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Ion Exchange Notas
Ion Exchange Notas
Resin Types:
Strong Acid Cation Resin
Weak Acid Cation Resin
Strong Base Anion Resin Type I
Strong Base Anion Resin Type II
Weak Base Anion Resin
Weak Acid Cation Resin
Weak Acid Cation Resin is used as a single resin for dealkalization in the H cycle and for
brackish water softening in Na cycle. In demineralization, the use of a weak acid cation in front
of a strong cation is preferred with feed waters containing a high proportion of temporary
hardness (>40%) and low FMA. This configuration has advantages in terms of regeneration
efficiency and operating capacity.
With sulfuric acid regeneration, two separate cation columns should be used in order to allow
acid dilution at the weak acid resin inlet. For counter-flow regeneration, a double compartment
layered bed cation including a facility for acid dilution at the weak acid cation inlet can be used,
but is more complex to operate. Selected resins are DOWEX MAC-3 or DOWEX UPCORE
MAC-3 for UPCORE systems.
Strong Base Anion Resin Type I
Strong Base Anion Resin Type I as a single resin is particularly recommended for treating low
FMA (Free Mineral Acid) water with high silica and where low silica leakage is required (~20
ppb in counter-current operation). The resin can be regenerated up to 50C (122F) for more
effective silica removal. DOWEX MARATHON A resin is designed for general demineralization
and for UPCORE plants, the resins are DOWEX UPCORE Mono A-500 or DOWEX UPCORE
Mono A-625 resin.
Strong Base Anion Resin Type II
Strong Base Anion Resin Type II is well suited for small plants, owing to its excellent
regeneration efficiencies for water compositions where CO2 and SiO2 are < 30% of the total
feed anions. Type II anions have a much better operating capacity and regeneration efficiency
compared to Type I, but are limited to lower temperature operation (<35C/95F caustic
treatment) and have a higher SiO2 leakage (~50 ppb in counter-current operation). DOWEX
MARATHON A2 resin is the resin of choice for general demineralization and DOWEX
UPCORE Mono A2-500 for the UPCORE system.
Weak Base Anion Resin
Weak Base Anion Resin is used as a single resin to obtain partially deionized water without
removal of CO2 and SiO2. For complete demineralization, the combination of weak base and
strong base anion is an excellent choice for larger plants, as it provides optimum operation
costs. The weak base has very high regeneration efficiency and provides additional capacity to
the system. The weak and strong anion combination is well suited to treat waters with low
alkalinity or degassed feed, when the FMA (Cl + NO3 + SO4) is typically > 60% of the total
anions. DOWEX MARATHON WBA resin is the resin of choice for general demineralization.
Weak base anions are particularly effective in handling natural organics, which are usually high
molecular weight weakly acidic compounds that affect both weak base and strong base anion
resins. In a weak base - strong base anion configuration, some of the organics will pass
through the weak to the strong base. The design should therefore account for SBA organic
loading at the end of the cycle, as the resin will require additional NaOH to desorb the organics.
There are important differences in loading capacity or reversibility to organics between different
anion types.
For treating resins contaminated with silica or organics, see silica removal (20KB PDF)
and brine cleaning of anion resins for organic contamination (26KB PDF).
The weak and strong anion resins can either be designed in two separate vessels or for
counter-flow regeneration in one vessel with or without a separation nozzle plate. For
separated anions, DOWEX MARATHON WBA and DOWEX MARATHON A resins are
recommended. DOWEX MARATHON WBA and DOWEX MARATHON A LB are designed to
be used together as a layered bed in a single column without a nozzle plate. For UPCORE
plants, the resins are DOWEX UPCORE Mono WB-500 and DOWEX UPCORE Mono A500 or DOWEX UPCORE Mono A-625.
---------------------------------------------------------------------------------------------------------------------------------Let's consider for example a strongly acidic cation exchange resin (SAC) used for softening,
and let's assume the water to be treated has a hardness concentration of 4.4 meq/L and the
resin, under specific operating conditions, has an operating capacity of 1.1 eq/L, which is
1100 meq/L.
Each litre of ion exchange resin will thus be able to treat 1100 / 4.4 = 250 litres of the hard
water before having to be regenerated. In ion exchange jargon, this means that the
throughput is 250 bed volumes. If the water hardness is higher, the throughput will be less,
and vice-versa.
Floating beds
Backwashing
Although not an item for routine testing, specific gravity is an important parameter for
successful plant operation. It is critical for all processes involving mixing or separation of 2
or 3 resins in the same column, and for adjustment of resin backwash flow rate.
Measurement of the specific gravity is made with a pycnometre.
Note that specific gravity varies with the ionic form of the resin. The ionic composition of a
resin varies all the time during a cycle, so it is difficult to predict the exact specific gravity.
This is important to understand when backwashing a resin bed.
Here are some typical values:
Resin type Ionic form
WAC
H
WAC
Ca
SAC
H
SAC
Na
SAC
Ca
WBA
Free base
WBA
Cl
WBA
SO4
SBA
OH
SBA
Cl
SBA
SO4
Density range
1.16 to 1.19
1.28 to 1.34
1.18 to 1.22
1.26 to 1.32
1.28 to 1.33
1.02 to 1.05
1.05 to 1.09
1.08 to 1.13
1.06 to 1.09
1.07 to 1.10
1.10 to 1.14
Typical
1.18
1.32
1.20
1.28
1.31
1.04
1.06
1.11
1.07
1.08
1.12
SAC
resins
in
For softening, potassium chloride (KCl) can also be used when the presence of
sodium in the treated solution is undesirable.
For nitrate removal, the SBA resin can be regenerated with other compounds
providing chloride ions, such as hydrochloric acid (HCl).
For decationisation the first step of a demineralisation process SAC resins must
be regenerated with a strong acid. The most common acids are hydrochloric and
sulphuric acids.
o
Hydrochloric acid (HCl) is very efficient and does not cause precipitations in
the resin bed.
Sulphuric acid (H2SO4) is sometimes cheaper and easier to store and to handle
in general, but less efficient than hydrochloric acid: the operating capacity of
the SAC resin is lower. Additionally, its concentration must be carefully
adjusted to prevent calcium sulphate precipitation (see below). Once a
CaSO4 precipitate is formed, it is very difficult to remove from the resin bed.
Nitric acid (HNO3) can also be used in principle, but is not recommended as
it can cause exothermic reactions; explosions have been observed in some
cases, so that the use of nitric acid is considered dangerous.
For dealkalisation, the WAC resin is best regenerated with hydrochloric acid (HCl).
When using sulphuric acid, the concentration must be kept under 0.8 % to avoid
calcium sulphate precipitation. Other, weaker acids can also regenerate WAC resins,
such as acetic acid (CH3COOH) or citric acid, a molecule containing three COOH
groups: (CH2COOH-C(OH)COOH-CH2COOH = C6H8O7). Have a look at the 3-dimensional
formula.
SBA
resins
are
always
regenerated
with caustic
soda (NaOH)
the demineralisation process. Caustic potash (potassium hydroxide KOH) is
principle also applicable, but usually more expensive.
WBA resins are usually also regenerated with caustic soda, but other regenerants
weaker alkalis can also be used, such as:
o
Ammonia (NH3)
in
in
In general, WAC resins can be regenerated with an acid having a pKa lower than that of the
resin itself. The pKa value of most WAC resins is 4.4 to 4.8. Thus acetic acid (pK 4.8) can just
regenerate WAC resins, and citric acid (pK 3.1) is efficient for this purpose, whilst carbonic
acid (pK 6.4) is not. In most cases, however, HCl or H2SO4, usually cheaper, are used.
In general, WBA resins can be regenerated with an alkali having a pK a higher than that of the
resin itself. The pKa value of styrenic WBA resins is around 8.5, that of acrylic WBAs is around
9.5. Thus ammonia, with a pKaof 9.3, can regenerate styrenic WBA resins. In most cases,
however, NaOH is used, being often cheaper and easier to handle.
SAC and SBA resins can only be regenerated with strong acids or strong bases respectively.
The most usual concentrations are:
Concentrations
NaOH (demineralisation): 4 %
H2SO4: for SAC resins, the acid concentration must be carefully selected between 0.7
and 6 % as a function of the proportion of calcium in the feed water (which is the
same in the SAC resin). For WAC resins, the concentration is usually 0.7 %. Too high a
concentration
may
cause
calcium
sulphate
precipitation.
For SAC resins, stepwise concentrations are often used: after a first step at a low
concentration, a second step is carried out at a higher concentration once a great
part of the calcium on the resin has been eluted. In rare cases, three steps are used.
The steps at higher concentrations reduce the quantity of dilution water and increase
the sulphuric acid efficiency.
There are cases where different concentrations (often lower, rarely higher) must be
selected.
Regeneration steps
The general regeneration procedure for ion exchange vessels is as follows:
1. Backwash resin bed (co-flow regeneration only) to remove suspended solids and
decompact the bed.
2. Inject regenerant diluted in appropriate water quality. The injection is at a low flow
rate, so that the contact time is 20 to 40 minutes.
3. Displace the regenerant with dilution water at the same flow rate.
4. Rinse the bed at service flow rate with feed water until the desired treated water
quality is obtained.
The above is valid for most ion exchange columns, e.g. softening, nitrate removal, dealkalisation. For demineralisation, the cation column is regenerated first with acid, then the
anion column with caustic soda; alternatively, both are regenerated at the same time.
A short cycle length is desirable in most cases. The practical limit is that the production run
should be at least as long as the regeneration process. As most ion exchange systems are
regenerated automatically, the duration of the production run does not have to be "at least
one day" as was the rule at the time (many decades ago) when the morning shift would
regenerate manually every day at 7 o'clock. Efficient systems have been designed with
running times as short as 3 hours.
The limits of the running time are also related to resin kinetics. When reading ion exchange
resin product data sheets, you will typically see that the specific flow rate in water
treatment should be between 5 and 50 bed volumes per hour (m 3/h per m3 of resin). At lower
flow rates, hydraulic distribution in the resin bed may be poor, and at higher flow rates,
kinetic effects may affect the speed of exchange, resulting in both cases in deterioration of
the treated water quality.
So in practice the running time must be selected as a function of the following parameters:
Specific flow rate between 5 and 50 bed volumes per hour (BV/h).
Make the system as small as possible for economical reasons (lower investment in
hardware and resins).
For packed bed systems, ensure that bed compaction is good both in the production
phase (e.g. AmberpackTM) and during regeneration (e.g. UpcoreTM).
With low salinity waters, e.g. when the feed water is good RO permeate, the running time
can be several days. Mixed bed polishers after a primary demineralisation will run for several
weeks before regeneration is required.
9. The resin volume V required (in litres) is equal to the ionic load [eq] divided by the
operating capacity [eq/L]:
o
10. At the end of this calculation, we must make sure that the specific flow rate of both
resin columns is compatible with the general recommendations of the resin producer.
The specific flow rate in h1(often expressed in bed volumes per hour BV/h) is equal
to the flow rate in m3/h divided by the resin volume in m3. The usual range is 5 to 50
h1. For a compact plant with minimum investment cost, use a specific flow rate
around 30 to 35 h1.
If the specific flow rates calculated from the resin volumes Vc and Va are too high,
increase the running time t. If they are too low, reduce the running time t.
This calculation is obviously only approximate, as we have taken in point 8 an estimated
operating capacity for both resins, not taking into account several parameters that, in
reality, affect this capacity: regeneration level, exact water composition, temperature,
selected endpoint, etc.
Furthermore, the additional ionic load caused by the quantity of ancillary water required to
dilute regenerants and rinse resins has not been taken into account. Depending on the feed
water salinity, this extra water can increase the ionic load by 2 to 10 %.
Besides, the calculation of WAC/SAC or WBA/SBA resin couples cannot be done by hand, as it
requires
iterations
for
the
optimisation
of
the
"overrun".
TM
A precise calculation can be done with a dedicated software, such as IXCalc for the resins
produced by Dow.
Example
Cations
Ca
3.2
Cl
1.1
Mg
0.7
SO4
0.6
Na
0.9
NO3
0.2
HCO3
2.9
Anions
4.8
SiO2
0.4
Cations
4.8
2. Cc = 4.8 meq/L
3. HCO3 = 2.9 meq/L a degasifier is recommended
Residual CO2 after degasifier = 0.25 meq/L
4. Ca = 1.1 + 0.6 + 0.2 + 0.25 = 2.15 meq/L
5. Select runnning time t = 12 h
6. Flow rate 60 m3/h
Throughput 60 12 = 720 m3
7. Ionic load
8. Operating capacity
o
9. Resin volumes
o
The specific flow rate values are OK, but one could reduce the running time to say 8
hours to make the plant smaller. The new data would then be:
o
Throughput 60 8 = 480 m3