Lenntech

info@lenntech.com Tel. +31-152-610-900

www.lenntech.com Fax. +31-152-616-289

1
Table of contents

1. INTRODUCTION....................................................................................................................... 3
1.1. Metals, water and ion exchangers ........................................................................................................ 3
1.2. Metal processing industry ..................................................................................................................... 5
1.3. What are ion exchangers? .................................................................................................................... 6
1.4. Ideal products and processes ............................................................................................................... 8

2. RAW WATER TREATMENT..................................................................................................... 9

3. TREATMENT OF PROCESS BATHS .................................................................................... 12

3.1. Regeneration of acidic process solutions ........................................................................................... 14
3.2. Recycling of chrome baths.................................................................................................................. 14
3.3. Recycling of sulfuric acid .................................................................................................................... 14

4. RECYCLING OF RINSE WATER ........................................................................................... 16

5. TREATMENT OF WASTEWATER ......................................................................................... 19

6. OUTLOOK .............................................................................................................................. 22

7. CONTACTS ............................................................................................................................ 22

2
1. INTRODUCTION
Ion exchangers are versatile filter materials
used for adjusting the quality of water and of
1.1. METALS, WATER AND ION aqueous solutions.
EXCHANGERS

This brochure is all about three things:

metals, water and ion exchangers. What do these
three have in common?

Figure 1.1.: Metals are fascinating materials because of their

versatile properties. Figure 1.3.: Ion exchangers are materials used for purifying
water and aqueous solutions and for keeping them clean.
Metals are sought-after construction
materials with special properties that are used in
more than half of all industrially manufactured This makes ion exchangers valuable tools to
products. the metal processing industry that fulfills the
following functions:
Good quality water is of paramount
importance when it comes to producing, processing Ensure the quality of semi-finished and
and working metals. finished products
Save resources, such as water, energy and
raw materials
Reduce wear and tear to technical
installations and tools
Eliminate toxic substances and ensure on-
the-job safety and protection of the
environment

Figure 1.2.: When it comes to producing, processing and

working metals, good quality water is of paramount
importance.

3
 Lewatit ion exchangers are available in
more than 150 different product qualities and with
various properties that are tailored to the type of
application.
Figure 1.4.: Lewatit ion exchangers as bagged goods at the
warehouse of the production plant in Bitterfeld (Germany).
LANXESS has more than 70 years of
experience with the production and application of ion
exchange materials.
The Lewatit brand stands for innovative
filtration media and, at the same time, also for
innovative and highly efficient technologies, such as
the fluidized bed or multistep process.
LANXESS is investing globally in new
production facilities for ion exchangers and other
products that are key to water treatment.
Figure 1.5.: The most state-of-the-art production facility for
monodisperse ion exchangers in the world can be found in
Bitterfeld. It was commissioned in 1999.
4
Numerous plants in the metal processing
industry have been relying on Lewatit ion
exchangers for decades and are using them to:
1. turn untreated water into quality water
that can be used for production
2. maintain and recycle water-based
process solutions
3. recycle rinse water and possibly recover
precious metals
4. purify wastewater before it is discharged
into the environment (final exchange
principle) and here too to possibly
recover precious metals
In this brochure, the listed options are
discussed in the above order. Reading this brochure
will give you an idea of the manifold application
fields of polymer adsorbent materials.
Figure 1.6.: Reaction container for the functionalization of ion
exchange beads in Bitterfeld.
Keep metals and the environment at its best
by using Lewatit-filtered water and process
solutions!
1.2. METAL PROCESSING
INDUSTRY

The metal processing and metal refining

industry includes many different trade groups. One
major group is the so-called electroplating branch,
which takes on commission orders e.g. by the
automotive industry to coat mainly small-type semi- Jewelry industry, coinage facilities, mirror
finished products. There are more than 4,000 such manufactories
businesses in Germany alone.

But the metal processing industry group Production of precision products, such as
does not only encompass these types of clocks, precision instruments, model railways,
subcontractors. In general, it can be said that all music instruments, optical devices etc.
production areas are of relevance that process
metals that are used for producing goods. The
following list provides an overview:

Production of semi-finished products, such

as screws, nails, wires, cables, pipes, steel
springs, sectional strips, ball bearings, axles
etc.
Construction of any type of vehicles

Production of electronic components, such

as conductor plates, computer chips, solar Production of fixtures, hinges, locks, handles,
cells and other electronic components mountings etc.

Production of construction elements for the

Production of tools, household appliances,
construction industry
machines and other commodities
and much more!

5
1.3. WHAT ARE ION EXCHANGERS?
selectivity). On the other hand, you can also see
Ion exchangers consist of superfine synthetic concentration effects: the higher the concentration in
beads with a diameter of 0.3 to 1.2 mm. They are the solution, the more readily will a weaker binding
added in bulk to filter devices. If mixed with an ion sort displace a stronger binding species ( law
aqueous suspension, they can be easily filled into of mass action).
the filter device or rinsed out, if desired.
polymer-
backbone functional
group

+ +

Figure 1.9.: The so-called ion exchange reaction at the

functional groups fixed in the pores is the basis of all filtration
processes described in the present brochure. Interaction
between exchanged particles and functional group takes
place via electrostatic forces.

After saturation of the ion exchanger with the

filtered-out impurities, the filters can be chemically
regenerated on site, so that they can be reused. The
concentrates can then be used for recovering
materials or they can be disposed of in a cost-
efficient and environmentally friendly manner.
Figure 1.7.: Ion exchangers are filled into filter devices in
bulk. Filtration takes place in the filter bed. Charge

The capability to filter out material from

aqueous solutions is based on so-called functional
groups that rest on the surface of fine pores that
homogenously run through the polymer beads,
reaching their innermost depths.

Regenerate Rinse

Figure 1.8.: View of the inside of an ion exchange bead: it is

permeated with fine pores that are filled with water. This way,
material that is dissolved in the water can diffuse in and out.

Material contained in water can penetrate the Figure 1.10.: Charging of an ion exchange filter bed, removal
beads through their pores. Likewise, material stored of the charge with a regenerant solution and rinse-out of the
in the resin can diffuse out of the beads and can be regenerant solution. After that, the filter is ready to be used
again.
released to the surrounding medium. If particles are
absorbed and dispensed at the same time, we speak
of an exchange. Preferably, charged particles so-
called ions are exchanged. Exchange at the
functional groups follows two driving forces: on the
one hand, different ion sorts have different binding
capabilities, i.e. stronger binding ions displace the
weaker binding ones (chemical driving force =

6
 Ion-exchange active filter materials differ SO3 Na
mainly in terms of the following properties: strongly acidic IAT (SAC)
(e.g. Lewatit SP 112)

Type of functional group CO2 H

weakly acidic IAT (WAC)
Monomer basis of the polymer structure (e.g. Lewatit CNP 80)

CH2 - N(CH3)2H Cl
Degree of cross-linking of the polymer
weakly basic IAT (WBA)
(e.g. Lewatit MP 62)
Gel-type or macro-porous structure of the CH2-N(CH3)2HCl
polymer
CH2-N(CH3)3Cl

Particle size distribution medium basic IAT

(e.g. Lewatit MonoPlus MP 64 WS)

Monodispersity or heterodispersity Tabelle 1.1, S.6

CH2 - N(CH3)3 Cl
Average grain size strongly basic IX type 1 (SBA1)
(e.g. Lewatit K 6362)
Fines
CH2 - N(CH3)2CH2-CH2-OH Cl
Charged form of the functional group strongly basic IX type 2 (SBA2)
(e.g. Lewatit K 6363)

Materials chemical purity CH2 - N(CH2-CH2-CH3)3Cl

strongly basic IX type 3

The type of functional group is the most (e.g. Lewatit Monoplus SR 7)
important distinctive criterion and it determines, in CH2-CO-O
-CO-O-Na
-Na
essence, the chemical properties of the exchanger CH2 - N
CH2-CO-O-Na
material. I.e., it defines what chemical substances IDA-chelating resin
(e.g. Lewatit MonoPlus TP 207)
can be preferably eliminated and with what water
O
composition this will be achieved.
CH2-P-O-Na
CH2 - N O-Na
Table 1.1. provides an overview of the H
various functional groups and states important AMPA-chelating resin
(e.g. Lewatit MonoPlus TP 260)
pertinent products from the Lewatit portfolio. SH
C=NH
What is important to know are the following CH2 - N ...
conventional names of ion exchangers and certain H
thiurea chelating resin
resin types: (e.g. Lewatit Monoplus TP 214)

IX: Ion Exchange Resin CH3 OH H OH OH

CH2-N -CH2- C - C - C - CH2OH
SAC: Strongly Acidic Cation Exchanger Methylglucamine IX
H OH H H
(e.g. Lewatit MK 51)

WAC: Weakly Acidic Cation Exchanger CH2 - N(CH3)2 FeO(OH)

hybrid adsorber
SBA: Strongly Basic Anion Exchanger (e.g. Lewatit FO36)
CH3 -CH2
WBA: Weakly Basic Anion Exchanger CH3-CH2-CH2-CH2-CH2-CH2-O
P
O
CH3-CH2-CH2-CH2-CH2-CH2-O OH
CR: Chelating Resin CH3 -CH2
Levextrel resin D2EHPA-saturated
(Lewatit OC 1026)
AR: Adsorber Resin
adsorber resin
(e.g. Lewatit VP OC 1064 PH)

Table 1.1.: Various functional groups of Lewatit ion

exchangers.

7
1.4. IDEAL PRODUCTS AND
PROCESSES
The performance of ion-exchange active
filters can be rated based on the following criteria:
1. Duration of the filtration cycle until next
regeneration
2. Consumption of regeneration chemicals and
rinse water per volume of purified water
3. Slip of substances running through the filter
unhindered
4. Release of impurities by the exchanger
material
5. Mechanical and osmotic stability
6. Lifetime of the resin until it has to be
exchanged
Premium products of the Lewatit brand have
been optimized in terms of the aforementioned
characteristics. Our customers can always expect
the best when it comes to these criteria.
At this point it must also be pointed out,
however, that performance does not only depend on
the filter materials quality but also on the concept of
the overall facility, its mode of operation and on
structural features of the filter device:
The aforementioned criteria are not the
responsibility of the resin producer. Therefore, it is
important to select an as qualified as possible
manufacturer to build your plant.
LANXESS will name qualified plant
manufacturers upon request.
Ion exchangers will show the following
advantages under suitable process conditions:
Small, compact systems that can be easily
automated and require little monitoring
Robust filter material that, depending on
utilization, will last up to ten years
Relatively low investment costs for the filter
bed
High competitiveness compared to other
technologies
Easy to maintain and clean if soiled
Easy to replace in case of damage
Use of selective exchangers allows for highly
efficient procedures and the possibility to
recover material

Most often, ion exchangers are aggregates

that work in combination with other treatments, e.g.
with prior deferrization or heavy metal precipitation.
Therefore, the mode of operation must be adjusted
accordingly.

What is also very important is proper water

management: the water that is fed into the ion
exchanger must be specified. Partial flows must not
be added randomly.

In order to ensure longevity of the ion

exchanger it needs to be maintained on a recurring
basis: e.g., the filter bed must be backwashed in
ascending flow on a regular basis in order to wash
out impurities and resin breakage and to loosen the
bed and even it out. Figure 1.11.: Water softening system using ion exchange
technology.
When constructing filter devices, one of the
most important things is to achieve optimum
distribution of the liquid above and within the resin
bed.

8
2. RAW WATER TREATMENT

Water is used for different purposes in
production:
Feeding of cooling water circuits
Rinsing of work pieces
Preparing and diluting solutions
Vapor generation
Operating sanitary facilities
Preparing drinking water for own staff
When selecting the suitable method or a
combination of methods, economic aspects play an
important role (investment and operating costs), but
practical aspects, such as logistics, user friendliness,
availability, reliability and space requirements are
also taken into consideration.
Raw Water

Different requirements on the quality of water are

made depending on the process, selection of device
types, and treated or produced products. These
quality requirements include the following:
Water
Treatment
Hardness (permanent, temporary,
overall hardness )
Iron and manganese content
Salinity as indicated by conductivity or
electrical resistance
Suspended matter content (TS)
Corrosiveness
pH level
Process Process
Dissolved gases (for example CO2, O2 ...)
Water Water
Dissolved organic matter (TOC, DOC)
Quality A Quality C
Odor and possibly taste
Sterility Process
and others Water
Quality B
Raw water may originate from the most various
sources, including the following:

Public supply network

Own well
Withdrawal from a body of surface water
Rainwater
Condensates Production
Wastewater of a neighboring production
Figure 2.1.: Normally, production will require water of various
plant that shows only minor contamination qualities, which is produced with the help of separate
processing lines.
Different treatment methods must be applied
depending on the quality of the raw water and the Ion exchangers are used mainly in three
required quality of the water used in production, areas when turning raw water into high-quality
including the following: production water:

Coagulation/precipitation Water softening

Wet oxidation Partial or complete desalination
Gas stripping Ultra desalination
Sedimentation
Sand filtration The following plays a minor role:
Ion exchange
Membrane filtration Deferrization and demanganization
Activated carbon filtration TOC removal

9
 Water softening is aimed at removing the
minerals that cause hardness, such as calcium,
magnesium and carbonate. There are two different
water softening methods that use ion exchangers:
During so-called decarbonization with weakly
acidic cation exchangers (e.g. Lewatit CNP 80 WS)
in H form, calcium and magnesium are bound. The
released H+ unites with carbonates and releases
carbonic acid. By eliminating calcium, magnesium
and the associated bicarbonate you will achieve
partial desalination. Regeneration takes place using
acid.
During water softening with strongly acidic
cation exchangers (e.g. Lewatit MonoPlus S 1567
or Lewatit C 249), the resin is used in sodium form.
Hardness is eliminated in exchange with sodium
ions. This keeps the salt level in the water at a
constant level. Regeneration takes place using a
concentrated NaCl solution.
For complete desalination, series-connected
cation exchangers and anion exchangers are used.
The cation exchanger removes all cations and
replaces them with protons (H+). The anion
exchanger then removes all anions and replaces
them with (OH-).
air, CO2
K+, A-
WAC
Salt
containing
rinse water
SAC
H+, A-
Figure 2.2.: Flowchart of a more complex complete desalination system with cation-exchanger column as a WAC/SAC
composite bed, gas washer, anion-exchanger column with a WBA/SBA composite bed and mixed bed for achieving
ultrapure water qualities with a resistance value of up to 18 M.
10
Because of the reaction between the
released ions H+ and OH- under formation of water
(H+ + OH- H2O), the discharge of the filter system
is almost free of charged particles and hence called
demineralized water. This way, residual water
conductivities of less than 1 S/cm can be easily
achieved.
Through the combined use of strongly and
weakly acidic or rather strongly and weakly basic
resins as a composite, investment costs and the cost
of regenerants can be reduced ( so-called
composite beds). CO2 stripping after the cation
exchanger stage also shows advantages, as it saves
the anion exchanger capacities for the absorption of
carbonate (see also figure 2.2.).
Regeneration of the acidic resins takes place
with acid and regeneration of the basic resins with
leach.
H+, A-
< 1 S/cm R > 18 M
WBA Fully
desalinated
H+ + OH- ->
water
H2O
SBA
MB
Luft
 If the water is to be desalinated even more to
achieve even lower conductivities, so-called mixed
bed filters (e.g. Lewatit MonoPlus S 108 H /
MonoPlus M 500 MB) are installed downstream of
the conventional complete desalination system. This
way, it is possible to achieve ultrapure water (UPW)
qualities of up to 18 M in specific electrical
resistance.
Figure 2.4.: The purity of water is shown by indicating the
If not by conventional means, iron and specific conductivity or rather the specific electrical resistance.
manganese can be removed from raw water For applications in the area of microelectronics, ultrapure
(deferrization/demanganization) through adsorption water qualities of up to 18 M in specific electrical resistance
to a strongly acidic resin through exchange against are required.
sodium.

Organic matter measured as TOC or rather

DOC can be mainly found where surface water is Products for
used as a source of raw water. Organic matter raw water treatment
originates mainly from natural sources and belongs
to the group of humins, building blocks and fulvic Softening, decarbonization
acids, among others. Since these substances are Lewatit CNP 80
mainly of an anionic nature, they can be adsorbed to Lewatit MonoPlus S 100
a great extent, at strongly or weakly basic resins. Lewatit MonoPlus SP 112
Lewatit MonoPlus S 108
Regeneration takes place using neutral or alkaline Lewatit C 249
brines. Lewatit S 1667
Ion exchangers used for removing the TOC /
DOC are usually installed upstream of the Cation exchange
desalination system to protect it against organic
Lewatit C 267
impurities. Therefore, they are also called Lewatit MonoPlus SP 112
scavengers. Lewatit MonoPlus S 108

Anion exchange
Lewatit MP 64
Lewatit MP 62 WS
Lewatit MonoPlus MP 68
Lewatit MonoPlus MP 500
Lewatit MonoPlus M 500
Lewatit MonoPlus M 800

Mixed beds
Lewatit NM 60
Lewatit NM 91
Lewatit UltraPure 1292 MD

Deferrization, demanganization
Lewatit MonoPlus SP 112

TOC scavenger
Lewatit MonoPlus MP 64
Lewatit MonoPlus MP 62 WS
Lewatit S 6268
Lewatit 6328 A
Lewatit A 8071

Figure 2.3.: Complete desalination system with cation

exchanger, CO2 stripper and anion exchanger.

11
3. TREATMENT OF PROCESS
BATHS
One of the main application areas of
electrochemical coating of metal surfaces is
corrosion prevention. Apart from that, hardness,
wear resistance, aging and temperature resistance
as well as decoration also play an important role.
Figure 3.1.: Various aqueous-based metallic salt solutions
(electrolytes) are used for treating surfaces.
The necessary electrolyte a process
stream in terms of this brochure is a liquid stream
containing a relatively highly concentrated active
agent that is dissolved in water. This active agent is
then reacted against a metallic surface or against a
surface consisting of another material. In addition to
that, materials can also be prepped for a further
process step by using other process baths. In that
case, the process stream acts as a reactant in a
chemical reaction. Examples include the following:
Etching of surfaces with an acid or brine (e.g.
electropassivation of aluminum in sulfuric
acid baths or derusting / slight etching of
steel surfaces in hydrochloric acid)
Creating fine structures through etching (e.g.
during production of conductor plates, in
micromechanics and other areas)
Chemical passivation of surfaces with brines
(e.g. chemical nickel, phosphating )
12
Electrochemical coating of surfaces (e.g.
chromizing, galvanizing, nickel coating etc.)
Chemical and mechanical polishing (CMP) of
silicon wafers
In all these cases, the process solution will
change over time. The active agent will be partially
consumed and at the same time byproducts or
rather impurities will build up in the process bath.
The consumed portion of the active agents can be
replenished. This way, for example a pickling acid
can be regenerated by adding concentrated acid.
Likewise, the zinc that is consumed during the
plating of steel can be topped up by adding
chemicals. Nevertheless, byproducts and impurities
will increasingly build up in the bath.
a) Electrochemical b) Chemical
metal separation metal separation
+ - Red
e -
e- Red
Red e-
Me2+
Me2+ Me2+
Me0 Me0
Me0
Figure 3.2.: Electrochemical and chemical coating of
surfaces. In the left-hand image the metal is reduced from the
circuit through electrodes and in the right-hand image through
a chemical reducing agent. The reduced metal deposits on
the surface.
The higher the concentration, the more
easily can these impurities impair the surface
treatment result. This lesser quality shows in form of
discolorations, stains or reduced corrosion protection.
 A) Complete
disposal after
consumption

Me2+
W N

if Me2+, N
exceed the
limit

W, N, Me2+

Figure 3.3.: A brand new galvanizing system just after its

installation (with the friendly permission of Gerhard Weber
Kunststoff-Verarbeitung GmbH, Minden)

So, in the past it was often common practice Waste disposal

to completely dispose of the process baths after a
certain time, which led to the following
consequences: B) Continuous
recycling
The active agent contained in the process
bath (acid, metallic salt, reagent) was lost for
good and had to be completely replaced. W

A relatively large volume of process solution

had to be treated at once in a relatively
large-scale wastewater treatment facility.

This led to a relatively large amount of

Me2+
secondary waste (e.g. heavy metal sludge,
W N
salt) that had to be further disposed of.

Thanks to the ion exchanger technology, it is W, N, Me2+ W

now possible in some cases to selectively remove
the byproducts and impurities from the bath while Recycling filter
experiencing only a very minor loss in active agents.
The following provides some examples of how this
technology works: N, Me2+

Alternatives A) Complete disposal and B)

Recycling of the electrolyte solution are further Waste disposal
explained in figure 3.4.
Figure 3.4.: When using process baths, active agent (W) is
consumed and replenished accordingly. At the same time,
byproducts (N) and metal (e.g. Me2+) build up. Me2+ is formed
by corrosion of the working piece. If the critical concentration
of N and Me2+ is exceeded, the bath can no longer be used. It
then has to be disposed of (case A) or recycled (case B).

13
3.1. REGENERATION OF ACIDIC
PROCESS SOLUTIONS
Unless acidic process solutions show high
concentrations in hydrogen ions, cationic impurities,
such as Fe2+, Zn2+, Al3+ etc. that have built up can be
removed with the help of strongly acidic cation
exchangers in H form. If such a process bath is
continuously run over an ion exchanger, impurities
can be kept at a tolerable concentration level, which
will considerably prolong the baths lifetime.
The relevant exchange reaction will effect a
true regeneration, since the take-up of foreign
metals will at the same time release an equivalent in
hydrogen ions into the solution.
One example of how the lifetime of an acidic
process bath can be prolonged is to remove cationic
metal ions from a phosphoric acid bath. In this case,
the ion exchanger Lewatit MonoPlus SP 112 in H
form can remove cations, such as Fe2+, Zn2+, and/or
Al3+.
Another example is the etching of steel with
hydrochloric acid. Here, Fe2+ ions will build up over
time. By adding H2O2 in a side stream, the Fe2+ can
be oxidized to Fe3+, which forms the anionic and
very dark colored [FeCl4]- complex in the acid. This
complex attaches in an extremely selective manner
to strongly basic anion exchangers, such as Lewatit
K 6362.
By letting the acid pass over the anion
exchanger, the iron can be removed to the largest
extent to leave behind a residual concentration of
less than 1 ppm. In this case, regeneration takes
place simply by letting water pass over. The
previously absorbed iron-chloro complex will break
down under these conditions. The anion exchanger
will repel the cationic iron and the latter will be
washed out by the water. This procedure is so
efficient that it can also be used for purifying
hydrochloric acid.
3.2. RECYCLING OF CHROME
BATHS
Depending on the base material to be
treated (iron, messing) or already existing coatings
(nickel, copper), chromium (VI) electrolytes can be
contaminated by foreign metals, such as copper,
zinc, iron and chromium (III). The built up of these
impurities result from surface corrosion and by
cathodic reduction of C(VI).
14
While small amounts of chromium (III) and
especially an iron content of 2-3 g/L will have a
positive effect on current yield, larger amounts of
foreign metals will result in poorer conductivity of the
electrolyte, reduced current yield and a poorer visual
appearance of the chrome coating.
Therefore, when it comes to recycling, the
bath is diluted to a concentration of approx. 100 g/L
CrO3 and cooled to room temperature, because
otherwise it would result in oxidative damage to the
ion exchanger. In order to remove iron, chromium
and other heavy metal cations, a strongly acidic
cation exchanger of the type Lewatit MonoPlus SP
112 H is used. Under the given circumstances it can
be charged with up to 20 g Fe/Cr per liter resin.
Regeneration takes place using 10% sulfuric acid.
After purification, the treated chromium (VI)
electrolyte is brought back to its original
concentration by means of evaporation and then
added to the bath.
3.3. RECYCLING OF SULFURIC
ACID
Large amounts of sulfuric acid are used
during the anodization of aluminum. Aluminum
builds up increasingly in the process bath and is
tolerated only up to a certain concentration.
Such baths are recycled using the so-called
acid retardation process. This method is basically
based on that a strongly basic ion exchanger can
absorb acids while repelling metallic salts. This
phenomenon is caused by the effect of charge, also
called Donnan effect.
The acid will normally enter from below into a
lean column filled with special resin, such as, e.g.,
Lewatit K 6387. At the top of the column, various
fractions will leave the column one after the other.
First of all, clean water that has remained in the
column from the previous cycle will be released. It
can be temporarily stored and then reused in the
next cycle. Then follows the fraction with the salt-
comprising impurities in this case aluminum sulfate.
This fraction is disposed of through the wastewater.
Finally, there is a stage in which the acid starts to
break through. Feeding of the column is stopped at
the beginning of this stage.
Now it is time for regeneration: to that end,
demineralized water is simply added from above
i.e. in opposite direction to the charge. The water will
completely absorb the acid adsorbed by the ion
exchange beads and wash it back into the process
bath.
 The name acid retardation has been H2O
+
derived from the fact that, during this process, first +
for regeneration

the salt and then the acid will leave the column with
retardation. Al

During charging as well as during

regeneration relatively low flow speeds are applied. H2SO4
anodization bath
The acid will break through already after approx. one SBA
filter bed volume. The cycle comprising charging and 10 % H2SO4,
H2O +
recycled
regeneration will take less than an hour. 5 g/L Al2(SO4)3 H2SO4
Al2(SO4)3
+ H2O
This procedure is most efficient when using
acids with a concentration of between 10 and 20 IX

percent. Normally, it will be possible to keep the

concentration of metal cations in the process bath at Wastewater
a level of 5 g/L to 10 g/L. But this method is not
suitable for the precision cleaning of acids. Residual
concentrations in the mg/L range cannot be
achieved with acid retardation.

LANXESS has developed the acid

retardation resin Lewatit 6387, which thanks to its
superfine beads (0.39 mm in diameter) allows for a
particularly high degree of separation between the
fraction with impurities and the fraction with acid.

And there are numerous other applications

apart from the aforementioned ones, where a
process bath can be purified in a similar way and its
lifetime considerably prolonged.

Table 3.1. provides an overview of the

most important known methods.

Figure 3.5.: Schematic diagram of the acid retardation

process and a technical system made by GOEMA.

Impurity Area of application Ion exchanger

weakly acidic process solutions, e.g.
Fe2+, Zn2+, Al3+, Cu2+ ... Lewatit MonoPlus SP 112
phosphoric acid, tartaric acid
Fe3+, Zn2+, Cd2+, Sn2+
concentrated hydrochloric acid Lewatit K 6362
complexes
Fe3+, Cr3+, Cu2+, Zn2+ Chrome (VI) acid < 10 % Lewatit MonoPlus SP 112
10 % - 20 % H2SO4, HNO3, HF, H3PO4,
Al3+, Fe3+ Lewatit K 6387
by means of retardation
Fe3+, Zn2+ from Cr (III) passivation bath Lewatit OC 1026
Fe3+ from Zn galvanization bath Lewatit MonoPlus TP 207
Zn2+ from Ni galvanization bath Lewatit OC 1026
TOC from Cr (III) passivation bath Lewatit VP OC 1064 PH
Cu2+ from CMP suspensions Lewatit MonoPlus TP 207
Cu2+ from NH4Cl etchants Lewatit MonoPlus TP 207

Table 3.1.: Application examples for the recycling of process baths or production streams.

15
4. RECYCLING OF RINSE WATER The recirculation system used for
desalinating the rinse water works similar to an ion
exchange system used in raw water treatment. It
Rinsing is an important and frequent basically consists of a series-connected cation
intermediate step when treating surfaces. Its goal is exchanger and anion exchanger.
to remove any process solution residues from the
prior treatment stage. This prevents the process Despite their similarity, recirculation systems
solution from being carried to the subsequent differ in the following respects from raw water
process step. treatment systems:
In order to save water and chemicals, many Complex composition of rinse waters: heavy
modern production plants have optimized their rinse metals, complexing agents, detergents, oils
processes. Nowadays, they use so-called dip and and fats
flow rinse tanks, as shown in below figure 4.1.
Risk of substances accumulating in the
Transport system
recirculation system
+

+ Risk of microbial contamination of the entire

installation

Clean Risk of damage to the ion exchanger caused

water
by certain substances, such as detergents or
Process bath deposition of insoluble salts

Normally, a macro-porous strongly acidic resin

(such as Lewatit MonoPlus SP 112) is combined
Dip rinse tank Flow rinse tank
with a weakly basic resin (such as Lewatit
MonoPlus MP 64) when used in recirculation
Contaminated
water
systems. Should the rinse water, however, contain
salts of weak acids, such as CN-, H2BO3-, HSiO3- or
bicarbonate, the weakly basic resin must be followed
by a strongly basic resin (such as Lewatit K 6362).
Figure 4.1.: State-of-the-art rinse process. Rinsing takes
place by dipping the work piece into several series-connected A weakly basic resin alone would not be able to
tanks. In the flow rinse tank water cascades onto the work absorb the aforementioned ions.
piece.

Where applicable, the concentrated rinse

water from the dip rinse tank is returned to the
upstream process after evaporation.

The water discharged from the lowest

container of the flow rinse tank is collected and can
be disposed of as wastewater or recycled.

Many rinse processes will generate water

that is contaminated only slightly with salt and often
has a lower salt content than the raw water used for
fresh water production. In these cases it makes Figure 4.2.: Surface rinsing is necessary between each and
sense to desalinate the water in a recirculation every process step.
system and to return the recovered and fully
desalinated water to the rinse process.

16
 If the rinse water contains not only salts but
also detergents (soaps, surfactants), a protective
filter (scavenger) should be installed upstream of
the desalination system, e.g. an activated carbon
filter or adsorber resin. Cationic tensides can form
an irreversible coating on cation exchangers and
anionic tensides an irreversible coating on anion
exchangers. Therefore, they should be removed
before reaching the ion exchanger.
If a strongly basic resin is used downstream,
as mentioned above, one must pay close attention
that the upstream weakly basic ion exchanger is not
passed over, because otherwise the strongly basic
resin might be irreversibly charged with metal
cyanide complexes, chromate or other components.
Various organic complexing agents acting on
the basis of monovalent or multivalent carboxylic
acids or amino or phosphoric acid are also absorbed
by the ion exchangers. They also adsorb metals in
complexed form: for example, a heavy metal
complexed with EDTA would attach to the anion
exchanger because the metal complex is anionic
i.e. negatively charged.
K+, A1-, A2 organic
Salt
containing
rinse water ( )
AR or
GAC
Organic
Recycled
rinse
water
Figure 4.3.: Schematic diagram of a recirculation system: the first and last filter is optional and required only for certain
water qualities. The scavenger removes dissolved organic matter, the cation exchanger removes cations, the weakly basic
anion exchanger the anions of strong acids (A1-) and the strongly basic anion exchanger the anions of weak acids (A2-).
One must pay attention that the water is
largely free from particulate matter before it is
treated with ion exchangers and that drops of oil or
emulsified oils are also not carried into the ion
exchange bed. I.e., the water should be pretreated
by way of demulsification, light liquid separation or
possibly membrane filtration.
One should also refrain from introducing
strong oxidants, such as peroxides or chlorine to the
water. These oxidants can cause irreversible
damage to the ion exchanger through degradation of
functional groups and dewetting of the polymer
structure.
A widespread problem in connection with
recirculation systems is microbial contamination and
uncontrolled growth of algae in pipelines, stackable
containers and the filter bed of ion exchangers. The
growth of algae in stackable containers can be
reduced by using UV lamps, and ion exchangers can
be disinfected with various methods, including
increased backwashing, use of acid and brine and
even controlled use of biocides.
K+, A1-, A2- H+, A1-, A2-
( )
SAC WBA SBA
K+ A1- A2-
Demineralized
water
17
 An easy but still very efficient way to reduce
algae growth is to use opaque construction material
and container covers.
If the objective is to produce quality water
with a residual conductivity of less than 1 S/cm, a
mixed bed, e.g. Lewatit UltraPure 1292 MD, may
have to be installed downstream of the combination
of Lewatit MonoPlus SP 112 and Lewatit
MonoPlus MP 64.
If the rinse water contains precious metals, it
may be possible to recover them from the pure
regenerants. If you are dealing with a mixture of
materials and if you are interested only in recovering
a subcomponent, it makes sense to use a selective
exchanger in the regenerant stream.

Scavenger
Lewatit VP OC 1064 PH

Cation exchanger
Lewatit MonoPlus SP 112
Lewatit MonoPlus S 108

Anion exchanger (for A1-)

Lewatit MP 62 WS
Lewatit MonoPlus MP 64
Lewatit MonoPlus MP 68

Anion exchanger (for A2-)

Lewatit K 6362

Mixed bed
Lewatit UltraPure 1211 MD

Table 4.1.: Products that are suited for Figure 4.4.: Recirculation system made by Decker VT.
rinse water recycling.

18
5. TREATMENT OF WASTEWATER
All water that has come into contact with
metallic components or electrolyte solutions during
production contains potentially toxic metallic salts.
This water must undergo treatment in accordance
with legal provisions before it is discharged into the
environment. For wastewater from the metal
processing industry in Germany the limits prescribed
in Annex 40 of the German Wastewater Ordinance
apply.
That is why in metal processing plants the
respective system is called detoxification system
(see figure 5.1.). Normally, detoxification takes
place in a multistage system and has the following
tasks:
Oxidative destruction of free cyanides and
cyanide-metal complexes
Oxidative destruction of organic complexing
agents (such as EDTA, NTA ...)
Electrochemical recovery of precious metals
Precipitation of heavy metal ions through
transformation into sparingly soluble
hydroxides, carbonates or sulfides
When performing precision cleaning of
wastewater, it is beneficial to use selective ion
exchangers. In this position they are also called
polishing filters. They make it possible to safely keep
the residual concentration of metals below a value
0.1 mg/L.
Since final exchangers also provide
protection against accidental release of metals in the
upstream treatment stages as a result of operating
errors, they are sometimes also referred to as
police filters.
The working mechanism of ion exchangers
in the final exchange position is shown in detail in
figure 5.2. especially the interaction between ion
exchanger and upstream precipitation stage.
The main load of heavy metals, such as
copper, nickel, chromium (III), cobalt, iron etc. is
separated during the precipitation stage. Caustic
soda or lime milk is preferably used for precipitation.
If final exchangers are employed, one can do without
adding sulfidic precipitants. The heavy metals are
transformed into sparingly soluble hydroxides in the
precipitation reactor and can then be separated, for
example with a filter press.

Separation and thickening of the heavy metal

sludge

Precision cleaning of wastewater to ensure

compliance with the limits Process
water

Recovered
metal
Production

Wastewater contaminated with

Detoxification system heavy metals

Chemical oxidation
Chem. reduction Extraction
(e.g. of cyanides
(e.g. of Cr (VI)) electrolysis
and organic ligands)

Polishing filter
Precipitation /
filtration IX

Heavy metal Purified

sludge wastewater

Figure 5.1.: Principle of the working mechanism of a detoxification system used in the metal
processing industry. The wastewater is first treated in partial streams and then precipitated. The
ion exchanger as a final exchanger is the final barrier before the wastewater is discharged into
the environment.

19
 Normally, precipitation and subsequent
solids separation will make it possible to eliminate
more than 99% of the pollutants from the water.
However, given an initial concentration of 1000 mg/L
and 99% separation, one will still be dealing with a
residual concentration of 10 mg/L, which in the case
of most heavy metals means that the limit is still
clearly exceeded.
The application described herein is mainly
about removing heavy metal ions, such as copper,
nickel, chromium, cobalt etc. in case they are
present as cations. This is the traditional area of
application for a chelation exchanger, such as
Lewatit MonoPlus TP 207. Most systems that are
being used in practice work according to this
principle.

In order to ensure that the wastewater to be
discharged complies with the discharge
requirements, one can install an ion exchanger
downstream which will further reduce the
concentration of pollutants through precision
cleaning.
The combination of high-performance stage
and precision-cleaning stage will lead to an overall
elimination of more than 99.9% of pollutants.
However, the wastewater produced in the
metal processing industry sometimes also contains
other pollutants that cannot be absorbed by Lewatit
MonoPlus TP 207. But there are ion exchangers that
can fulfill this task through selective binding:
Precious metals, such as gold, silver,
platinum, palladium, rhodium, iridium etc. can if
present as anionic complexes be bound with
Lewatit K 6362 or Lewatit MonoPlus TP 214.

The spent regenerant solution is normally
returned to the precipitation tank where it is admixed
to the main wastewater stream. I.e., it needs no
special treatment and as a result heavy metals will
only be released through one single outlet namely
the filter press.
Mercury can be reliably removed using
Lewatit TP 214.
Anionic chromate, molybdate and tungstate
is best bound by Lewatit MonoPlus MP 62 WS or
Lewatit K 6362 in a weakly acidic to acidic solution.

The heavy metal sludge is then either When it comes to removing arsenate or
disposed of at a dump site or used as a resource in antimonate, Lewatit FO 36 works selectively.
extractive metallurgy, e.g. at a copper smelting plant.

Heavy metal Heavy metal Heavy metal

> 1000 ppm < 10 ppm < 0.1 ppm

Heavy metal Precipitant Regenerant (HCl)

wastewater (CaO, NaOH) Conditioner (NaOH)
Rinse water

Polishing
Precipitation filter
Filter pH
reactor
press adjustment

Purified
wastewater

Dump

Heavy metal hydroxides Sludge

Regenerant stream

Figure 5.2.: Cooperation between polishing filter and upstream precipitation system. While heavy
metal precipitation can normally reduce heavy metals to residual concentrations of less than 10
ppm, ion exchangers can achieve a further reduction to more than 0.1 ppm. Given an initial
concentration of more than 1,000 ppm this means an elimination of more than 99.9% of pollutants.

20
 Perfluorinated tensides (e.g. PFOS) can be
reduced to the ppb or even ppt range using weakly
or strongly basic resins, such as Lewatit MP 62 or
Lewatit K 6362.
Boron is selectively separated using Lewatit
MK 51, and fluoride selectively attaches to
aluminum-loaded Lewatit MonoPlus TP 260.
If the wastewater contains several impurities
at the same time, which cannot be bound by one
and the same type of selective exchanger, it is
recommended to combine several suitable resin
filters.
The advantages of using ion exchangers as
final exchangers can be summarized as follows:
Very low residual concentrations, which
ensures compliance with limits through
multistage effect in the filter column
Selectivity allows for targeted absorption of
trace impurities, leaving behind harmless
components, such as calcium, magnesium,
chloride etc.
No use of expensive and polluting
organosulfur precipitants

Relative tolerance of suspended solids, such

as gypsum and limestone precipitations

Recovery of recyclable fractions

Products that can be used as polishing filters

Adsorption of cationic
Lewatit MonoPlus TP 207
heavy metals, such as Cu2+, Zn2+, Cd2+, Cr3+, Ni2+
Adsorption of quicksilver and precious metals
Lewatit MonoPlus TP 214
(Au, Ag, Pd ...)
Adsorption of precious metal cyanide complexes
Lewatit MP 62 WS / Lewatit K 6362
([Au(CN)2]-, [Ag(CN)2]- )
Adsorption of anionic
Lewatit MP 62 WS / Lewatit K 6362
heavy metals (CrO42-, MoO42- )
Adsorption of PFT (PFOS ) Lewatit K 6362
Adsorption of As, Sb, CN- Lewatit FO 36
Adsorption of boron (B(OH)3) Lewatit MK 51
Adsorption of fluoride (F-) Lewatit TP 260 (Al form)

Table 5.1. Lewatit products that can be used as polishing filters.

21
6. OUTLOOK
This brochure shows how versatilely
and effectively ion exchangers can be used in the
metal processing industry. But this brochure
describes only a limited selection of the many
different types of use. As a matter of fact, there are
numerous other technical applications.
For more detailed technical information,
please contact our team of experts here at
LANXESS.
Comprehensive product descriptions and
safety data sheets can be downloaded at
www.lewatit.de/produkte.
Ion exchangers have great innovative
potential and should always be checked for their
suitability when developing new technologies.
Please also take advantage of our
expertise when conducting research projects. Our
team of application engineers and researchers will
gladly support you in your efforts to develop new
tailored solutions.
7. CONTACTS
Lenntech
info@lenntech.com Tel. +31-152-610-900
www.lenntech.com Fax. +31-152-616-289
22
The above information and our technical
advice whether verbal, in writing or by way of trials
is give in good faith but without any warranty. This
also applies where proprietary rights of third parties
are involved. Our advice does not release you from
the obligation to check its current validity and, in
particular, the validity of our safety data sheets and
technical information and to test our products for
suitability for your intended procedures and
purposes. The application, use and processing of
our products and of the products manufactured by
you on the basis of our technical advice is beyond
our control and, therefore, entirely your own
responsibility. Our products are sold in accordance
with the current version of our General Terms and
Conditions of Sale and Delivery.
The above formulation is intended solely as
a guide for our business partners and other parties
interested in our products. As the concrete areas of
use and application of the suggested formulations
are beyond our control, it is imperative to test them
at least under technical, environmental, health and
safety aspects to see whether they meet your
specific requirements and whether they are suitable
for the intended use and application. Although the
ingredients, dosages and compound and article
properties indicated herein reflect our
recommendation at the time of publication, the
formulations are not subject to continuous review
and/or updating, and you agree that use is
undertaken at your own risk. We cannot be held
liable for any changes to ingredients and their
processing behavior that may occur at a later point
in time or for their effects on the properties of the
articles/products that are produced using these
suggested formulations.
2010 All Rights Reserved
LANXESS Deutschland GmbH