Ind. Eng. Chem. Res.

1997, 36, 1665-1674 1665

Wastewater Neutralization Control Based in Fuzzy Logic:

Simulation Results
Rau
l Garrido, Manel Adroer, and Manel Poch*
Laboratori dEnginyeria Qumica i Ambiental, Departament dEnginyeria Qumica, Agra` ria i Tecnologia
Agroalimenta` ria, Campus Montilivi, Universitat de Girona, 17071 Girona, Spain

Neutralization is a technique widely used as a part of wastewater treatment processes. Due to

the importance of this technique, extensive study has been devoted to its control. However,
industrial wastewater neutralization control is a procedure with a lot of problemssnonlinearity
of the titration curve, variable buffering, changes in loadingsand despite the efforts devoted to
this subject, the problem has not been totally solved. In this paper, the authors present the
development of a controller based in fuzzy logic (FLC). In order to study its efectiveness, it has
been compared, by simulation, with other advanced controllers (using identification techniques
and adaptive control algorithms using reference models) when faced with various types of
wastewater with different buffer capacity or when changes in the concentration of the acid present
in the wastewater take place. Results obtained show that FLC could be considered as a powerful
alternative for wastewater neutralization processes.

Introduction
Neutralization is a technique commonly used in
chemical engineering as part of the process used in the
treatment of wastewater. Given the importance of this
technique, extensive study has been devoted to its
control. However, because of the difficulties involved
and despite the efforts devoted to this subject, the
problem has not been totally solved.
The titration curve directly gives the neutralization
process model, since it is the direct relation between the
pH and the base flow ratio or versus the base concen-
tration in the reactor (Cb). It can be observed in Figure
1 that the titration curve of any acid is markedly
nonlinear. For instance, in a strong monoprotic acid
three clearly differentiated zones are distinguishable:
at low base concentrations there is a zone in which the
pH varies slightly, the so-called buffering zone; in the
second zone (which occurs for a very small range of
concentrations) there is a sudden change in the pH
curve, which value passes from acid to basic, with great
sensitivity of the pH to changes in the base concentra-
tion. Finally there is a third zone in which changes in
the pH are small as in the first one. Due to the shape
of the curve, the controller has to be sufficiently
versatile: rapid in the buffered zones and sensitive
around neutrality (Moore, 1978).
The problem is increased when instead of a single
acid, the wastewater presents a combination of acid (or/
and base) types, with possibly different pK values.
Morover, when processing wastewater which may have
variations in the concentrations of each acid or respec-
tive flow, the control process becomes more difficult.
Finally when developing an efficient control algorithm,
it will be necessary to bear in mind the possible
limitations of the process as regards dead time.
The difficulties have led to various alternatives being
put forward to solve each one. Thus, many authors
propose different solutions to the problem: predictive
combined with traditional control algorithms (Riggs,
1990; Gaulian, 1990), modified PI controller (Costello,
* To whom correspondence should be addressed. E-mail:
eqampe@fc.udg.es. Telephone: 34.72.418438. FAX:
34.72.418150.
S0888-5885(95)00654-3 CCC: $14.00
Figure 1. Tritation curve of an acid.
1994), adaptive control (Kurtz, 1985), and predictive-
adaptive control (Aragon, 1993; Palancar, 1993; Proll
1994).
One of the alternatives recently applied to the control
of chemical processes in general, and to pH control in
particular, is the use of fuzzy logic. This logic provides
a simple, orderly means of introducing expert knowledge
into the process under control, whether by means of a
model or in an intuitive way. Fuzzy logic is based in
the implementation of a set of decision-making rules
combined with a linguistic system of its own, which
allows the problem of process control to be tackled from
an almost human point of view. A fuzzy controller
converts linguistic variables into numerical values by
means of membership functions which, in turn, interact
with the rules determing the control action required at
any given moment.
In the case of pH control, numerous papers have been
written in the past years, putting forward control
algorithms or testing regulator design methods. Of
these, the following can be mentioned: nonadaptive
controllers (Galluzo, 1991), in association with neural
networks (Lee, 1990; Nie, 1994; Cheng, 1993), those
using fuzzy models (Kelkar, 1994), those used in com-
bination with traditional control methods (Kwok, 1993),
those optimized with genetic algorithms (Karr, 1993),
and in-line control (Parekh, 1994).
In the present paper the authors present the results
of comparing the application of a fuzzy controller with
1997 American Chemical Society
1666 Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997

some of the others mentioned in the Literature Cited,

testing them in computer simulations. Among the latter
there are two which are based on the knowledge, by
different types of identification, of the characteristics
of the titration curve of the acids present in the water,
and a third adaptive controller based on a reference
model. Their respectives advantages and disadvan-
tages, depending on the conditions in which they are to
be used, are assessed from the point of view of the end
user.

Proposed Fuzzy Controller

The proposed fuzzy controller has two inputs and one
output. The inputs are the error (e), which is the
difference between the pH set point and the actual pH,
and the error velocity (v), which is the difference
between the actual error and that of the preceeding
iteration, bearing in mind that data acquisition is
spaced at equal time intervals:

e ) pHsp - pH (1)

v ) ek - ek-1 (2)

The output variable is S. This variable enables us to
calculate the actual flow ratio by means of the equation
ratk ) ratk-1 10S/K (3)
This equation carries out the final control action on the
basis of the last flow ratio, ratk-1 and on an exponential
operator which makes the pH regulation faster and
more versatile. The K factor makes it possible to adjust
the output of the fuzzy algorithm by attenuating the
response during the course of the process. In this way
it becomes unnecessary to keep modifying the fuzzy
controller membership functions, which can be the same
with any type of acids. A small K is used when the
water is buffered; for wastewater containing strong
acids the process is very sensitive to changes in the flow
ratios. In order to avoid possible instabilities in the
process, large K values are used. This study has sought
to avoid possible instabilities and has therefore selected
a large K (a value of K ) 200 was chosen), suitable for
water with low buffering capacity. Bearing this fact in
mind, the proposed controller is seen at its worst when
highly buffered water is simulated.
Classification of the Variables
There are many types of functions which allow us to
classify the variables which intervene in the fuzzy
controller. For this particular controller, the so-called
-function (Yamakawa, 1992) has been used. This has
some advantages compared with the typical triangular
and trapezoidal or Gaussian functions: the first is that
it is continuous and the second is that it can easily be
made to approximate triangular, trapezoidal, or Gauss-
ian forms by modifying three parameters: a (the
midpoint abscissa of the function), W (the width for
) 0.5), and n (the order of the function):
1 will never be applied. However, in the interest of the
( )
(x) ) n
(4)
2(x - a)
1+
W
The values are in the range of 0-1. Several -shaped
Figure 2. -shaped membership function.
membership functions with different n values are
represented in Figure 2.
It was decided to work with a high number of
elements in the sets: seven for each of the input
variables and nine for the output variable. In this way,
a response with few sudden changes is obtained. The
membership functions were distributed in such a way
that those in the center were closer to each other, thus
giving greater precision of response around the set point.
The elements of the fuzzy sets overlap, to some extent,
between them.
In Figure 3 the velocity fuzzy set, the error fuzzy set,
and the output fuzzy set are presented.
Rules
For the implementation of the fuzzy logic control it
is necessary to define a series of rules through which
the knowledge of the behavior of the system is applied.
These rules are of the following type: if the error is BM
and the velocity is PL, then the response of the output is
NL.
The rules to be applied are constantly changing
depending on input perturbations. For example, if
buffered water goes into the plant, the velocity variable
would be small, which means that it will be necessary
to modify more quickly the flow ratio than if the velocity
were great, but taking also into account the solutions
pH so as not to go too far beyond the set point. If the
absolute value of the error were small, the modification
should be made smaller than if the absolute error were
great. A process based on similar reasoning, taking into
account all the possible input case combinations, per-
mits the definition of all the other control rules. The
control system has a total of 49 rules, of which some
controller stability, it was felt that all eventualities
should be taken into account.
The decision matrix implemented is presented in
Table 1. It shows the elements of the output fuzzy set
 Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997 1667
In the inference step the elements of the output fuzzy
set become activated. In this work this is made accord-
ing to the following process: the elements of the input
fuzzy sets having functions greater than zero are
paired one element of the error (e) variable set to one
element of the velocity (v) variable set, making all
possible combinations. Looking at the rules, defined
previously, to each pair corresponds an element p of the
output fuzzy set (S). The truth value of this output
element will be calculated as

po(S) ) min(i(e),j(v)) (5)

This means that if element i of the error fuzzy set and

element j of the velocity fuzzy set have functions not
equal to zero, according to the rules, element p of the
output fuzzy set will have a o function equal to the
minimum of the two input function values.
If any one of the output fuzzy set elements is activated
more than once, its final o function will be the sum of
all the o functions of this element.

po(S) ) po(S) + po(S) (6)

Any nonactivated element of the output fuzzy set will

have an o(S) equal to zero.
In the defuzzification stage a numerical final output
value must be obtained. This is done through an
average integral including all the output fuzzy set
elements having a o greater than zero:

io(S)S)Min Si(S) dS
S)Max i

i
Figure 3. Velocity (a, top), error (b, middle), and output (c, Scen ) (7)
io(S)S)Min i(S) dS
S)Max i
bottom) fuzzy sets. The acronyms for the velocity set elements are
NR for negative rapid, NM for negative medium, NL for negative i

low, L for velocity around zero, PL for positive low, PM for positive
medium, and PR for positive rapid. The acronyms for the error where io ) truth value of the i output fuzzy set element
fuzzy set elements are BA for basic high, BM for basic medium, obtained using eqeqs 5 and 6, Mini ) minimum S values
BB for basic low, OP for error around zero, AB for acid low, AM for which the function has nonzero values, Maxi )
for acid medium, and AA for acid high. The acronyms for the
output fuzzy set elements are NR for negative high, NM for
maximum S values for which the function has nonzero
negative medium, NL for negative low, NSL for negative small, values, and Scen ) output that goes to eq 3.
OP for response around zero, PS for positive small, PL for positive
low, PM for positive medium, and PR for positive high. Other Controllers Studied
Table 1. Decision Matrix As already mentioned under the previous section, this
velocity paper proposes a fuzzy logic based controller for the pH
error control of acid wastewater. In order to observe its
NR NM NL L PL PM PR efficiency, it will be compared, through computer simu-
BA NR NM NM NR NM NM NM lations, with other controllers mentioned in the Litera-
BM NM NL NL NM NL NL NL ture Cited.
BB NL NS NS NS NS NS NS
OP NS NS OP OP OP PS PS
1. This is a controller which identifies the evaluation
AB PS PS PS PS PS PL PL curve being approximated by means of a single hypo-
AM PL PL PL PM PL PM PM thetical acid. It combines a general model control
AA PM PM PM PR PM PR PR (GMC) algorithm with its identification of the curve in
order to determine the appropiate control action. In this
that will become activated as a function of the pairs of paper it will be referred to as SAGMC (single acid
input fuzzy sets elements, as is stated in the rules general model control) (Riggs, 1990).
developed. 2. This controller identifies the evaluation curve off-
line, interpolating the curve by means of a set of
Algorithms hypothetical acids determined by the controller. On the
basis of its knowledge of the evaluation curve, it
There are three steps in the calculation of the output determines the gain of a feedback controller which
of the fuzzy controller: fuzzification, inference, and performs the final control action. During the identifica-
defuzzification. tion stage the system is without control. The controller
In the fuzzification stage a value (in the range of will be referred to as MAFBC (multi acid feedback
0-1) must be assigned to all the elements of the input control) (Gaulian, 1990).
fuzzy sets. This is made computing the membership 3. This is an adaptive controller which uses a
functions , for every element of both sets, in accordance reference model. It will be referred to as RMAC
with their respective input values. (reference model adaptive control) (Kurtz, 1985).
1668 Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997
Figure 4. Flow diagram of the fuzzy logic controller.
Figure 5. Diagram showing the neutralization process.
For further information on these controls, see Ap-
pendix B.
Results
Characteristics of the Process Studied. The
different control systems were suposed to operate under
the same process conditions. The input water flow was
considered constant, at 2 L/min, in all the simulations.
The neutralization tank volume was 0.7 L, except for
the SAGMC controller, which had two tanks of 0.3 and
0.4 L, respectively, with the total volume identical to
that described for the previous controllers. In all the
cases the tanks were considered to be perfectly mixed.
The concentration of the base, NaOH, was 250 mmol/
L. Finally, the actions of each controllers were per-
formed every 2 s. No dead time was considered. Figure
5 schematically shows how a neutralization process
works and gives a general view of the components
required to implement a pH controller.
It should be pointed out that the controllers obtained
from the Literature Cited were optimized to ensure that
they were in perfect condition when the study was
carried out. A factorial design was made for each
controller in order to select a set of parameters. As a
test, a step change in concentration (varying from 10
to 30 mmol/L) was done with an acid with pK ) 2. The
optimization criterion used was the time needed to settle
the disturbance. With this criterion, several sets of
parameters according to a central composition design
were tested, selecting for each controller the set giving
the best performances.
Studies Performed. In order to carry out a com-
parative study of the different controllers, two separate
subordinate studies were proposed as those thought to
be the most appropiate to the problems posed by the
wastewater neutralization process: (1) behavior of the
process controllers in relation to various types of
wastewater with differing buffer capacity; (2) behavior
of the process controllers in relation to changes in the
concentration of a strong acid present in the water.
The first point of the study aims to observe the effect
caused by the presence of acids with differing buffering
strengths on the regulating capacity. This study evalu-
ates the versatility of the various controls. The second
point monitors the control in relation to changes in the
concentration of an acid with pK ) 2, and observes the
recovery speed of the controls, as well as their possible
instability.
In all the studies the set point was fixed at pH ) 7.
Most procedures require that the wastewater have pH
values between approximately 6 and 8, and if the water
did not fulfill this condition, it was required that it
should rapidly be adjusted.
1. Behavior of the Process Controllers in Rela-
tion to Various Types of Wastewater with Differ-
 Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997 1669

Figure 6. pH evolution with time for the different controllers;

changes in acid concentration are implemented.

Figure 7. Maximum deviation vs pK, with different controllers

ing Buffer Capacity. In this case simulations were as step changes in acid concentration are implemented.
made using in every one of them an acid with a specific
pK, thus enabling us to compare the behavior of the
different controllers under the same conditions. These
pK values were uniformly distributed throught the
whole working pH range (varying from 1 to 7). Com-
paring the groups of simulations among themselves, it
was possible to study the influence of the acids pK on
the performance of the different controllers.
In every simulation step changes of the acid concen-
tration were introduced during the process. The changes
were from 10 to 20 mmol/L, and back from 20 to 10
mmol/L at 10 min intervals. The criteria for evaluating
the behavior of the controllers were the pH deviations
and the time needed to bring the pH within an interval
of (0.25 units of pH around the set point.
Figure 6 shows the evolution over time of the pH of
one group of simulations with different controllers and
the same acid strength (pK ) 3). In the figure the step
changes in the acid concentration are shown. The
MAFBC controller is the one which, because of its
operating mode (involving the off-line adjustments of
the evaluation curve), maintains the pH closest to the
set point. It is the one which shows the smallest
deviations, as well as being able to stabilize the process
within the time interval between stages. The FLC is
also able to bring the pH close to neutral in the 10 min Figure 8. Time (in minutes) needed for the different controllers
interval, but its degree of deviation is much greater than to reach a pH close to the set point vs the acids pK.
in the MAFBC controller. The RMAC and SAGMC
controllers are those which perform least well, altough identification of the model which it carried out before
SAGMC shows less pH deviation. the control began. Thus the internal feedback control-
In Figure 7 the pH deviations vs the pK of each acid lers gain is constantly the best. The FLC has a high
considered are presented. It could be observed that deviation value at pK ) 7, compared with the other
there is a general tendency for the maximum deviation controllers, but works much better, in a comparative
to decrease as the pK of the simulated acid increases way, at low pK.
(FLC at high pK is an exception). This effect is due to Figure 8 shows a general tendency, for the time
the fact that, as pK increases, the process gain becomes needed to settle the pH disturbance, to diminish as the
less sensitive around pH ) 7, and therefore small pK of the simulated acid increases, except in the case
changes in the flow ratio do not lead to any major of the FLC. This is due to the fact that, for the same
variation in the pH. reason which accounted for the deviation behavior, as
We can see that MAFBC is the control with best the pK increases, the process becomes less sensitive to
performances and with a lower deviation rate in all the the variations in the flow, and therefore the pH values
points studied. This is because the control system is at show smaller fluctuation, reaching the range 6.75-7.25
all times aware of the titration curve, thanks to the more quickly.
1670 Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997
Figure 9. pH disturbances for an acid concentration step change
from 50 to 80 mmol/L (pK ) 2).
The fuzzy control, at high pK, behaves in a way
opposite the value of other controllers. The reason for
this being that, in all the simulations, a constant K was
used, which is best suited for the control of low buffering
capacity wastewater. This K considerably lessens the
response of the controller so that it remains stable even
when strong unbuffered acids are present in the water
to be treated. It will also be stable with weak acids,
but the response will be too slow. If a smaller value of
K is used, the system takes less time to reach the
required pH interval.
2. Behavior of the Controllers in Processes with
Changes in the Concentration of an Acid Present
in the Water. In order to study this point, a series of
simulations were performed, similar to those described
before, with an acid having pK ) 2 and introducing
different step changes in its concentration. The acid
concentration was 50 mmol/L at the beginning of the
process, and step changes, of either positive or negative
sign, were implemented. The minimum concentration
value has been 1 mmol/L and the maximum 110 mmol/
L. In Figure 9 the recovery time of the system needed
to reach the zone of pH ) 7 ( 0.25, vs the concentration
step changes, is presented (using different controllers).
In the abscissas we can see the values of the steps
(positive or negative) with reference to the initial 50
mmol/L concentration.
It can be seen that, after the disturbance, the fuzzy
controller regulates most quickly the pH and brings it
within the parameters of the criterion. The pH devia-
tion of the MAFBC is considerably less, but the recovery
time is greater. The slowest acting controller is the
SAGMC, while the RMAC shows the greater pH devia-
tion with a time recovery between those of MAFBC and
SAGMV.
The process was not found to be unstable in any of
the simulations carried out. In this subordinate study,
if each controller is studied in turn, it can be found that
all of them show a similar trend: as the absolute value
of the step disturbances decreases, the time that the
process takes to become stabilized decreases. However,
the controllers show differences in the speed to overcome
the disturbance. The fuzzy control is the fastest under
Figure 10. pH recovery time from a disturbance vs concentration
step change.
the proposed conditions, being approximately 3 times
faster than the MAFBC, 5 times faster than the RMAC,
and 7 times faster than the SAGMC.
Conclusions
It must be taken into account that the neutralization
process studied only treats acid wastewater by strong
base, but it is possible to extrapolate the conclusions if
basic wastewater were treated. Following the results
presented in the previous two points, we proceed to
make a comparative evaluation of each controller.
Influence of the Acid pK. Unbuffered waters are
considered those which because of their composition
have no weak acid species (pK < 3). These waters are
the most difficult to control, due to their great sensitivity
to changes in the neutralizer flow around neutral pH.
In the conditions studied, MAFB controller is always
better than SAGM controller and RMA controller, both
regarding the pH deviation values as well as the
recovery time, in the whole range of pKs. This is due
to its determination of the titration curve before starting
the control.
The FLC presents important differences in its behav-
ior related to the acids pK value. In unbuffered waters
it is the fastest in bringing the pH to around set point,
even better than MAFBC, and pretty good regarding pH
deviation, not as good as MAFBC but better than
SAGMC and RMAC. This may be due to the fact that
it acts more directly on the manipulated variable on
account of its rule-based configuration.
In buffered waters the fuzzy controller loses efficiency,
compared with the other controllers. Its response
velocity decreases considerably for pK ) 5-6 and the
pH deviation increases a lot, becoming the worst of all
the tested controllers in both criteria. This is due to
its having been designed (uses a large K) to work with
wastewaters containing strong acids.
With the exception of FLC we can see there is a
general trend that the value of the pH deviations and
the length of the recovery time decrease as the pK of
the acid increases.
 Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997 1671
Looking at Figures 9 and 10, it could be concluded o ) -function value for the output set elements
that the size of the step change does not seem to have [ ] ) ion concentration
an influence on the trends presented above. Evidently
the size of the pH disturbance and the recovery time Appendix A. Ionic Model
increase if the size of the step increases.
The model used for carrying out the simulation is
Water Variability. This factor affects particularly
based on the balance of electrical charges inside the
the MAFB controller, which makes an off-line determi-
solution (Stumm, 1970). The balance of charges for any
nation of the titration curve. Therefore many changes
monoprotic acid, neutralized to any proportion with
in the acid species present, with different dissociation
NaOH, is determined by the following equation:
constants, will render the controller ineffective. In some
circumstances it could spend more time identifying
curves than controlling.
[A-] + [OH-] ) [Na+] + [H+] (8)
where [Na+] is equal to the concentration of neutralizing
Nomenclature base added.
The model has the capacity to simulate the joint
a ) midpoint of the -function behavior of three monoprotic acids in solution. The
a0 ) integral correction parameter, RMAC equilibrium constants Ka will be supposed to remain
Ci ) concentration of the i ion constant during the process, and that is equivalent to
Ca, Cai ) total acid concentration (acid + conjugate base) saying that the temperature and the ionic strength will
Cb, Cbi ) total base concentration (base + conjugate acid) also remain constant. The acid and conjugate basic
Cbadd, Cbaddi ) strong base concentration added species are broken down into ionic fractions, which
Cbase ) base concentration in acid wastewater plus base depend exclusively on pH and Ka.
concentration added In order to illustrate how the ionic model works, we
Cbinput ) base in acid wastewater input are now going to suppose that there is a single acid, but
Cbneut, Cbneuti ) strong base needed to neutralize the acid on the basis of the deductions carried out, the model
wastewater, SGMC, MAFBC can be extended to more acids. The balance of charges
e ) pH error, FLC input will be as follows:
infresp ) inference output
k1, k2 ) controllers adjustement parameter, SAGMC [H+][H+]
Ka ) (9)
K ) FLC adjustment parameter [HA]
Ka ) equilibrium acid constant
Kc ) controller gain, MAFBC Ca ) [A-] + [HA] (10)
Kfg ) gain factor, MAFBC
KI ) reference velocity factor, RMAC [H+]
[HA] ) Ca ) R0Ca (11)
Kp ) process gain Ka + [H+]
KR ) adaptive controller gain, RMAC
Kw ) equilibrium water constant Ka
n ) order of the -function [A-] ) Ca ) R1Ca (12)
pHact ) actual pH in the stirred tank, MAFBC Ka + [H+]
pHsp ) set point pH
Kw
pHss ) GMC output, SAGMC R1Ca + - Cb ) 0 (13)
pH3 ) output pH from second CSTR, SAGMC [H+]
q1, q2 ) controllers adjustment parameter, RMAC
Q ) output flow from CSTR where Cb is the concentration of NaOH added.
Qbadd ) base flow added
In the equations there are three variables Ca, [H+],
and Cb. The variables Ca and Cb have a similar behavior
Qinput ) acid wastewater input flow
determined by the differential equations of a CSTR.
rat ) flow ratio, base flow/acid wastewater flow
ratact ) flow ratio at the actual pH, MAFBC dCa Q
ratsp ) flow ratio at the pH set point, MAFBC ) (Cainput - Ca) (14)
dt V
rulek ) result of a fuzzy rule applied
S, Scen ) FLC output dCb Q
t ) time ) (Cbadd - Cb) (15)
dt V
T0 ) time interval between data gathering
v ) error velocity variation of pH, FLC input where Q is the output flow from the CSTR, V its volume,
x ) FLC input or output Cainput is the total acid concentration from the waste-
xw ) pH error, RMAC water, and Cbadd is the total base concentration, due to
W ) width of the -function when (x) ) 05 the base addition, in the total flow.
zi ) charge of the i ion The equation system is solved by using Runge-
R ) time constant of the reference velocity Kuttas fourth order method of numerical integration,
Ri ) ionic fractions of species in solution
which calculates the equation independently of pH, and
then the pH is calculated by means of the balance of
Cbneut ) variation of the concentration to neutralize the
acid wastewater
charges.
KR ) adaptive controller gain variation, RMAC
xw ) error variation velocity, RMAC
Appendix B. SAGMC, MAFBC, and RMAC
xwref ) reference error variation velocity, RMAC 1. SAGMC. This controller has two distinct parts
) -function value which operate interactively.
1672 Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997
Identification of the Curve. Because of its design,
this controller requires divided addition of NaOH into
two separate tanks. The controller adds 75% (in their
study, Riggs and co-workers propose 60-90% addition)
of the total quantity of NaOH in the first tank, and the
remainder in the second. In order to identify the curve,
it measures the pH at the input (pH1), at the output
from the first tank (pH2), and at the output from the
second tank (pH3), and by knowing the concentration
of the base added at each of the tanks, three points on
the pH vs Cbadd (concentration of base added) are
obtained. From the balance of charges and the equi-
librium equation for a monoprotic acid, together with
the definition of pH, we obtain the following:
(c + Cbadd) 10-pH
Ka ) e-G/RTKa -
(Ca - c - Cbadd)
[A-] ) Cbadd + [H+] - [OH-] ) Cbadd + c
Kw
c ) 10-pH -
10-pH
There are three equations for the experimentally
measured points (pH1, pH2, pH3, vs Cb1 ) 0, Cb2, Cb3),
and two unknown variables Ca and Ka. The problem is
solved by applying an algorithm based on the minimiza-
tion of an objective function, in which the quadratic
errors for each measuring point are summed, thereby
enabling the three points measured to be adjusted to a
curve determined by the concentration and acid con-
stant of an hypothetical acid. The objective function is
( )
i)3
1 Ca - ci - Cbadd
Obj ) Ka
- (19)
i)1 10-pHi(ci + Cbadd)
Ka can be taken from the previous expression and be
given as the explicit function of Ca as a weighed average
of the three point values:
( )
i)3 Ca - ci - Cbadd
1 i)1 (10-pHi)2(ci + Cbadd)2
( )
) (20)
Ka i)3
1
i)1 10 -pHi
(ci + Cbadd)
GMC Algorithm. Once the parameters of the model
are known, the GMC is used to determine the variable
pHss. On the basis of the proportional and integral
error, this variable allows us to calculate the base to be
added:
pHss ) pH3 + k1(7 - pH3) + k2 0t(7 - pH3) dt
where k1 and k2 are the controllers adjustment param-
eters.
In both the algorithms previously explained it is
possible to interact simultaneously. From the knowl-
edge of the process, based on a single acid model,
calculate the base concentration necessary to achieve
the condition pH ) pHss where pHss is determined by
the algorithm GMC. In order to do this, the balance of
electrical charges in solution is applied to calculate the
concentration of the base in solution Cbneut needed. This
value will be used to determine the flow of base to be
added at any given moment, by means of the following
equation:
Cbneut
Qbadd ) Q (22)
Cbadd
where Qbadd is the total base flow for the tanks, Q is
the output flow, Cbneut is the concentration of base, in
the total flow, required to neutralize the acid waste-
water, and Cbadd is the concentration in the base
neutralizing flow.
The values of the fixed parameters used in the
simulations were
k1 ) 1.25 k2 ) 0.02
) 0 (16)
2. MAFBC. Like the previous controller this has two
distinct parts, identification and actual control, although
(17) these do not interact. Instead, the identification algo-
rithm calculates the curve off-line and, following iden-
tification, the control is carried out.
(18) Identification of the Curve. The identification
algorithm acts by modifying the quantity of base added,
and the pH in solution is measured once the system has
reached an approximately stationary state. Using this
methodology a number of experimental points on the
evaluation curve are determined, pH vs flow ratio.
When these experimental points are known, the evalu-
ation curve is modeled, using hypothetical acid species
determined by the program, as will be shown below.
According to the concept of the balance of electrical
charges in solution, the positive charges must be
equaled by the negative ones, so that the overall solution
2 is neutral:
i)n
Cizi ) 0 (23)
i)1
where n is the total number of different ionic species in
solution, Ci is the concentration of the i ion, and zi is its
charge.
Taking into account all the species present in solution,
the balance of electrical charges would be as follows:
-Ca1Ra1 - Ca2Ra2 - ... - CanRan + Cb1Rb1 + Cb2Rb2 +
... + CbmRbm + [H+] - [OH-] ) 0 (24)
where Cai is the total concentration (acid + conjugate
base) of the i acid, Cbj is the total concentration (base +
conjugate acid) of the base j, and Rai and Rbj are the ionic
fractions of the species in solution (see Appendix A).
Considering the neutralization of an acid water, it will
be supposed that all the basic species correspond to the
alkaline cations, which will be totally disssociated bases.
(21)
Therefore the ionic fractions are independent of pH and
will have the unit value
Rb1 ) Rb2 ) ... ) Rbn ) 1 (25)
This means that all the Cbj may be grouped together:
Cbase ) Cb1 + Cb2 + ... + Cbn (26)
Furthermore, the base concentration present in the
system can be divided into two parts:
Cbase ) Cbinput + Cbadd (27)

where Cbinput is the base present in the input water and
Cbadd is the base added in the neutralization process.
The balance of electrical charges is as follows:
Ca1Ra1 + Ca2Ra2 + ... + CanRan + -Cbinput ) [H+] -
[OH-] + Cbadd (28)
From this equation a system of linear equations, one
for each of the experimental points, could be obtained.
The pH and the dissociation constants of the hypo-
thetical acids are known, thus allowing calculation of
Rai and Cbadd. The concentration of the neutralizing base
is also known, and the concentrations [H+] and [OH-]
can be calculated from the measurement of the pH and
the dissociation constant of the water, Kw. Thus we
have grouped together on the right side of the previous
equation all the known terms, which we call D:
D ) [H+] - [OH-] + Cbadd (29)
The only unknown terms will be the concentrations Cai
and Cbinput present in the input water. Thus, on the
basis of the experimental points taken during the
identification stage, a system of linear equations is
obtained. If the number of equations were equal to the
number of unknown terms, that is, n + 1 ) p, the vector
of the concentrations could be found, thus solving the
linear system of equations. However, the method is
unstable because negative values may be obtained for
some of the concentrations of the hypothetical acids, a
fact which makes no sense in physical terms. In fact, a
technique is applied to decompose the matrix of the
coefficients into singular values (SVD), based on the
adjustment of the experimental points by means of the
minimization of the quadratic errors, that enables
finding a solution for the concentration vector. With
this technique a solution can be found even in the case
of having more equations than unknowns or more
unknowns than equations. Thus it is possible to elimi-
nate the acids having negative concentrations values.
Ultimately, there always remain a series of acids
(eventually only one) which fit the titration curve.
The parameter which characterizes the hypothetical
acids is the pK. It is good to start the calculations with
a series of acids, with pK uniformly distributed
thorought the whole working pH range, that will span
the space between the maximum and the minimum pH
of the experimental points. Working this way, the curve
adjustment is much better. This fact has been taken
into account in the implementation of this controller.
Control Algorithm. The control algorithm consists
of a PI-feedback loop with variable gain:
Cbneutn ) Cbneutn-1 + Cbneut (30)
where Cbneutn is the concentration of the base, in the
total flow, needed to neutralize the acid wastewater, in
the n iteration, Cbneutn-1 is the concentration of base
added in the n - 1 iteration.
The feedback loop calculates the quantity of base
Cbneutn which is going to modify the actual base
dosification.
(
Cbneut ) Kc e(t) +
1
0te(t) dt) (31)
where Kc is the controller gain and is the reset time.
Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997 1673
The aim is that the product of Kc and the process gain
be constant at all times, that is, that the total gain in
the loop will be always constant.
The evaluation curve model is used to determine the
process gain on the basis of the actual pH in the
solution, pHact:
pHsp - pHact
Kp ) (32)
ratsp - ratact
where pHsp is the pH set point, pHact is the actual pH,
ratsp is the flow ratio at the pH set point, and ratact is
the flow ratio at the actual pH, in the model.
It is extremely important that the flow ratios consid-
ered above be always those of the theoretical curve;
otherwise, errors could occur in the calculation of the
process gain, and these in turn would affect the calcula-
tion of the controller gain. If the total concentration of
acids does change but the slope of the curve around
neutrality does not change too much, the model would
be still valid and the Kp obtained using eq 32 could be
used without impairing the control. Anyway if there
was a significant change in the pH vs rate curve slope,
it would be necessary to proceed to a new identification
of the system during which the process would be left
without control.
The calculation of Kc is made as is shown in the
following equation:
Kfg
Kc ) (33)
Kp
where Kfg is the gain factor.
Once the Cbneutn concentration of base needed to
neutralize the acid wastewater has been determined,
the required dose of basic solution flow can be calcu-
lated:
Cbneutn
Qbadd ) Q (34)
Cbadd
where Qbadd is the flow of neutralizing basic solution,
Cbadd is the concentration of the neutralizing base
solution, and Q is the output flow from the CSTR.
The values of the fixed parameters used in the
simulations were
Kfg ) 25 )3
As in the case of the previous controller, it is necessary
to know the base concentration Cbadd in the neutralizing
solution.
At the beginning of the process it will be always
necessary to make a system identification; new identi-
fications will be needed if the control becomes too
sluggish or erratic.
3. RMAC. This controller has a different approach
from those previously mentioned, since it does not
attempt to model the evaluation curve, but rather on
the basis of a reference model of the velocity of the error
variation (or variation in the control deviation) assesses
the control action required at any given time.
The controller gain is manipulated by a higher adap-
tive loop, so that in the event of a deviation in the
velocity of error variation in relation to that of the
reference model, it modifies the gain depending on the
direction and degree of the deviation.
1674 Ind. Eng. Chem. Res., Vol. 36, No. 5, 1997
The behavior of the reference model determines the
dynamic behavior of the entire control system. The
reference model is a decreasing integral function cor-
responding to a first order delay.
The definition of the control system is as follows:
Control Algorithm.
Qbadd(k) ) Qbadd(k-1) + KR(xw(k) + q1xw(k-1) +
q2xw(k-2)) (35)
where Qbadd is the flow base dose, k is the number of
discrete time intervals, KR is the adaptive control gain,
q1 and q2 are the constant controller parameters, and
xw is the pH error.
The control equation is a second order filter, which
calculates the manipulated variable on the basis of the
information on the actual and the two preceding errors.
Value of the Control Velocity. xw(k) is the control
deviation or error, and its delta is the variation in the
error over a period of time, that is, the velocity of the
error variation:
xw(k) ) pHref - pH(k)
xw(k) ) xw(k) - xw(k-1)
Calculation of the Reference Velocity. The refer-
ence velocity is given by
xwref(xw) ) -KIT0(1 - e-|xw|/R) sign(xw)
where KI is the controller factor, T0 is the time interval
between data gathering, and R is the time constant of
the reference model.
Integral Correction Gain. After each measure-
ment and following calculation of reference velocity, the
controller gain is corrected:
( )
KR(k) xwref(xw(k)) - xw(k)
) a0
KR(k-1) xwref(xw(k))
KR(k) ) KR(k-1) + KR(k)
xw(k) ) 0 if sign(xw(k) xw(k)) ) 1
xw(k) ) xw(k) if sign(xw(k) xw(k)) ) -1 (41)
By using the integral correction, the controller gain
increases as the controlled pH variable moves away
from the pH set point and also as it approaches it more
slowly than the established reference velocity. The
controller gain always decreases when the pH ap-
proaches the pH set point more rapidly than the
reference velocity.
The values of the fixed parameters used in the
simulations were
q1 ) -1.63 q2 ) 0.666 a0 ) 0.3
KI ) 0.01 R ) 0.3
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Received for review October 25, 1995
Revised manuscript received December 30, 1996
Accepted December 31, 1996X
IE950654U
X Abstract published in Advance ACS Abstracts, March 15,
1997.