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PH Measurement and Control
PH Measurement and Control
pH Measurement
And Control
Leached
layer
he mechanical design and material science of pH-sensor technology have evolved dramatically
over the last century. Currentday uses include a wide range of applications from high-purity pharmaceutical processing to wastewater
treatment. Some of these applications
pose high challenges to pH measurement, including high-temperature and
otherwise harsh measuring environments, stability (particularly in pharmaceutical processes), low conductivity measurement and more-stringent
pH control in processes. This article
outlines the basics of pH measurement and control, with focus on some
of these applications, and explores recent advances such as the development of embedded memory chips and
transmitters with smarter diagnostics
and wireless communication that
have been developed to offer predictive maintenance, portability and
greater stability.
pH Basics
Soren Sorensen of the Carlsberg Laboratory of Copenhagen defined the hydrogen exponent as the negative logarithm of hydrogen-ion concentration
equated to ion activity. This introduced
the concept of pH and started the era
of its measurement. The science behind the pH-glass formulation, reference-electrode designs, electrolytes
and buffer solutions rapidly developed
[1, 2] and prompted the appearance
of the first laboratory-type pH meters. Soon afterwards, industrial pH
sensors were produced and environmental mandates prompted the use
32
Glass electrodes
Process
liquid
Reference
electrolyte
Glass
bulk
7.00 pH
Temperature
compensation
Glass
electrode
Reference
electrode
Reference
junction
Liquid junctions
Orifice-junction
Helical pathway
reference
Process
liquid
though the choice and performance of tion. The choice of the materials for
the glass is critical, the performance the reference junction can vary from
Reference
of the pH sensor also depends upon Temperature
Teflon to ceramic,
to wood, to just a
compensation
electrode
the design and integrity of the refer- tiny hole, as shown
in Figure 3. The
ence electrode.
purpose of the reference junction is
to provide electrical continuity with
the
process liquid.
It also serves as a
Reference electrodes
Reference
Glass
to prevent junction
the process liquid
The purpose of the reference electrode guard
electrode
is to create a stable reference poten- from penetrating and contaminating
tial against which the pH signal can or poisoning the sensor.
Process
Each liquid
and every component of the
be measured. Having a constant reference potential is essential for high reference electrode contributes to
impedance measurement. After all, the reference potential. This is why
a pH sensor is essentially a high im- it presents an engineering challenge
pedance voltmeter (Figure 2). The to create a stable design. Typically,
stability of the reference potential the reference impedance is an order
can be achieved through a variety of of magnitude less than the glass immechanical designs, such as single, pedance. The reference impedance can
double and triple-junction; differential also be monitored by the analyzer if
design, which can be described as hav- the pH sensor has a solution ground.
ing a pH sensor inside the pH sensor; A gradual increase in the reference
application-appropriate choice of the impedance is indicative of a coating
junction materials and electrolytes of the reference junction. The sensor
needs to be cleaned regularly to have
(Figure 3).
The typical reference in commercial an extended service life. However, an
pH sensors uses a potassium chloride increase in reference impedance may
electrolyte to satisfy all of the require- also be symptomatic of a plugged juncments for the reference fill solution tion and depletion or poisoning of the
[2]. The consistency of the electrolyte reference electrolyte. If the pH sensor
can vary from liquid to gel to solid in is rebuildable instead of disposable,
order to slow down the migration of its possible to prolong service life of
process ions inside the reference that the sensor by replacing the outer junccome in through the reference junc- tion and refilling the electrolyte. The
tion. Depending on the application, cost of ownership of the rebuildable
the chemistry of the electrolyte can type is usually less than that of a disbe tweaked or even changed to satisfy posable sensor.
specific requirements of the chemical
process. The highly competitive mar- Installation and wiring
ketplace offers rebuildable sensors The process-installation procedure is
with a variety of fill solutions.
an important factor for the service life
The reference junction is usually a of a sensor. Improper installation can
part of a rebuild-kit and is pre-soaked cause incorrect readings and even dein the corresponding electrolyte solu- stroy the sensor. Most glass electrodes
Chemical Engineering www.che.com August 2010
33
14
Feature Report
12
10
8
pH
6
High-temperature performance
High temperature processes (for example, ethanol production, geothermal plants, and breweries) put a lot
of stress on a glass electrode. Premature aging and the decrease in the
34
2
0
11
10
8
pH 7
6
5
4
3
Figure 4. While titration curves are essential for every aspect of pH-system design, you must get numerical values for the spectrum of operating temperatures and
feed conditions and avoid mistakes, such as insufficient data points in the control
region near the setpoint
Sensor status
Actions
Glass impedance
increases over time
Glass is aging or
gets coated
Schedule maintenance/
inspection
Glass is aging or
gets dehydrated
Schedule maintenance/
inspection
Reference impedance
increases over time
Coating or
poisoning
Coating or
poisoning
High-purity processes
pH
Set point
B
Er = 100% Fimax
Frmax
Ss = 0.5 Er
Where:
A
=
B
=
Er
=
Frmax =
Fimax =
Ss
=
Control band
Influent pH
Reagent flow
Influent flow
Controller tuning
pH-control challenges
The challenges of pH control are actually a separate subject from pH measurements. However, measurement is
an integral part of the pH-loop performance for control. If you consider the
scale of 014 pH, the glass electrode
can measure hydrogen ion concentrations of 1 to 1014 normality. The
extraordinary range and sensitivity
of the pH measurement creates exceptional challenges for pH control in
Graphical deception
pKa (where pKa = pKw pKb). The effect of the associated acid or base concentration and process temperature
on the slope is the greatest at these
points on the curve [6].
Nearly all of the implications for process control can be analyzed in terms
of the slope of the titration curve,
which is representative of the process
gain (change in pH for a change in reagent addition). Systems with strong
acids and bases are the most difficult
to control because the slope changes
by a factor of 10 for every pH-unit deviation from the neutral point (7 pH at
25C), which translates into a process
gain at neutrality that is potentially
107 times larger than the process gain
at the ends of the pH scale. Most laboratory titration curves show a vertical
straight line in the neutral region (4
to 10 pH), which gives the illusion that
the process gain is constant and the
process is linear. However, a zoom centered on the neutral point would reveal another S-shaped titration curve
if there were sufficient data points
(Figure 4). Successive zooms on what
appears to be a straight line would
reveal further S-shaped curves. Furthermore, the slope depends upon process temperature via the dependence
of the dissociation constants for water
(pKw), acids (pKa), and bases (pKb) on
temperature. The presence of a weak
acid or base will cause a moderation
of the slope centered at a pH equal to
the pKa. To spot this effect, the pKb of
a base is converted to the equivalent
The controller gain is inversely proportional to the process gain. Consequently, the change in controller tuning due to the nonlinearity of pH, is
way beyond what you experience in
other process control loops unless you
are lucky enough to have high concentrations of weak acids or weak bases
and are operating close to their pKa.
Tuning settings are either scheduled
based on pH, or the controlled variable
is converted from pH (y-axis) to percent reagent demand (x-axis) based on
a representative titration curve to reduce the nonlinearity. The scheduling
and linearization is not perfect due to
changes in process temperature and
feed concentrations, but is better than
no embedded process knowledge.
Control-valve design
35
Feature Report
(A) traversed on the titration curve
[6]. It is important that data are used
rather than the plot from a laboratory titrator, that there be at least five
data points in the control region, and
finally that the x-axis be converted to
a ratio of reagent to feed flow.
Concentration and feed disturbances are amplified by the process
gain just as the disturbance from valve
resolution was in Figure 5. Similarly,
the variability in reagent concentration from non-ideal mixing is amplified. The smoothing of oscillations and
fluctuations is inversely proportional
to the residence time of a well mixed
volume. The attenuated amplitude per
Equation (1) must be translated from
the x-axis (ratio of reagent to feed flow)
to an amplitude on the y-axis (pH) of
the titration curve to include the effect
of the nonlinear process gain [6].
Ao Ai s
To
2sP sTp
(1)
Where:
Ai is the amplitude of input oscillation
into volume (reagent to influent ratio)
Ao is the amplitude of output oscillation from volume (reagent to influent
ratio)
To is the period of oscillation, minutes
p is the process time constant from
mixing (residence time), minutes
Control solutions
Traditional solutions. The classical solution was to have a large, wellmixed vessel for every 2 pH units of
the feed pH from the setpoint. For a
feed around 2 pH or 12 pH, three wellmixed vessels in series were used.
For the 2 pH case, the setpoints of
the vessels were 4, 6, and 7 pH. The
first vessel typically had the largest
volume to cross neutralize the influent and the largest control valve to
provide a coarse adjustment to move
the pH most of the distance along the
flatter part of the titration curve. The
last vessel had the smallest volume
and smallest control valve to provide
a trim adjustment. The volumes were
designed to be significantly different
in size to prevent the resonance of oscillations since the natural frequency
of the loop was thought to be mostly
dependent on volume. These vessels
had a large capital cost and footprint,
and were prone to large and slow oscillations from the limit cycle of the
large valve on the first volume that
were not effectively smoothed by the
last volume.
Maintenance
Recent advances
memory chip are gaining more popularity. Advanced diagnostics offer undisputable advantages to the plant operation. The pH sensor that can carry
the factory calibration, serial number
and several diagnostics data can ease
the maintenance burden. First of all,
this smart sensor does not need buffer
calibration at the installation point. It
means that the service engineer does
not need to carry the buffers, beakers
and rinse water to the place where
the sensor is installed. It really makes
sense if you are in unfriendly environmental conditions, such as rain, snow
or blazing sun. The calibration can be
done in the laboratory and can be remotely or locally digitally accessible
after installation. Since the sensor
has an embedded factory calibration,
the instrument can always be reset to
the default calibration, without any
special efforts. Furthermore, several
diagnostic data sets and time stamps
stored on the memory chip make it
easy to see the trend of the diagnostics data (Table 1). Until recently, this
historization was possible only by
manual data logging.
Wireless transmitters
37
Feature Report
limiting that has been found to be important for cascade control. The reset
time is set equal to the process time
constant, and the contribution to the
reset mode is based on the elapsed
time since the last updated measurement to provide a correction that
matches the time response of the process. The derivative mode only makes
a change in the controller output if
there is an update and computes the
rate of change based on the elapsed
time from the last update rather than
the execution time of the controller.
Thus, integral and derivative action
only occurs when there is a measurement update. Figure 7 shows how the
new communication rules and enhanced PID provided tight control of
a single-use-bioreactor batch, while
increasing battery life and ignoring a
spike from ground noise [9].
In control studies, the PID enhancements improved the stability for any
control system whenever there was a
Figure 8. The enhanced, wireless PID performance (bottom row) has value beyond wireless operation by providing tighter and more stable control of processes
with significant measurement delays from at-line analyzers. The Lambda factor is
used for computing controller gain, and is inversely proportional to it
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38
www.myronl.com
Authors
Edited by Dorothy Lozowski
References
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Chemical Engineering www.che.com August 2010
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