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(Presented at EPRI's 8th International Conference on Cycle Chemistry in Fossil and Combined

Cycle Plants with Heat Recovery Steam Generators - June 20-23, 2006 Calgary, Alberta Canada)

DEGASSED CATION CONDUCTIVITY MEASUREMENT

Otakar Jonas, P.E., PhD.


Lee Machemer, P.E.
Jonas, Inc.
1113 Faun Road
Wilmington, DE 19803

Abstract

This paper discusses the measurement and interpretation of degassed cation conductivity (DCC).
There are three designs of DCC instruments: reboiling before or after cation exchange and
nitrogen sparging after the cation column at ambient temperature. Each of these designs yields
different results. Reboiling before cation exchange only removes free CO2. However, cation
exchange converts all salts to acids, which are more volatile than salts, and reboiling after cation
exchange removes most carbonates and portions of the volatile acids. In addition, the following
instrument design and water chemistry factors influence the measured DCC: reboiling vs.
sparging, purity of the sparging gas, intensity and length of degassing, removal of vapors,
temperature compensation from ~100°C to 25°C (for reboiled DCC), effectiveness of cation
exchange, and pH and type of alkalizing agents, salts, and acids in the sample. The main
question is about the meaning of the various DCC measurements in relation to corrosion and
flow-accelerated corrosion.

Introduction

Specific conductivity (SC) and cation conductivity (CC) are core parameters for monitoring
cycle chemistry. The instruments are accurate, reliable, and inexpensive. SC is a measure of the
concentration of a mix of unknown dissolved chemical species, usually dominated by ammonia
or amines. CC measures a mix of anions and H+ after removal by ion exchange of all (most?)
cations and converting salts to the corresponding acids.

In an effort to expand the range of cycle chemistry monitoring and get information on the
concentration of CO2, use of degassed cation conductivity (DCC) was patented in 1958 [1].
Initially, there were a few users of this method but its use has increased during the last decade,
mostly because of the concerns about FAC, expanded use of organic chemicals that decompose
forming CO2, and in an effort to meet turbine steam cation conductivity limits by substituting
DCC for CC.

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Most users of DCC, including the authors, had been under the impression that the DCC
instruments remove only the free CO2, a less corrosive chemical species in steam, condensate,
and feedwater. DCC was included as a monitoring parameter in the first comprehensive U.S.
cycle chemistry guidelines [2]. After the extensive monitoring project [3], where DCC exhibited
poor accuracy (Figure 1) and there was a suspected removal of roughly 1/2 to 2/3 of formic and
acetic acids, it was not recommended in the guidelines that followed [4-7]. At the time of the
monitoring project [3], the instrument was tested for retention of HCl and HF, but not for organic
acids.

Figure 1
Degassed Cation Conductivity; Measured vs. Calibration Solutions Supplied from
Standard Sample Synthesizer - Six Mixtures Representing Typical Power Plant Water and
Steam [3]

The use of degassed cation conductivity has become popular in many combined cycle plants due
to their inability to meet manufacturer turbine steam cation conductivity limits. Instead, they
apply the same limits to degassed cation conductivity in an effort to ignore the effects of high air
inleakage, poor makeup water purity (aerated), and organic water treatment chemical
decomposition products (carbon dioxide and organic acids) on cycle chemistry control.

Cation conductivity is a critical control parameter for modern water and steam systems [2-7].
The cation conductivity of the superheated or reheated steam has a recommended normal limit of
between 0.15 and 0.35 µS/cm, depending upon the steam cycle design and selected water
treatment [2-7]. Carbon dioxide (Figure 2) and organic acids (Figure 3) often significantly
contribute to the measured cation conductivity, sometimes resulting in cation conductivity
readings above limits even when the concentrations of mineral acids are low. There are several
sources of carbon dioxide in the boiler water and condensate including makeup water (and

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aerated makeup storage tanks), air inleakage, decomposition of carbonates in the boiler, and
decomposition of organic compounds [8].

Figure 2
Contribution of Carbon Dioxide to Cation Conductivity [9]

Figure 3
Contributions of Chloride, Sulfate, and Organic Acids to Cation Conductivity [9]

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Degassed cation conductivity is the cation conductivity of a solution after the carbon dioxide
has been removed either by sparging the solution with a non-reactive gas (typically nitrogen) or
by heating close to boiling at ambient pressure. The measurement is supposed to provide an
indication of the concentration of corrosive salts and acids in the sampled stream without the
influence of carbon dioxide. Degassed cation conductivity is commonly measured on
superheated steam samples, however, it can also be applied to saturated steam, condensate, and
feedwater sampled after the deaerator.

An example of field CC and DCC data is in Figure 4. The data for two superheated steams (HP
and LP) are from commissioning of a three drum combined cycle unit using phosphate boiler
water treatment with deaeration only in the condenser. As can be seen, there is a large difference
between CC and DCC, particularly for the LP steam.

DCC Instruments

Currently, there are several possible arrangements and two methods commonly used for
removing carbon dioxide (degassing) in order to measure degassed cation conductivity:
x Reboiling – the sample is heated to 100ºC after the cation exchange column to remove
volatile species, sometimes followed by cooling of the sample for analysis [12, 14 to 19]
x Sparging – the sample is nitrogen sparged after the cation exchange column to remove
volatile species [20]

The instrument arrangements include:


x Reboiler or sparger before or after cation exchanger
x Sample cooler after reboiler before DCC measurement at ambient temperature
x No sample cooler after reboiler, DCC measurement at ~100°C

One example of a DCC flow diagram for degassing after a cation column is shown in Figure 5.

An instrument for monitoring degassed cation conductivity was patented by Larson and Lane in
1958 [1] and has been utilized to determine the purity of steam and condensate after removal of
ammonia and carbon dioxide. The Larson and Lane patent includes “the use of the ion exchange
bed without pre-boiling of the condensate, and the other of which provides for re-boiling of the
condensate to remove a major portion of the carbon dioxide before the ion exchange treatment
to remove ammonia and/or amines. Re-boiling following the ion exchange treatment is provided
in the lower unit to reduce the carbon dioxide contact to a minimum”.

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Figure 4
Cation Conductivity and Degassed Cation Conductivity for HP and LP Superheated
Steam. Commissioning of a 3 Pressure Combined Cycle Unit (Courtesy of Jonas, Inc.)

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Figure 5
Flow Diagram for One Type of DCC Instrument [12]

Reboiling

Heating the sample to its boiling point increases the volatility of some species, causing them to
enter the vapor phase and be removed from the sample. The typical reboiler design has the
sample flow into the reboiler, where it is heated to slightly below 100ºC for a short time period,
then exits the reboiler and the conductivity of the solution is measured. The residence time in the
reboiler is designed to allow enough time for significant removal of volatile species while
maintaining a relatively fast response time to changes in sample chemistry.

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Sparging

When a sample is sparged with a non-reactive gas (such as nitrogen), the partial pressure of the
volatile impurities causes a fraction of the impurity to diffuse into the nitrogen bubbles to
achieve equilibrium. As more nitrogen comes in contact with the liquid, more of the volatile
impurities are removed. In the case of carbon dioxide, when it is dissolved in water, a fraction of
it forms carbonate, a weak acid that increases the conductivity. However, when the nitrogen
removes the dissolved carbon dioxide in the water, the carbonate converts to carbon dioxide in
an effort to maintain equilibrium. This results in more carbon dioxide being removed, until all of
the carbon dioxide in the water is eliminated. As long as sufficient contact time is provided,
complete removal of the carbon dioxide can be achieved.

Differences between Instruments and Causes of Errors

The main difference in DCC measurements is between the instruments with degassing before the
cation column and after. This difference depends on pH which determines the concentration of
CO2 gas. The second difference is between the degassing at close to 100°C and at ambient
temperature (Figure 6). Gas stripping has a higher CO2 removal efficiency than reboiling [15].

Figure 6
Removal of CO2 vs. pH [21]

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The following are causes of errors and other differences:
x Removal of organic acids by degassing [3] – open cycle vs. volatility. An example of a
removal of other volatile acids besides the carbonic acid is shown in Table 1, where the DCC
is lower than that predicted by subtraction of the CO2 contribution. The data are from a
combined cycle unit using an organic oxygen scavenger where the volatile acids removed
were probably formic and acetic acids.
x Incomplete removal of CO2 – removal depends on pH (Figure 6)
x Incomplete cation exchange – amines, oxygen scavengers
x Intensity and length of reboiling and sparging
x Rate of vapor removal
x Purity of the sparging gas (NOX, SO2, CO2, organics)
x Temperature compensation from ~100°C to 25°C vs. chemical species present (see Figure 7
for the large conductivity difference which needs to be compensated for)

In some DCC designs [16, 17, 18] that include a reboiler, the degassed cation conductivity is
typically measured at close to 100ºC to eliminate the cost of an additional sample cooler.
Computerized temperature compensation is then used to adjust the measurement to the
equivalent conductivity at 25ºC [13]. The temperature compensation used is independent of the
impurities present, which makes the compensation susceptible to errors. In order to avoid these
problems, the conductivity should be measured at 25ºC.

Table 1
CC and DCC for Three Samples Obtained from a Combined Cycle Plant (Courtesy of
Jonas, Inc.)

Cation Conductivity after


Superheated Cation Conductivity Degassed Cation
Subtraction of CO2
Steam (µS/cm) Conductivity (µS/cm)
Contribution (µS/cm)

LP 0.53 0.08

IP 0.21 0.08 0.12

HP 0.80 0.15 0.20

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Figure 7
Temperature Effects on the Conductivity of High Purity Water [10]

Conclusions

1. Degassed cation conductivity is an interesting but controversial steam and condensate


monitoring parameter. Different instruments give different values which cannot be
practically interpreted, the instruments are difficult to calibrate, and the measured values are
non-conservative in relation to turbine corrosion and feedwater and extraction piping flow-
accelerated corrosion where CO2 and organic acids can play a major role.

2. There are two different designs of degassed cation conductivity analyzers: one with the
“degassing” (reboiling or sparging) before the cation exchanger and one with “degassing”
after.

Degassing after the cation exchanger is not recommended because it removes an unknown
mix of acids and the resulting degassed cation conductivity information cannot be properly
interpreted. Also, the conductivity measured at ~100°C and compensation to 25°C can
introduce errors.

3. To monitor the cation conductivity of samples without CO2, the degassing should be before
the cation exchange, as originally intended by the inventors of the method. Depending on
sample pH, this would leave some CO2 in the sample as carbonate and bi-carbonate, such as
in the actual condensate. In saturated and wet steam, CO2 and carbonates will be distributed
between the gas and liquid phases.

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4. The actual removal of chemical species in the “degasser” depends on their volatility, time
and intensity of degassing, temperature (100°C vs. ambient), removal of the vapor, and the
cation exchanger. In instruments with N2 sparging, impurities, such as NOx, CO2, SO2, can
be introduced. The volatility depends on the chemical equilibrium in the liquid phase.
About 7% of acetate could be removed by reboiling.

In cases where amines and certain organic oxygen scavengers are used, their ion exchange in
the cation column may not be complete, introducing additional errors.

5. In relation to the purpose of the degassed cation conductivity measurement – to monitor only
corrosive impurities, such as chlorides and sulfates, degassed cation conductivity is a non-
conservative parameter because, at lower temperatures, CO2, carbonates, and organic acids
are also corrosive. Their corrosive effects include stress corrosion cracking of carbon and
low alloy steels and enhancement of flow-accelerated corrosion by lowering pH.

6. In monitoring condensate and feedwater in most plants, free CO2 is already removed by
condenser and deaerator deaeration.

References

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2,832,673. April 29, 1958.

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April 1996. TR-105041.

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12. "Standard Test Method for On-line Determination of Anions and Carbon Dioxide in High
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Water Sample.” Annual Book of ASTM Standards. ASTM. New York. Volume 11.01.
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14. R.W. Lane. “Cation and Degassed Conductivity” Sentry Equipment Leaflet. March 1993.

15. N. Drew. “Evaluation of Degassed After-Cation-Exchange Conductivity Techniques.”


PowerPlant Chemistry. June 2004. 6(6).

16. “High Purity Condensate Monitoring.” Application Data Sheet, Rosemount Analytical. ADS
4900-81/Rev.B. August 2004.

17. “Condensate Analysis.” Product Application Data. Foxboro Company. PAD P4100-029.
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18. “Martek Dissolved Carbon Dioxide Analyzer.” Product Leaflet. Martek Instruments. 2006.

19. “DCCP: Degassed Cation Conductivity Panel.” Product Leaflet. Sentry Equipment. 1.43.1
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20. “Sparger Assembly.” Product Leaflet. Waters Equipment. 2005.

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