Condensate Purification Purolite Technology
Condensate Purification Purolite Technology
Condensate Purification Purolite Technology
C O N D E N S AT E
P U R I F I C AT I O N
The Influence of Operating Conditions on
the Ion Exchange Processes
CONTENTS
INTRODUCTION
Page 2
T H E N E E D F O R C O N D E N S AT E P U R I F I C AT I O N P L A N T
Page 2
CONDITIONING CHEMICALS
Page 2
WAT E R Q U A L I T Y R E Q U I R E D
Page 3
FA C T O R S A F F E C T I N G T H E P E R F O R M A N C E O F
C O N D E N S AT E P U R I F I C AT I O N P L A N T
Page 3
Page 4
Page 5
5 . 3 C o m p o s i t i o n o f W a t e r t o b e Tr e a t e d
Page 7
Page 7
Page 8
Page 9
5.7 Filtration
Page 10
Page 10
CONCLUDING COMMENTS
Page 11
Page 12
Index
Page 16
Page 1
INTRODUCTION
T H E N E E D F O R C O N D E N S AT E
P U R I F I C AT I O N P L A N T
Why is it necessary to treat condensate which may already be in
a high state of purity? There are several reasons, but the most
outstanding need arises from the fact that traces of soluble
impurities present in the feed water entering a high pressure
boiler can be concentrated within the system. The degree to
which this occurs depends on the design of boiler, heat flux,
oxide thickness at heat transfer surfaces, and the level of
insoluble impurities. For example, concentration factors as high
as 104 to 106 can arise at local sites within drum boilers: this
means that g/kg quantities of impurities or even lower can
concentrate up to mg kg-1 levels.
In a once-through type of boiler all the water entering a tube is
evaporated in a single pass and salt concentration occurs at the
water/steam transition point. The result of these concentration
mechanisms is that there is a risk of corrosion of boiler tubes by
ions such as chloride and sulphate, and if failures occur the economic penalties are very severe.
A special situation arises with once-through boilers operating
under supercritical conditions, i.e. such that the critical pressure
(221 bar) and temperature (374C) is exceeded and a single
phase fluid exists rather than two phase water/steam conditions.
In this case, all the impurities in the boiler fluid will be present as
the fluid enters the turbine. Consequently, there is a subsequent
risk of substances depositing within the turbine. At the
temperatures and pressures involved this includes metallic
elements like copper and iron which have an appreciable
solubility under the boiler conditions which reduces rapidly as
the fluid passes through the high pressure section of the turbine
CONDITIONING CHEMICALS
Page 2
WAT E R Q U A L I T Y R E Q U I R E D
<0.06
<0.3
<0.5
<0.3
<4
S/cm at 25C
g/kg
g/kg
g/kg
g/kg
It can be seen from the above that, progressively, a higher quality water has been demanded from CPP. The following sections
will show how these requirements have affected the design and
operation of CPP, and the choice of ion exchange resins.
P E R F O R M A N C E O F C O N D E N S AT E
P U R I F I C AT I O N P L A N T
A CPP has to produce the quantity of treated water required to
the water quality specification at all times and this will include a
variety of operating conditions. The ability of the plant to meet
this requirement is dependent on both the design and operating
conditions, and how these might affect the ion exchange
process has to be a prime consideration. The performance and
life of the ion exchange resins used might be affected,
CONDENSATE
MIXED
BED
MIXED
BED
RESIN
MIXED
BED
RESERVE
CHARGE
OF RESIN
TRANSFER
REGENERATION PLANT
(ONE OR TWO VESSELS)
TREATED WATER
TO FEED SYSTEM
RESIN
TRANSFER
RESIN
TRANSFER
CHEMICAL STORAGE
DILUTION AND
MEASUREMENT
EQUIPMENT
Flow rate
Regeneration procedures and conditions
Composition of water to be treated
Quality and quantity of treated water to be produced
Page 4
Page 5
From the above it follows that the cation and anion resins need
to be of suitable size and density to allow good separation to
occur on backwashing.
INTERFACE
ISOLATION
VESSEL
SEPARATION
/ANION
REGEN.
VESSEL
CATION
REGEN.
VESSEL
CONDUCTIVITY
CELL
Page 6
of resin to be used without affecting the kinetics and also resulting in a lower headloss.
CATION
REGENERATOR
ANION
REGENERATOR
DILUTE ACID
DILUTE CAUSTIC
CONDENSATE
INLET
LEAD CATION
ANION
TRAIL CATION
CONDENSATE OUTLET
Page 7
Page 8
Physical stability
Sodium/amine selectivity
Resin separation (density/particle size)
Capacity/acid requirement for regeneration
Page 9
H Form Operstion
Under these conditions the physical strength and separation
characteristics are likely to dictate the choice of resin.
Selectivity differences between resins are slight and can be discounted. Both 10% gel or 12% macroporous cation resins could
have satisfactory resistance to breakdown. However, the gel
resin will also have enhanced separation characteristics due to
its slightly higher density relative to a macroporous type.
Additionally, it would also be expected to have a higher operating capacity.
Morpholine Form Operation
In this case, the presence of morpholine in the treated water
affects the equilibrium leakage of sodium from the mixed bed.
The leakage values depend on the selectivity coefficient
Na
K morpholine
of the cation resin and the sodium content of the
resin.
Now the data in Ref 16 indicates that the selectivity coefficient
increases with DVB content and hence to minimise sodium leakage a resin of the highest possible DVB content should be used.
From selectivity considerations, therefore, a 20% DVB resin
would be preferred when operating with morpholine. However,
the risk of breakdown of this material is high and clearly outweighs its potential advantage on selectivity grounds.
If we then consider the 12% DVB resin which would have
adequate strength we find that it has a much lower (factor of 20)
selectivity coefficient than the 20% DVB material, and is only a
factor of two higher than that of a 10% gel resin (which also has
a satisfactory physical strength). It follows that there will not be
an outstanding difference between the 10% gel and the 12%
macroporous resin in terms of equilibrium leakage of sodium.
The sodium content of the resin is dictated by two main factors.
The quantity of cation present in the anion resin after
separation which is subsequently in contact with sodium
hydroxide.
The level of sodium remaining on the separated cation
resin after regeneration.
Separation procedures such as described earlier should be
capable of ensuring that a satisfactory low level of cation in
anion resin is obtained in the absence of breakdown of cation
resin.
However, if breakdown of the cation resin occurs with the
production of small fragments of beads it could be then increasingly difficult to effect the required degree of separation. It
follows that physical stability must be a prime consideration,
and hence when choosing between a 10% DVB gel and 12%
DVB macroporous resin a critical factor will be their relative
resistance to physical breakdown.
When the resins are similar to those employed in deep bed ion
exchange. The particle size of the resin is approx. 30 micron and
when the cation and anion resins are mixed, a bulky floc forms.
The characteristics of the floc vary depending on the ratio of
cation/ anion resin used. To form the coat the mixed resin floc is
passed on to the element and water is circulated until a satisfactory coat is obtained. The unit can then be put into service
and operated until either a specified increase of pressure differential is reached or up to exhaustion of ion exchange capacity.
The dry weight of the resins used to form the filter coat is equivalent to 1 kg per m2 of element surface, and the usual service
flow rate is 100 - 200 m-2 min-1. The coat has a low resistance
to flow, and typical pressure differentials are 0.1 - 0.2 bar for a
freshly pre-coated unit. The unit can be operated to exhaustion
of ion exchange capacity, or to a specified pressure differential
(1.7 bar), if filtration is the main function.
5.7 Filtration
The water/steam circuit of power plant may be contaminated by
insoluble corrosion products such as iron and copper. This
occurs mainly during initial commissioning when concentrations
of iron as high as 2000 g/kg can be experienced. Subsequent
high levels of debris are likely to be present only during startups, when the system is disturbed. At this time concentrations of
100 - 200 g/kg may arise. During normal load operation total
concentrations will usually be <5 g/kg.
In older CPP, filters of various types were included prior to the
ion exchange section. In subsequent designs, however, the ion
exchange beds had also to act as filters. If a cation bed
precedes the mixed bed this obviously acts as the main stage of
filtration. In some cases, pre-coat filters are provided to operate
either before or after the mixed bed unit.
A deep bed exchange unit acts as an efficient filter and depending
on the inlet concentration of debris, 70 - 90% removal of debris
is obtained. Particle size of the debris will dictate the degree of
removal achieved. The debris can be satisfactorily removed from
the bed by air scouring and backwashing.
There is no evidence that the type of resin used i.e., gelular or
macroporous, affect the filtration efficiency.
When the end point is reached the spent resins are removed by
passing a flow of water in the reverse direction to that employed
during the service cycle.
The unit is then ready for recrating and the spent resins being of
no further value are usually discarded.
The powdered cation resin can be supplied in hydrogen and
ammonium forms, whilst the strongly basic anion resin is
supplied in hydroxyl form. Additionally the Purolite Microlite
powdered resins can be supplied already mixed in various
cation/anion ratios, and in the required ionic form. This has a
distinct advantage in the preparation of pre-coats. They can
also be provided with a proportion of fibre.
Powdered resin systems have been used widely in the USA and
Europe within condensate purification systems. In the USA they
are used in conjunction with deep mixed beds and alone.
However, their use alone is confined to stations where fresh
water cooling is employed and in the event of a condenser leak,
water of very low concentration relative to sea water enters the
system. This highlights the limited ion exchange capacity of the
process relative to conventional deep beds, and its main application is therefore likely to be as a polishing treatment after a
deep bed or as a filter situated before a mixed bed.
Few powdered resin systems have been installed, for example in
the UK at one power station such units are situated down stream
of mixed beds, whilst in a sister station the units precede the
mixed beds. At both installations the powdered resin units can
be operated alone if required .
Page 10
When installed after mixed beds, the main role of the units is to
provide an additional ion exchange facility in the event of a
premature breakthrough of the mixed beds, and to remove any
residual soluble impurities present after the mixed bed stage.
This could arise following the regeneration of a mixed bed, when
sulphate concentrations in the treated water can be higher than
in the middle of a service cycle. Under these conditions, the precoat units are capable of maintaining sulphate concentrations in
the final treated water at <0.2 g/kg S04 throughout the service
cycle of a mixed bed.
Filtration may be the main function of a powdered resin system
if the units are installed to procede the mixed beds. This is
particularly useful during commissioning when high levels of
debris may be present.
As might be expected, powdered resins have excellent filtration
properties and even with high inlet debris levels the quality of the
treated water can normally be maintained at <5 ppb. However,
during periods when debris levels are high there will be a cost
advantage in using cheaper filter media such as cellulose fibre.
Such material can be used either along or in combination with
the powdered ion exchange resin. The Purolite product Microlite
FC is suitable for this application.
v)
CONCLUDING COMMENTS
Page 11
HIGH
: resistance to osmotic shock and attrition (physical
strength)
: rates of reaction
: cation: anion separation characteristics
: capacities
: resistance to fouling
: thermal and oxidative stability
: uniformity of physical size
LOW
: resistance to flow (pressure loss)
: organic leachables content
CATION UNIT
MIXED BED
(Including Conesep, Ammonex, Seprex)
Cation
H:OH operation
NH4:OH operation
Amine: OH operation
Anion
H:OH operation
NH4:OH operation
Amine:OH operation
TRIPOL
Cation H:OH
NH4:OH
Amine:OH
Anion
H:OH
NH4:OH
Amine:OH
Purolite SGC100x10TL
Purolite SGC100x10TL
Purolite SGC100x10TL
Purolite SGA400CL
Purolite SGA400CL
Purolite SGA400CL
PRE-COAT FILTERS
Cation H:OH
NH4:OH
Anion
H:OH
NH4:OH
Filter Fibre
Microlite PrCH
Microlite PrCN
Microlite PrAOH
Microlite PrAOH
Microlite FC
OG-4H
OG-4N
OG-6N
OG-7H
OG-12H
OG-12N
Page 12
Acid/Base
Acid/Base
Acid/Base
Acid/Base
Acid/Base
Acid/Base
Acid/Base
Acid/Base
Acid/Base
Acid/Base
Acid/Base
Acid/Base
Acid/Base
Acid/Base
H+/OHNH4+/OHH+/OHNH4+/OHH+/OHNH4+/OHH+/OHNH +/OH-
RATIOS
C/A
1/1
1/1
2/1
2/1
3/1
3/1
3/2
3/2
H+/OHNH4+/OHNH4+/OHH+/OHH+/OHNH +/OH-
RATIOS
F/R
C/A
1:1
1:1
1:1
1:1
2:1
2:1
1:2
3:1
1:2
4:5
1:2
4:5
U.S. gmp/ft 2
Percent resin breakdown is then assessed after a cerain number
of cycles depending upon the generic category of resin under
test.
120
Table 2 shows breakdown percentage criteria that Puroiite follows in the manufacture of their various products.
TABLE 2
Standard gel
C100 x 10
A 400
25
< 10
25
< 20
No of cycles
% Breakdown*
Supergel
Macroporus
SGC100x10 SGA400
100
< 10
100
< 10
C150
A500
500
<5
500
<5
110
100
BC
D E
F
90
80
70
60
50
40
30
20
10
10
15
2
20
3
A
B
C
D
E
F
TO CATCH POT CH 1
=
=
=
=
=
=
1:2
1:2
1:1
1:1
2:1
2:1
20C
30C
20C
30C
20C
30C
TO CATCH POT CH 2
For gel resin combinations allow 5-10% increased flow rate for
same bed expansion.
EXHAUSTANT
NON-RETURN
VALVE
REGENERANT
NON-RETURN
VALVES
EXHAUSTANT
NON-RETURN
VALVE
ATTRITION
TUBES
CHANNEL 1
CHANNEL 2
PULSE
VALVES
SLOW
DRAIN
VALVES
SIEVE CH2
DRAINAGE COLLECTOR
TO
DRAIN
U.S. gmp/ft 2
0.9
20
25
30
35
40
45
50
60
3.5
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0.1
Gel resin
combination
3.0
2.5
2.0
Macroporous resin
combination
1.5
1.0
0.5
50 60
70 80
55
SIEVE CH1
FAST
DRAIN
VALVE
FAST
DRAIN
VALVE
Page 14
PUROLITE SGC-100x10TL
PUROLITE C-150TL
>95%
>95%
Functional Groups
Polystyrene Sulphonate
Functional Groups
Polystyrene Sulphonate
H+ form
(lb/ft3)
820 (51)
Effective Size
0.8mm
Uniformity Coefficient
Moisture Retention H+ form (Na+ form)
Reversible Swelling (Na+H+)
1.25 max
47-50% (40-43%)
5% max
(NH4+H+)
4% max
H+ form
(lb/ft3)
Effective Size
0.8mm
Uniformity Coefficient
Moisture Retention H+ form (Na+ form)
1.25 max
54-59% (48-53%)
5% max
4% max
1.20 (1.29)
1.18 (1.25)
140 (285)
H+ form
pH Range
760 (47.5)
(dry weight)
120 (250)
No limitations
140 (285)
120 (250)
pH Range
No limitations
PUROLITE SGA-400TL
PUROLITE A-500TL
>95%
>95%
Functional Groups
Functional Groups
690 (43)
Effective Size
0.55mm
Uniformity Coefficient
1.35 max
48-54%
20%
1.08
(dry weight)
Max Operating Temperature C (F) CL- Form
OH- Form
pH Range (Stability)
680 (42.5)
Effective Size
0.55mm
Uniformity Coefficient
1.35 max
53-58%
10%
1.07
>1.5 eq/l min
>3.7 meq/g min
100 (212)
(dry weight)
Max Operating Temperature C (F) CL- Form
60 (140)
OH- Form
60 (140)
0-14
Page 15
pH Range (Stability)
100 (212)
0-14
INDEX
Subject
Page
3
3, 10, 11
7, 11
2, 3, 7, 8, 11
8, 11, 12, 13
5
2, 3
2, 3
5
5, 11
2, 3
2, 7, 8, 9, 10
6, 11
2, 6
2, 3, 10
5
3, 6, 10, 11, 13
6, 7, 8, 9, 10, 12
10
4
5
4
2, 3
6
2, 3, 6
6
4, 5, 7, 8
10
4
3, 9, 11
4, 9, 12, 13
2, 3, 8, 11
2, 10, 11
4, 10, 13
3
7, 8
8, 9
7, 11
3, 5, 6, 7, 8, 9, 11
10
5,11
5
3
7, 11, 12
5
Page 16
REFERENCES
1. Sadler M.A. Bates J.C., Darvill M.R. and Ellis G.W. Morpholine form condensate
polishing at Oldbury P.S. Society of Chemical Industry, Ion Exchange for Industry
Ed M. Streat, Pub, Ellis Horwood, Chichester (1988).
2. Harries R.R. & Ray N.J. Anion Exchange in high Flow Rate Mixed Beds. Effluent
and Water Treatment Journal 24, 131, Feb 1984.
3. Emmett J.R. and P.M. Grainger Ion Exchange Mechanisms in Condensate
Polishing. Proc 40th International Water Conference Pittsburgh 1979.
4. Sullivan D.J. Experience with a Conesep Condensate Polishing Plant. 8th E.P.R.I.
Condensate Polishing Workshop, Little Rock Arkansas 31st May - 2 June 1989.
5. Sadler M.A. and Bolton H.R. Regeneration of condensate Polishing Mixed Bed
Resins:
Review
of
10
years
Experience
with
the
Conesep
Page 17
BUSINESS CENTRES
Corporate Offices
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The Purolite Company and Purolite International Limited have one of the most complete ranges of ion exchange resins worldwide. For further information
please contact your local Purolite office.
All suggestions and recommendations given concerning the use of Purolite products are based on tests and data believed to be reliable. However, as
Purolite cannot control the use of its products by others, no guarantee is either expressed or implied by any such suggestion or recommendation by
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