Degassed Cation Conductivity Measurement

(DCACE) to Reduce Startup Time

Measuring Principle for Cation Conductivity

Measurement (CACE)
The principle of cation exchange is the same as in any ion
exchange process. This process is used in many demineralised
(DM) water plants. The DM plant uses anion and cation
exchangers to remove anions and cations and make the water
free from salts and dissolved impurities. In the steam and water
analysis system (SWAS) package, the cation exchange principle
is used to eliminate masking effects of known chemicals such as
ammonia or dissolved amines.

The conductivity measurement is a blind method of cross

checking if water is ultrapure or whether there are dissolved
impurities present in the sample. Ultrapure water has very low
conductivity since it is very poorly ionised. On addition of even a
small amount of salt, like NaCl, the conductivity shoots up
drastically. A similar situation arises on addition of chemicals.

Typical Reaction in the Cation Column

In the cation columns, the resins present are charged with H(+)
ions. These ions replace the +ve ions of any salt / dissolved
impurity as it dissovled in water.
1) Na(+) + Cl(-) => H(+) ions => HCl + Na(+) ions
2) NH4(+) + OH (-) =>. H(+) ions => H2O + NH4(+) ions
Rotameter
In case (1), the cations replace Na ions and the outcome is the
corresponding acid, i.e. HCl.
In case (2), the cations replace NH4 ions and the outcome is
H2O, i.e. pure water
The conductivity in case (1) is three times that imparted by the CE CT
salt (here NaCl), while in case (2), the conductivity imparted by
the chemical (here NH4OH) gets eliminated and the outcome is
3-Way Ball Valve
pure H2O.
Thus cation conductivity measurement eliminates the masking Cation Columns
effects of known/desired dosing chemicals (mainly ammonia). 1 2
The figure shows a typical layout of cation conductivity
measurement. The conductivity is measured before the sample
enters the cation column. This is called ‘specific conductivity’
measurement. The sample then flows through the cation
column. The 3-way ball valve at the entry is used to pass the CE CT
sample through the desired cation column (the duty column -
column-1 in this case). The position of the 3-way ball valve at the
bottom is also selected in the same way. column-2 can be
selected when the resin in the first column gets exhausted.

Energy Conservation | Environment | Process Efficiency www.forbesmarshall.com

Measuring Principle of Degas Cation Conductivity (DCACE)

As explained above, the cation column removes the effect of

ammonia and alkalising agent, but dissolved gases like CO2 still
contribute to the CACE value. Carbon dioxide can form carbonic
acid and carbonate on dissolution in water. This can severely
CO2
affect not only cycle corrosion, but also mask early condensate pH
SPECIFIC
and conductivity measurements in cycle regions where NH4+, OH+
- DEGASSED CATION
condensation sets in. The most likely paths for CO2 ingress are air Na+, H+, Cl H, Cl, OH
-
and cooling water leakage in, makeup water, ion exchange resins, HCOM , CO2

and plant cycle additives. By precise heating of the process

solution to near-boiling after a cation column, carbon dioxide and
other low molecular organics are volatised and removed.
CATION R-NH4+ DEGAS
EXCHANGER COLUMN
A degas reboiler system is a compact device designed to remove R-Na+
R-H+
dissolved carbon dioxide and lighter amine contaminants present
in ultrapure water sample streams. When used in conjunction with
cation conductivity measurement, it can provide continuous
degassed cation conductivity measurements meeting ASTM
CATION
D4519 standards. -
H+, Cl , CO2,
-
HCO3 , OH+

Forbes Marshall Relisafe-CO2

The Relisafe-CO2 system provides real-time data making it the

ideal analytical tool for monitoring high purity processes in nuclear
and high-performance fossil fuel power plants, HRSG (Heat
Recovery Steam Generators) and condensate polishing systems.
Cell-1 CE CT
A cooled cation conductivity sample stream is fed to the degas
Dual Cation
reboiler system. The sample flow is controlled by a flow meter and
Column
sent to the reboiler where it is heated to near boiling, allowing
carbon dioxide and other gasses to be vented off through an Cell-2 CE CT
expansion chamber. The hot sample stream is then directed
through a conductivity sensor that can measure the degassed Relisafe-CO2
conductivity. If the corresponding conductivity analysers are Electronics
capable, the differential analysis between the cation and Rotameter
degassed conductivity values can then be displayed along with a
corresponding carbon dioxide concentration.
Degassification
Unit

Cell-3 CE CT
Significance of CACE and DCACE Values for Steam Purity in Steam Turbines

Importance of Steam Purity During Startup

Steam purity is one of the most important factors for healthy and efficient operation of a steam turbine. Chemical analysis of
steam during startup and inspection of the turbine helps to understand if these values are suitable, or should be tightened or
relaxed. Such decisions may also be based on fleet experience with similar power cycles. Chemical analysis of the steam
should include measurement of sodium, anions and cations CACE. This ensures that no anions or contaminants which can
cause corrosion of turbine blades are present.

Main steam CACE values are monitored continuously during plant startups. As specified in various international standards
(IAPWS/ VGB/EPRI), steam with CACE value <0.2 μS/cm is not allowed to enter steam turbine. Startup is delayed just to
ensure that CACE values are within specified limits. During startup CACE values also have a masking effect of dissolved
CO2 which delays plant startup.

Source of Carbon Di-oxide in Condensate and Superheated Steam

Carbon dioxide is an impurity that enters the steam / water cycle mostly as air in-leakage or by decomposition of organic
matter (impurities or added treatment chemicals).

Dissolved CO2 in CACE is considered non-corrosive to the steam turbine when concentration is within reasonable limits
(e.g. CACE in steam <0.5 μS/cm). However, it adds to overall CACE levels and masks the presence of other impurities like
chlorides and other anions which can cause corrosion and failure.

Differential analysis between cation and degassed conductivity measurements can provide a more accurate cation
conductivity value which can be directly correlated to CO2 concentration and result in a more realistic assessment of the
process chemistry.
Steam for Steam Turbines

Without additional With additional

measurement of measurement of
degassed, acid degassed, acid
conductivity conductivity

Acid Conductivity µS/cm N ' '

AL 1 0.20 0.5

Case # 2
AL 2 0.50 0.8

AL 3 1 1.3

Degassed, Acid µS/cm N - '

Case # 1
Conductivity AL 1 - 0.20

AL 2 - 0.50

AL 3 - 1

Silica (SiO2) µg/kg N '

AL 1 20

AL 2 50

AL 3 -
Sodium (Na) µg/kg N '

AL 1 5

AL 2 10

AL 3 20

Iron (Fe), Total µg/kg N '

AL 1 20

AL 2 -

AL 3 -

Copper (Cu), Total µg/kg N '

AL 1 3

AL 2 -

AL 3 -

AL 1: Action Level 1 steam turbine can be started only after achieving values below this level

The higher action limits (column "with additional measurement of degassed, acid conductivity") may be
applied when the increase in acid conductivity is associated with carbon dioxide, and organic degradation
products are excluded as the cause.
Reference : Recommendations from VGB-S-010-T-00 2011-12 EN standard
Case Study in 660MW Supercritical Power Plant

In this plant, we have monitored the online trend of specific conductivity

Conductivity after cation exchange (CACE)

Degassed conductivity after cation exchange (DCACE)

For (main) superheated steam during startup of the 660MW power plant after routine shut down. During cold startup
operation of 660MW power plant we have logged in table below.

As illustrated, both CACE and DCACE values reduce as run time progresses.

Date & Time Specific Cond. Cation Cond. Degas Cond. Degas Temp. CO2 Calculated
(µS/cm) (µS/cm) (µS/cm) (Deg C) (ppb) pH

5/24/2018 14:20 3.6622 1.4562 0.62081 81.62 599.07 9.14

5/24/2018 14:25 3.3842 1.45048 0.47928 98.69 777.83 9.09
5/24/2018 14:30 3.1844 1.02909 0.4172 99.08 355.99 9.09
5/24/2018 14:35 2.8239 0.78241 0.35892 93.38 199.34 9.04
5/24/2018 14:40 2.64055 0.6673 0.22374 97.87 213.98 9.01
5/24/2018 14:45 2.77025 0.60455 0.18163 97.9 198.93 9.03
5/24/2018 14:50 2.755 0.53307 0.15641 98.19 167.08 9.03
5/24/2018 14:55 4.94111 0.53736 0.13676 97.97 183.24 9.29
5/24/2018 15:00 4.22607 0.47837 0.12551 97.87 151.68 9.22
5/24/2018 15:05 4.81904 0.41333 0.11692 95.4 117.82 9.28
5/24/2018 15:10 4.28687 0.41085 0.11387 98.73 118.14 9.23
5/24/2018 15:15 3.93424 0.37089 0.10629 97.94 100.38 9.19
- - - - - - -
5/24/2018 18:05 4.50503 0.21644 0.13252 64.63 23.14 9.25
5/24/2018 18:10 4.19913 0.2059 0.12651 64.55 21.67 9.22
5/24/2018 18:15 3.38086 0.19155 0.12217 63.36 18.49 9.13
5/24/2018 18:20 3.13576 0.18731 0.11745 60.14 18.64 9.1
5/24/2018 18:25 3.02275 0.1762 0.11773 57.25 15.16 9.08
5/24/2018 18:30 2.92595 0.17438 0.11454 60.21 15.57 9.07
5/24/2018 18:35 3.00725 0.17262 0.11211 55.96 15.78 9.08

Case#1 Steam Turbine taken into Operation Based on Comparison of CACE and DCACE Value
At 15:00 hrs on 5/24/2018 DCACE value fell to 0.1255 µS/cm (below target value of 0.2 µS/cm) and CACE value to
0.47837µS/cm (below target value of 0.5 µS/cm).

Case#2 Steam Turbine taken into Operation Based on CACE Value

At 18.15 hrs on 5/24/2018 CACE Value was 0.19155 µS/cm (below target value of 0.2 µS/cm). In absence of DCACE
measurement this is time when steam is passed to turbine and power production is initiated.

Quick startup of steam turbine for power generation results in a clear saving of 3-4 hrs run time, thereby reducing
fuel costs.
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