denote the
contaminant load left of the vertical line as ∆mTef and the
contaminant load right of the vertical line as ∆ms. If the total
wastewater is discharged with a contaminant load of ∆ms, the
concentration of the wastewater has to be Ce. Therefore, the
contaminant load right of the vertical line (∆ms) can be
discharged safely to the environment, and the remaining load
(∆mTef) has to be treated. Thus, ∆mTef kg/h amount of load has
to be removed from the system to satisfy environmental
regulation (see Figure 5).
The performance of the effluent treatment system is given
by the removal ratio (r) of the contaminant load from the
system.2 It is defined as
fTCTin - fTCTout CTin - CTout ∆mTef
r) ) ) (3)
fTCTin CTin ∆mTef + m0
To remove ∆mTef kg/h of contaminant load in the effluent
treatment unit, the input load for the treatment plant must be
some (∆mTef + m0) kg/h. Equation 3 may be rewritten to
calculate the input load (∆mTef + m0).
∆mTef
∆mTef + m0 ) (4)
r

Point “Q” in Figure 5 denotes the point with contaminant

load of (∆mTef + m0) kg/h. Any treatment line, i.e., the line

Figure 4. Network satisfying freshwater, wastewater, and effluent treatment

targets for example 1. (The values show flow rate in t/h with contaminant
concentrations in ppm within braces.) Figure 5. Targeting effluent treatment flow rate.
5292 Ind. Eng. Chem. Res., Vol. 45, No. 15, 2006
Figure 6. Wastewater composite curve and effluent treatment line for
example 1.
Table 5. Targeting Minimum Effluent Treatment Flowrate for
Example 1
contaminant cumulative mass treatment flow
concentration (ppm) load removed (kg/h) rate (t/h)
250 0 31.58
200 1.25 33.22
150 2.5 35.96
100 5 28.95
50 7.5 7.89
20 9 -55.26
0 10
that represents the removal of contaminant load on a concentra-
tion (C) vs contaminant load (∆m) diagram, must pass through
the point for fixed removal ratio. The equation of the treatment
line is given as
∆m ) ∆mTef/r - fTC (5)
The minimum treatment flow rate can be targeted by rotating
the treatment line with point Q, i.e., (∆mTef/r, 0), as the pivot
point such that it just touches the active wastewater composite
curve. The point at which the treatment line touches the
wastewater composite curve is called the treatment pinch.
Similar to the previous subsections, an algorithmic approach
is described below for targeting minimum effluent treatment
flow rate.
2.3.a. Algorithm for Targeting Minimum Effluent Treat-
ment Flow Rate
Step 1. Determine ∆mTef from the wastewater composite
curve that corresponds to the environmentally acceptable
concentration (Ce).
Step 2. Determine effluent treatment flow rate using the
formula fT,i ) [(∆mTef/r) - ∆mww,i]/Ci. The maximum entry in
the last column defines the minimum effluent treatment flow
rate.
To demonstrate the above algorithm, example 1 is considered
with the environmental limit as 50 ppm, and the removal ratio
of the treatment unit is assumed to be 0.95. Results are tabulated
in Table 5. The concentration and corresponding cumulative
contaminant mass load removed by wastewater from Table 3
(from the first and last columns, respectively) are tabulated in
first two columns for better understanding. Corresponding to
Ce ()50 ppm), the cumulative mass load removed wastewater
denotes ∆mTef, the contaminated load to be removed in the
effluent treatment unit. For example 1, ∆mTef ) 7.5 kg/h.
From Table 5, it is evident that the targeted minimum effluent
treatment flow rate is 35.96 t/h and corresponding treatment
pinch is 150 ppm. Source composite curve, wastewater com-
posite curve, and the treatment line for example 1 are shown in
Figure 6. Figure 4 includes the treatment units to represent the
network of overall water management for example 1.
Figure 7. Network satisfying freshwater, wastewater, and effluent treatment
targets for example 1 with Cfw ) 20 ppm. (The values show flow rate in
t/h with contaminant concentrations in ppm within braces.)
Table 6. Targeting Minimum Effluent Treatment Flowrate for
Example 1 with Cfw ) 20 ppm
contaminant cumulative mass treatment
concentration (ppm) load removed (kg/h) flow rate (t/h)
250 0 36.04
200 1.25 38.80
150 2.5 43.40
100 5.5 35.11
50 8.56 9.01
20 10.4 -69.47
For completeness, the proposed algorithm is applied to
example 1 with a contaminated freshwater supply (Cfw ) 20
ppm). Corresponding values are tabulated in Table 6. The target
for minimum effluent treatment flow rate is 43.4 t/h, and the
corresponding treatment pinch is 150 ppm. Figure 7 represents
the process flow diagram for the solution of the entire water
management for example 1 with Cfw ) 20 ppm.
2.4. Minimum Removal Ratio (rmin). Observe from eq 4
that, for a fixed ∆mTef, a decrease in removal ratio (r) leads to
an increase in m0. Therefore, the pivot point (point Q in Figure
5) shifts horizontally toward the right. The maximum horizontal
shift is possible such that the entire wastewater is treated in the
effluent treatment plant. This corresponds to end-of-the-pipe
effluent treatment with a limiting value of removal ratio. If the
removal ratio is lower than this limiting value, then treatment
of the entire wastewater in a single treatment unit is not
sufficient to remove the required amount of contaminant from
the wastewater. In such a situation, either of the following steps
may be taken:
(i) More freshwater may be used to dilute the effluent.
(ii) A local recycle across the effluent treatment may be
provided.
(iii) Multiple treatment units may be used in series.
Other than these three options, the designer may choose an
alternative technology with a higher removal ratio. However,
in this paper, we restrict attention to the cases where the removal
ratio of the wastewater treatment plant is assumed to be fixed.
Before discussing the implications of these three cases, it is
important to derive the minimum removal ratio for a given
problem.
At a minimum removal ratio, Ce is going to hold the treatment
pinch and the entire wastewater is treated in the treatment plant.
Hence, by rearranging eq 5, the minimum removal ratio can be
calculated as follows:
∆mTef
rmin ) (6)
∆mTef + fwwCe
 Ind. Eng. Chem. Res., Vol. 45, No. 15, 2006 5293

Table 7. Limiting Process Data for Example 2 2.4.b. Case (ii): Minimum Recycle Flow Rate across the
inlet/demand outlet/source Treatment Unit. The treatment unit reduces the concentration
contaminant flow rate contaminant flow rate
of the effluent stream. If some amount of the treated effluent is
processes conc (ppm) (t/h) conc (ppm) (t/h) recycled across the treatment unit, the inlet concentration of
the combined effluent may be reduced to meet the environmental
P1 0 120 100 120
P2 50 80 140 80 norms. On the basis of the definition of removal ratio for a
P3 50 80 treatment unit (eq 3), the outlet concentration of the treatment
P4 140 140 180 140 unit can be expressed as
P5 170 80 230 80
P6 240 195 250 195 CTout ) (1 - r)CTin (8)
Cfw ) 0 ppm, Ce ) 20 ppm, and r ) 0.95
As the outlet concentration is limited by the environmental
Minimum removal ratios for example 1 with freshwater (C0 norms, the inlet concentration has to be Ce/(1 - r). Using mass
) 0 ppm) and contaminated freshwater (C0 ) 20 ppm) are balance, the minimum amount of recycle flow rate (fr) to achieve
calculated to be 0.75 and 0.737, respectively. It is interesting this concentration is calculated to be
to note that an increase in contaminant level in freshwater
increases the minimum wastewater output by 22.5%. However, (1 - r)∆mTef
in the case with contaminated freshwater, the minimum removal fr ) - fww (9)
rCe
ratio of the treatment unit is reduced slightly (1.8%).
The minimum removal ratio indicates the limit up to which
For example 1 with r ) 0.7, eq 9 implies that at least 14.29
only one treatment unit is sufficient to meet the environmental
t/h of treated effluent has to be recycled across the treatment
norms. If the removal ratio of a particular treatment unit is <rmin,
unit to satisfy environmental regulations.
then any one of the three cases may be considered to meet the
2.4.c. Case (iii): Minimum Number of Treatment Units
environmental limit.
in Series. A single treatment unit is sufficient whenever CTout
2.4.a. Case (i): Minimum Freshwater Flow Rate to Dilute
is not more than the environmental limit Ce. However, for a
the Effluent. As the removal ratio of the treatment unit is <rmin,
treatment unit with a removal ratio less than the minimum
removal of required amount of the contaminant load from the
removal ratio (r < rmin), multiple (say n) such treatment units
wastewater is not possible. By treating all the available
are required to meet the environmental norm. In the case of a
wastewater (fww), the amount of contaminant removed from the
series arrangement, the outlet concentration of the effluent
systems can be calculated to be r(∆mTef + fwwCe) and the
treatment may be expressed as
concentration of the treated effluent is expressed as (1 - r)-
(∆mTef/fww + Ce). To achieve the environmental limit, the
CTout ) (1 - r)nCTin ) Ce (10)
additional amount of freshwater (fadd) required can be expressed
as
This is equivalent to a single treatment unit with minimum
removal ratio.
(1 - r)∆mTef rfwwCe
fadd ) - (7)
Ce - Cfw Ce - Cfw CTout ) (1 - rmin )CTin ) Ce (11)

To illustrate, let us consider example 1 with a removal ratio Rearranging the above equations, the minimum number of
of 0.7, a value less than the minimum removal ratio of 0.75. treatment units can be calculated as

[ ]
Application of previous methodology results in targeting 64.29
fwwCe
t/h of effluent treatment flow rate. This is clearly not possible, ln
as the total wastewater available is 50 t/h. To satisfy the ln(1 - rmin ) ∆mTef + fwwCe
n) ) (12)
environmental limit, as per eq 7, an additional 10 t/h of ln(1 - r) ln(1 - r)
freshwater is required.
In this case, more than the minimum freshwater is required Thus, eq 12 gives the minimum number of treatment units
to satisfy the environmental limit. Though it defeats the original required to meet the environmental norm. However, eq 12 may
objective of designing the effluent treatment system utilizing predict the number of treatment units in fraction. The smallest
the minimum freshwater requirement, it still serves as an integer greater than this fraction should be considered as the
alternate solution for the design engineer. target for the minimum number of treatment units. In other

Table 8. Generation of Source Composite Curve, Targeting Wastewater, and Generation of Wastewater Composite Curve for Example 2
wastewater cumulative cumulative
contaminant net cumulative mass cumulative wastewater flow rate, wastewater mass load treatment
concentration flow rate flow rate load mass load flow rate after second flow rate remove flow rate
(ppm) (t/h) (t/h) (kg/h) (kg/h) (t/h) pinch (t/h) (t/h) (kg/h) (t/h)
250 195 195 0 0 110.20 85 85 0 105.89
240 -195 0 1.95 1.95 106.67 66.67 85 0.85 106.77
230 80 80 0 1.95 111.30 80 85 1.7 107.71
180 140 220 4 5.95 120.00 120 5.95 114.02
170 -80 140 2.2 8.15 114.12 120 7.15 113.67
140 -60 80 4.2 12.35 108.57 120 10.75 112.31
100 120 200 3.2 15.55 120.00 120 15.55 109.24
50 -160 40 10 25.55 40.00 120 21.55 98.47
20 0 40 1.2 26.75 40.00 120 25.15 66.18
0 -120 -80 0.8 27.55 0.00 120 27.55
5294 Ind. Eng. Chem. Res., Vol. 45, No. 15, 2006

Table 9. Limiting Process Data for Example 3

inlet/demand outlet/source
contaminant flow rate contaminant flow rate
processes conc (ppm) (t/h) conc (ppm) (t/h)
P1 0 50 200 50
P2 100 50 300 50
P3 100 30 500 30
P4 300 60 500 60
Cfw ) 0 ppm, Ce ) 20 ppm, and r ) 0.75

words, the minimum number of treatment units should be such

that

(1 - r)n-1 g (1 - rmin ) g (1 - r)n (13)

For example 1 with r ) 0.7, eq 13 suggests that (1 - 0.7) >

Figure 8. Source composite curve, wastewater composite curve, and
(1 - 0.75) > (1 - 0.7)2. Therefore, a minimum of two treatment treatment line for example 2.
units in series is requited to meet the environmental discharge
criterion.
The optimal structure for the treatment is generic (for brevity,
the proof is not included in this paper). It suggests that a portion
of the effluent will pass through one treatment unit, and the
combined treated and untreated effluent should pass through
the remaining (n - 1) treatment units in series. Since all the
effluent is passing through (n - 1) treatment units in series,
the minimum effluent-treatment flow rate corresponds to
minimal effluent passing through the single unit. To find the
minimal effluent-treatment flow rate, the same procedure
described above can be employed. However, eq 5 should be
modified as follows:

∆m ) 1 -
[ 1 - rmin
(1 - r) n-1 ]( )
∆mTef
rminr
- fTC (14)
Figure 9. Water allocation network including treatment unit for example
For the modified example 1 with two treatment units in series, 2. (The values show flow rate in t/h with contaminant concentrations in
only 9.52 t/h of most contaminated effluent has to be treated in ppm within braces.)
the first treatment unit, and the combined wastewater has to be
treated in the second unit to achieve the environmental discharge 3.1. Example 2: Six-Process Example. Limiting process
limit of 50 ppm. It may be noted that, in thse case of local data for this example is given in Table 7.7 Freshwater
recycle, the total amount of treated effluent flow rate (64.29 t/h concentration is 0 ppm. The environmental limit and the removal
for modified example 1) is always more than that of the last ratio of the effluent treatment unit are assumed to be 20 ppm
case (for modified example 1, it is 59.52 t/h). and 0.95, respectively. Results concerning generation of the
The appropriate choice of a particular method to meet the source composite curve, wastewater line, and wastewater
environmental regulation primarily depends on the economic composite curve are tabulated in Table 8. Wastewater can be
tradeoffs between the operating cost and the capital investment targeted directly as 120 t/h. Freshwater targets can be set through
for extra treatment units. The process designer should be able overall mass balance as (120 + 80) t/h, i.e., 200 t/h. Interest-
to take a proper decision based on cost of freshwater, availability ingly, in this problem, there are two pinches, at 100 and 180
of freshwater, operating cost of effluent treatment, types of ppm. However, the upper pinch controls for wastewater genera-
contaminants, capital cost for setting multiple treatment unit, tion. In this example, wastewater is generated at two concentra-
turndown ratio for the overall plant, availability of space, etc. tion levels: 85 t/h of wastewater is generated at 250 ppm and
(120 - 85) t/h, i.e., 35 t/h, of wastewater is generated at 180
ppm. Note that no wastewater is generated at 100 ppm. A
3. Illustrative Examples
minimum removal ratio for example 2 is calculated to be 0.913.
To demonstrate the applicability of the methodologies Hence, only one treatment plant is sufficient. Results for effluent
developed in this paper, several published examples are solved treatment flow-rate targets are also tabulated in Table 8. The
in this section. target for minimum treatment flow rate is 114.02 t/h. Source
Table 10. Generation of Source Composite Curve, Targeting Wastewater and Generation of Wastewater Composite Curve for Example 3
cumulative wastewater cumulative cumulative
contaminant net cumulative mass mass wastewater flow rate, wastewater mass load treatment
concentration flow rate flow rate load load flow rate after first flow rate removed flow rate
(ppm) (t/h) (t/h) (kg/h) (kg/h) (t/h) pinch (t/h) (t/h) (kg/h) (t/h)
500 90 90 0 0 88 86.67 86.67 0 40.53
300 -10 80 18 18 86.67 80 86.67 17.33 9.79
200 50 130 8 26 90 90 26 -28.7
100 -80 50 13 39 50 90 35 -147.3
20 0 50 4 43 50 90 42.2 -1096.7
0 -50 0 1 44 90 44
 Ind. Eng. Chem. Res., Vol. 45, No. 15, 2006 5295

Figure 10. Source composite curve, wastewater composite curve, and

treatment line for example 3.
Figure 11. Water allocation network including three treatment units in
Table 11. Limiting Process Data for Example 4
series for example 3. (The values show flow rate in t/h with contaminant
inlet/demand outlet/source concentrations in ppm within braces.)
contaminant flow rate contaminant flow rate
processes conc (ppm) (t/h) conc (ppm) (t/h)
reactor/thickener 100 80 1000 20
cyclone 200 50 700 50
filtration 0 10 100 40
steam system 0 10 10 10
cooling system 10 15 100 5
Cfw ) 0 ppm, Ce ) 50 ppm, and r ) 0.9

composite curve, wastewater composite curve, and treatment

line are plotted in Figure 8. The corresponding water-allocation
network and the treatment unit are shown in Figure 9.
3.2. Example 3: Fixed-Contaminant-Load Problem. Lim-
iting process data for this example is given in Table 9.22 Results
concerning generation of the source composite curve, wastewater
line, wastewater composite curve, and effluent treatment flow
rate are tabulated in Table 10. Wastewater can be targeted
directly as 90 t/h. Freshwater targets can be estimated through
overall mass balance as (90 + 0) t/h, i.e., 90 t/h. The pinch
concentration is 200 ppm. In this example, wastewater is
generated at two concentration levels: 86.67 t/h of wastewater
is generated at 500 ppm and (90 - 86.67) t/h, i.e., 3.33 t/h, of
wastewater is generated at 200 ppm. A minimum removal ratio
for example 3 is calculated to be 0.959. Therefore, one treatment
unit is not sufficient to meet the environmental regulation. Using
eq 7, the additional freshwater requirement is estimated as 460
t/h. On the other hand, 613.33 t/h of treated effluent may be
recycled across the treatment unit to satisfy the environmental
discharge limit. Alternatively, three treatment units may be
operated in series. The target for minimum treatment flow rate
is 40.53 t/h for one unit and combined effluent to be treated in
two treatment units in series. Source composite curve, waste-
water composite curve, and treatment line are plotted in Figure
10. The corresponding water-allocation network and the treat-
ment unit are shown in Figure 11.
Figure 12. Source composite curve, wastewater composite curve, and
treatment line for example 4.
3.3. Example 4: Specialty Chemical Plant. Limiting process
data for this example is given in Table 11.5 The removal ratio
of the effluent treatment unit is assumed to be 0.9. Table 12
shows results related to the generation of the source composite
curve, wastewater line, wastewater composite curve, and effluent
treatment flow-rate targets. Wastewater can be targeted directly
as 50.64 t/h. Freshwater targets can be estimated through overall
mass balance as (50.64 + 40) t/h, i.e., 90.64 t/h. Pinch
concentration is 700 ppm. In this example, wastewater is
generated at two concentration levels: 20 t/h of wastewater is
generated at 1000 ppm and (90.64 - 20) t/h, i.e., 70.64 t/h, of
wastewater is generated at 700 ppm. A minimum removal ratio
for example 4 is calculated to be 0.939. Therefore, a single
treatment unit is not sufficient to satisfy the environmental norm.
Using eq 7, the additional freshwater requirement is estimated
as 32.26 t/h. Using eq 8, the amount of treated effluent that

Table 12. Generation of Source Composite Curve, Targeting Wastewater, and Generation of Wastewater Composite Curve for Example 4
cumulative wastewater cumulative cumulative
contaminant net cumulative mass mass wastewater flow rate wastewater mass load treatment
concentration flow rate flow rate load load flow rate after first flow rate removed flow rate
(ppm) (t/h) (t/h) (kg/h) (kg/h) (t/h) pinch (t/h) (t/h) (kg/h) (t/h)
1000 20 20 0 0 41.45 20 20 0 17.94
700 50 70 6 6 50.64 50.64 6 17.06
200 -50 20 35 41 2.25 50.64 31.32 -66.8
100 -35 -15 2 43 -15.50 50.64 36.39 -184.3
50 0 -15 -0.75 42.25 -16.00 50.64 38.92 -419.2
10 -5 -20 -0.6 41.65 -20.00 50.64 40.94 -2298
0 -20 -40 -0.2 41.45 0.00 50.64 41.45
5296 Ind. Eng. Chem. Res., Vol. 45, No. 15, 2006

additional treatment units, a process designer can evaluate

different options and take appropriate steps.
Proposed methodologies and algorithms are applicable for
systems with a single contaminant. In many multicontaminant
problems, there exists a limiting component and other compo-
nents are consistent with the limiting component. In such
problems, the proposed methodology can be applied based on
the limiting contaminant. Present research is directed toward a
general approach for general multicomponent problems.

Nomenclature
C ) contaminant concentration, ppm
f ) flow rate, t/h
∆m ) contaminant mass load, kg/h
Figure 13. Water allocation network for example 4 incorporating two m0 ) excess mass load of contaminant at treatment unit inlet,
treatment units. (The values show flow rate in t/h with contaminant kg/h
concentrations in ppm within braces.)
n ) number of treatment units
may be recycled across the treatment unit is calculated to be P ) contaminant load in a concentration interval, kg/h
35.85 t/h. On the other hand, two treatment units may be Q ) cumulative flow rate, t/h
operated in series. Results for effluent treatment flow-rate targets R ) cumulative wastewater flow rate, t/h
are tabulated in Table 12. The target for minimum treatment r ) removal ratio
flow rate is 17.94 t/h for one unit and combined effluent to be Subscripts
treated in the next treatment unit. Source composite curve,
wastewater composite curve, and treatment line are plotted in add ) additional
Figure 12. The corresponding water-allocation network and the e ) environmental
treatment unit are shown in Figure 13. ef ) effective
i, j, k, l ) index number
4. Conclusion in ) inlet
min ) minimum
Integrated water management in a chemical process industry out ) outlet
consists of optimal allocation of reusable water among different P ) pinch
water-using operations to reduce freshwater requirement and r ) recycle
optimal design of effluent treatment units to honor environ- T ) total, treatment
mental norms. A new methodology for targeting minimum w ) water
freshwater and minimum effluent treatment flow rate is proposed ww ) wastewater
in this paper. Optimal design of effluent treatment units is 1, 2, ... ) index number
addressed in conjunction with the problem of optimal allocation fw ) freshwater
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ReceiVed for reView March 6, 2006
ReVised manuscript receiVed May 5, 2006
Accepted May 10, 2006
IE060268K