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Evaluation of Degassed After-Cation-Exchange Conductivity Techniques

Evaluation of Degassed After-Cation-Exchange


Conductivity Techniques

In feed and boiler waters, the effect of the anions on con-


Nigel J. Drew
ductivity is masked by the presence of the alkali. For many
decades, the use of after-cation-exchange conductivity
(ACC) has been the solution to this problem. A typical sys-
tem is shown in Figure 1 and a brief example of the im-
ABSTRACT
provement in sensitivity available by replacement of
After-cation-exchange conductivity (ACC) systems are sodium as a counter ion with hydrogen ion is shown be-
the universally used method for rapid detection of an- low. Measurements are corrected to a sample tempera-
ionic impurity ingress into the steam/water circuit of ture of 25 C.
power plant. In some utilities, ACC is measured after
 Pure water has a conductivity of 0.055 S cm1.
degassing the sample. It is generally considered that
carbon dioxide is the least aggressive contaminant of  10 mg kg1 of sodium chloride in pure water raises
1
feedwater that is normally present and causes eleva- conductivity to 0.077 S cm .
tion of the measured ACC. The elevation of ACC by
 1 mg kg1 of ammonia in a sample would have a con-
carbon dioxide can be particularly noticeable when the 1
ductivity of 6.721 S cm but with the addition of
oxygen scavenger is carbohydrazide, or the water con- 1
10 g kg of sodium chloride this rises to
tains dosed amines or neutral organic compounds in 1
6.743 S cm .
the make-up water. Ingress of carbon dioxide could be
considerable in the case of tube leakage in some parts  The cation exchange column (with R = resin + sulpho-
of the boilers of gas-cooled nuclear stations. The ele- nate group) replaces cations, thus:
vated ACC then delays unit start-up. There are two
+ +
widely used techniques for degassed ACC systems: Na + R-H  Na-R + H (1)
gas stripping with nitrogen and heating to near boil-
and
ing. Membrane gas-exchange systems are now also
beginning to appear on the market. British Nuclear NH4+ + R-H  NH4-R + H+ (2)
Fuels Plc. and British Energy arranged for an evalua-
tion of these three types of system to determine if they  The resulting solution containing HCl from 10 g kg1
would be sufficiently effective for use in their power of sodium chloride and 1 mg kg1 of ammonia has an
1
stations. The results of the evaluation are summarised ACC of 0.098 S cm .
here and measured values are compared with theoret-
ical calculations for ACC and degassed ACC.

INTRODUCTION
Feedwater, boiler water and steam in generating plant
should contain as little as possible of any ionic species
known to initiate or enhance corrosion, such as chloride,
sulphate, acetate and formate. To ameliorate the effects
of any traces of these ions alkalising agents are added to
ensure that the resulting water (or salts deposited) remains
alkaline, typically in the range of pH 9 to pH 9.8 at 25 C
in the feedwater. The alkali added may be ammonia, amine
(such as morpholine) or, in drum boilers, sodium phos-
phate or sodium hydroxide. The presence of ionic impuri-
ties in water is readily detectable by measuring the elec-
trolytic conductivity of the water, a technique that is ro-
bust and responds rapidly. Identification of the individual
ions requires more complex techniques, such as ion chro-
matography, with each analysis taking some time to be
completed.

Figure 1: A typical after-cation-exchange conductivity


2004 by PowerPlantChemistry GmbH. All rights reserved. system.

PowerPlant Chemistry 2004, 6(6) 343


Evaluation of Degassed After-Cation-Exchange Conductivity Techniques

Using the cation exchange column has nearly doubled the except when investigating the effect of sample flow rate
conductivity from the presence of sodium chloride and variations.
eliminated the background contribution from ammonia ad-
dition. When measuring direct conductivity, variations in
large background conductivity will make the small contri- Gas Stripper
bution from sodium chloride undetectable. The after-col-
umn technique is particularly sensitive in the detection of Another manufacturer loaned a gas stripping system. This
condenser tube leaks when measuring condensate. comprised a cation exchange column with downward flow,
followed by a ~ 0.6 x 0.05 m gas stripper that used a
Another contaminant of boiler water and condensate is counter-current flow of nitrogen applied through a stain-
carbon dioxide. There are several sources of this, such as less steel sinter. Sample from the DGCC measuring cell
absorption from air in the condenser at start-up, decom- had to be returned to the system for liquid height control
position of any organic compounds in the feed such as of the gas stripper. Water and sample flows were 160 and
3 1
those deliberately introduced, e.g., amines, carbohy- 700 cm min respectively, except when investigating the
drazide (for oxygen removal), and from polysaccharides effect of sample flow rate variations.
and humic acids in make-up. Dissolved carbon dioxide
alone will promote corrosion of mild steel. However, when
carbon dioxide and excess alkali (e.g., ammonia) are both Membrane Gas Stripper
present, the high temperature pH remains protectively al-
A prototype system was supplied on a single panel with a
kaline [1]. [2] calculates the effect of anions with ammonia
cation exchange column and a polysulphone-membrane
on pH (at 100 C) and puts them in the following order: 2
gas exchanger of an approximate active area of 1.38 m .
Chloride > sulphate, formate >> acetate >> carbon dioxide Two conductivity cells measured ACC and DGCC, being
connected to a dual channel conductivity analyser with
This order of the effect on pH and thus potential for corro- "acid" temperature compensation selected. Being a pro-
sion is the reason why many operators would prefer ACC totype, optimum operating conditions were not well es-
not to include the contribution from carbon dioxide. tablished until the effect of sample flow rate variations had
been investigated. Optimal sample water and gas flow
Currently, there are three techniques available to measure 3 1
rates were then found to be 150 and 250 cm min re-
degassed conductivity directly: spectively. The manufacturer is subsequently considering
 Heating the sample to boiling or near boiling point fitting a second membrane to operate with lower gas flow
rates and some results from an early 2-membrane system
 Gas stripping with a "bubbler" system
are included here.
 Diffusion of dissolved gases out of the sample through
a membrane.

Systems based upon these three methods were evaluated


TEST PROCEDURES
by British Nuclear Fuels Plc. (BNFL) Nuclear Sciences and
Technology Services and the results are reported here. The three measurement systems were supplied with sam-
This paper attempts to look at the generic merits of each ple water from a recirculating de-ionising system as shown
method, without reference to the particular manufacturer schematically in Figure 2. Solutions of known concentra-
of the systems. Systems that extract and measure the car- tion of sodium chloride and sodium carbonate were ap-
bon dioxide concentration and then calculate its effect on plied using a flow dilution technique, in which concen-
conductivity were not examined. trated solutions prepared volumetrically were continuously
added from a motorised syringe into known flows of sam-
ple water. Flow rates were calibrated by gravimetric meth-
ods. Solutions of organic acids were prepared and applied
SYSTEMS TESTED in the same fashion. However, when adding acids, ammo-
nia solution was simultaneously applied by a second mo-
Heating torised syringe, such that the concentration of ammonia in
1
A widely used "reboiler" system was loaned by the manu- the sample would be 2 mg kg .
facturer. It consisted of a single cation exchange column
with downward flow, a vented reboiler operating near After-cation-exchange conductivity (ACC) and degassed
100 C and three conductivity cells connected to a single conductivity (DGCC) were measured on the systems' in-
transmitter. The conductivity of the incoming sample was ternal instrumentation (where fitted) and on a reference in-
measured at sample temperature, as was the ACC value, strument. All values quoted here have been "normalised"
with the degassed conductivity (DGCC) measured near as if taken by the reference instrument; see Figure 2.
100 C. The optimum sample flow rate was found to be in
3 1
the range of 170 to 200 cm min and the system was Test solutions were devised and applied as in Table 1 to
operated near the mid-point of this range during all tests ascertain the following:

344 PowerPlant Chemistry 2004, 6(6)


Evaluation of Degassed After-Cation-Exchange Conductivity Techniques

i. Did ACC values match theo-


retically calculated values for
the concentrations applied?
ii. Did degassing affect the val-
ues for mineral and light or-
ganic acids?
iii. Did degassing remove carbon
dioxide from water?
iv. What was the combined ef-
fect of degassing on solutions
containing both acids and
carbon dioxide?
v. Did variations in sample tem-
perature affect the degassing
system?

Figure 2:
Test apparatus.

Solution Nominal ACC Chloride Carbon dioxide Formate Acetate


1 1 1 1
[S cm ] [g kg ] [g kg ] [g kg ] [g kg1]
1 0.14 10
2 0.31 25
3 1.2 100
4 0.14 25
5 0.32 100
6 0.54 250
7 0.11 10
8 0.45 50
9 0.15 20
10 0.32 50
11 0.62 10 250
12 1.5 100 250
13 0.83 250 50
1
14 0.055 2 000 g kg NH3

Table 1: Test solutions and their nominal conductivity.

PowerPlant Chemistry 2004, 6(6) 345


Evaluation of Degassed After-Cation-Exchange Conductivity Techniques

THEORETICAL VALUES and any excess in background from 0.055 S cm1 has
been deducted from the measured values in Table 3.
ACC is an important measurement in power plant, hence
the opportunity was taken to compare the theoretically
calculated conductivity to the measured value for each so-
Effect of Degassing on Acids
lution applied. During the experimental programme, theo-
retical values were calculated using a computer pro- All three systems exhibited negligible differences between
gramme written by the Central Electricity Generating measurements of ACC and DGCC with acids (in the ab-
Board (CEGB) in the UK. The programme had not been sence of carbon dioxide). Results are shown in Table 4,
verified against more recent data for ionisation, equilib- where a positive difference between the ACC and DGCC
rium and mobility constants but used the values accepted value would indicate that some of the anion species had
in the 1980s. Table 2 compares the values calculated from been removed, and a negative value that some contami-
the CEGB programme and those from the EPRI code nation had been added. Notice that when adding formic
1
CCHEM v. 0.91 (2002) quoted in [2]. or acetic acids to the sample, 2 mg kg of ammonia had
also been added prior to the ion exchange column.
It can be seen that for calculation of the ACC values pre-
sented here, the two methods differed only in the last sig-
nificant figure. (The two calculation methods exhibited Effect of Degassing on Carbon Dioxide
more significant disagreements for mixtures of ammonia
Table 5 shows the results when the sample contained
and salts, but this was not relevant to the work reported
sodium carbonate, and hence carbon dioxide after the col-
here.)
umn. Concentrations are given for the resulting carbon
dioxide after the cation exchange. Each system removed
some carbon dioxide and hence DGCC was lower than
ACC. These reductions are given as percentages of the
reduction in conductivity that would be achieved if all car-
RESULTS bon dioxide were removed. The equation used was:
Comparison of ACC with Theoretical Values Reduction in ACCmeasured DGCCmeasured
= 1003 (3)
All three systems gave excellent agreement between the conductivity ACCtheory DGCCtheory
calculated and measured ACC values as shown in Table 3.
All indications were that the uppermost values (above The results indicated the difficulty of removing all the car-
1
1 S cm ) were consistently lower than the calculated bon dioxide from pure water in the absence of any other
value by some 3 to 4 %. Background conductivity values acids, a situation that would represent an unlikely extreme
1
when pure water was applied were near 0.070 S cm on power plant.

Concentration 20 g kg1 50 g kg1 60 g kg1


Species EPRI CEGB NNC EPRI CEGB NNC EPRI CEGB NNC
HCl 0.249 0.250 0.250 0.603 0.604 0.604 n/a 0.724 0.724
H2SO4 0.191 0.192 0.192 0.451 0.453 0.453 0.539 0.542 0.542
Formate 0.190 0.191 0.191 0.450 0.452 0.452 0.537 0.539 0.540

Concentration 20 g kg1 50 g kg1 250 g kg1


Species EPRI CEGB NNC EPRI CEGB NNC EPRI CEGB NNC
Acetate 0.145 0.145 0.145 0.321 0.323 0.323 1.371 1.380 1.380

Concentration 20 g kg1 200 g kg1 1 000 g kg1


Species EPRI CEGB NNC EPRI CEGB NNC EPRI CEGB NNC
CO2 0.123 0.124 0.123 0.474 0.476 0.472 1.149 1.153 1.140

Table 2: A comparison of methods of calculating after-cation conductivity.


All data are stated in S cm1.
EPRI values calculated by EPRI CCHEM v. 0.91
CEGB values calculated by CEGB programme MIXT2
NNC values calculated using a programme recently derived by B. Handy of NNC Limited, courtesy of
NNC Limited

346 PowerPlant Chemistry 2004, 6(6)


Evaluation of Degassed After-Cation-Exchange Conductivity Techniques

Species Concentration Calculated ACC Measured ACC


1 1 1
[g kg ] [S cm ] [S cm ]
Pure water 0.055 0.061 to 0.079
10.3 0.141 0.146
Chloride 25.7 0.316 0.309
102.7 1.234 1.169
25.7 0.143 0.146
Carbon dioxide 102.7 0.324 0.320
256.7 0.549 0.548
10.3 0.113 0.136
Formate
51.3 0.463 0.443
20.4 0.148 0.159
Acetate
51.0 0.329 0.333
10.3 / 256.7 0.625 0.610
Chloride / CO2
102.7 / 256.7 1.484 1.420
Formate and CO2 51.3 / 256.7 0.847 0.856

Table 3: Comparison of calculated and measured after-cation-exchange conductivity (ACC) values.

Species Concentration Difference ACC DGCC (measured)


1
[g kg ] [S cm1]
Reboiler Gas stripper Membrane
10.3 0.003 0.007 0.014
Chloride 25.7 +0.003 0.002 0.003
102.7 +0.019 +0.005 +0.014

NH3 2 000 0.001 +0.001 0.001

10.3 0.009 +0.019 +0.003


Formate *
51.3 0.085 +0.013 +0.010
20.4 0.011 +0.009 0.005
Acetate *
51.0 0.004 +0.008 +0.004
Table 4: The effect of degassing on acids in the absence of carbon dioxide.
* 2 mg kg1 of ammonia had been added prior to the ion exchange column.

Solution applied Efficiency of reduction in degassed conductivity value


[%]
Reboiler Sparger Membrane
1
25.7 g kg CO2 58 70 40; with 2 membranes: 48
1
102.7 g kg CO2 46 70 59
1
256.7 g kg CO2 28 70 63

Table 5: The efficiency of degassing solutions containing carbon dioxide.

PowerPlant Chemistry 2004, 6(6) 347


Evaluation of Degassed After-Cation-Exchange Conductivity Techniques

Solution applied Efficiency of reduction in degassed conductivity value


[%]
Reboiler Sparger Membrane
1
256.7 g kg CO2 and
28 70 58; with 2 membranes: 64
10.3 g kg1 chloride
256.7 g kg1 CO2 and
1 44 89 83
102.7 g kg chloride
256.7 g kg1 CO2 and
11 84 82
51.3 g kg1 formate

Table 6: The efficiency of degassing when other anions are present.

Effect of Degassing on Other Species The membrane diffusion system showed slight evidence
of small increases in degassing efficiency with increasing
Table 6 shows the results when both "strong" acids and
sample temperature. However, like the gas stripping sys-
carbon dioxide are present in the degassing system. Not
tem, the largest effect was related to the gas/water flow
surprisingly, the efficiencies have increased because wa-
ratio. The membrane system was tested with only some
ter has poor buffering capacity and carbon dioxide solu-
35 % of the flow used for the gas stripper, i.e., over a range
bility reduces with reduced pH. Calculated pH values with
of 1.0 to 1.7 for the gas/water flow ratio. The prototype
chloride present were 6.5, 5.8 and 5.55 for concentrations
1 membrane system had significant potential for further de-
of 10, 50 and 100 g kg respectively.
velopment to improve degassing efficiency.

Influence Quantities
The test programmes used by BNFL are derived from a
SUMMARY
Company Standard for Chemical Analysis Equipment [3].
This standard incorporates developments in instrument The measured effect for ions on the ACC was in excellent
evaluation techniques since the 1960s, but in the 1990s agreement with values calculated by two independent
was aligned with procedures and nomenclature in modern methods. The effect of dissolved carbon dioxide was also
IEC standards [47]. In accord with the Company Stan- as predicted by calculation. This confirms that indicative
dard, each system was subjected to the appropriate tests impurity concentrations calculated from ACC values are
for the effects of influence quantities. These were: varia- correct.
tion of sample flow rate, variation of gas flow rate (where
appropriate), variation of sample temperature and electri- The three systems tested all significantly reduced the con-
cal supply variations. Each system required some degree tribution to ACC from dissolved carbon dioxide (i.e., DGCC
of optimisation, for example for sample flow rate. The re- was lower than ACC). None of them achieved 100 % re-
sults, in as much as they pertain to the method of de- moval of carbon dioxide, although the presence of other
gassing, are summarised below. acid species aided degassing.

The reboiler system could be affected if the electrical sup- For on-line operation on power plant each system has its
ply was reduced or sample flow increased to a point where advantages and disadvantages. The advantage for the re-
the reboiler temperature was not maintained. Very low boiler was that it required no supply of nitrogen. However
sample temperatures also reduced the efficiency of the re- the solubility of carbon dioxide is not zero even at 100 C,
boiler system. so the efficiency may not be 100 % even at boiling point.
A significant disadvantage was that the displaced carbon
The gas stripping system showed no marked effect with dioxide could be entrained in the sample and re-dissolve
variations in sample temperature. However, degassing ef- if the sample was cooled. Hence, measurement of the de-
ficiency was significantly increased by decreasing sample gassed conductivity at elevated temperature was essen-
flow rate and/or increasing gas flow rate. The values tial, thus requiring highly accurate sample temperature
quoted in Tables 5 and 6 are therefore only indicative of compensation over a 75 C range.
efficiencies obtainable within the manufacturer's rated flow
ranges. The sample used during flow variation tests con- The gas stripping system had the advantage of simplicity
1 1
tained 257 g kg of carbon dioxide with 10.3 g kg and within the conditions used for this evaluation showed
of chloride. Efficiency rose from 61 % to 80 % as the the highest degassing efficiency. However, for this high
gas/water flow ratio was increased from 2.7 to 6.7; the re- degassing efficiency the nitrogen usage would amount to
sults in Tables 5 and 6 were taken with a ratio of 4.7. typically one cylinder per week.

348 PowerPlant Chemistry 2004, 6(6)


Evaluation of Degassed After-Cation-Exchange Conductivity Techniques

Both the above systems were vented and, hence, provided THE AUTHOR
a final sample having little pressure to operate a column
Nigel J. Drew (B.S., Ph.D., University of Nottingham,
rinsing down, which would be useful because these sys-
England) started his career in the power industry in 1978,
tems only had one column.
with the South Western Scientific Services of the Central
Electricity Generating Board. He worked with suppliers to
The membrane system tested showed a similar efficiency
assist with development of chemical instrumentation for
to the gas stripper, but with much lower gas consumption
gas analysis, oil in water, moisture in gases and water oil.
and outlet sample was at pressure. The membrane itself
During the last 25 years, the emphasis of Nigel Drew's
took some time to rinse to low conductivity and initially in-
work has changed to mainly chemical instrument evalua-
dicated a slightly elevated conductivity with pure water.
tion (of water and gas instrumentation), and monitoring
The system was a prototype and showed potential for fur-
applications for decommissioned nuclear plants. His em-
ther development.
ployers since 1990 have been nuclear power generation
companies in the United Kingdom. He was a member of
IEC SC65D during the drafting of the international stan-
dards for chemical analyzers for gas and water. He is a
REFERENCES
member of the Royal Society of Chemistry and a
[1] Bursik, A., PowerPlant Chemistry 2003, 5(4), 225. Chartered Chemist.
[2] Bursik A., PowerPlant Chemistry 2002, 4(10), 597.
[3] Magnox Company Standard M/CS/TCED/100, 1997.
Magnox Electric plc., Berkeley, United Kingdom.
[4] IEC Standard 770, 1984. International Electro- CONTACT
chemical Commission, Geneva, Switzerland.
Nigel Drew
[5] IEC Standard 60359, 2001. International Electro- BNFL
chemical Commission, Geneva, Switzerland. Nuclear Sciences & Technology Services
Berkeley Centre
[6] IEC Standard 60746, 2002. International Electro-
Berkeley, GL13 9PB
chemical Commission, Geneva, Switzerland.
United Kingdom
[7] IEC Standard 61207, 1994. International Electro-
chemical Commission, Geneva, Switzerland. E-mail: nigel.j.drew@magnox.co.uk

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