ASTM D6302-98(2004)
(Practice)Standard Practice for Evaluating the Kinetic Behavior of Ion Exchange Resins
Standard Practice for Evaluating the Kinetic Behavior of Ion Exchange Resins
SIGNIFICANCE AND USE
This practice is intended to evaluate changes in the performance of ion exchange resins used in mixed beds operating as polishing systems for solutions of low ionic strength, typically, 10 mg/L dissolved solids, that are intended to produce very high purity effluents. It is recommended that when new resins are installed in a plant it be used to provide a base line against which the future performance of that resin can be judged.
The conditions of this test must be limiting kinetically, such that kinetic leakage, and not equilibrium leakage, is tested. This leakage is influenced by a combination of influent flow velocity and concentration, as well as bed depth.
It is recommended that the practice be followed with the resin ratio, flow rate, and influent quality as indicated. The design of the apparatus permits other variations to be used that may be more appropriate to the chemicals used in a specific plant and the nature of its cooling water, but the cautions and limitations noted in the practice must be accommodated.
It is possible that the cation resin could experience kinetics problems. In many cases, however, the anion resins are more likely to experience the types of degradation or fouling that could lead to impaired kinetics. Testing of field anion and cation resins together is an option, especially when historic data on the mixed bed will be compiled. Recognize, however, that many variables can be introduced, making it difficult to interpret results or to compare to historical or new resin data on separate components.
Provision is made for calculation of the mass transfer coefficient in the Appendix X1. When such calculation is to be made, a full wet sieve analysis, as described in Test Methods D 2187, also is required. Electronic particle sizing may be substituted if it is referenced back to the wet sieve method.
This practice is intended to supplement, not displace, other indicators of resin performance, such as exchange capacity, % regeneration, ...
SCOPE
1.1 This practice is intended to evaluate changes in kinetic performance of ion exchange resins used in mixed beds to produce high purity water. Within strict limitations, it also may be used for comparing resin of different types. This standard does not seek to mimic actual operating conditions. Specific challenge solutions and conditions are specified. At the option of the user, other conditions may be tested.
1.2 This standard does not purport to address the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.
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Designation:D6302–98 (Reapproved 2004)
Standard Practice for
Evaluating the Kinetic Behavior of Ion Exchange Resins
This standard is issued under the fixed designation D 6302; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. A
superscript epsilon (e) indicates an editorial change since the last revision or reapproval.
1. Scope effluent is measured by conductivity, and if agreed upon, other
appropriate analytical procedures.
1.1 This practice is intended to evaluate changes in kinetic
performance of ion exchange resins used in mixed beds to
5. Significance and Use
produce high purity water.Within strict limitations, it also may
5.1 This practice is intended to evaluate changes in the
be used for comparing resin of different types. This standard
performance of ion exchange resins used in mixed beds
does not seek to mimic actual operating conditions. Specific
operating as polishing systems for solutions of low ionic
challenge solutions and conditions are specified. At the option
strength,typically,<10mg/Ldissolvedsolids,thatareintended
of the user, other conditions may be tested.
to produce very high purity effluents. It is recommended that
1.2 This standard does not purport to address the safety
when new resins are installed in a plant it be used to provide a
concerns, if any, associated with its use. It is the responsibility
baselineagainstwhichthefutureperformanceofthatresincan
of the user of this standard to establish appropriate safety and
be judged.
health practices and determine the applicability of regulatory
5.2 The conditions of this test must be limiting kinetically,
limitations prior to use.
such that kinetic leakage, and not equilibrium leakage, is
2. Referenced Documents tested. This leakage is influenced by a combination of influent
flow velocity and concentration, as well as bed depth.
2.1 ASTM Standards:
5.3 It is recommended that the practice be followed with the
D 1129 Terminology Relating to Water
resin ratio, flow rate, and influent quality as indicated. The
D 1193 Specification for Reagent Water
design of the apparatus permits other variations to be used that
D 2187 Test Methods for Physical and Chemical Properties
may be more appropriate to the chemicals used in a specific
of Particulate Ion-Exchange Resins
plant and the nature of its cooling water, but the cautions and
D 2687 Practices for Sampling Particulate Ion-Exchange
limitations noted in the practice must be accommodated.
Materials
5.4 It is possible that the cation resin could experience
D 5391 Test Method for Electrical Conductivity and Resis-
kineticsproblems.Inmanycases,however,theanionresinsare
tivity of a Flowing High Purity Water Sample
more likely to experience the types of degradation or fouling
3. Terminology that could lead to impaired kinetics. Testing of field anion and
cation resins together is an option, especially when historic
3.1 Definitions—For definitions of terms used in this prac-
data on the mixed bed will be compiled. Recognize, however,
tice, refer to Terminology D 1129.
that many variables can be introduced, making it difficult to
4. Summary of Practice
interpretresultsortocomparetohistoricalornewresindataon
separate components.
4.1 An apparatus is described in which a specified volume
5.5 Provision is made for calculation of the mass transfer
of regenerated resin sample is mixed with a corresponding new
coefficient in theAppendix X1. When such calculation is to be
resin. The mixed bed then is operated at a controlled high flow
made, a full wet sieve analysis, as described in Test Methods
rateonaninfluentofknowncomposition,andthequalityofthe
D 2187, also is required. Electronic particle sizing may be
substituted if it is referenced back to the wet sieve method.
5.6 This practice is intended to supplement, not displace,
This practice is under the jurisdiction of ASTM Committee D19 on Water and
other indicators of resin performance, such as exchange capac-
is the direct responsibility of Subcommittee D19.08 on Membrane and Ion
ity, % regeneration, and service experience records.
Exchange Materials.
Current edition approved June 1, 2004. Published June 2004. Originally
6. Interferences
approved in 1998. Last previous edition approved in 1998 as D 6302 – 98.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
6.1 Interferences in the conventional sense are minimal, but
contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
variations in test conditions, such as flow rate, temperature,
Standards volume information, refer to the standard’s Document Summary page on
the ASTM website. resin ratio, particle size, column configuration, regeneration
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
D6302–98 (2004)
efficiency, and influent concentrations can cause major differ- 7. Equipment
ences in performance. This practice fixes or measures these
7.1 Backwash/Separation and Regeneration Apparatus, see
variables so that true changes in resin kinetics can be demon-
Test Methods D 2187.The column should be 50-mm ID 3 600
strated accurately. Other means will be needed to investigate
or 900-mm length.
other resin or equipment problems.
7.2 Kinetics Test Apparatus (see Fig. 1):
6.2 Contaminant ions in the resins themselves, if present
7.2.1 Feed Pumps, capable of controlled delivery of 0.5 to 3
when they are loaded into the test apparatus, may impact
mL/min. One is required, the second is optional for use where
performance significantly and must be considered in the
another reagent, such as ammonia, is to be added.
interpretation of the results. If the contaminant ions are
7.2.2 Circulating Pump, capable of delivery of 1 to 1.5
different from those in the challenge solution, they may be
L/min.
determined by ion chromatography.
7.2.3 Glass Column, nominal 25-mm ID 3 600 mm. The
column shown in Fig. 1 of Test Methods D 2187 may be
6.3 Aconstantvelocityintherangeof50–60gpm/ft isused
toinsurethatflowisturbulentandthereislittleornoresistance modified for this purpose.
to mass transfer from the bulk solution to the resin surfaces. 7.2.4 Mixing Chamber.
This constant velocity insures the desired testing of surface 7.2.5 Conductivity Meter With Recorder and Temperature
kinetics at the boundary layer. Compensation—See Test Method D 5391.
1. Water supply, ASTM Type I
2. Mixed bed polishing column
(Required for recirc mode)
3. Polished water reservoir
(Required for recirc mode)
4. Pump
(Required for recirc mode)
5. Conductivity meter
(Required for recirc mode)
6. Flow meter
7. and 8. Feed solution reservoir
9. and 10. Proportional metering pump
11. Mixing chamber or static mixer
12. Influent sample tap
13. Test column
14. Effluent sample tap
15. Conductivity meter
16. Conductivity meter
17. Cation column
NOTE—Recirculation of water is optional; final effluent also can be directed to drain.
FIG. 1 Test Apparatus for Kinetics
D6302–98 (2004)
7.2.6 Flow Meter—Capableofmeasuringflowsintherange mL/min into 1 L/min flow, the concentration in the influent
of about 1 L/min. should be 1.5 mg NH /L.
7.2.7 Cation Column, nominal 25-mm ID 3 600-mm col-
NOTE 2—Ammonium hydroxide generates irritating ammonia vapors.
umn, typically with a 15–45-cm depth of resin. This column
8.5.2 Sodium Sulfate Feed Solution (0.9 g Na SO /L)—Dry
2 4
should be prepared the day before testing to allow to rinse to
the Na SO for1hat 100–105°C, then store in a desiccator.
2 4
>17.5 MV (see 8.3).
Weigh 0.900 g of the anhydrous sodium sulfate, and dissolve it
NOTE 1—Pressure relief should be provided for this system to allow no
in 1 L of water. Mix well. When delivered at the rate of 0.5
more pressure than the materials can tolerate, typically 50 psig or less.
mL/min into 1 L/min flow, the concentration of the influent
should be 0.145 mg/L Na and 0.300 mg/L SO .
8. Reagents 4
8.6 Regenerant, Sodium Hydroxide Solution (87 g/L)—Add
8.1 Purity of Reagents—Reagents meeting the specifica-
345 g NaOH to 3.5 Lof water with stirring. Cool and dilute to
tionsoftheCommitteeonAnalyticalReagentsoftheAmerican
4.0 L. This solution is caustic and liberates heat during
Chemical Society may not be suitable for use in this practice.
dissolution. This is equivalent to 8 % NaOH by weight.
All reagents used should be of the highest grade commercially
available and should be tested for both anionic and cationic NOTE 3—This solution is intentionally stronger than typical field
processes so that maximum % regeneration is achieved.
impurities by ion chromatography after the feed solutions have
,
3 4
been prepared.
Reagent grade 50 % NaOH (763 g NaOH/L) also can be
8.2 Purity of Water—Unless otherwise indicated, references
used and would require 456 mL to make 4.0 L.
to water shall be understood to mean reagent water conforming
8.7 Regenerant, Hydrochloric Acid Solution (1 + 9)—
to Specification D 1193, Type I. It shall be checked by ion
Carefully pour 200 mLof hydrochloric acid (HCl, sp. gr. 1.19)
chromatography at the ppb level prior to use, if ion chroma-
into 1800 mL of water, stirring constantly. Cool to 256 5°C.
tography will be used for analysis.
NOTE 4—For field cation samples, sulfuric acid typically would be
8.3 Standard Cation Resin—New hydrogen-form, strong
substituted for HCl, since H SO is the usual regenerant in the field.
2 4
acid, cation resin is to be used; nuclear grade is preferred. Do
not regenerate this resin. This resin should be stored in
9. Sampling
impermeable containers at temperatures that do not exceed
9.1 Collect the sample in accordance with PracticesD 2687.
25°C.Backwashtheresinwithwaterat100 %expansionforat
It is extremely important that the resin sample properly
least 15 min. The resin should be rinsed thoroughly with water
represent the entire bed being evaluated. Core sampling is
to$ 17.5 MV resistivity before being used in a kinetics test.
required. A sample containing at least 300 mL of anion, or
The same cation resin may be used in the test column, as well
cation resin, or both, must be provided. The sample may be
as the cation column. It is recommended that a specific type
taken before or after separation of a mixed bed, so long as it is
and brand of resin be used consistently where results are to be
representative. Use a plastic or glass container with a water-
compared.
tight cap and label in accordance with Practices D 2687.
8.4 Standard Anion Resin—Use new, hydroxide-form,
9.2 Subsamples taken in the laboratory also must be taken
strong base anion resin; nuclear grade preferred. Follow other
by careful coring to preserve the representativeness of the
requirements as given in 8.3.
sample.
8.5 Test Solutions—Test solutions can be modified for
specific systems, however, the following are recommended for 10. Backwash and Separation Procedure
routine testing. Although a target feed injection rate of 0.5
10.1 Place about 800 mL of mixed bed resin sample or
mL/min is used here, the feed concentrations and metering
about 500 mL of individual resin sample in the backwash/
pump flows can be altered, so long as the test column influent
separation apparatus. Backwash with water at a flow sufficient
concentrations and flow rate are nominal as specified.
to give about 50 % bed expansion. This should allow crud to
8.5.1 Ammonia Feed Solution (3.0 g/L as NH ) Optional for
3 rinse away while separating any cation from the anion in the
Use with Ammoniated Systems—Tare a beaker with about 50
sample.
mL of water on an analytical balance with 0.01-g sensitivity.
10.2 Using a siphon or aspiration assembly, remove and
Add20.9gofconcentratedammoniumhydroxide(sp.gr.0.90)
collect the resin of interest, anion resin (above the interface) or
from a dropping bottle. Transfer to a 2-L volumetric flask, and
cation resin. Try to minimize cross-contamination by leaving
dilute to volume. Mix well. When delivered at the rate of 0.5
behind or wasting resin as needed. This, however, must be
minimized in order to avoid sample bias. Inspection of the
interfacewithahandlensmayshowabeadsizevariationatthe
interface. If less than 300 mL of the resin of interest is
Reagent Chemicals, American Chemical Society Specifications, American
recovered, repeat 10.1 with another portion of sample.
Chemical Society, Washington, DC. For suggestions on the testing of reagents not
listed by the American Chemical Society, see Analar Standards for Laboratory
10.3 Remove a small amount of the separated resin to a
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
plastic petri dish and examine under low power (12–15X)
and National Formulary, U.S. Pharmaceutical Convention, Inc. (USPC), Rockville,
magnification to estimate the percentage of whole beads. If the
MD.
resin is less than about 90 % whole beads, this practice should
McNulty J. T., Bevan C.A., et al., “Anion Exchange Resin Kinetic Testing:An
Indispensable Tool for Condensate Polisher Troubleshooting,” Proceedings of the
not be continued.
47th International Water Conference, Engineers’ Society of Western Pennsylvania,
October 1986. NOTE 5—Ion exchange kinetics are affected by particle size and shape.
D6302–98 (2004)
NOTE 6—Iftheresinispoorlymixedorcontainsairpockets,testresults
10.4 After decanting excess water, measure, by coring, 300
will be erroneous. If resin stratification or air bubbles can be seen in the
mL of the separated resin in a graduated cylinder under water.
column, remove the resin to the beaker, and repeat the mixing and transfer
Tap gently to settle before measuring resin. Disconnect the
steps.
regeneration column, and transfer the resin as a slurry to the
column. Keep a small amount of water above the resin and try
11.4 Fill the cation column to a depth of at least 15 cm with
to minimize air bubbles. Leave the bottom effluent line shut off
the new hydrogen-form cation resin (8.4), then reconnect it in
while filling the column. Open it and immediately begin the
the test apparatus. This column is not used if the sample tested
flow of regenerant. Regenerate the resin as follows. For anion,
is cation resin.
use NaOH regenerant solution at a flow rate of 25 mL/min for
11.5 Before connecting to the test apparatus, turn on the
60 min, maintaining a temperature of 50°C either by jacketing
water supply system and allow it to recirculate or flush to drain
thecolumnorwarmingtheregenerant.Forcationresin,usethe
untiltheconductivityindicatorreads0.06µS/cmorless.Adjust
HCl regenerant with the same conditions, except that ambient
the valves to allow flow to the test co
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