Application Note Chemical

pH & Conductivity Measurements for Scrubbers

Introduction/Background
Industrial scrubbers are used for the removal of potentially harmful
and polluting gas emissions from various processes. The gases
removed by scrubbing include sulfur dioxide (SO2) from combustion
by utilities and industrial users, and a variety of by-product or waste
gases such as chlorine (Cl2), hydrogen chloride (HCI) and hydrogen
sulfide (H2S) by producers and users.
situations best suited for conductivity and pH can be outlined as
follows:
Applying Conductivity
Conductivity measurement is best suited to measuring the
concentration of the scrubber chemical in batch scrubbers.

The Process Conductivity is non-specific and will respond to both the

Scrubbers operate by spraying the gas stream with a scrubbing
scrubbing chemical and the scrubbing by-products produced by
solution that contains a scrubbing chemical, which dissolves or
scrubbing. As scrubbing chemical is depleted, its contribution
destroys the harmful gas. This process is illustrated in Figure 1.
to the scrubber solution conductivity will decrease. At the same
time, the concentration of the by-products is building up and their
The effectiveness of the scrubbing solution in removing the harmful
contribution to the total conductivity is increasing.
gas depends upon the concentration of the scrubbing chemical,
which is continuously depleted during scrubber operation. To ensure
If there is a measurable change in conductivity (usually a decrease)
the effectiveness of the scrubber, the concentration of the scrubbing
as the scrubbing chemical is depleted, then the scrubbing chemical
chemical must be maintained. Conductivity and pH can be used to
concentration can be measured. A good example of this is batch
monitor the strength of the scrubber solution.
scrubbing of chlorine gas (Cl2) using strong caustic (10–15 % NaOH).

Scrubbers can include multiple scrubbing operations, i.e., more

Difficulties can arise, however, when more than one gas is being
than one individual scrubber and solution. Control of the solution
scrubbed. Depending upon the relative proportions of the gases,
strength (concentration) can be roughly classified as using one of
the by-products formed will differ, leading to variations in the
two methods:
conductivity background. Deriving concentration from conductivity
can be difficult or impossible, although a conductivity measurement
The first is the batch type scrubber, which operates using an initial
may still provide a useful alarm point to alert the operator to check a
high concentration of scrubbing chemical, that is allowed to deplete
grab sample.
to near exhaustion, followed by blowdown and replenishment by
fresh, full strength scrubber solution.
In scrubbers where the scrubbing chemical concentration is
maintained by continual replenishment and blowdown, conductivity
The second method is to maintain a certain concentration of
can be used to initiate blowdown to prevent high dissolved solids
scrubbing chemical by continual replenishment and blowdown.
build-up.

The chemical composition of the scrubber solution at any point in

time will depend upon how it is being controlled and, of course, the
scrubbing chemical and the gas being scrubbed. By-products of the
scrubbing process are formed from the reaction of the scrubbing
chemical and the gas being scrubbed. The choice between pH and
conductivity will ultimately depend upon the scrubber solution
composition and its changes during the scrubber operation. While
each scrubber application should be looked at individually, the
Chemical

Applying pH
A pH measurement is often the choice for scrubbers using continual
blowdown and replenishment. Scrubbing of acid gases, such
as sulfur dioxide (SO2), is controlled by maintaining an excess
concentration of a basic scrubbing chemical, such as caustic (NaOH)
or lime (CaO). Since pH is specific to hydrogen ion (H+), which is
related to the concentration of basic scrubbing chemical, it can be
used with minimal effects from the build up of by-products in the
scrubber solution.
In batch scrubbers, where concentration measurement is desired
(typically caustic scrubbers), the Model 56 Analyzer can be used. The
best way to monitor the process using the analyzer is to measure the
conductivity of the scrubber solution over at least three cycles and
use the conductivity data gathered, along with concentration data
from titrations to develop the conductivity/concentration curve to
be input into the Model 56 Analyzer.

A common misapplication is to use a pH measurement in a batch

pH
The biggest problem encountered in scrubber applications is sensor
scrubber using strong caustic (10–15 % NaOH). The initial caustic
coating, especially in applications using lime as the scrubbing
concentration is off scale (greater than 14 pH) and can destroy the
chemical. The Model 396R TUpH™ sensor is ideally suited for this
glass electrode. The pH response follows a strong acid/strong base
application. To minimize coating effects, the sensor should be
titration curve, which results in a reading that only drops back on-
mounted so as to be exposed to a high sample flow rate. In more
scale near the point of complete exhaustion of the caustic, followed
extreme cases, a flow-powered cleaner or jet spray cleaning can
by a sudden drop at the exhaustion point.
reduce the need for manual cleaning, depending upon the nature of
particulates present.
ORP (Oxidation-reduction potential) measurement may also be used
along with a pH measurement, if the scrubbing reaction involves an
pH is not applicable to batch scrubbers using strong caustic
oxidation and reduction reaction. In general, the ORP measurement
(10–15 % NaOH). Strong caustic dehydrates the pH glass and greatly
is limited to indicating the complete exhaustion of a particular
reduces sensor life. The effects on the pH measurement of the by-
chemical and is not a good indication of concentration.
products of the scrubbing reaction should be considered. Strongly
oxidizing solutions, which can poison the reference electrode, can
Additional Applications of pH sometimes result.
and Conductivity
The scrubbing chemical in a spent scrubber solution is sometimes Important Question for Scrubber
regenerated on-site for reuse in the scrubber. An example is the
regeneration of caustic (NaOH), in spent sulfur dioxide (SO2)
Applications
1. Which gas or gases are being scrubbed?
scrubbing solution, from sodium sulfate (Na2SO4) using lime (CaO).
2. What is being used as the scrubbing chemical, and what is its
Conductivity can be used to measure the concentration of the
concentration range?
caustic produced.
3. How is the scrubber operated?
a. Is a target concentration of scrubbing chemical being
The by-products from the scrubbing reaction in spent scrubber
maintained with continual blowdown and replenishment?
solution can sometimes be recycled for use in the plant or sold.
or
These include sodium hypochlorite (NaOCI) from chlorine scrubbing
b. Is the scrubbing chemical allowed to deplete down to a certain
with caustic; gypsum (CaSO4) from sulfur dioxide scrubbing with
concentration? What is that concentration?
lime; and ammonium sulfate (NH4HSO4), as a raw material for
fertilizers, from sulfur dioxide scrubbing with ammonium hydroxide (TM) TUpH is a registered trademark of Rosemount Analytical
(NH4OH). pH and conductivity can be used in the processing of these
by-products.

Instrumentation
Conductivity
Toroidal conductivity should be used for scrubber solution
measurements, due to its resistance to fouling and corrosion. The
sensor should be located where it will be exposed to a representative
sample. The Model 228 Sensor is generally applicable to scrubbers,
but, in cases where there is a large loading of particulates, the large
bore Model 226 or, in extreme cases, the Model 242 Flow-Through
Sensor is preferred.

Page 2
 Chemical

Instrumentation
56 Analyzer Model 242 Flow-Through Toroidal
Conductivity Sensor
ƒƒ High resolution user help screens and on-
screen data trend graphs ƒƒ Small, compact design available in many
materials and sized for maximum flexibility
ƒƒ Data logger and Event Logger - Download
process data and alarm conditions via ƒƒ Integral Pt100 for accurate temperature
USB 2.0 data port compensation
ƒƒ Digital Communications - HART® and ƒƒ Flow-through design ideal for viscous and
Profibus® DP communications with full abrasive solutions
features and functionality
ƒƒ Measurements - pH, ORP, Conductivity, Total Chlorine, Chlorine,
Oxygen, Ozone, Turbidity, Pulse Flow, Temperature, and others Model 226
via 4–20 mA input from any device Toroidal Conductivity Sensor
ƒƒ Dual sensor capability ƒƒ Suitable for high solids, low conductivity
applications
ƒƒ Available in PEEK (polyetheretherketone)
Model 396 R pH/ORP
TUpH Retractable Sensor
ƒƒ Rugged titanium and polypropylene Model 228 Retractable Toroidal
construction to provide maximum chemical Conductivity Sensor
resistance
ƒƒ Convenient isolation of sensor for cleaning or
ƒƒ Longer sensor life and reduced maintenance replacement
ƒƒ Retractable version for greater insertion ƒƒ Easy insertion/retraction of sensor
depths
ƒƒ Flush ports on assembly chamber allow
sensor cleaning

Table 1 - Typical Scrubber Applications

Typical Scrubber Applications

Gas Scrubber Solution Measurement

Chlorine Caustic (10–15 %) Conductivity
White Liquor pH, ORP
(pulp and paper)
Sulfur Dioxide Lime pH
Magnesium Oxide pH
Caustic (weak) pH
Caustic (strong) Conductivity
Hydrogen Chloride Caustic (10–15 %) Conductivity
Hydrogen Sulfide Caustic (10–15 %) Conductivity
Sodium Hypochlorite Conductivity, ORP

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Figure 1 - A Typical Scrubber

Waste Gas

Scrubber
Solution

Recirculation
Line

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