2/4/2020 Ion exchange regeneration methods

Regeneration methods
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for ion exchange units
Update
18 Oct 2019
Introduction
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Most ion exchange resins are used in columns. Ion exchange operation is
basically discontinuous: a loading phase, called service run, is followed by
Search page regeneration of the exhausted resins. There are two main methods for the
regeneration process:

Co-flow regeneration, where the fluids are flowing from the top to the
bottom of the column both during the service run as well as during
regeneration.
Reverse flow regeneration, where the fluids are flowing alternatively
upwards and downwards during service and regeneration.

We will also give information about MB regeneration, regenerant quantities

(regeneration ratio), thoroughfare regeneration, and regenerant types and
concentrations. Separate pages give information about the water quality
required for regeneration, and regenerant neutralisation.

See also the pages about capacity, ion exchange columns, description of a
full cycle, and principles of plant design.

Co-flow regeneration (CFR)

This regeneration technique has been used used at the beginning of ion
exchange: the solution to treat flows from the top to the bottom of the
column, and the regenerant uses the same path.

The problem is that strongly acidic and strongly basic resins are not
completely converted to the H or OH form at the end of the regeneration,
because this would require too large an excess of chemical regenerant. As a
result, the bottom layers of the resin bed are more contaminated than the
top layers at the end of regeneration, so that when the next loading run
begins the leakage is high due to the displacement of the contaminating ions
by the H+ (or OH—) ions produced in the exchange.

Top
The dark zone in the picture above
represents the proportion of
exhausted resin, the yellow zone
the proportion of regenerated
resin. The small picture on the
right explains what I mean: for
instance, at level A, the resin is

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50% exhausted and 50% regenerated. Above the exchange zone, the resin is
fully exhausted, and below it is fullly regenerated.

With co-flow regeneration, the only way to reduce this permanent leakage is
to increase the quantity of regenerant so as to leave less contaminating ions
at the outlet of the column.

Reverse flow regeneration (RFR)

This is also called "counterflow regeneraton". In the past, it was called
counter-current regeneration, but the term is not strictly correct as the resin
bed does not move. With reverse flow regeneration the regenerant is
injected in the opposite direction of the service flow. There are two sub-
cases:

1. Upflow loading and downflow regeneration, as in the floating bed and

AmberpackTM processes.
2. Downflow loading and upflow regeneration, as in the UFDTM and
UpcoreTM processes.

In this case, the regenerant doesn't have to push the contaminating ions
through the whole resin bed. The layers which are less exhausted will be
regenerated first and will be the cleanest when the next loading run
(exhaustion) starts.

Or with upflow loading:

Reverse flow regeneration offers two significant advantages: Top

1. The treated water has a much higher purity than with co-flow, due to
a very low leakage.
2. Less regenerant is required, as the contaminating ions don't have to be
pushed through the whole bed, and the leakage is almost independent
of the regenerant dosage.

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Treated water quality

At the end of regeneration, the exit layer of the column regenerated in CFR
has the highest concentration of impurities, whereas in RFR the exit layer
contains the most highly regenerated resin. This is why in CFR the
contaminants at the bottom find their way into the treated water, more at
the beginning than in the middle of the run, due to a "self regeneration"
effect, whereas in RFR any displaced contaminant from the inlet layer gets
immediately removed from a layer underneath.

The graph shows the typical leakage profile during the loading phase (e.g.
conductivity in µS/cm but it can be any other leakage depending on the
process). The ionic leakage obtained with reverse flow regeneration is
usually so low, that it does not depend on the amount of regenerant used.
With co-flow, low leakage values are obtained only with high regenerant
dosage.

No backwash with RFR

The whole effect of reverse flow regeneration relies on undisturbed resin
layers. The resin with the highest degree of regeneration should always be at
the column outlet. Therefore, the resin bed should not be backwashed
before regeneration, and should not be allowed to fluidise at any time. So
either the columns are completely filled with resin (packed beds) or the bed
is held down during regeneration. See the "column design" page for the
concepts of holddown and packed beds.

Regeneration steps
The general regeneration procedure for ion echange 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. Top
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, de-alkalisation. 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.

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Additional steps may be required in some special applications (see below).

Mixed bed regeneration

Internal regeneration of a mixed bed
unit is more complicated. The steps
are:

1. Backwash resin bed to separate

the cation from the anion resin.
2. Let the resins settle.
3. Optionally: drain the water
down to the resin bed surface.
4. Inject caustic soda diluted in
demineralised water.
5. Displace the caustic with
dilution water.
6. Inject acid diluted in
demineralised water.
7. Displace the acid with dilution
water.
8. Drain the water down to the resin bed surface.
9. Mix the resins with clean compressed air or nitrogen.
10. Refill the unit slowly with water.
11. Do the final rinse with feed water at service flow rate until the desired
treated water quality is obtained.

Note 1: If no NaOH distributor is available, caustic "rains" from the top of the
column down to the water level. This creates some dilution and the
distribution is not as even as with a dedicated distributor.
Note 2: Cation and anion resin can be regenerated simultaneously to save
time. Otherwise, always start with the anion resin.
Note 3: In condensate polishing, mixed bed units are usually regenerated
externally.
Note 4: The regenerant level for mixed bed units is higher than that of
separate columns, because regeneration efficiency is lower. Recommended
values:

HCl: 80 - 120 g (@ 100 %) per litre of cation exchange resin

H2SO4: 100 - 160 g (@ 100 %) per litre of cation exchange resin
NaOH: 80 - 140 g (@ 100 %) per litre of anion exchange resin

Regeneration efficiency

The three pictures on the left show the conversion of totally exhausted resins
(in the Na+ or Cl— form), as a function of regenerant dosage. The y axis
"% Regeneration" represents the percentage of conversion of the resins to the
H+ and OH— form respectively. We can observe the following things:

1. Hydrochloric acid is more efficient than sulphuric acid to regenerate a

strongly acidic cation exchange resin (SAC) initially in the Na+ form.
With 50 g HCl per litre of resin, a conversion of 60 % to the H+ form is
achieved. Top
With 50 g H2SO4, a conversion of only 40 % is achieved.
2. Even expressed as equivalents, hydrochloric acid is more efficient:
36.5 g HCl (1  eq) will convert the resin to 45  %, whereas 49  g H2SO4
(1 eq) convert only 39 %.
3. To obtain total conversion, i.e. 100  % in the H+ form, we need about
6.5 eq HCl (240 g/L) but 8 eq H2SO4 (400 g/L).

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4. This is due to
the fact that
the second
acidity of
sulphuric acid
is
considerably
weaker than
the first
acidity.
5. Regeneration
of a strongly
basic anion
exchange
resin (SBA)
initially in the
Cl— form with
caustic soda is
more
difficult:
With 50 g
NaOH per
litre, only
37  % of the
resin are
converted;
with 40  g
(1  eq) only
32 %.
As much as
37.5 eq NaOH
(1500  g) are
required to
convert the
SBA resin to
about 100 % in
OH— form.
6. The reason
why SBA
resins of type
1 are more
difficult to
regenerate
than SAC
resins is the
selectivity
coefficient:
K(Cl/OH) = 22
whilst K(Na/H) =
1.7.

In practice, SAC and SBA resins are not regenerated to a high conversion
level, which would be uneconomical in view of the high regenerant
consumption.

On the other hand, weakly functional resins (WAC and WBA) have a near-
linear regeneration curve: the can be regenerated with a dosage close to the Top
stoichiometric value, so they are fully converted (see below) at the end of
each regeneration.

Note: all regenerant values are expressed as grams of pure chemical (100 %)
per litre of resin.

Regeneration ratio
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Definition:

Introduction

The regeneration ratio — also called stoichiometric ratio or regenerant

ratio — is calculated as the total amount of regenerant (in equivalents)
divided by the total ionic load (also in equivalents) during one cycle.
It is is also equal to the number of eq/L regenerant per eq/L of resin
operating capacity.
A (theoretical) regenerant ratio of 1.00 (i.e. 100 %) would correspond
to the stoichiometric quantity.
All resins need a certain excess of regenerant above the stoichiometric
quantity.

Example

Amberjet 1000
regenerated with 55 g HCl per litre
operating capacity : 1.20 eq/L
55 g/L HCl = 55/36.5 = 1.507 eq/L
Regenerant ratio = 1.507/1.20 = 1.26 = 126 %

Excess

The difference between ionic load and regenerant quantity is called excess
regenerant.

Excess [in eq]= regenerant [eq] - ionic load [eq]

Excess [in %] = 100 x (regenerant ratio – 1)

Minimum values

WAC resins require just above the stoichiometric quantity. A safe

number is 105 to 110 %.
WBA resins require 115 to 140  %, because most of them they have
some strongly basic functional groups.
When regenerated with ammonia or sodium carbonate, WBA resins
require a regenerant ratio of 150 to 200 %. These regenerants can be
used for WBA only, not for SBA resins.
SAC and SBA resins require a larger excess than their weak
counterparts.
Co-flow regenerated SAC and SBA resins require more than those
regenerated in reverse flow.
SAC resins regenerated in reverse flow with hydrochloric acid need an
absolute minimum of 110 % regeneration, but a safer value is 120 %. If
the water contains high hardness or low alkalinity, the minimum value
must be increased.
SAC resins regenerated with sulphuric acid require a larger excess than
those regenerated with HCl. At least 40 % more.
Top
For SBA resins, there is no easy way to estimate a minimum, as it
depends on the type of SBA resin (styrenic type 1 vs type 2 or acrylic
resins).
Important note: when calculating the regenerant ratio for SBA resins,
one must take 2 equivalents of NaOH for each equivalent of CO2 or
SiO2.

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WAC/SAC couples can be regenerated with a global ratio of about

105 %.
WBA/SBA couples can be regenerated with a global ratio of 110 to
120 %. More is required if the silica level is high in the feed water.
The regenerant ratio for silica should be at least 800 %. This should be
calculated separately as the quantity of NaOH (in eq) divided by the
load of silica (in eq) during one cycle. One equivalent of silica is taken
as 60 g as SiO2.

Thoroughfare regeneration
When a weak and a strong resin are used in series, the following two rules
must apply:

1. The feed water must pass first through the weak, then only through
the strong resin.
2. The regenerant must pass first through the strong, then through the
weak resin.

Separate columns in service Separate columns in regeneration

Why is it so?

1. The weak resin has a high capacity and good regeneration efficiency,
but does not remove all ions. Therefore it must be placed first, and
the strong resin will be used to remove whatever the weak resin has
not removed, albeit with a lower efficiency.
2. The strong resin requires a high excess of regenerant. The weak resin
requires almost no excess. Therefore the regenerant passes through
the strong resin first, and the weak resin is regenerated with the
excess regenerant coming out of the strong resin.

The above pictures are for old-fashioned, separate columns with co-flow
regeneration. Below the same for an Amberpack double compartment
column.

Amberpack in service Amberpack in regeneration

Top

All the above applies equally to a couple of weak acid and strong acid cation
exchange resins.

Regenerant types and concentrations

T f
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Types of regenerant

Sodium chloride (NaCl) is normally used to regenerate SAC resins in the

softening process, and SBA resins used for nitrate removal.
For softening, potassium chloride (KCl) can also be used when the
presence of sodium in the treated solution is undesirable.
In some hot condensate softening processes, ammonium chloride
(NH4Cl) can be used.
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.
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. If you intend to use nitric acid, contact
me: I will provide more details.
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) in the
demineralisation process. Caustic potash (potassium hydroxide KOH) is
in 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:
Ammonia (NH3)
Sodium carbonate (soda ash, Na2CO3)
A lime (calcium hydroxide, Ca(OH)2) suspension

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 pKa 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 pKa of 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. Top

Concentrations

The most usual concentrations are:

NaCl (softening and nitrate removal): 10 %

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HCl (decationisation, de-alkalisation and demineralisation): 5 %

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.

Quality of water for regeneration

The required water quality for each regeneration step is shown in a separate
page.

Neutralisation of the regenerants

See another page on the way to neutralise regenerants and increase ion
exchange capacity.

Special applications

Sweetening-off and -on

In several applications other than water treatment, the solution treated by

resins must be displaced before regeneration, to recover as much treated
solution as possible, avoiding losses in the regeneration waste. This
additional step is called "sweetening off" because it was first introduced in
sugar treatment processes. Similarly, a "sweetening on" step is carried out
after regeneration and rinse before feeding the raw solution to be treated,
to avoid dilution of the treated solution. The complete regeneration process
consists then of the following steps:

1. Backwash with the raw solution (optional)

2. Sweetening off: displacement of the solution with water
3. Regenerant injection
4. Displacement of the regenerant with water
5. Fast rinse with water
6. Sweetening on with the solution to be treated

The sweetening-off fraction is sometimes recycled, particularly when the

solution contains valuable components (precious metals, expensive chemical
compounds).

When the solution has a high density, which can be higher than the resin, the
service run — which often takes place at a low flow rate — can be carried out Top
upflow to pack the resin bed and thus avoid its floating and fluidisation. This
procedure is often used in the treatment of sugar solutions.

Merry-go-round

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To increase the concentration of the eluate and the operating capacity of the
resin, a system consisting
of at least three columns
can be used, where two
columns are in service, in
series, and the third in
regeneration, as shown in
the picture on the left.
The "lead" column is
exhausted past its
leakage breakthrough,
whilst the "lag" column
acts as a polisher and
guarantees a low leakage
in the treated solution.

When the eluate contains

a valuable compound
removed on the resin,
this compound is eluted
at a higher concentration
than with a single
column.

© François de Dardel

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