Water Chemistry Book PDF

Confidential
WATER (Pre-) TREATMENT

COURSE
Ml48
MODULE 1
BOILER FEED AND COOLING WATER
TREATMENT
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0 SHELLINTERNA~ONALOJLPRODUCTSB.V.,THEHAG~JF~
M148-1: BOILER FEED AND COOLING WATER TREATMENT
v’
CONTENTS:
section 1 Basic Water Chemistry pre--reading material

section 2 Pretreatment
2.1 Clarification
2.2 Filtration
2.3 Precipitation Sotkning
2.4 Aeration
section 3 Purification
3.1 Ion Exchange Fundamentals
3.2 Ion Exchange Processes
._l 3.3 Ion Exchange Design Calculations
3.4 Ion Exchange Problems
3.5 Reverse Osmosis
3.6 Distillation Processes
Section 4 Deaeration & 02 scavenging
Section 5 Steam Generation
5.1 Boiler (feed) water treatment
5.2 Boiler cleaning
5.3 Materials philosophy for Cooling water and Boilers
5.4 Water side standby protection of Boilers
Section 6 Condensate
6.1 Condensate Treatment
---A
6.2 Condensate Mechanical Issues
Section 7 Cooling Water Treatment
7.0 Cooling Water Treatment Basics
7.1 Cooling Water Case Histories
7.2 Cooling Water Glossary of Chemistry
7.3 Chlorination and Storage of Hypochlorite
M14E_W
Confidential
Ml48
MODULE 1
WATER (Pre-) TREATMENT COURSE
SECTION 1
INDFXIDDC: 22108197
Section 1: BASIC WATER CHEMISTRY
CONTENTS
1. INTRODUCTION 2
2. CONTAMINATION OF PURE WATER 2

2.1 Suspended matter 3
2.2 Soluble matter 4
3. PHYSICAL AND CHEMICAL TERMS 4

3.1 Dissolved Solids 4
3.2 pH 6
3.3 Conductivity 7
3.4 Alkalinity 8
3.5 Hardness 10
X-/
4. CHEMICAL REACTIONS
4.1 Dissociation of water 11
4.2 Neutralisation 11
4.3 Flocculation 11
4.4 Lime treatment 11
4.5 Cation exchange 11
4.6 Anion exchange 12
4.7 Deminerahzation 12
4.8 Phosphate treatment 13
4.9 02 scavengers 13
5. IMPURITIES IN WATER 14
M148_10 Basic Water Chemistry

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1. INTRODUCTION
The consumption of water for domestic, agricultural and industrial purposes is increasing at such a
pace, that in many countries it is becoming more and more difficult to meet the demand. This is true
not only for those countries which traditionally have a shortage of water but also for those countries
where water is apparently abundant. Take for instance the Netherlands,
precipitation 10
Input (in lo6 m3/a) : 88 rivers Rhine 70
Meuse 8
domestic 0.7
Consumption (in lo6 m3/a) : 1.6
industrial 1.6
So in theory there is a large surplus of water, however, in practice there is not, as the rivers are polluted
upstream by chemicals and by sewage.
Here we come to a very important aspect of water and water supply: one must clearly define what
requirements are necessary for a given purpose.
For cooling, all water including sea water is suitable as long as it is reasonably clear
and not too hot.
For high pressure boilers, feed water must be demineralized to prevent scale formation
For drinking, water must be selected very carefully for flavour and bacteria.
The main body of water on earth is of course the sea, which covers 71% of the surface area. The sea is
also the main supply of fresh water.
Per day 1000 l lo6 m3 evaporate from the sea

900 l lo6 m3 fall back into the sea
100 l lo6 m3 fall on land.
2. CONTAMINATION OF PURE WATER
Contamination of pure ram water starts the moment it is formed:
1. by gases such as 02, CO2 (0.04% present in the atmosphere), SO2, SO3 and NH3;
2. by insoluble matter like dust;
3. by soluble matter like salts (e.g. in sea atmosphere).
The level of contamination increases rapidly when the water comes into contact with the ground.
The water absorbs minerals e.g. CO2 in the water reacts with Calcium carbonate (CaC03) in the
ground to form soluble Ca(HC03)2. Calcium sulphate, salts from the mining industry, man-made
chemicals - such as nitrates and phosphates from fertilisers, detergents etc. are also absorbed.

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2.1. SUSPENDED MATTER
In addition to soluble matter large quantities of insoluble matter are also taken up as a result of the
mechanical action of water.
Examules:
- water from melting glaciers is often milky white due to pulverised rocks;
- rivers contain sand, soil and clay;
The transport capacity of water for suspended particles varies with the sixth power of its horizontal
velocity. Suspended matter of any nature, present in a water supply is called turbidity.
A distinction is sometimes made between suspended matter which settles rapidly (sediment) and that
which settles slowly or, for all practical purposes, not at all. The term turbidity would then be more
aptly used for the slowly settling material.
The settling of suspended matter is governed by Stokes law:
_I_ (0 -p)gd*
v=18 Tt
V = free fatling speed of particles

n = density of particle
P = density of fluid
g = acceleration due to gravity
d = diameter of particle
11 = viscosity of fluid.
This equation must be used with a consistent system of units e.g. c.g.s. units.
The following table gives a semiquantitative picture of the settling of suspended matter:
TABLE
Settling time for particles of different size in water
Particle diameter Time to settle

(microns) 1 ft in still water at Typical material
dens& 2.65 g/cm3 IO’C (50°F)
10,000 0.5 s gravel
1,000 2s coarse sand
100 lmin fine sand
10 Ih silt
1.0 1OOh bacteria
0.1 500 days clay
0.01 150 years colloidal substances

-4-
From the table it is clear that not all suspended matter can be removed by gravity settling. Removal is
carried out by coagulation/flocculation. This subject will be dealt with later in this course.
One could of course ask whether fine colloidal clay need be removed at all. Normally it must, because
it tends to come out in ion exchangers and boilers (scale-priming).
2.2 SOLUBLE MATTER
Surface water (i.e. rivers, lakes etc.) is sometimes coloured due to very fine organic matter which is
usually extracted from decaying vegetation.
Ground water (i.e. springs, wells etc.) does not normally contain large quantities of suspended or
organic matter because of the natural filtering action of the soil. However, ground water, especially
from deep wells, tends to contain a higher salt concentration and is often harder. Furthermore the
quantity is usually limited. This is especially true when one needs it for cooling water for which
purpose it is very suitable in view of its constant temperature during winter and summer. Ground water
is often aggressive to steel because of the presence of CO2 and the combination of sulphates and
sulphate-reducing bacteria. These bacteria simultaneously oxidise organic compounds and reduce
L_/ sulphur compounds (sulphates) to H2S, often causing the external corrosion of buried water pipes.
Pipelines transporting sulphate containing water may be corroded on the inside by the same process.
SO: + Org. mat -+ S” + 2H+ + Hz0 (H2.S)
Ground water is normally clear when it comes out of tbe ground but it often shows a fine yellowish or
brown sediment from the presence of iron bicarbonate which reacts with the oxygen from the air:
F e (HCO& + Fe(OH)z + 2 CO2
4 Fe(OH)2 + 02 + 2 Hz0 -+ 4 Fe(OH)34
Quantities of iron over 0.5 ppm stain clothes.
Removal of both iron and manganese is carried out by base-exchange or aeration, settling and filtration.
-
3. PHYSICAL AND CHEMICAL TERMS
3.1. DISSOLVED SOLIDS
Minerals and salts dissolve either as such or because of the reaction of CO2 in the water. When a salt
dissolves it splits into cations and anions.
NaCl -+ Na+ + CI-

cation anion
Ions are the positively (cation) or negatively (anion) charged atoms or groups of atoms which together
form the molecules of the salt.
M148_IO Basic Water Chemistry

In natural waters we can expect the following ions:
w
Cations Anions
Calcium Ca++ Bicarbonate HCO;
Magnesium Mg++ Carbonate co;
Sodium (Natrium) Na+ Sulphate so,=
Potassium (Kaliwn) Kt Nitrate NO;
Iron (Femun) Fe*/Fe- Fluoride F-

Ahuninium Al- Chloride Cl-
zinc zn++V==) Nitrite NO;

C o p p e r (Cuprum) Cu*
W
In water analysis reports it must be clearly stated which compounds or elements the data represent.
It is usual to report in ppm, but not all laboratories apply the general rule explained below.
1 ppm = 1 part per million (weight by weight) is equivalent to mg/l assuming that for practical
purposes the specific gravity of water is 1 kg/l (true at 4 degrees C).
MetuL9 are reported as the element (Na, Al, Fe etc.) except calcium and magnesium which are usually
reported in ppm CaC03.
Anions are reported as the anion (NO;, SO:, Cl- etc.) except silica which is reported as SiO2 and
bicarbonates which are reported as ppm CaCO3.
M andpalkalinities are reported as ppm CaC03.
With the exception of routine analysis, the analysis should also be expressed in milligram-
equivalent/litre (mg.eq/l, meqll or sometimes what is for practical purposes the same epm = equivalent
U
per million).
The number of milligram-equivalents of an ion per litre is the number of milligrams per litre divided by
the equivalent weight.
The equivalent weight ofan ion, is the atomic weight (or sum of atomic weights for a group like S04)
divided by the valency (number of electrical charges).
Example:
The gram ion weight of the sulphate (SO:) anion is calculated as:
1gionSOl = 32+4x16 = 96g
M 148-l 0 Basic Water Chemistry

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The valency is 2. Therefore the equivalent weight of 1 g eq. SO: is 96 : 2 - 48 g

V
I mg eq. SO; is 48 mg.
Thus, a solution containing say 300 ppm (mg/l) of SOi will contain 300 : 48 = 6.25 mg eq./l.
TABLE
Ion Ion weight Equivalent weight

Na+ 23 23
Cafe 40.1 20.05
Mg++ 24.3 12.15
CI- 35.5 35.5
so; 96 48
(32(s) + 64(04))
HCO; 61 61
(l(H) + 12(C) + 48(03)
As a salt solution is always neutral in an electrical sense it means that the number of milligram-
equivalents per litre of positive ions (cations) is equal to the amount of milligrain-equivalents of
negative ions (anions) per litre. In a complete water analysis the sum of cation equivalents should equal
the sum of anion equivalents thus providing a check on the analysis.
Example:
A solution containing 1 mg mol.* (142 mg) sodium sulphate (NaS04) per litre contains
2 mg ion = 2 mg eq. (= 46 mg) Na+ and 1 mg ion = 2 mg eq. (= 96 mg) SO,.
3.2. pH
Pure water is dissociated into positively charged hydrogen ions (H+) and negatively charged hydroxyl
ions (OH-)
Hz0 = H + + OH-
ln pure water the concentration of the H+ and OH- ions is 1 Oe7 g/ion/l
(I-I”) = concentration of H+ ions (g/ion/l.)
The product (I-I”) x (OH-) is constant (at 25’C) = 10-14.
l 1 mg/mol. is amount equal to molecular weight in mg.

It should be remembered that I gram-molecule or I gram-ion always contains the same number of molecules or ions
(Avogadro’s number - 6 x 102’).

-7-
As the.pH is defined as the negative logarithm of the H+ ion concentration, the pH of pure water is 7
(neutral). U
The lover the pH value, the more acidic the solution (pH below 7); the higher the pH value, the more
alkaline the solution (PH above 7).
Example: pH of water to which hydrochloric acid HCI is added.
HCI is fully dissociated into H+ and Cl-
2%HCI = 2OgA
20
H+ ion concentration = -
1+36.5 - 0.5 = 5 x 10-l g/ion/l.
pH = 1 -log.5 (0.7) = 0.3
Example: pH of water to which caustic soda (NaOH) is added.
NaOH is fully dissociated into Na+ and OH-
2% NaOH = 20 g/l.
20
OH- ion concentration = 23+,6+1 = 0.5 g/ion/l.
10-14
H+ ion concentration = 0.5 = 2 x IO-l4 g/ion/l
pH = l4-log2(0-3) = 13.7
3.3. CONDUCTIVITY
When two electrodes, placed in a salt solution, are connected to a current source. the salt solution
conducts the current to some extent: the solution has a certain conductivity.
The conductivity is related to
I. the concentration of the electrolyte (Ci&)

2. the type of ions present
3. the temperature of the electrolyte.
The following table shows the conductivity of various relatively pure types of water expressed in micro
mho cm-l.
Ml48_10 Basic Water Chemistry

-8-
Conductivity of water of high purity at 2oOC
Type of water Conductivity-m

micro mho cm-3.
Theoretical minimum conductivity 0.04

Pure water in equilibrium with atmospheric air I
Ion exchanged water: one cation/one anion exchanger 10-20
Mixed bed, with strongly basic anion resin less than I
Pure water vith 1 ppm NaCl 1.9
Pure water vith 1 ppm NAOH 5.6
The conductivity is often used to determine the purity of for example distillate of sea water distillation
units and the condensate of steam condensers. It helps to detect in these cases leakage of salt water.
The influence of the temperature is rather large, a few degrees centigrade temperature difference gives
approximately a 10% deviation from the above figures.
3.4. ALKALINITY
Alkalinity is a measure of the degree to which water will neutrahse acid and is caused by the presence
of hydroxides, carbonates and bicarbonates e.g.
NaOH Ca(OH)z Mg(OH)z
Na2C03 CaC03
NaHC03 Ca(HCO312
To determine the alkalinity we titrate with HC 1. Assume we start with water of a pH above 9, then we
first use phenoldhthalein as an indicator. At a pH = 8.3 we see that the liquid which was red becomes
colourless. The amount of acid required gives the p-afknlinity.
V
At this point the following reactions will have been completed.
NaOH + HCI + NaCl + H20
Na2CO3 + HCl -+ N a H C 0 3 + NaCl
Now we add methyl orange and continue titrating with acid till the colour changes from yellow/orange
-+ red (at pH - 4.3). The total amount of acid required gives the m-ofkalinity.
The reaction completed during this stage of the titration will be:
NaHC03 + HCI + NaCl + Hz0 + CO2

-9-
Thus P-Alkylinity is a measure of
Total hydroxide + % Carbonate
And M-Alkylinify is a measure of
(Total hydroxide + % Carbonate) + % Carbonate + Total bicarbonate.
Water with a pH < 8.3 contains in addition to bicarbonates also free CO2 which can be determined by
titrating with NaOH to the phenolphtalein end point (pH = 8.3).
Information which can be obtained from acid titration can be summarised in the following table.
Result of titration Hydroxyl (OH-) Carbonate (CO, Bicarbonate (HCO;)

mgeq/l mgeq/l mg eq/l
0 0 m
0 2P m-2p
0 2P 0
2p-m 2(m-p) 0
p=m i
P 0 0
Example:
If p = 0.8 mg eq/l. and m = 5 mg eq/l.

Calculate Hydroxide, carbonate, bicarbonate, free CO2.
Hydroxide
From Table if 2 p < m hydroxide = 0

As this is the case no hydroxide is present.
Carbonate
P = hydroxide + % carbonate
0.8 = 0 + % carbonate
.. carbonate = 2 x 0.8 = 1.6 mgeq/l.
Bicarbonate
m = hydroxide + % carbonate + % carbonate + bicarbonate

5 = 0 + 0.8 + 0.8 + bicarbonate
.. bicarbonate = 5 - 1.6 = 3.4 mgeq/l.
Free CO2
As there is p-aikylinity present pH will be above 8.3 and no free CO2 will be present.

-lO-
3.5. HARDNESS
I-
Hardness is normally due to the presence of calcium and magnesium salts, though iron, aluminium and
manganese may be present in small quantities and may contribute to the hardness.
The amount of hardness present in natural waters varies greatly and depends on the geological
formations with which the water has been in contact.
Tunporarv (corbonute) Hardness. Although limestone (CaCO3) is only slightly soluble (0.015 g/l), a
lot of calcium carbonate can dissolve because of presence of CO2 in rain water which converts
insoluble carbonate to soluble bicarbonate.
CaCO3+ COz+ Hz0 + ca(Hco3)2
Ca(HCO3)2 is a very unstable salt, so unstable that it cannot be isolated. If a solution containing
Ca(HCO3)2 is boiled, the calcium bicarbonate decomposes completely reversing the above reaction.
ca(Hco3)2 + CaCO3 & + Hz0 + CO2
The hardness due to bicarbonates is called temporary hardness.
Permanent (non-carbonate) Hardness. Anions other than Cog-- and HC03- are normally also
present e.g. SO4- and Cl-. CaS04, CaClz, MgSO4, and MgC12 do not decompose when boiled,
consequently this part of the total hardness is called permanent hardness.
Total Hardness is the sum of temporary and permanent hardness.
Classification I Carbonate hardness Non-carbonate hardness

Calcium hardness CaW0312 caso4
CaCO3 CaC12
Magnesium hardness Mg(HCO3)2 MgSO4
MgCO3 MgC12
‘V
In the UK the term alkaline hardness is used. It is the hardness due to the Ca- and Mg-bicarbonates,
carbonates and hydroxides. In natural waters hydroxides are as a rule not present, consequently for
natural water:
alkaline hardness = carbonate hardness.
As we saw CaC03, is only sparingly soluble (O-015 g/l) and for this reason it is possible to reduce the
hardness of water containing Ca(HC03)2 by adding Ca(OH)2.
Ca(HCO$ + Ca(OI+ + 2CaC02 J + 2 Hz0 (lime softening)

-ll-
4. CHEMICAL REACTIONS INVOLVED IN WATER TREATMENT
4.1. DISSOCIATION OF WATER
H2 CJ H+ + OH-
4.2. NEUTRALIZATION
NaOH + HCI + NaCl + H20
H2SO4 + Ca(OH) 2 + CaS04 + 2 Hz0
4.3. FLOCCULATION
A2(SO4)3 + 3 Hz0 + 2 Al(OH)3& + 3 H2SO4
FeCl3 + 3 H20 + Fe(OH)3& + 3 HCI
A,z(SO4), + 2 Na2AlO3 + 2 Al(OH)3& + NazS04
FeS04 + Cl + 3 Hz0 Fe(OH)3& + HCI + H2SO4
when acid is produced in these reactions, it may be necessary depending on the alkalinity of the water,
to neutralize this for example with Ca(OH)2 (see above).
4.4. LIME TREATMENT addition of Ca(OI-02
A process to remove the temporary hardness and CO2
Ca(HCO3)2 + Ca(OH)2 + 2 CaCO3& + 2 Hz0

Mg(HC03)2 + Ca(OH)2 + CaCO3J. + MgCO3 + 2 H20
MgCO3 + Ca(OH)2 + CaC03J + Mg(OH)2
CO2 + Ca(OH)2 + CaCO3& + H20
4.5. CATION EXCHANGER: softening TDS is not reduced
_R indicates ion exchange resin.
Ca++ Ca
+ Na .B + _R+Nasahs
Mg* Mg
(softened water
hardness (Ca* Mg*)
replaced by Na)

- 12-
‘-
Ca* CaCl2
.R + NaCl + Na.R + MgCl2
MS++
NaCl brine for regeneration wastedbrinetodraii
4.6. ANION EXCHANGER (weak base) for alkalinity removal
HC03
+R*CI + R SO4 + NaCl
CO3
(water, alkalinity
removed and replaced
by Cl-)
- Regeneration:
HC03 HC03
R SO4 + NaCl + R l Cl + Na SO4
i CO3 CO3
L J.
NaCl brine for wasted brine
regeneration to drain
A weak base anion exchanger does not remove silica.
The silica content of the water can be reduced by using a mixture of NaCl(90%) and NaOH (10%) for
regenerating the resin.
4.7. DEMINERALIZATION
All cations and anions are removed by exchanging vith H+ and OH- in 3 steps:
i/
Ca HC03
1. Cation exchanger : Mg 804 +H*R + R_*{; +H{“’
Na i 1 Cl
in the water
2. Degasification : H2CO3 + CO2 t +H20
SO4 so4
+ Hz0 (demineralized water)
3. Anion exchanger : H c, +R*OH + R c,

- 13-
Cation exchanger with HCI or H2SO4

Regeneration :
{ Anion exchanger with NAOH
4.8. PHOSPHATE TREATMENT
Phosphate treatment is applied to remove any residual hardness of the water, which might have
remained after the softening process either by lime treatment or ion exchange (cation + weak base
anion).
2 Na3P04 + 3 Ca(OH)2 + Ca3W4)2 + 6NaOH
3 Ca3 @04)2 + CW-02 + CaioV-02 PO4k

(Calcium hydroxy,
apatite-final product)
This Ca salt (sludge) is not deposited on the boiler tubes and is removed as sludge with the boiler blow-
down.
4.9. OXYGEN SCAVENGERS
02 may cause serious corrosion of steel.
Without oxygen being present the following reactions take place:

below 50°C Fe + 2 Hz0 + Fe(OH)z + H2 forming a non-protective layer of iron hydroxide.
At temperatures above + 50°C the iron hydroxide is converted into magnetite as follows:
3 Fe(OH)2 + Fe304 + 2 Hz0 + Hz
At still higher temperatures, e.g. ranging from 22OT to 57OT magnetite is formed directly
3 Fe + 4 Hz0 (steam) + Fe304 + 4 H2
If oxygen is present sten at spots where the Fe304 film is damaged the steel exposed will react as
follows:
4Fe+2n*H20+302 -+ 2(Fe203 l nH20)
the powdery hydrated Fe203 thus formed is non-protecting and promotes pitting type corrosion
In order to remove any 02 from the water, deaeration equipment is used. Any remaining 02 is
removed with hydrazine, sulphite, etc.
Hydrazine N2b + 02 + Hz0 + N2
Sulphite 2 Na2SO3 + 02 -+ 2 Na2S04

- 14-
5. IMPURITIES IN FRESH WATER

‘V
1) TURBIDITY
Formula : None - expressed as FTU and NTU.
Problems : Imparts unsightly appearance to water; deposits in water lines, process equipment, etc.;
interferes with most process uses.
Treatment: a) Filtration alone for small amounts of turbidity; adding coagulant directly ahead of filters
if clearer effluent is required. b) Coagulation, flocculation, settling and filtration for larger amounts of
turbidity; prechlorination is usually beneficial; alkali addition, if needed for optimal pH-value; a
flocculant aid (usually a polymer) often improves the floe formation.
2) SUSPENDED SOLIDS
Formula : None- expressed as ppm, determined gravimetrically; measure of undissolved matter.
Problems : Deposits in heat exchange equipment, boilers, water lines, etc.
Treatment: Subsidence; filtration, usually preceded by coagulation and settling.
3) COLOUR
Formula : None - API-IA (American Public Health Association) units. Colour or “true colour” refers to
ir colour that is due to substances in solution; it is the colour of the water a&r the suspended matter has
been removed (by centrifuging, rather than filtration. The platinum - cobalt method of measuring
colour shall be considered as the standard. (Note: The colour standards are usually prepared by
appropriate dilutions of the standard stock solution, which is preferably made according to the above
quoted authority as follows: Dissolve 1.245 g of potassium chloroplatinate - K2PtCl6 - containing 0.5
g of platinum, and l g of crystallised cobaltous chloride - CoC12.6H20 - containing about 0.248 g of
cobalt in water with 100 ml of concentrated HCI, and dilute to 1 litre with distilled water. This solution
has a colour of 500). Problems : Non-aesthetic appearance of drinking water; deposits and fouling of
ion exchange units, heat exchange equipment, lines, etc.
Treatment: Same as 1 b), but addition of clay or other weighting agents, to density floes. if water has
low amounts of suspended matter.
4) HARDNESS
Formula :, Calcium and magnesium salts expressed as ppm CaC03. In fact iron and manganese can
also be classified as hardness, however, usually the amounts of iron and manganese in natural waters
are so low, that their influence on the hardness is negligible.
Problems : Major source of scale in heat exchange equipment, boilers, pipe lines, etc.
- Treatment: a) Cold, warm, or hot lime-soda process: precipitation, settling and filtration. b) Ion
exchange: softening, demineralisation. c) Boiler water treatment: internal softening with phosphates.
5) ALKALINITY
Formula : Bicarbonate (HCO3-), carbonate (CO3--) and hydroxide (OH-), expressed as CaC03. It
should be noted that the alkalinity of boiler water is also influenced by phosphates and silica.
Problems : Na2C03 and NaHC03 will decompose in the boilers as follows:
2NaHC03 + heat ----> Na2C03 + H20 + CO2

Na2C03 + I-I20 + heat ----> 2NaOH + CO2
The CO2 will be carried over with the steam and will cause corrosion in condensate return lines.
NaOH may cause embritdement of boiler steel. A high alkalinity of the boiler water may result in
foaming and carry over of solids with the steam.
Treatment : a) Cold, warm and hot lime-soda process. b) Ion exchange: hydrogen zeolite softening,
demineralisation, de-alkalisation by anion exchange. c) Acid treatment (reduction of pH via acid
dosing, followed by degasifier).

- 15-
6) CARBON DIOXIDE u
Formula : CO2
Problems : Corrosion in water lines, in particular steam and condensate lines.
Treatment : Aeration in degasifiers, deaeration, neutralisation with alkalies, e.g. ammonia or hydrazine,
which decomposes in the boiler to ammonia, which is carried over with the steam. In order to prevent
CO2 corrosion in condensate lines, often neutrahsing amines are being applied. Also brands of
neutralising amines with varying distribution ratios are applied, e.g. Nalco Triact 1800. In this way the
steam part of the system, the condensing part of the system and the liquid part of the system are
protected. The amine dosing should be continuous (e.g. in the suction of the BFW pumps); the dosage
rate has to be such that a pH-value of 8.5-9.0 in the return condensate should be aimed for.
7) FREE MINERAL ACIDITY (FMA)

Formula : H2SO4, HCI and HN03, expressed as ppm CaC03.
Problems : Corrosion.
Treatment. : Neutralisation with alkalies, or removal with anion exchange.
8) pH-VALUE
Formula : Hydrogen ion concentration, defined as: pH = - log [ H+]. d
Problems : pH varies according to acidic or alkaline solids in water; most natural waters have a pH of
6.0 - 8.0. Low or high pH could cause corrosion etc. to steel.
Treatment : pH can be increased by alkalies and decreased by acids. The pH of BFW can be controlled
with volatile chemicals (e.g. morphohne, hydrazine, ammonia, etc.), or non volatile chemicals (e.g.
caustic, tri-sodium phosphate, etc., which are used for the boiler water). The pH of the boiler water
can only be controlled with non-volatile chemicals.
9) SULPHATE
Formula : SO4--
Problems : Adds to solids content of water, but in itself is not usually significant; combines with
calcium to form calcium sulphate scale.
Treatment : Demineralisation, reverse osmosis, evaporation.
10) CHLORIDE
Formula : Cl-
Problems : Adds to solids content and increases corrosive character of water.
11) NITRATE
Formula : N03-
Problems : Adds to solids content, but is usually not significant. High concentrations cause
methemoglobinemia in infants, and should therefore be limited in drinking water.
12) FLUORIDE
Formula : F-
Problems : Cause of mottled enamel in teeth; also used for control of dental decay.
Treatment : Adsorption with magnesium hydroxide, calcium phosphate or bone black; aluminium
coagulation.

-16-
13) SODIUM
.-’ Formula : Na+
Problems : Adds to solids content of water; when combined with OH- causes corrosion in boilers under
certain conditions.
Treatment : Demineralisation, reverse osmosis, evaporation,
14) SILICA
Formula : Si02
Problems : Scale in boilers and cooling water systems; insoluble turbine blade deposits due to silica
vaporisation. Silica in natural waters can be present as reactive silica and non-reactive (colloidal)
silica. Colloidal silica will not be removed by ion-exchange, nor will it be observed by silica analysers.
Under boiler conditions the non-reactive silica will be converted to the reactive form. Examples:
Tabangao, Pililla, Sriracha.
Treatment : Hot and warm lime process with magnesium salts; adsorption by strong base anion
exchange resin (special grades for non-reactive silica), reverse osmosis, ultra filtration, evaporation.
15) IRON
Formula : Fe2+ (ferrous), Fe3+(ferric)
V Problems : discolours water on precipitation, source of deposits in water lines, boilers, etc.
Treatment : Aeration, coagulation / filtration, lime softening, cation exchange, contact filtration,
surface-active agents for water retention.
16) MANGANESE
Formula : Mn2+
Problems : Same as iron.
Treatment : Same as iron.
17) ALUMINIUM
Formula : Al3+
Problems : Usually present as a result of floe carry over from clarifier; can cause deposits in cooling
systems and contribute to complex boiler scales. Can help to form deposits in cation units of demin
plant.
Treatment : Improved clarifier and filter operation,
18) OXYGEN
V Formula : 02
Problems : Corrosion of water lines, heat exchange equipment, boilers, return lines, etc
Treatment : Deaeration, oxygen scavengers, corrosion inhibitors.
19) HYDROGEN SULFIDE

Formula : H2S
Problems : Cause of “rotten egg” odour, corrosion.
Treatment : Aeration. chlorination, strong base anion exchange resin
20) AMMONIA
Formula : NH3
Problems : Corrosion of copper and zinc alloys by formation of complex soluble ion.
Treatment : Cation exchange with hydrogen zeolite, chlorination; deaeration.

- 17-
21) DISSOLVED SOLIDS

Formula : None, expression is TDS v
Problems .: Refers to total amount of dissolved matter, determined by evaporation; high concentrations
are objectionable because of process interference and as a cause of foaming in boilers.
Treatment : Lime softening, demineralisation, reverse osmosis, evaporation.
22) TOTAL SOLIDS

Formula : None
Problems : Refers to the sum of suspended and dissolved solids, determined gravimetrically.
Treatment : See dissolved solids and suspended matter.
Ml48_10 Basic Water Chemistry

Confidential
Ml48
MODULE 1
SECTION 2
INDEXI.DOC: 22108197
SECTION 2: PRETREATMENT
Contents:
Subsection:
2.1 Clarification
Introduction
Flocculating agents
Mechanism of floe formation
Clarifiers
2.2 Filtration
Multimedia filters
Activated Carbon filters
Cartridge flters
Precoat filters
2.3 Precipitation Softening
Introduction
Lime softening process
Calculations HPS units
2.4 Aeration
General
Aeration by trickling
Aeration by water spray
Diffised aeration
Oxydation by strong oxidisers
‘V
M148_2l_clarification
Page I
SECTION 2: PRETREATMENT
SUBSECTION 2.1: CLARIFICATION
INTRODUCTION
TURBIDITY should be removed, for e.g. prevention of fouling of ion exchange resin, bacterial
purification of drinking water, etc. For once-through cooling water clarification is not required
As turbidity results from clay or organic matter, it is usually present in surface water, but is often slight
in well water owing to natural filtration in the water bearing formation. However, if there is any iron or
manganese in the well water, this may, on exposure to air, lead to turbidity from ferric hydroxide or
manganese dioxide.
CLARIFICATION of turbid water for industrial usage is a combination of flocculation, settlement

and filtration.
For FLOCCULATION, a suitable flocculation agent is added to the water so that the small particles,
which form the turbidity, cling together and form larger particles, the floe, with better settlement
behaviour. All flocculation units consist of two compartments: the flash mixing basin, where the floe is
formed and the floe growth basin followed by a third step: the separation of the floe from the water by
e.g.:
l Sedimentation or
l Floatation or
l Filtration
LIME TREATMENT is applied to prepare boiler feed water from turbid and hard water. Sometimes
this step is combined with clarification in one step.
WASTE WATER TREATMENT is essential for environmental protection. “Primary treatment”

consists of oil and sludge removal in shimming tanks and plate interceptors such as API, CPI, TPI.
“Secondary treatment” includes Flocculation, Flotation; a deep removal of suspended solids, dispersed
- oil and dissolved H2S and, if required, reduction of calcium, magnesium and fluoride by addition of
chemicals. Next secondary treatment step is the biological treatment where dissolved pollutants as
hydrocarbons, phenols, chemicals, ammonia are degraded,
This handout describes briefly the principles, layouts operation parameters of the flocculation,
sedimentation and filtration and the use of flocculation and filtration aids.
FLOCCULATION AGENTS
The classical practice of flocculation is to add some ppm’s of ferric or aluminium salt. These salts
form a voluminous floe of ferric or ahnninium hydroxide respectively, which encloses the suspended
particles. The pH should be controlled within the range of minimum solubility of ferric hydroxide or
aluminium hydroxide.
Since sludge disposal is getting more difficult, the use of even more expensive polyelectrolytes becomes
attractive.
M148_2l_claritication
Page 2
Some details on flocculation agents: d
Aluminium Salts
A widely used coagulant is ahuninium sulphate known as filter alum with the composition
A#O4)3*18H2O. Ahminium saks are applicable within a pH range of 5.5 to 8.0; the reaction to
form aluminium hydroxide consumes alkaliity by the production of acid:
N2(SO4)3 + 6 Hz0 - 2 A1(0H)3 + 3 H2sO4
Ifthe natural alkalinity (bicarbonates) of the water is not enough soda or lime must be added to
neutralise the acid, alternatively, a mixture of al&urn sulphate and sodium aluminate (Na+lO3)
can be used to prevent a pH drop without the need for caustic addition:
A2(SO4)3 + 2 Na3AlO3 + 6 Hz0 - 4 AI + 3 Na2SO4

Note that the salt content of the treated water is increased by this method.
Iron Salts
Iron salts such as ferric sulphate and ferric chloride act by precipitating ferric hydroxide, similarly to ‘c/
ahuninium salts. Ferric salts can be applied over a pH range of 4.0 to 11 .O. Ferrous sulphate
(copperas; FeS04*7H20) has to be used in a higher pH range of 8.5 to 11 to promote oxidation by
oxygen in water. Often chlorine is added to produce ferric sulphate; this use of “chlorinated copperas”
is of course similar to that of ferric salts.
Polyelectrolytes
Polyelectrolytes are long chaii polymer molecules, the long chains attach themselves to suspended
particles, thus creating larger particles which can settle; their action will be discussed under the heading
“coagulation”. There is a wide variety on synthetically prepared polyelectrolytes on the market.
Different &ii length (molecular weight) in the different groups: cationic, anionic and neutral.
Note that many of those polyelectrolytes should not be used in drinking water.
MECHANISM OF FLOC FORMATION

Turbidity is caused by small particles (size some mihnicrons) dispersed in water. These particles are
too small to settle; they do not combine to larger particles, as they carry an electrical charge and repel
each other. Clay particles are usually negatively charged. T’he electrical charge of these (colloidal)
particles is demonstrated as they move in an electric field; the electrical charge is quantified as the so-
called zeta potential.
Aluminium and ferric salts, having trivalent ions of positive charge (Al-; Fe-), have a strong
tendency tb neutralise the charge of negatively charged clay particles. When this charge is zero (zeta
potential zero) the particles can adhere to each other and form larger particles, a process called
coagulation.
Under some conditions, e.g. when flocculation is carried out at a low pH (sometimes desired to remove
colour from the water), the dosage of Al* (or Fe-) has to be kept within narrow limits.
A too high dosage makes the particles from negatively, positively charged and thus proper coagulation
is not obtained. Good coagulation is a prerequisition to obtain good flocculation.
The use of polyelectrolytes in coagulation is important.
M148_2l_chilication
Page 3
Polyelectrolytes are long chain polymer molecules, either positively (cationic) or negatively (anionic)
L charged or non-ionic. If a small dosage of polyelectrolyte is added which is opposite in charge to the
particles present, its action can be explained by assuming that the long chains attach themselves to
several particles and thus produce larger settling particles. Polyelectrolytes are used in combination
with ahnninium or iron(3) salts or sometimes alone. As they are rather expensive in comparison with
ahnninium or iron salts, their use is sometimes limited to cases where difficulties occur temporarily,
e.g. in seasons of high turbidity in river water or where the capacity of the flocculation equipment is
becoming too small.
To promote settling, weighting agents are sometimes added.
To obtain the most efficient and economical flocculation, laboratory tests are made to determine in a
series of jar tests the best flocculation agent to use, the dosage which is required and the optimum pH
for flocculation.
CLARIFIERS
Clarifiers
Clarifiers consist of one basin with two built in compartments in which the floe is formed and settled
Mixing compartment
The flocculation agent should be mixed rapidly and homogeneously with the water in order to ensure
efficient flocculation with minimum dosage.
Flocculation compartment
Gentle stirring brings the small particles together so that they can increase in size. The stirring speed
should be well controlled, as too high a speed may break down floes already formed. The residence
tune may vary from 10 to 20 minutes. Recirculation of floe siurry is often applied to obtain a larger
floe.
Sedimentation basin
Most clarifiers operate by sedimentation because of the lower unit cost per vohune processed. There
are rectangular and circular settlers available. The cross sectional area of the settling chamber must
ensure that the downward velocity of tbe particles is greater than the velocity of the water surrounding
ti the particles and may vary between one and two and a half m/h ((m3/h)/m2).
Settled floe accumulates on the bottom of the sedimentation basin. The sludge is usually mechanically
scraped into a sump, from which it is drawn off as slurry.
M118_2I_clarikation
SUB SECTION 2.2: FILTRATION
Usually clarification of water is followed by filtration, in particular filtration through a filter-bed. L/
In these filters floes, carried-over from the preceding clarifier and/or formed during after-reactions
are removed. The filters contain layers of granular filter media, such as silica sand, anthracite and
garnet. We can distinguish down-flow pressure-type filters (vertical or horizontal) or up-flow
(immedium) pressure-type filters. In the down-flow tihers “surkce filtration” is employed; in the up-
flow filters “in-depth filtration” is employed. The end of service cycle of the filters is determined by
the d.i&rential pressure across the filter bed. By means of backwashing, in combination with air
scouring an exhausted filter bed can be restored to its original condition. Following the filtration step
the raw water is suitable as feed to ion exchange units and drinking water preparation facilities, and
as make-up water to a recirculating cooling water system.
1 ‘Multi media filters

CIKEA REFERENCE : WAT - 013O/A230
GEN - Utilities-Excellence manual page 3013 1
Multi media filters are used primarily to remove susuended solids. Multi media filters are horizontal
or vertical, carbon steel, rubber-lined vessels, containing two or three filter media. Since the most W
optimum filtering is achieved with coarse to tine filtration, in down-flow filters the filter media
should have a different grade and specific gravity, e.g.:
Anthracite : g r a i n s i z e =l.Omm - specific gravity = 1.6;
Silica sand : gram size = 0.5 mm - specificgravity = 2.65;
Garnet : grainsize = 0.2-0.4 mm - specific gravity = 4.5;
This type of filter operates with a linear velocity of some 10 m/h. The end of the service cycle is
determined by a high dP or by end service cycle time (24 hours).
Design guidelines :
Design aim is that filtered water should have a turbidity < 1 NTU.
System should be designed such that peak daily average can be met with one filter out for
maintenance and another in backwash.
For single media filters (e.g. sand or anthracite) 7.5 to 10 m/h.
For multi media (garnet, sand and anthracite) 15 to 17.5 m/h. -
Backwash flow rates for anthracite filter : 20 to 25 m/h.
Backwash water rates for sand filters : 30 - 37.5 m/h.
Air scouring as backwash step is strongly recommended for new installations.
Backwash water needs to come from its own pumps. It can be either feedwater or filtered
water.
The design backwash frequency should be once every day.
2 Activated carbon filters
The activated carbon (A/C) filters are used for the removal of organic material from the water and
the 1-2 ppm of suspended solids, carried over from the multi media filters. The units serve as a
mechanical filter as well, in particular if a bottom layer of garnet is applied.
(Note: It may be possible at this stage to apply precoat filtration. Usually A/C filters are applied in
the pre-treatment of sea water and precoat filtration in the pre-treatment of surface water.)
This will increase the lifetime of the down flow located cartridge filters. Activated carbon is a
microporous form of carbon. The internal surface area can exceed 200 ni? per gram of activated
carbon. The end of the service cycle of an NC filter is determined by a high pressure drop. Regular
back washing is advised anyhow to avoid development of bacteria. Usually treated (filtered) water is
used for back washing.
The service life of activated carbon depends on the amount and composition of organics and/or
hydrocarbons in the inlet water and varies from a few months to a few years.
Exhausted activated carbon may be reactivated using steam (when the carbon has been contaminated
with compounds that evaporate between 100 and 150 degrC), or thermally, i.e. burning off
contaminants from the carbon surface at temperatures between 800 and 1000 degrC (this
reactivation process is usually done by the carbon manufacturer). There are no SIOP-advised
Operating companies where reactivation of exhausted carbon is being practised; the activated carbon
is simply renewed.
The hydraulic load of an NC filter should be maximum 3 BVWh; minimum contact time should
therefore be 20 minutes. I
4 Cartridge filters
Reverse osmosis (R/O) units are very sensitive for fouling. Therefore, upstream of the R/O units
usually cartridge filters are installed in order to ensure that all types of traces of suspended material
(e.g. turbidity, carriedover floe particles, colloidal material, colour, etc.) will be removed from the
supply water.
Depending on the type and the degree of fouling, these cartridge filters have to be renewed (thrown
away) on a frequent basis.
5 Precoat filters
Amongst other duties, precoat filters may be utilised to remove fine suspended material, which has
slipped through the preceding multi media filters, thereby increasing the lifetime of the downstream
located.
The precoat filter medium comprises a layer of finely divided fibrous or granular materials attached
on a porous medium (candle). These materials can be removed easily by means of backwashing. The
filter layer (precoat) has a thickness of a few millimetres and it is attached to the outside of the
candle by charging the suspended filter medium solution through the candle. The filter may contain
up to 300 candles.
Before the filter can be taken into service, the filtrate should be clear. The normal operating cycle
can start at a rate varying normally between 1 to 15 m/h. depending on the nature and the
concentration of the substances to be removed and the duration of the service cycle.
The service cycle or the filtration rate can be increased by injecting extra precoat material during the
filtration cycle. This type of injection, which is referred to as “body-feed”, prevents the rapid
increase of head loss. Backwashing is carried out by means of water (in combination with air), when
the maximum acceptable head loss is reached.
For the R/O option cellulose fibres are used. Cellulose fibres are especially suitable to remove
suspended solids, in particular metal oxides, down to an average size of 0.5 micron.
SUBSECTION 2.3: PRECIPITATION SOFTENING
1. INTRODUCTION
In the early days of industry water treatment was unknown. Readily available types of water,
originating from surface waters (like rivers and lakes) or underground waters (like springs and
wells), were fed directly to the boiler systems without any pre-treatment. Natural-type waters
always contain (to a certain extent) a large number of impurities, which can be classified in
three major groups (see also Appendix 1):
- Group I : ionic/dissolved impurities
- Group 2: non-ionic/undissolved impurities
- Group 3: gaseous impurities
Owing to these impurities a large number of problems were experienced, such as corrosion,
formation of scale and deposits, poor steam quality, etc. In order to overcome these problems
some basic internal treatment programs were developed, e.g. dosing of soda, vegetables, etc.
However, with the development of larger boiler units with progressively increasing steam
pressures and temperatures, a more stringent control on the water quality became a necessity.
In the course of years special water treatment processes were developed, all aiming at \c/
removing the undesired impurities from the raw water before feeding it to the boiler systems.
These water treatment processes can be categorised as external water treatment or internal
water treatment.
In external water treatment processes the impurities in the raw water are partly or completely
removed, e.g. by means of aeration, clarification (coagulation/flocculationkdimentation),
filtration, cold and hot lime soRerung, desalination, ion-exchange, etc., prior to feeding the
water to the boilers.
In internal water treatment processes the objectionable effects of impurities are partly or
completely neutralised, e.g. by means of boiler water conditioning programs, protective
measures for condensate systems, etc., within the steam raising plant.
This part of the workshop deals with the hot lime softening (external treatment) process.
2. LIME SOFTENING PROCESS
2.1 General
Lime softening is a precipitation process which is applied as a first-stage treatment followed w
by ion-exchange for boiler feedwater make-up, or to prepare water for direct use as cooling
water make-up.
The lime softening process can take two forms:
- the “coldll lime sofiening process (CPS) - operating temperature: 4-32T;
- the “hot” lime softening process (HPS) - operating temperature: 102-l 10°C.
In both processes the treatment is accomplished mainly by the use of lime. Depending on the
composition of the raw water to be treated, and the required product water quality, additional
chemicals may be dosed. such as magnesium salts, soda ash and gypsum.
The objectives of the lime softening process are as follows:
I) reduction of “carbonate’‘hardness (hardness associated with alkalinity);
2) reduction of alkalinity;
3) reduction of silica *) see note.
In addition, in lime softening the turbidity of the water will be reduced, while free Cot will be
removed completely. In genera) it can be stated that results achieved with HPS units are better
than with CPS units, in particular with respect to the removal of silica.
*) Note: silica removal
Some natural waters (e.g. well water in the PSPC and PPC refinery in the Philippines),
contain appreciable amounts of colloidal silica, which is also called non-reactive silica.
Colloidal silica cannot be removed by ion-exchange, nor will it be detected via quality
instruments or routine laboratory analysis. At boiler conditions colloidal silica will be
converted to the ionised form. This may cause unexpectedAmknown excessive carry-over
of vaporous silica with the steam, resulting in problems with downstream steam turbines
(e.g. blade deposits, loss in efficiency, vibrations, sticking governor valves, etc.).
The lime softening process, in particular the HIPS, is one of the few processes which
- efficiently removes colloidal silica from the water.
2.2 Chemical Reactions
The following chemical reactions may play a role in the lime softening process:
a) CO1 + Ca(OH)? + CaCO& + Hz0
This reaction takes place in an CPS unit only; this means that some extra lime has to be
dosed.
In an HPS unit free CO2 will be removed via deaeration.
b) CaW03)2 + Ca(OH)I + 2CaCO& + 2Hz0
Mg(HCO$ + Ca(OHh + CaCO& + MgCO, + 2H20
MgCO, + Ca(OH)l + CaCOJ + Mg(OHhd
These are the most important chemical reactions in the lime softening process. It should
be real&d that only hardness associated with alkalinity (temporary hardness or
carbonate hardness) will be precipitated with lime. Non-carbonate hardness or permanent
hardness (hardness associated with sulphate, chloride, etc.) will not be precipitated by
lime.
V
c) M&l, + Ca(OHh + CaCll + Mg(OI-Q&
MgSO4 + Ca(OHh + CaS04 + Mg(OH)&
Mg(NO& + Ca(OHh + Ca(NO& + Mg(OH)2&
The above reactions show that the addition of lime to magnesium (permanent) hardness
will result in the formation of calcium (permanent) hardness, With other words: the
permanent hardness will not be reduced!
Permanent hardness can be (partly) reduced by the dosage of soda ash (Na2C02). The
reactions proceed as follows:
Na2C0, + CaC l2 + CaCO,-l + 2NaCL
Na2COp + MgC 12 + MgCO3 + 2NaCI
MgGO, + Ca(OH)* + Mg(OH)I& + CaCO&
It should be realised that in this case the reduction of hardness will result in an increase
of alkalinity in the product water.
d) 2NaC0, + Ca(OHh + CaCO,& + Na2CO3 + 2H20
Na2C0, + Ca(OH)? + CaCO& + 2NaOH
The above reactions are not desired in view of the formati6n of free NaOH. Alkalinity
associated with sodium can be reduced by the dosage of gypsum (CaSOJ. The reactions
proceed as follows:
NaHCO, + CaS04 + Ca(HCO& +Na2SOd
Ca(HCO32 + Ca(OHh + ZCaCO,J + 2H20
It should be real&d that in this case the reduction of alkalinity will result in an increase
of hardness in the product water. However in case the lime softening unit is followed by
zeolite softeners (which is normally the case) this is no problem.
2.3 Chemicals in Lime Softening
The following chemicals may be applied in lime softening:
- CaO (IIslakd’ lime)
- Ca(OH)* (“hydrated” lime)
- MgO
- Mg(OH)z
- MgSO, (“Epsom” salt) W
- CaO.MgO (“Dolomitic” lime - 60%/40%)
- caSo4 (“Gypsum”)
- Na2C0, (“Soda ash”)
The following should be noted:
1) Too much agitation in the lime storage tanks should be avoided to minimise the formation
of CaCO, by the CO1 present in air.
2) MgO is more active than Mg(OH)*.
3) The above mentioned chemicals may contain impurities.
2.4 Tvnes of Water to be treated
With regard to lime softening natural waters can be classified in the following major groups:
4 Total hardness > m-alkalinitv
This type of water contains carbonate (temporary) hardness e.g. Ca(HCO)I and
Mg(HGO& and non-carbonate (permanent) hardness e.g. CaC llr CaSO+ MgC 12,
MgSO+ etc.
The lime dosage rate is based on the sum of m-alkalinity and total magnesium.
(N.B.: The total magnesium does not include any magnesium added for silica reduction.)
Silica will be removed (partly) by magnesium.
The amount of magnesium to be dosed depends on the magnesium content of the water to
be treated and the required silica content of the product water.
b) Total hardness < m-alkalinitv
Tbis type of water contains carbonate hardness only: Ca(HCO,), Mg(HCO,) and
NaHCO,.
The lime dosage rate is based on the sum of m-alkalinity and total magnesium.
(N.B.: The total magnesium does not include any magnesium added for silica reduction).
In order to remove the alkalinity associated with sodium, gypsum (CaSO,) may be dosed.
Silica will be removed (partly) by magnesium.
The amount of magnesium to be dosed depends on the magnesium content of the water to
be treated and the required silica content of the product water.
4
Note: It should be real&d that in theory some waters may be character&d by ‘II-I = m
however, in practice this is generally not the case.
2.5 Intluence of LP Steam on ion-balance in HPS Units
In an HPS unit the chemical dosage rates should take into consideration the contribution of
condensed LP steam to the total water to be treated. The dilution ef%ct of the condensed steam
to the ion-balance of the raw water to be treated may be considerable!
2.6 Ontimisation in Lime Softening
Optimisation of the lime softening process is a difficult task. It is possible to optimise either
on the reduction of hardness, or on the reduction of alkalinity. The most optimum result will
be achieved when the quality of the product water complies with the equation:
where: p = p-alkalinity
m = m-alkalinity
The equation 2p - m = 0 implies that the product water of the HPS unit does not contain
hi-carbonate ions (HCO3-), nor hydroxide ions (OH-).
Overdosage of lime means: 2p-m>O
Underdosage of lime means: 2p-m<O
In practice optimum efficiency is achieved with a slight excess of lime, i.e.: 2p - m = 5 to 10
ppm as CaCO,.
The optimum pH value of the process is 10.0-10.4.
Optimum removal of silica can only be achieved in an HPS unit in combination with a certain
minimum concentration of magnesium. If there is insufficient magnesium present in the raw
water additional magnesium has to be added. This can be in the form of MgO, Dolomitic lime
(CaO.MgO) or Epsom salt (MgSO&
The optimum pH value ofthe process is 10.0-10.4.
2.7 Lime softening eouioment
On the next page are shown simplified sketches of an CPS and an HPS unit.
Please note that the temperature of the HPS unit is controlled by a pressure controller.
Sometimes this is done by a temperature controller, however, in that case the response is
somewhat slower.
Chemical reactions in a CPS unit are slower than in an HPS unit.
Therefore the retention time in an CPS unit Is longer (typically 90 min. vs. 60 min.)
The objectives of lime softening are as follows:
- reduction of carbonate hardness;
- reduction of alkalinity;
- reduction of silica *) see note.
In addition in lime softening, turbidity and the free CO? of the water will be removed. Silica,
including colloidal silica will be removed, however, only with the warm and hot lime softening
process.
CPfj LiNIT ( C O L D PROCESS 5OeENER)
RAW W A T E R
TREATED WATER
OUTLET TO FILTERS
RATE OF FLOW
INOICATOI
HOT PROCESS SOFTENER

TYPE “U’
3. CALCULATIONS HPS UNITS
3.1 General
Chapter 2.4 shows that in practice I-IPS units are treating two types of raw water:
waterwithTH>m,or
waterwithTI-I<m.
The block scheme of Appendix 2, shows the major steps which
have to be followed by an I-IPS unit, in order to cope with either
type of water.
For the calculation of the dosage rates of the various chemicals graphs have to be used. These
graphs have been developed over the years, and they are based on practical experience and
(or) empirical laboratory experiments.
Below will be discussed in detail the calculation steps to be followed with an HPS unit,
operating on:
a) PSPC wellwater -TH<m *) seenote
b) PPC well water -TH>m *)seenote
Note: It should be realised that the quality of the well water in both Tabangao and Pililla may
vary considerably during the year.
3.2 Calculations HPS Unit Tabangao
Appendix 3 shows the results of the various calculation steps which have to be followed with
the HPS unit at PSPC.
First of all it is essential that a matching ion-balance can be produced of the raw water to be
treated i.e. TCs = TAs aotal Cations = Total &ions). Therefore ppm’s as such (ref. table A
- Appendix 3) have to be converted to ppm’s as ppm CaCO, (ref. table B - Appendix 3).
Conversion factors are shown in Appendix 8.
It should be noted that the silica of the raw water is not part of the ion-balance (silica in the
raw water is not present in the ionised form). The same applies to free carbon dioxide.
The ion-balance of the raw water to be treated should be corrected in view of the “dilution”
effect of the condensed LP steam. In this case it is assumed that some 15% of the total water
to be treated by the HPS originates from the steam. The corrected balance is shown in table C
- Appendix 3).
step:
Table C - Appendix 3 shows:
Total Hardness TH = 267 ppm as CaCO,, and
m-Alkalinity m = 285 ppm as CaCO,.
Conclusions:
a) water to be treated has a composition TH < m;
b) NaHCO3 content is 285 - 267 = 18 ppm as CaCO,
In order to prevent problems associated with NaHCO,, permanent hardness in the form of
CaS04 (Gypsum) is added to the water. In order to be on the safe side always some excess of
CaSO, is dosed; typically some 10 ppm as CaCOI. The dosage rate in this case is 30 ppm
CaSOd (expressed as CaCOa!). Thus excess is 12 ppm as CaCOa. Following the dosage of
CaS04 table D - Appendix 3 can be finished as follows: W
- calcium is: 160 + 30 = 190 ppm as CaCO,;

- magnesium and sodium remain the same;
- TCs are: 190 + 107 + 61 = 358 ppm as CaCO,;
- bicarbonate and chloride remain the same;
- sulphate is: 18 + 30 = 48 ppm as CaCO,;
- TAs are: 285 + 25 + 48 = 358 ppm as CaCO,;
- TH is: 190 + 107 = 297 ppm as CaCO,;
- m-alkalinity remains the same.
-4:
Table D - Appendix j shows that the non-carbonate hardness is 297 - 285 = 12 ppm as
CaCOr following the dosage of Gypsum.
Via table 1, Appendix 4, it can be found that the residual magnesium hardness of the treated
water will be 6 ppm as CaCO>.
-5:
W
Via graph 1, Appendix 4, it can be found that, based on the NCH of the water (12 ppm as
CaCO,) the residual carbonate-alkalinity of the treated water is expected to be 27 ppm as
CaCO, (guaranteed 34 ppm as CaCO,).
ster,:
TAs of the treated water: 27 + 25 + 48 = 100 ppm as CaC03 (ref. table E - Appendix 3).
Calcium hardness in treated water will be: 100 - 6 - 61= 33 ppm as CaCO,.
The residual total hardness (33 + 6 = 39 ppm as CaCO,) will be further reduced by the zeolite
sottening units.
!&lJ:
Via table 2, Appendix 5 it can be found, that, in order to reduce the silica to 1.5 ppm a total of
some 230 ppm of magnesium is required (expressed as ppm CaCO,!).
The water to be treated contains already 107 ppm magnesium as CaCOI. The required dosage
rate is therefore: 230 - 107 = 123 ppm as CaCO,.
w
Amount of lime to be dosed: m + magnesium = 285 + 107 = 392 ppm as CaCO,.
Summarv of dosage rates:
I) lime dosage rate 392 ppm as CaCO,;
2) magnesium dosage rate 123 ppm as CaCO,;
3) gypsum dosage rate 30 ppm as CaCO,
3.3 Calculations HPS Unit Pililla

Appendix 6 shows the results of the various calculation steps which have to be followed for
the HPS unit at PPC.
w:
A no&& ion-balance should be produced of the raw water to be treated, i.e. TCs = TAs.
Therefore ppm’s as such (ref. table A - Appendix 6) have to be converted to ppm’s as CaCO3
(ref. table B - Appendix 6). Conversion factors are shown in Appendix 8.
Silica and free CO* do not form a part of the ion-balance.
The ion-balance of the raw water to be treated should be corrected for the dilution effect of the
condensing LP steam.
It is estimated that at PPC some 15 % of the raw water to be treated originates from the LP
steam. Therefore a correction factor of 0.87 has been applied. Corrected figures are shown in
table C - Appendix 6.
Table C - Appendix 6, shows:

Total Hardness TH = I67 ppm as CaCO,, and
m-Alkalinity m = 146 ppm as CaCO,.
Conclusions:
a) water to be treated has a composition: TH > m, and
b) non-carbonate hardness (NCH) of tbe water to be treated is:
167 - 146 = 2 1 ppm as CaCOa.
steu4:
With the corrected NCH-figure of 2 I ppm as CaC03 (ref. table C - Appendix 6) it can be
found in table I - Appendix 4, that the residual magnesium hardness of the treated will be
8 ppm Mg, expressed as CaCO, (ref. table D - Appendix 6).
ster,:
Via graph I - Appendix 4, it can be found that, based on the NCH of 21 ppm as CaCOs, the
residual carbonate-alkalinity of the treated water is expected to be 24 ppm as CaCO, (ref.
table D - Appendix 6) and is guaranteed for 33 ppm as CaCO,.
S&&6:
Table D - Appendix 6, can be finished as follows:
- bicarbonate becomes 0;
- TAs of the treated water: 24 + 37 + 17 = 78 ppm as CaCO,;
- calcium-hardness of the treated water becomes: 78 - 8 - 33 = 37 ppm as CaCO,;
- TH following treatment is: 37 + 8 = 45 ppm asCaC0,;
- NCH = 21 ppm as CaCO,.
St&:
Via Table 2 - Appendix 5, it can be found that, in order to reduce the silica to 1.5 ppm as
SiO?, a total of some 230 ppm magnesium is required, expressed as ppm CaCO3.
The water to be treated contains already 89 ppm magnesium; the required dosage rate is
therefore 230 - 89 = 141 ppm as CaCO,.
step:
Amount of lime to be dosed: m + magnesium 146 + 89 = 235 ppm as CaCO,.
Ster,:
The NCH can be removed by dosing soda ash. Usually an overdosage of some 25 ppm
Na2C03, expressed as CaCO, is applied. From graph 2, Appendix 7, it can be found that,
with this overdosage and this particular case, the residual hardness of the treated water will be
some 2 I ppm as CaCOI. In this hardness the magnesium content is 2 ppm as CaCO, (by
definition!).
The total amount of Na2C0, to be dosed is: NCH + overdosage = 21+25 = 46 ppm as
CaCO,.
Table E - Appendix 6 can now be finished as follows:
- calcium hardness will be: 21 - 2 = 19 ppm as CaCO,;
_ sodium will be: 33 + 46 = 79 ppm as CaCO,;
- TCs will be: 19 + 2 + 79 = 100 ppm as CaCO,;
- chloride and sulphate remain the same;
- alkalinity following the dosage of soda ash has increased from 24 ppm as CaCO, to
100 - 37 - 17 = 46 ppm as CaCO,;
- TH=21ppmasCaCOx.
Summarv of dosaae rates:
1) lime dosage rate: 235 ppm as CaCO,;
2) magnesium dosage rate: 141 ppm as CaCO,;
3) soda ash dosage rate: 46 ppm as CaCO,.
4. HPS CALCULATIONS WITH LOTUS l-2-3

Recently MFSW53 developed an HPS computer program, based on Lotus l-2-3, which
performs automatically all calculations as per chapter 3.1 and 3.2, i.e.:
- the raw water analysis is converted from ppm’s as such to ppm’s as CaCO,;
- the raw water analysis is corrected for the dilution effect of the LP steam;
- the program selects the type of raw water to be treated, i.e.:
a) lime/magnesium/soda ash treatment in case: TH > m
b) gypsum/lime/magnesium treatment in case: TH < m;
- for the selected type of water to be treated the dosage rates of the relevant chemicals are
calculated;
- the expected quality of the product water is shown;
- the program includes a (limited) number of warnings, including the remedial actions to be
taken.
A copy of a printout of the calculations as per chapter 3 are shown in Appendix 9.
SUB SECTION 2.4: AERATION
1 General
Aeration techniques use the oxygen present in the air and work according to the laws of gas and
liquid phase mass transfer. It should be remembered that the oxygenation of water by aeration can
produce substantial - and undesirable - increases in scale-forming and aggressive properties. Co2
stripping tends to increase the liability to scale formation and may even bring about precipitation of
calcium carbonate.
Aeration processes can be categorised according to the method used for bringing the liquid and the
air into contact:
l water trickling
l waterspray
l air injection
Different aeration methods produce widely differing losses of head and thus have a determining
effect on the overall hydraulic gradient of the treatment plant. Bubbling techniques will produce e
pressure drops of a few centimetres while spraying techniques may reduce pressure by a bar or
more.
2 Aeration by trickling
Cascade aerators use the effect similar to the water from a tap mixing air into a bucket of water.
Very little pressure drop required.
3 Aeration by water spray

Water is sprayed through nozzles mounted on one or more manifolds, the idea being to maximise the
surface area of water coming into contact with air. The necessary spray pressure will depend on the
type and number of nozzles used. Moderately effective aerators are mainly used for the removing of
iron and manganese salts. If the capacity is to be kept within acceptable limits, this technique will
only admit slight variations.
4 Diffused Aeration
This technique consists of dispersion of pressurised air into the water. Pressurised aerators are often
used for removing Iron salts from deep-source well waters. The oxidation column in these devices is
closed and has a bed of volcanic rock supported on a floor. The water to be treated is pressurised
and mixed with pressurised water in a mixer. The water / air mixture is sent through the packing
bed, any excess air is let out into the atmosphere through the relief valve and the aerated water is
taken off from the upper part of the column.
5 Oxidation by strong oxidisers

For disu-rfection of potable water, chlorine, chlorinedioxide and ozone are used. A very detailed
description of the processes is given in Degremont’s water treatment handbook ~878 and further.
Confidential
Ml48
WATER (Pre-) TREATMENT COURSE COURSE

-
SECTION 3
PURIFICATION
INDEXIDOC:22108/97
Confidential
Ml48
MODULE 1
SECTION 3.1
INDEXI.DOC; 22/08/97
L
SECTION 3: PURIFICATION
SUBSECTION 3.1: ION-EXCHANGE FUNDAMENTALS
TABLE OF CONTENTS
1.0 INTRODUCTION .......................................................................................... 2

2.0 BRIEF HISTORY OF ION-EXCHANGE .................................................... 2
3.0 ION-EXCHANGE THEORY ........................................................................ 3
3.1 RESIN STRUCTURE (PART I) ............................................................ .
3.2 GROUPS OF ION-EXCHANGERS ...................................................... .3
3.3 STRONG/WEAK CATION/ANION EXCHANGERS ............................ 4
3.4 AFFINITY OF ION-EXCHANGERS .................................................... .4
3.4.1 Strong acid cation-exchangers ..................................................4
3.4.2 Weak acid cation-exchangers ....................................................5
3.4.3 Strong-base anion-exchangers ....................................................
3.4.4 Weak-base anion-exchangers ................................................... .6
3.5 SERVICE CYCLE OF ION-EXCHANGERS.. ...................................... .6
3.6 REVERSIBILITY OF ION-EXCHANGE REACTIONS ....................... .7
3.7 PERMANENT ION-LEAKAGE............................................................ .9
3.8 REGENERATION STEPS .................................................................. .I0
3.9 CO-CURRENT AND COUNTER-CURRENT REGENERATION ..... .I3
3.10 NEUTRALIZATION OF REGENERANT EFFLUENT.. .................... .14
3.11 EXERCISE: NEUTIZALISATION ....................................................... 15
3.12 RESIN STRUCTURE (PART 2) .......................................................... 17
4.0 ION-EXCHANGE EQUIPMENT ............................................................... 18

5.0 ION-EXCHANGE VOCABULARY, ABBREVIATIONS,
TERMS AND DEFINITIONS .................................................................... .20
- 6.0 REGENERANT QUALITY.. ...................................................................... .21
M148_3LDOC
- 2 -
-- 1.0 INTRODUCTION
As we have seen natural-type waters contain three major groups of impurities. Generally, those
impurities will for the greater part be removed in external water treatment processes.
This part of the course deals with ion-exchange processes. The ion-exchange treatment is a
method whereby the ionic/dissolved impurities are removed from the water.
The removal of non-ionic/undissolved impurities and gaseous impurities from raw waters will be
the subject of separate lectures.
2.0 BRIEF HIiTORY OF ION-EXCHANGE
All waters contain, to a certain degree, dissolved salts which dissociate into electrically charged
particles, called “ions”. The positively charged ions are called “cations”, the negatively charged
ions are called “anions”. Water is always in a state of electro-neutrality, which means that the
number of positive charges always balances the number of negative charges.
There are some natural and synthetic insoluble compounds which have the property to exchange
certain ions from a solution against certain ions from those compounds of equal charge. This
process, called ion-exchange, is widely applied in water treatment. The above-mentioned
compounds, which are used mainly in the form of resin beads, are called ion-exchangers.
The earliest research work on ion-exchange was carried out in 1850 by Thomson and Way in the
field of agricultural chemistry. They discovered that, when an ammonia-containing fertiliser
solution was passed through a column of soil, the soil retained the ammonia in exchange for
calcium, which could be found in the bottom of the column, They were of the opinion that ion-
exchange reactions were irreversible.
Eichhom proved in 1858 that the ion-exchange reactions are reversible and that exhausted
exchange material can be restored to its original condition by contact with a regeneration
chemical. This process is called “regeneration”.
Gans developed in 1905 the “softening” process with synthetic cation exchange materials, called
L “zeolites”. In this process the calcium and magnesium cations in the water, the main cause of
hardness, are exchanged for the sodium cations of the zeolite. Brine is used for regeneration. The
sodium zeolite softening process was very successful; however, it had certain limitations. Only
calcium and magnesium cations are exchanged, the anions are left unchanged. The softened
water therefore contains just as much bicarbonate alkalinity, sulphate, chloride and silica as the
raw water. This may result in serious boiler problems, e.g. due to decomposition of NaHC03 to
NaOH and CO2
Those problems led to the development of the hydrogen-based cation exchange process. In this
process all salts are converted into their corresponding acids. All bi-carbonates are thus
converted into CO2, which can be removed via aeration, A new hydrogen-based cation-
exchanger, called “Dusarit”, was developed in Holland in 1935. This resin, which is based on
sulphonated carbons, is regenerated with acid. The hydrogen-based cation exchange process also
had its limitations. The product water still contained the sulphate, chloride and silica anions.
The silica. in particular, became a serious problem in HE boiler systems.
Subsection 3.1: Ion Eschange Fundamentals

-3-
Thanks to research work of Adams and Holmes (1935) and D’Alelio (1944) new types of cation .J
and anion resins were developed. Since 1945 resin manufacturers have developed ionexchangers
of increasing stability and capacity. ln 1949 the first demineralisation unit, using strongly basic
anion resin for removal of silica, was commissioned. Nowadays, demineralisation processes have
been refined such that ultra pure water for e.g. the electronics industry can be obtained.
3.0 ION-EXCHANGE THEORY
3.1 RESIN STRUCTURE (PART 1)
Modem resins are made by polymer&&ion of various organic compounds. The most frequently
used compounds are styrene and divinyl benzene. The long-chained copolymer formed from these
compounds, contains a major proportion of styrene @O-92%) and a minor proportion of divinyl
benzene (S-20%). The latter acts as cross-links to hold the long polymeric chains together. To
this framework or “matrix” are grafted, by special patented techniques, the immobile charged
sites, called “functional groups” or “radicals”, to which are attached the mobile (exchangeable)
ions of opposite charge. (An enlargement of a cross-section of an ion-exchanger bead is shown
on page 2 1).
3.2 GROUPS OF ION-EXCHANGERS
Ion-exchangers can be classified in the following two major groups:
1) Cation-exchangers, containing immobile, negatively charged functional groups and

mobile, exchangeable cations.
2) Anion-exchangers, containing immobile, positively charged functional groups and

mobile, exchangeable anions.
Cation-exchangers are able to exchange cations from a solution for the mobile cations attached to
the cation-exchanger. Anion-exchangers are able to exchange anions from a solution for the
mobile anions attached to the anion-exchanger. This can be represented by the following
equations: d
X-H + NaCl + X-Na + HCI

X - O H + NaCl + X-Cl + NaOH
Subsection 3.1: Ion Exchange Fundamentals

3.3 STRONG/WEAK CATION/ANION EXCHANGERS
Ion-exchangers can further be classified in strong and weak cation and anion resins (see items
3.4.1-3.4.4). The type of functional group (or radical) determines whether a resin is strong or
weak (see pages 22 and 23). Typical functional groups for the various resins are listed below:
Resin type Functional Group
Strong acid cationexchanger (SAC) S03.H (Sulphonic acid)

Weak acid cation-exchanger (WAC) CO0.H (Carboxylic acid)
Strong base anion resin-type I (SBA)* N(CH&OH (Trimethyl amine)
Strong base anion resin-type 2 (SBA)* N(CH3)2C2HqOH.OH (Di-methykthanol a m i n e )
Weak base anion resin (WBA) N(CHj)z.OH (Tertiary amine)
NCH3H. OH (Secondary amine)
NH2.OH (Primary amine)
* SBA resins-type 1 have less exchange capacity, but are more stable than SBA resins-type 2
In general it can be said that cation resins are physically more stable than anion resins. Cation
resins also have a larger total exchange capacity than anion resins.
With total exchange capacity is meant the weight of ions which can be theoretically exchanged
per litre of resin. The ion-exchange capacity is expressed in gr CaCO$ltr of resin or in
equivalent&r of resin.
3.4 AFFINITY OF ION-EXCHANGERS
All ion-exchange operations make use of the fact that ion-exchangers have preference for certain
ions. As a general rule it can be said that a resin has a higher affinity for ions with a larger
number of electrical charges, e.g. it prefers Ca2+, with its two charges, to Na+, which has only
one charge.
Between ions with the same number of charges, the resin shows a higher affinity for the larger,
heavier ion> e.g. it prefers Ca2+, with its equivalent weight of 20, to Mg2+, which has an
equivalent weight of 12 only. This preference for certain ions can be expressed in the so-called
“affinity series”. For commonly encountered ions the following affinity series can be
distinguished:
X4.1 Strong Acidic Cation (SAC)-exchangers
Fe3+ > A$+ > Ca2+ > Mg2+ > K+ > Na+ > H+
This means that iron-ions combine much more strongly with the resin than the sodium-ions.
In practice the iron-ions will supersede ions of aluminium, calcium, magnesium, etc. from the
exchanger and calcium-ions will supersede the ions of magnesium, potassium, sodium and
hydrogen. If a neutral salt solution, e.g. calcium chloride, is passed through a column of a strong
acid cation-exchanger in the hydrogen cycle, the calcium-ions will supersede the hydrogen-ions
Subsection 3. I: Ion Exchange Fundamentals

-
-5-
from the resin, since the resin has a higher affinity for calcium than for hydrogen. The reaction
can be represented as follows:
CaCh + 2 X-H -_) 2X_Ca+2HCl
The cationexchanger in the hydrogen cycle means that almost all mobile cations within the
exchanger are hydrogen ions.
Strong acid cationexchangers are able to convert neutral salts into their corresponding acids.
They function well at all pH ranges.
When operated in the hydrogen cycle they will remove all cations from the water:
Ca 2 HC03 2 I-UC03
Mg SO4 +2X-H + 2X- H2SO4
2Na 2 Cl 2 HCl
3.4.2 Weak Acidic Cation (WAC) exchangers
H+ > Fe3+ > N3+ > Caz+ > Mg2’ > K+ > Nat
This affinity series is equal to that of a strong acid cation- exchanger, except for the hydrogen-
ion, which is standing in front. This means that this type of exchanger has the strongest affmity
for the hydrogen-ion.
Weak acid cation-exchangers can remove cations associated with hi-carbonate alkalinity only.
The hi-carbonates are converted into carbonic acid. They do not diction at pH levels below 5.0.
Ca Ca
Mg @1C03)2+2x-H + 2x- Mg +2H2CO3
2Na I 2Na
3.4.3 Strong Base Anion (SBA) exchangers
S042- > NO3- > Cl- > HC03- > HSiOp > OH-
Strong-base anion-exchangers in the hydroxide cycle are able to convert neutral salts into their
corresponding bases. The reaction can be represented as follows:
NaCl + X-OH + X-Cl + NaOH
The anion exchanger in the hydroxide cycle means that almost all mobile anions within the
exchanger are hydroxide ions.

-6-
-.__ Strong-base anion-exchangers can remove anions of both strong and weak acids. They can
operate over the entire pH range. :
H2SO4
2 HCI 2 Cl
+ 2 X-OH + 2x - +2H20
2 H2SiO3 2 HSi03
2 H2CO3 1 2 HC03
3.4.4 Weak Base Anion (WBA) exchangers
OH- > SO4*- > NO3- > Cl
Weak-base anion-exchangers are essentially mineral acid neutralisers. These resins will not
remove weak acids such as silicic acid and carbonic acid. They work most efficiently at pH
ranges below 4.0.
L H2so4 . . ..so4
2 HCI + 2 X-OH + 2x - 2 Cl +2H20
2 HNo3 2 NO3
3.4.5 Mixed Base Anion exchangers
Resin manufacturers combine the excellent regeneration efficiency of Weak Base Anion
wxchangers with the weak acid removal capacity of Strong Base Anion by combining weak and
strong groups in one resin bead.
3.5 SERVICE CYCLE (EXHAUSTION CYCLE) OF ION-EXCHANGERS
Raw water containing ions of iron, calcium, magnesium,

potassium and sodium is passed through a column of a strong
X - Fe’*
acid cation-exchanger in the hydrogen condition. Those cations
will be exchanged with hydrogen ions from the resin according x-CP’
to the affinity series. Consequently different zones will develop
X-t&$
in the resin bed. These zones will supersede each other, as the
ion-exchange process proceeds. The top layer of the bed will X-K’
be loaded with the ion with the highest affinity : iron. The ion
X-NI*
with the lowest affinity, sodium, can be found in the lowest
zone. X-H
During the service cycle those zones slowly move downwards.
The sodium zone will finally reach the bottom of the resin bed.
Continuation of the process will result in breakthrough of
sodium ions followed by breakthrough of potassium ions, etc. Fig. I
(see Fig. 1). We say that the resin is exhausted.

-7-
A similar process takes place in a column containing a strong-

1
H
base anion resin in the hydroxide condition. Different zones will
develop during the service run. The silica zone moves ahead in x-SO,+
the filter bed, followed by the carbonic acid X-Cl
(see Fig. 2).
Fig. 2
3.6 REVERSIBILITY OF ION-EXCHANGE REACTIONS/REGENERATION
The aflinity series, discussed in Chapter 3.4, are valid only for approximately equal concen-
trations of the different ions present in the raw water. However, if the concentration of the
ions with a lower affinity is large enough, those ions can supersede ions with a higher aflinity
from the resin. This means that the ion-exchange reactions can be forced to the reverse side. This
process is called regeneration. A sodium-based cation-exchanger which, for instance, is
exhausted with calcium ions, can be restored to its original condition by regeneration with a
sodium chloride solution (surplus of sodium ions). This equation can be represented as follows:
2X_Ca+2NaCl + 2 X-Na f CaClz
Similarly exhausted hydrogen-based cation resin can be brought back to its original condition by
a surplus of hydrogen ions, e.g. a hydrochloric acid or sulphuric acid solution. Exhausted
chloride-based anion resin can be regenerated with a sodium chloride solution (surplus of chloride
ions), and exhausted hydroxide-based anion resin can be regenerated with a caustic SC& solution
(surplus of hydroxide ions).
The amount of regenerant chemicals used per liter of resin is called the regenerant level. The
regenerant level is the major factor which determines the exchange capacity of a resin. However,
it should be real&d that an increase in the regenerant level does not proportionally increase the
exchange capacity of the resin. Consequently, for economical reasons, an exhausted resin is
never regenerated to the maximum extent. This also means that in practice only a part of the total
exchange capacity of a resin is used.
This is shown in Fig. 3, which typically represents the exchange capacity of a cation resin as a
function of the acid consumption and regeneration method.

-8-
Cation Capacity
Capacity
Counter-Current
DWN
o-Current
.u
Sulphuric Acid [g/r] -->
Fig. 3 Salt consumption versus operating capacity
In this graph, it can be seen that a 100% increase in salt consumption ( 150 + 300 gr NaCl per
litre of resin) would result in a 36% increase in exchange capacity only (50 + 68 gr CaC03 per
litre of resin).
In order to obtain an acceptable usetkl exchange capacity of the resins, always an excess of
regenerant chemical (reagent) has to be applied. This excess determines the regeneration
effkiency.
Regeneration efficiency = Equiv. of reagent used per litre of resin

Useful capacity (equiv./ltr of resin)
Due to the favourable place of the hydrogen and hydroxide ion in the aIIinity series, the weak
cation and anion resins require far less excess of regenerant chemical than the strong cation and
anion resins. Generally* the following regeneration efficiency is applied:
Weak cation and anion resins : 1 lo- 120%

Strong cation and anion resins : 250-300%.
* This applies for co-current regeneration (see Chapter 3.9).
3.7 PERMANENT ION-LEAKAGE
In Chapter 3.6, it was discussed that an ion-exchange resin is never fully regenerated. As a
result, there will always be an ion-leakage during the service cycle. (In Part III “PLANT
DESIGN”) it can be seen that the ion-leakage also depends on the composition of the water to be
treated and other factors.)

-9-
Fig. 4 shows a cation exchanger bed before and after an acid regeneration. After regeneration the v’
bottom of the bed still contains a small zone with resin in the sodium form. When the next
service cycle starts, the cations of the influent water are exchanged for the hydrogen ions of the
resin in the top of the bed. Those hydrogen ions are then exchanged for the sodium ions in the
bottom of the bed, releasing the sodium as cation leakage into the effluent water. This permanent
ion-leakage is called auto-regeneration effect. As the run progresses, the sodium leakage
decreases because the sodium zone at the bottom of the bed is gradually consumed.
Besides a sodium leakage, there is also a hardness leakage, a silica leakage, etc.
End of Service Cycle End of Regeneration
Fig. 4 - Permanent ion-leakage

- 10 -
‘L 3.8 REGENERATION STEPS
The regeneration of an ion-exchange bed usually consists of four steps:
Step 1 - Backwash
During back washing an upward flow of

water is passed through the resin bed.
This reverse flow removes accumulated
suspended matter from the top resin layers
and also reclassifies the resin (the smaller
beads go to the top of the unit, the larger
beads go to the bottom).
Backwashing should be carried out for

approx. IO-15 minutes, at a flow rate
sufficient to expand the bed for at least 50%.
The manufacturer’s recommendations should
be carefully followed,
Backwashing should be performed in a

“controlled” way in order to avoid resin
losses. For that reason often backwash filters
are applied.
Fig. 5 shows the quantity of backwash water required to reahse the recommended bed expansion
of a typical cation resin.
Fig. 5 Bed expansion vs. backwash flowrate

- 11 -
Step 2 - Introduction of regenerant

solution
After the completion of the backwash, the

regenerant solution is percolated through the
bed. The flow rate should be slow enough to
provide sufficient contact time between the
regenerant and the resin. The manufacturer’s
recommendations should be carefully
followed. The regeneration period usually
takes 30-60 minutes.
W
Step 3 - Slow rinse
After step 2 a low flow of water is percolated

through the bed, displacing all the regenerant.
This period takes approx. 30-60 minutes.
Step 4 - Fast rinse
During the fast rinse a high flow of water is

passed through the bed in a downward
direction for removal of residual regenerant
and eluted ions. As soon as the quality of the
rinse water reaches the required specification
limit, the unit is ready for its next service
cycle.
This period takes approx. IO-20 minutes.

- 12 -
The quality of the water used for regenerant dilution and rinsing will effect the quality of the
product water in the service cycle.
This is shown in Fig. 6.
IO to 30 40 so (0 70 (0 90 100
%rprntiq --- cycle.
Fig. 6 Effect of using untreated water for regenerant dilution and rinsing
(4 = treated water for dilution and rinsing

a4 = untreated water for dilution; treated water for rinsing
(4 = untreated water for dilution and rinsing.
- 13 -
3.9
_-
CO-CURRENT AND COUNTER-CURRENT REGENERATION
Fig. 4 shows tbat the regeneration is performed in the same direction (downwards) as the raw
water to be treated. This mode of operation is called co-current regeneration. The regeneration
may also take place in a direction opposite to the direction of the influent water. This process is
called counter-current regeneration. Both methods are shown in Fig. 7.
I’
--------7
Fig. 7a
-7
Fig. 7b Fig. 7c
Q @ !;
Co-Current
_ Service water
-------+ Regeneant
Counter-Current
_____ -__
In the co-current process (Fig. 7a) it can be seen that the best regenerated part of the resin bed
will be the top resin layers. The bottom resin layers which determine the final quality of the
water to be treated, will be regenerated less efficiently. In addition, during the regeneration first of
all, the ions with the higher aflinity will be removed from the resin by the regenerant chemical.
Those ions will thereupon supersede (to a certain extent), ions of a lower affinity in the following
resin layers. With other words, those higher-affinity ions have to be removed more than once
from the resin during the regeneration.
In the counter-current mode of operation (Fig. 7b and 7c) it can be seen that the best regenerated
part of the resin bed will be the resin layers which determine the final water quality. The
regeneration process also proceeds more efficiently since the first ions which will be removed
from the resin are the lower-affinity ions, which will not supersede higher-aflinity ions in the
following resin layers.
In the counter-current process, backwashing is normally not applied and the resin bed is kept
“compact” during the service cycle as well as during the regeneration cycle. This means that the
resin layers remain at the same place. This is especially important for the last resin layers which
determine the tinal water quality. Bed compaction can be established by means of hold-down air,
hold-down water and other techniques, which will be discussed later. Since backwashing is not
applied. it is important that the suspended solids content of the influent water is negligible in

- 14 -
order to avoid excessive differential pressures over the resin bed. ln case backwashing has to be
performed (usually once every 20-50 cycles), a double regeneration is required.
Concluding, it can be stated that counter-

current processes offer the following
advantages:
I) The ion-k&age during the service cycle

is lower and consequently, the quality of
the effluent water is better (see Fig. 8).
2) The chemical consumption is lower.
3) The rinse.-water requirement is lower.

Fig. 8 Co-current vs. counter-current
regeneration
3.10 NEUTRALIZATION OF REGENERANT EFFLUENT
As was discussed earlier, always a surplus of regenersnt chemicals has to be applied during the
regeneration cycle. The regeneration efficiency for weak cation and anion resins is I IO-120%
(IO-20% surplus) and for strong cation and anion resins is 250-300% (150-200% surplus). This
means that the regenerant effluent always contains “unused” acid or caustic. Normally the
regenerant effluent streams are collected in a neutralisation pit. ln this pit the pH-value of the
water is corrected by addition of acid or caustic prior to discharging the water to the sewage
system. (A typical neutralisation system is shown on page 25). In view of economical
considerations, the addition of neutralising chemicals should be minimised as much as possible,
e.g. by properly designing of the ion-exchange units.

- 15 -
Introduction:
A demineralisation unit consists of one Cation-Exchanger and one Anion-Exchanger.

The Cation-Exchanger contains 4000 litres of strong acid cation resin; the Anion-Exchanger
contains 4500 lures of strong base anion resin. The regeneration efficiency for the cation resin is
225% and for the anion resin 250%.
Regenerant levels are as follows:
- Cation resin : 60 gram HCI( 100%) per litre of resin

- Anion resin : 60 gram NaOH( 100%) per litre of resin
Both exchangers are regenerated simultaneously.

The regenerant effluents are sent to a neutralisation pit.
Additional Information:
Equivalent weight HCI is 36.5.

Equivalent weight NaOH is 40.
Exercise:
Calculate the amount of caustic soda or hydrochloric acid which has to be dosed to the
neutralisation pit to titlly neutralise the regenerant effluents following a regeneration.

- 17 -
3.12 RESIN STRUCTURE (PART 2)
The degree of cross links (proportion of divinyl benzene) plays an important role in the matrix
structure, since it determines the physical properties of the resin, such as swelling, moisture
content and porosity.
When placed in water, resin swells so that the chains of the matrix spread apart and permit the
diffusion of ions. The degree of swelling depends on the degree of cross links. The larger the
number of cross links, tbe less the swelling.
During the swelling a more or less greater or smaller amount of moisture is taken up by the resin:
the hydration water or moisture content. This hydration water is very important, as it acts as
transport medium, allowing the ions in and out of the ion-exchanger. The higher the moisture
content, the easier the ion di!Tusion and the higher the exchange capacity. The moisture content
depends on the degree of cross links. The larger the number of cross links, the less the moisture
holding capacity.
The size of an ion that can migrate through the matrix is limited by the distance between the
macromolecules of the matrix. This is often referred to as apparent porosity. The degree of cross
links determines the porosity. The larger the number of cross links, the less the porosity.
From a kinetic viewpoint, it would be desirable to have as low a degree of cross links as possible
(improved swelling, moisture content and porosity), but this would result in poor hydraulic
resistance (too small a degree of cross linkage makes resin jelly-like and soft). Therefore, the
design of a commercial ion-exchanger resin involves a choice of cross linkage that represents a
compromise between kinetic and hydraulic performance. Ion exchangers used nowadays can be
classified according to their porosity in the following groups:
1) Gel-type or microporous-type resins
Even in a low cross-linked gel-type resin, the apparent porosity is usually not larger than 40
Angstrom. This type of resin is able, to a certain extent, to take up organic matter.
However, the elution during regeneration is incomplete, thus resulting in an increased
irreversible fouling (mainly the anion exchangers are affected).
2) Macroreticular or macroporous-type resins
These resins have a special matrix with larger pore channels (macropores). The average
pore diameter is 300-500 Angstrom. This type of resin is able to absorb larger molecules or
ions during the service cycle and also allow those molecules and ions to be eluted during
regeneration.
3) Acrylic-type resins
The acrylic resins are more hydrophylic than the styrene resins. This improves ditTusion
kinetics, operating capacity and reversible removal of high molecular-weight ions.

- 18 -
4.0 ION-EXCHANGE EQUIPMENT
Ion-exchange vessels are usually of the vertical pressure type. The sizes range from 2-12’
diameter. The vessels are constructed of carbon steel or stainless steel, often lined internally with
a 3116” rubber lining. Normal working pressures range from 3-7 barg. The vessels are usually
equipped with a manhole.
To avoid channelling and to ensure uniform contact of the water and the regenerant with all parts
of the resin bed, well-designed distributors and collectors are essential.
An inlet d~Mutor is installed to prevent disturbance of the top of the resin bed due to
impingement by the influent stream, resulting in channelling. The distributor dampens the
dynamic effect of the large it&tent flow by breaking up the flow into a number of smaller
streams of low velocity.
A regeneranl disfributor, installed in the bottom of the void space some inches above the top of
the resin bed, distributes the regenerant uniformly. The distributor must be well supported to
prevent damage by the rising resin bed during backwashing.
An interface distributor is used in mixed-bed units only. It is located at the interface between the
cation and anion resin following the classification of the two resins by backwashing. The
interface distributor collects spent caustic and spent acid during regeneration and the blocking”
flow. It is important too that this distributor is well supported in order to be able to withstand
upward or downward pressures.
An underdruin system is used to collect the unit’s effluent uniformly. This collecting system can
consist of
- a number of nozzles, screwed in a bottom plate;

- a collection system of a header and o&iced laterals with or without stainless steel mesh
“SO&S”.
Sometimes the underdrain system is installed in a specially designed porous bottom. In some
occasions subfills are used (acid-resistant siliceous gravel for cation units and anthracite for
anion units). The advantage of the subfill is that the orifices in the underdrain system can be made
large enough to prevent their being clogged. The disadvantages are that rinsing water
requirements are increased and channelling can occur owing to backwash upsets.
In order to be able to check that backwashing is performed correctly, the vessel is often equipped
with sight glosses, sometimes in combination with a lamp. In order to prevent resin losses during
backwashing, ion-exchange units are often equipped with specially constructed bockwush fibers
(resin screens).
Ion-exchange units used in water treatment are usually regenerated with diluted solutions of
sodium chloride, sulphuric acid and caustic soda. Since the latter two chemicals are dangerous.
certain precautions should be followed in their handling and storage. Personnel should be
provided with protective clothing, goggles, gloves. etc. A safety shower should be installed in the
immediate vicinity of the unit.

- 19 -
Strong sulphuric acid storuge tanks are made of unlined steel. When the strong acid is diluted,
its corrosiveness is greatly increased. Therefore, water must not be allowed to enter the storage
tank. To prevent moisture of the air entering the tank via the vent, often a dry breather pot is
installed in the vent. Moisture absorbents used are calcium chloride, silica gel, etc. Strong 66’
Be sulphuric acid freezes at a temperature below 29’F. If the storage tank is located outdoors,
protection against freezing may have to be provided.
Caustic soda storage tunks are usually made of unlined steel. Sometimes an epoxy coat lining is
applied. 50% caustic soda freezes at a temperature below 56°F. If the storage tank is located
outdoors, protection against freezing may have to be provided.
For controlling the dilution and measuring the amounts of regenerant injected during each
regeneration, several systems are available, e.g.
- a system, using a measuring tank;

- an in-line chemical-diluting system.

- 20 -
5.0 ION-EXCHANGE VOCABULARY, ABBR., TERMS AND DEFINITIONS v

SAC = Strong acid cation exchanger
WAC = Weak acid cation exchanger
SBA = Strong base anion exchanger
WBA = Weak base anion exchanger
DVB = Divinyl benzene
FMA = Free mineral acidity

This is the sum of all the strong mineral acids formed when passing water through
an SAC in the hydrogen form (expressed in meq/l or mg CaC03fl). It is also the
sum of the strong mineral anions (Cl-, SO@-, N03).
TH = Total hardness
In most natural waters it represents the sum of calcium and magnesium.
TMA= Total mineral acidity (= FMA)

W
TC = Total cations (expressed in meq/l or mg CaC03/1)
TA = Total anions (expressed in meq/l or mg CaCO3/l)
Total ion capacity The maximum weight of ions that can be exchanged (or fixed) and
which is a property of a given resin. It is expressed in eq/l resin or
gr CaC03/l resin.
Useful ion capacity : The weight of ions which can be exchanged (or fixed) till the
moment that the maximum allowable leakage of undesired ions
appears in the effluent.
BV Bed volume - the ratio of the volume of liquid to be treated per

volume of ion-exchanger.
BVlh Bed volumes/hour - ratio of the volume of liquid to be treated per w

volume of ion-exchanger per hour
Regeneration level : Weight of regenerant used to regenerate 1 litre of resin.
Regeneration efficiency : Equivalents of regenerant used per litre of resin divided by the
useful capacity (in eq/l).
Attrition Mechanical wear of the resin.
Service cycle time : Time (in hours) during which water is produced between two
successive regenerations.
Total cycle time Duration (in hours) of one service cycle + time required for
performing a regeneration.

- 21 -
6.0 REGENERANT QUALITY
In general the chemicals used for regeneration will, to a certain extent, contain chemical by-
products. Depending on the type and the concentration of those products, this may seriously
influence the regeneration efficiency, e.g. it may result in:
- a reduced exchange capacity of the resin;

- an adverse change in product water quality;
- resin fouling,
- Foubng of the valves, level legs etc. in the regeneration facilities
In order to avoid those problems, the regenerant chemicals should comply to certain
specifications.
SIOP otkn use the DIN-recommendations @eutsches brstitut fir ~ormung).
The DIN-recommendations for the most applied regenerant chemicals: sodium-chloride, sulphuric
acid, hydrochloric acid and caustic soda, are shown on page 22.

- 22 -
SPECIFICATIONS FOR BEGENEBANT-CHEMICALS
ACCORDING TO DIN-GUIDELINES
Brine - NaCl
(act. to DIN-19604, dated February 1970)
% NaCl : min. 97 % (wt)

% Water : max. 2 % (wt)
% Sulphate (SO& : max. 1 % (wt)
% Calcium and magnesium
compounds (expressed as Ca2+) : max. 0.4 % (wt)
% Soluble iron-compounds : not detectable
Hydrochloric acid - HCI

(act. to DIN-19610, dated November 1975)
W
% HCI min. 30 % (wt)
% Sulphate (S042-) max. 0.5 % (wt)
% Iron (expressed as Fe3+) max. 0.002 %(wt)
% Chlorine (expressed as C12) max. 0.01 % (wt)
% Organic chloride - compounds
(expressed as Cl-) max. 0.02 g/l
Hydrosulphuric acid - H2SO4

(act. to DlN-19618, dated June 1984)
% H2SO4 min. 93 % (wt)

% Iron (expressed as Fe3+) max. 0.002 % (wt)
Caustic soda - NaOH

(act. to DIN-19616, dated December 1971)
% Chloride (expressed as Cl max. 0.2 % (wt)

% Oxidants (expressed as 02) max. 0.001 %(wt)
% Sulphates (expressed as SO42-) max. 0.1 % (wt)
% Silica (expressed as SiO max. 0.01 %(wt)
% Iron (expressed as Fe3+) max. 0.001 %(wt)
% Ahuninium (expressed as A13+) IllCiX. 0.005 % (wt)
% Calcium and magnesium
compounds (expressed as Ca2+) max. 0.01 % (VA)

Confidential
.-
Ml48
MODULE1
SECTION 3.2
INDEXI.DDC: 22/08/97
-l-
- SUBSECTION 3.2: ION EXCHANGE PROCESSES
TABLE OF CONTENTS
1.0 INTRODUCTION .......................................................................................... 2
2.0 SODIUM ZEOLITE SOFTENING PLANT ................................................. 2

3.0 SPLIT-RANGE SOFTENING PLANT ......................................................... 3
4.0 SOFTENING/DE-ALKALISING PLANT .................................................... 4
5.0 DEMINERALISATION PLANT ................................................................... 5
6.0 MIX-BED UNIT ............................................................................................. 7
7.0 STRATIFIED BED (STRATA BED) .......................................................... 10
8.0 SPLIT-FLOW REGENERATION UNIT ................................................... 12
9.0 “SCHWEBE-BED” PRINCIPLE ................................................................ 13
10.0 LIFT-BED SYSTEM.. ................................................................................. .15
11.0 RINSE-BED SYSTEM ................................................................................. 16
12.0 UP-CO-RE SYSTEM .................................................................................. .18
13.0 CATALYTIC REMOVAL OF OXYGEN .................................................. 19
14.0 MULTIBED SYSTEMS ............................................................................... 20
15.0 EXERCISE: DEGASSER NECESSARY”................................................... 20
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-2-
1.0 INTRODUCTION
Ion-exchangers are applied in the field of water treatment and in the field of special applications
such as: selective removal of radio-active waste material in nuclear power stations, selective
recovery in biochemical and pharmaceutical processes, separation of rare earth metals, nutrients
in soilless cultures, etc.
In 1967 approx. 80% of the resins were applied for water treatment and 20% for special
applications. In the year 2000 it is estimated that these percentages will be 60% and 40%
respectively.
The choice of the type of a water treatment ion-exchange unit, including the applied resins will
depend mainly on the pursued water quality. Specifications requirements for boiler feed water for
HP boilers are of course far more stringent than for LP boilers.
For supercritical VHP boilers the boiler feed water specifications are extremely stringent.
2.0 SODIUM ZEOLITE SOFTENING PLANT

The sodium zeolite softening process was the first commercial application of ion-exchange.
In this process the raw water passes through a bed of strong cation resin which has been
converted to the sodium condition (or “sodium cycle”). Sodium-ions from the resin are exchanged
for the scale-forming ions of calcium and magnesium. The operation of the zeolite softener unit
is illustrated on page 23.
The exchange of ions can be represented as follows :
PI I so4 I P- 2 NaHCO,
L,a L.a
Mg
I 2 Cl
2 HC03
+ 2X-Na + X-
1 Mg
+ Na2SO4
2 NaCl
where X = functional group of the resin,
Characteristics of tbis process are:

- Only hardness is replaced by sodium.
- Residual hardness in the product water is less than 1 ppm as CaC03.
- Alkalinity, silica and TDS of the product water is equal to that of the raw water.
- The process produces NaHC03. Under boiler conditions this will split up via a two-step
reaction into NaOH and CO2.
This is shown in the following reactions :
2 NaHCO, + Na2CO3 + Hz0 + CO2 ?
NqCO3 + Hz0 + 2 NaOH + CO2 ‘?
Exhaustion of the resin will be characterised by a steep increase of the residual hardness of the
product water.
Regeneration of the resin is achieved by reversing the ion- exchange reactions. The exhausted
resin is treated with a IO- 15 % sodium chloride solution (surplus of sodium ions).
The regeneration proceeds as follows :
Ca Ca
X- + 2 NaCl + 2 X-Na + Mg Cl2
i Mg
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-3-
Following the regeneration, the useful resin capacity varies from 0.7 to 1.4 eq/l resin, depending -J’
on :
- the regenerant level (50- 180 g NaCl/l resin);
- the ratio sodium/total cations in the intake water;
- the hardness level in the intake water;
- the flow rate.
3.0 SPLIT-RANGE SOFTENING PLANT

A split-range softening plant consists of one or more sodium zeolite softeners, placed in parallel
with one or more hydrogen zeolite softeners, a degasifier and a blending control system.
The operation of the split range unit is illustrated on page
The operation of the sodium zeolite softener was discussed earlier. In the hydrogen zeolite
softener, the hydrogen ions from the resin are replaced by the calcium, magnesium and sodium
ions from the intake water. The exchange of ions can be represented as follows :
so4 H2so4
Ca Ca
2 Cl 2 HCI
Mg -+ 2 x - Mg + 2 H2CO3
2Na 2HCO3 + 2x-H
2Na
2 HNo3 1 2 HNo3
where X = functional group of the resin.
The total concentration of the produced strong acids is called the free mineral acidity or FMA
(HzSO4, HCI and HN03).
Exhaustion of the resin bed will be characterised by a marked reduction in the concentration of
the FMA of the product water. This will be in conjunction with a decrease in conductivity and an
increase in pH. Regeneration of the resin is achieved by reversing the ion-exchange reactions. The
resin is treated with 5- 10% sulphuric acid or 8- 10% hydrochloric acid (surplus of hydrogen ions).
Ca CaS04
2x - Mg + H~SO~ + 2X-H + MgSO4
1 Na
2 1 NaS04 W
The capacity of the strong cation resin in the hydrogen form varies from 0.8 to 1.6 eq/l resin.
The product water is free of calcium and magnesium ions, and almost completely free of sodium
ions.
The sodium “slippage” depends on:
- The ratio of sodium ions/total cations in the raw water
- The ratio of alkalinity/total anions in the raw water
- The concentration of the regenerant.
As we have seen, the sodium zeolite product water contains a mixture of sodium salts. The
hydrogen zeolite product water contains a mixture of acids. The NaHC03 in the sodium zeolite
product water is used to neutralise the strong acids in the hydrogen zeolite product water,
according to the following reactions:
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-4-
2 HCI 2 NaCl
2NaHCO3 + HzSO4 + Na2SO4 + 2H2CO3
2 HNo3 i 2 NaN03
The produced carbonic acid can be removed via a decarbonator. By varying the percentages of
sodium zeolite and hydrogen zeolite product water, the alkalinity of the blended water can be
adjusted to a desired level. (The higher the sodium zeolite percentage, the higher the alkalinity;
the higher the hydrogen zeolite percentage, the lower the alkalinity.) The desired proportion can
be calculated with :
Ar-Ab
% hydrogen zeolite = Ar + pMA
where :
Ar = alkalinity of the raw water
FMA = free mineral acidity of the hydrogen zeolite product water
Ab = desired alkalinity of the blended water.
Characteristics of the split-range softener are
- Hardness is replaced by sodium in the sodium-based exchanger.
- All cations are replaced by hydrogen in the hydrogen-based exchanger. The produced bi-
carbonates will be (partly) converted to carbonic acid. The carbonic acid is removed by
degasification.
- The desired alkalinity in the product water can be obtained by mixing the two streams of the
sodium-based and hydrogen-based exchangers.
- The total dissolved solids in the effluent are less than in the intake water. The decrease
depends on the quantity of carbon dioxide removed.
4.0 SOFTENING / DE-ALKALISING PLANT

These plants use one or more sodium zeolite softeners in series with one or more chloride anion
de-alkalisers (strongly basic anion resin columns in the chloride form). The operation of this unit
is illustrated on page
Characteristics of these plants are as follows:
The hardness of the intake water is replaced by sodium in the sodium zeolite softeners.
Residual hardness in the product water is less than one ppm as CaC03.
The major part of the alkalinity of the intake water is replaced by chloride
(approx. 90-95%).
Silica is not replaced by chloride.
The TDS content in the product water is equal to that in the intake water.
Ion-exchange reactions in the sodium zeolite softener have been discussed earlier.
Ion-exchange reactions in the de-alkalisers can be represented as follows:
Na2S04 SO4
2 NaHC03 + 2x-Cl + 2 x - 2 HCO3 + 2 NaCl
2 NaN03 i 2 NO3
where X = functional group of the anion resin.
M148_32
The capacity of the strongly basic anion resin varies from 0.6-1.2 es/l resin, depending on :
- The alkalinity level of the intake water
- The chloride concentration of the intake water
- The concentration of the regenerant.
Exhaustion of the resin bed will be characterised by a steep increase in the alkalinity of the
product water.
Regeneration of the resin is achieved by reversing the ion- exchange reactions. The resin is treated
with a lo-15% brine solution, to which has been added a small amount of caustic soda (approx.
l%)*. Addition of a small amount of caustic soda will increase the e xchange capacity of the
anion resin.
The regeneration proceeds as follows:

so4 Na2SO4
2x - 2 HC03 + 2 NaCl + 2x-Cl + 2 NaHC03
2 NO3 2 NaN03
5.0 DEMINERALISATION PLANT
Demineralisation of water is the removal of all inorganic salts by ion-exchange. A typical

demineralisation unit may consist of a strong cation unit, followed by a strong anion unit.
The operation of this unit is illustrated on page
In the cation unit, the following reactions take place :
H2SO4
Ca 2 HCI
2 HCI
Mg + 2X-H -+ 2 HNo3
2 HC03
2Na 2HzCO3 d
2 NO3
2 H2SiO3
where X = functional group of the strong-cation resin.
In the anion unit the following reactions take place :
1
H2SO4 SO4
2 HCI 2 Cl
2 HNo3 + 2Z-OH -+ 22 - 2 NO3 + H20
2 H2CO3 2 HC03
2 H2Si03 2 HSi03
where Z = functional group of the strong-anion resin.
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-6-
- The above reactions suggest the complete removal of ail cations and anions from the water,
however, even with very efficient units, some leakage of undesired ions will always occur,
depending on:
- The applied regeneration levels.
- The quality of the intake water.
Dernineralisation systems for producing water of extremely high purity, use mixed bed units (an
intimate mixture of strongly acidic cation and strongly basic anion resins in the same column).
Exhaustion of the cation resin will be characterised by a reduction in the FMA concentration of
the cation unit’s effluent, an increase in sodium slippage, an increase in pH and a reduction in
conductivity.
Exhaustion of the anion resin will be character&d by a short, slight reduction in the conductivity
of the anion unit’s effluent, followed by a marked increase in conductivity, an increase in silica
slippage and a reduction of pH.
Regeneration of the exhausted cation resin is achieved by treating the resin with sulphuric acid or
hydrochloric acid.
Regeneration of the exhausted anion resin is achieved by treating the resin with a 4% caustic
-
solution.
so4 Na2S04
2 Cl 2 NaCi
22 - 2 NO3 + 2NaOH + 2Z-OH + 2 NaN03
2 HC03 2 NaHC03
2 HSi03 2 NaHSi03
M148_32
-7-
6.0 MIX-BED UNIT

One could visualise that ultrapure demineralized water can be obtained by operating a number of
cation- and anion units in series. The slippage of sodium cations from the primary cation unit
wilI then be intercepted in the subsequent cation units. Similarly the silica leakage from the
primary anion unit will be caught by the following anion units.
It would not be practical and economical to design such a unit. However, it is feasible to combine
the cation- and anion resin in one vessel. In this so-cahed “mix-bed” unit it looks like an infinite
number of cation- and anion units have been placed in series.
A mix-bed unit is usually applied to catch the ion-leakage of preceding cation- and anion units.
In doing so, water is produced of a very high quality. Mix-bed units are also frequently applied
for the polishing of recovered condensate.
In many occasions the end of the service cycle of a mix-bed unit is determined by the volume of
the water to be treated, and (or) by the differential pressure over the resin bed, rather than by the
of the product water.
Fig. 1 shows schematically a mix-bed unit.

Before regeneration the cation /anion-mixture
has to be backwashed, after which separation
of the resins takes place owing to the
difference in density. The lighter anion resin
will be found in the top of the bed following
separation. Next the anion resin will be
regenerated co-currently and the cation resin
counter-currently.
During regeneration “blocking” water has to
be applied. After the regeneration the resins
have to be mixed intensively.
Fig. 1 Mix-Bed Unit
Even with correct backwashing a full separation of the cation- and anion resin will never be
obtained. At the location of the separation zone, where the drain-collection system for the
regenerant solution is installed, a resin mixture can always be found following backwashing.
This mixture may comprise approx. 7% of the total resin volume. As a result, part of the cation
resin will be converted to the sodium-form during the regeneration of the anion resin, and part of
the anion resin will be converted to the chloride-form (or sulphate-form) during the regeneration
of the cation resin. The above will cause an adverse change in product water quality.
Likewise it is difficult to determine the correct location for the drain-collection system since the
resins continuously expand and shrink during the service cycle and during regeneration. In order
to reduce this problem, an improved version of the mix-bed unit is frequently applied:
the “trio-bed” unit.
In a trio-bed unit a considerable improvement can be achieved by combining the cation- and anion
resin with a third resin. This third resin is an inert resin, which does not participate in the ion-
M148_32
-8-
exchange process. The inert resin acts as a separation barrier between the ration and anion resin.
For the trio-bed unit special types of resins are selected with different bead size and density in
order to accomplish the desired separation.
Fig. 2 shows schematically a trio-bed unit,

The height of the inert resin layer is t-=
determined by the formula:
H,=0.15+0.1I-&
where:
Hi = height inert resin (m)
I& = height cation resin (m)
Fig. 2 Trio-Bed Unit
Table 1 shows the typical bead size and density of the resins to be applied in a trio-bed unit.
Type s.g. Diam. (mm)

Anion resin 1.1 0.4-0.85
Inert resin 1.15 0.6-0.9
Cation resin 1.2 0.7-I .25
Table I
It is feasible to convert existing mix-bed units to trio-bed units. Care should then be taken that
the void space which remains above the resin bed is large enough for the required bed expansion
during backwashing.
The advantages of the trio-bed unit can be summarised as follows:
I. Better separation ( 1% resin mixture)
2. Reduced leakage of Na+ and CI-
3. Improved conductivity of the product water
4. Reduced rinse water requirements
5. Improved exchange capacity.
In an English power station (Fawley) a considerable improvement was obtained following the
conversion of conventional mix-bed units to trio-bed units. Most of the impurities reduced by a
factor of201.
M148_32
-9-
7.0 STRATIFIED BED (STRATA BED)

As was discussed earlier, owing to the favourable location of the hydrogen ion and the hydroxide
ion in the affinity series of the weak cation and weak anion resins, these resins require far less
surplus of regenerant chemicals (lo-20%), than the strong cation and anion resins (150-200%).
Therefore, the “spent” regeneration chemicals of strong cation exchangers, resp. strong anion
exchangers are often utilised for the regeneration of weak cation, resp. weak anion exchangers.
This method of regeneration (see Fig. 3), minimises the consumption of regenerant chemicals.
Acid in “.C.I in
I--*
iii!3
C----
SAC
c.ustie out
.- r-
u.t.r out Y
Fig. 3 Minimisation of use of regenerant chemicals: thorough fare regeneration
The above-mentioned application can be further improved by the so-called “stratified bed” or
“strata bed” concept.
In a stratified bed, two types of cation resins (WAC and SAC) or two types of anion resins
(WBA and SBA) are placed together in one single vessel.
Due to the lower density the weak resins will be located on top of the strong resins.
The stratified bed, also called “layered” bed, is always operated in the counter-current mode.
This means that backwashing should not be applied to avoid mixing of the resins. (In the
exhausted condition the density of the resins will be almost equal).
Backwashing should only then be applied if the pressure drop across the resin bed exceeds a
certain limit.
In case backwashing has to be applied, a double regeneration should be performed according to
the following sequence:
regeneration - backwash - regeneration
During regeneration, first of all the strong cation resin, resp. the strong anion resin, receive their
surplus of regenerant chemicals, after which the weak cation resin, resp. the weak anion resin will
be regenerated with the “spent” acid, resp. the “spent” caustic.
Stratified beds of anion resins have been applied more than stratified beds of cation resins.
M148_32
-lO-
Fig. 4 shows the stratified bed concept of

anion resins. During the service cycle the
Stratified Bed
anions of the strong acids and organic Raw Water
material of the influent water will be removed l
.._..... ._*________.
.. ?, _..,_ ._____.._. .
by the weak anion resin. The anions of the ‘L..,
. Downtlow ’
weak acids (carbon-dioxide and silica) are Reduction ;+&&s&#+
next removed by the strong anion resin. l Delta rho:
During the regeneration step the resin bed lftcr resell
remains in a compact, layered condition by
means of “holddown” water or “hold-down” :
air. &ga”wa”t I’.. . .._..__..I 3
. . . +.i . *
Fig. 4 Stratified Bed or Strata Bed
8.0 SPLIT-FLOW REGENERATION UNIT

Raw water, originating from certain water pretreatment facilities (e.g. clarification/filtration
units), may contain appreciable amounts of suspended solids. These suspended solids will
usually be removed by the filtering action of the cation exchanger. In order to prevent excessive
differential pressures across the resin bed, the suspended solids have to be removed on a regular
basis via back-washing. As we have seen previously, back-washing should be minim&d in a
counter-currently regenerated unit. In case back-washing is applied, a double regeneration has to
be carried out.
In order to be able to remove suspended solids from a counter- currently regenerated unit, without
applying double regenerations, sometimes the “split-flow regeneration” unit is applied. In this
system the top part of the resin bed (some 30% of the total resin volume), which mainly collects
suspended solids, may be backwashed whenever required. The bottom part of the resin bed is
regenerated counter-currently while the top part of the bed is regenerated co-currently.
As can be seen in Fig. 5, the regenerant for the top part of the bed replaces “blocking” water (or
“hold-down” water).
Split Flow Regen

Raw Water
_.... -..- ___.._ b,
Fig. 5 Split-Flow Regeneration Unit
Ml48_32
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9.0 “SCHWEBE-BED” PRINCIPLE

During the last 15-20 years counter-current ion-exchange processes have been developed. As
compared with the conventional co-current processes, these counter-current systems offer the
following major benefits:
1. reduced regenerant consumption;
2. improved water quality.
In most of these counter-current processes the mass of resin is kept in a compressed condition
throughout the entire operating cycle, i.e. in the exhaustion phase as well as in the regeneration
phase.
Bayer A.G. have developed three new systems based on upflow exhaustion and downflow
regeneration.
In the “Schwebe-bed” process (WS process), the equipment comprises a vessel with bottom and
top nozzle plates. The space between the two plates is almost entirely filled with resin.
A small amount of inert resin is usually applied, which, owing to its low specific gravity, floats.
The inert resin prevents clogging of the top nozzles. The void space between the active resin and
the inert resin is approx. 50-100 mm.
During the exhaustion flow a compressed resin bed and a fluid&d resin bed are formed
(WS = Wirbel Schicht = Fluid&d Bed). The compressed bed/total bed ratio depends on the flow
rate.
The compressed resin bed, which is the actual polishing section, should amount to at least 25% of
the total, but in practice the compressed part of the bed is considerably larger.
To establish the compressed bed immediately upon start-up, it is recommended to start with a
flow rate of approx. 10 m/h. Once this part of the bed is formed, the flow rate may be reduced
without losing much of the compressed zone.
The recommended bed-depth is 2-2.2 metres maximum, while the flow rate is 5-50 m/h.
The maximum diameter of the vessel is approx. 4000 mm.
The WS system is claimed to have the following advantages:
a. The differential pressure over the bed is lower than in conventional units, since the head
loss is almost completely controlled by the compressed part of the bed. The fluidized part
of the bed has a negligible influence on the differential pressure.
b. No channelling of the compressed part of the bed is observed, owing to the self-regulating
effect of the fluid&d bed. This results in lower leakage rates.
C. Uniform distribution over the total diameter is obtained, resulting in a very distinct
exhaustion zone and, consequently, low leakage rates and a high operating capacity.
d. The system is self-regulating with regard to flow variations: the higher the throughput. the
larger the compressed fraction of the bed.
e. The system is less dependent on the raw water composition than the conventional systems,
since the finer resin particles, with their relatively larger exchange surface. are located in
the top of the compressed polishing section. These particles are thoroughly regenerated
during the (downflow) regeneration.
f. During regeneration low rinse water volumes are required, since the water displaces the
higher-density regenerant solutions, beginning at the top of the bed.
In a WS system it is not necessary to back-wash the bed every cycle. Back-washing is usually
performed once every 50- 100 cycles in a dedicated back-wash vessel.
M148_32
- 12-
The WS system is particularly suitable for:

- water with a low salt concentration;
- water with a high organic matter content;
- condensate polishing;
- high flow rates.
Fig. 6 shows schematically the Schwebe-bed process
Fig. 6 “Schwebe-Bed” Process (production mode)
M148_32
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10.0 LIFT-BED SYSTEM

In this system, developed by Bayer A.G., the equipment comprises a vessel with two chambers
arranged one on top of the other. Both chambers are filled with the same ion-exchange resin.
The upper chamber is nearly completely (95-100%) filled with resin, while the lower chamber has
a free-board of approx. 100%. The latter is used for back-washing
The two chambers are co~ected by suitable devices to transport resin from one &amber to the
other.
During upflow exhaustion the upper chamber is completely filled, while the lower chamber is
partially filled. This leads to the formation of a small compressed bed below the central nozzle
plate.
The recommended flow rate is 5-50 m/h, while the maximum diameter of the vessel is approx.
4000 mm. In addition to the advantages already reported for the WS system this system offers
the following advantages:
a. Large overall bed-depth of the ion-exchange resin and, consequently, optimum utilisation
of the operating capacity.
b. Minimum overall head loss. W
C. Low-pressure load on the central nozzle plate.
d. The system is extremely suitable for repeated start-up and shutdown without sacrificing the
quality of the treated water, since the exchange column remains fixed in the upper chamber
and cannot become mixed when shuttingdown the system.
The lift-bed system is (according to Bayer) recommended for:
1) water with a high salt concentration 2) water with a high suspended matter content 3)
intermittent operation 4) low head loss 5) low leakage rates 6) high operating capacity 7) high
regeneration efficiency.
M148_32
- 14-
11.0 RINSE-BED SYSTEM

This Bayer A.G. system is also based on upflow exhaustion and downflow regeneration, the
merits of which have previously been discussed.
The simple equipment comprises a vessel, inside which a perforated plate is fitted above the
second thud of the vessel’s height. The plate’s perforations are wide enough to allow free passage
of the resin particles.
The water is passed through the resin column in an upward flow and is extracted from the column
by an outlet collector located just below the perforated plate. The column is, however, filled with
ion-exchange resin to a level above that of the perforated plate (see Fig. 8).
Fig. 8 Rinse-Bed System

The recommended flow rate is up to 20 m/h, while the maximum diameter of the vessel is approx.
2000 mm. Back-washing can be carried out in the upflow direction, using an extraction point
located in the highest point of the vessel. During this phase the resin bed expands through the
perforated plate. After back-washing the smallest resin particles will be located above the
perforated plate, which means that they cannot clog up the slots of the outlet collector. There is,
therefore, no need to apply an inert resin layer.
Ml48_32
- 15-
During rinsing and displacement there is one special feature which makes this system very Li
attractive for certain applications. During rinsing, the layer of resin covering the perforated plate
adsorbs the ions present in the rinse water and, in this way, prevents the polishing section, which
ends at the outlet collector, from becoming contaminated with ions. The top layer has such a high
degree of effectiveness that is possible to apply raw rinse water for cation units and decationized
water for anion units, without affecting the quality of the treated water.
Comparison of the Bayer A. G. Systems
Table 3 shows in detail the technical advantages, the specific characteristics and the main
applications of the three systems developed by Bayer A.G.
Table 3 - Comparison of systems developed by Bayer A.G.
SB LB RB
Inlet water Low salt concentration +++ + ++
High salt concentration + +i+ ++
Undissolved compounds + -H-+ ++
Organic material +++ + ++ w

Condensate +++ ++
Service-cycle Intermittent + +++ ++
High velocity +++ ++ +

Low differential pressure ++ +++ +
Backwash + +++ ++
Low ion-leakage ++ +++ +
Design Large dimensions +++ ++ +
Small height ++ + +++
Simple design ++ + +++
Cheap execution ++ + +++

Large exchange capacity ++ +++ +
Efficient regeneration ++ +++ +
M148_32
- 16-
L. 12.0 UP-CO-RE SYSTEM

The UP-CO-RR (UPflow-COuntercurrentREgeneration) process is a further development in
optimising the utilisation of ion-exchange resins in water treatment plants.
The system comprises a packed resin bed regenerated in the counter-current mode.
The system is especially suited to convert co-current regenerated plants to the counter-current
mode of operation, whereby the ion-exchange capacity will be increased considerably.
In addition, it is possible to treat waters containing suspended material.
The service run is operated in downflow which allows suspended solids to be efficiently filtered
out by the compacted surface layers of the resin bed (see Fig. 9).
Regeneration is effected upflow during which time the resin bed is compacted against a floating
inert material which covers the upper collector system.
The removal of suspended solids takes place during the initial stage of regeneration. During that
stage the linear velocity of the regenerant is rather high. The inert material has a particle size
distribution which allows dirt and any resin fines to pass out with the regenerant effluent. During
this stage, the resin bed is compacted.
Once compacted the resin bed will remain in place even at reduced a flow rate (see Fig. 10).
out
Flow rate (m/h)
Fig. 9 UP-CORE System Fig. 10
M148_32
- 17-
13.0 CATALYTIC REMOVAL OF OXYGEN ‘4

In boiler systems dissolved oxygen in the feed-water plays an important role with regard to
corrosion problems. In order to avoid those problems, the dissolved oxygen is usually removed
from the water by means of thermal deaeration, sometimes in combination with chemical
deaeraton.
However, there are processes which require oxygen-free water of a certain (low) temperature. In
that case it is uneconomical to firstly obtain oxygen-free water via thermal deaeration, and next
cool the water to the desired temperature.
During the last few years a simple and economical method has been developed to remove
dissolved oxygen from the water in an alternative way, i.e. by reduction with hydrogen at which
the chemical reaction is accelerated by applying a resin as catalyst, e.g. Lewatit OC-1045.
The reaction proceeds as follows:
kat’
02+2H2._, 2 Hz0
The rest-oxygen of the water can be controlled by the quantity of hydrogen dosed. It is easy to
obtain residual oxygen figures below 20 ppb. The applied resin is a strong base anion resin (type
l), which is covered by a coating of palladium. Fig. 11 shows schematically the process. The
system comprises a hydrogen dosing system, a mixer and a rubber-lined reactor vessel, which is
filled with Lewatit OC 1045. The minimum vessel diameter is 500 mm, the bed height is
minimum 900 mm.
The linear velocity of the water to be treated may be 100 litres per hour per litre of resin to obtain
a residual oxygen figure of 20 ppb (see Fig. 12). Oxygen removal is not influenced by the type of
water which has to be treated
Fig. 11
The pH-value of the water to be treated hardly influences the reaction speed. Water with a
pH-value of 2.0-8.0 may be treated without problems. From time to time the resin bed has to be
backwashed in order to remove undissolved solids and small deposits.
M148_32
-IS-
14.0 MULTIRED SYSTEMS / UDF
Various licensing partners have developped versions of multi beds. In these units, one vessel is
separated into compartments which each fimction as a separate vessel. Especially where space is
at a premium, these vessels show advantages.
For weak / strong resin separation, Degremont uses this concept, similar to the Stratified bed,
with the difference, that the resin will remain separated at all times because of the separating
nozzle plate between the two resin types.
15.0 EXERCISE: INSTALLATION DEGASIFIER NECESARY?
15.1 Introduction:
Raw water containing 79.3 ppm bicarbonate (as HCO;) has to be treated in an ion-exchange unit.
Throughput of the unit (net) is 200 m3/h.

Service cycle = 12 hours.
Regeneration water required = 5%.
The following options have to be evaluated:
- A demineralisation unit consisting of one strong acid Cation Exchanger, one Degasifier and
one strong base Anion-Exchanger.
- A demineralisation unit consisting of one strong acid Cation Exchanger followed by one
strong base Anion-Exchanger.
For both options the useful exchange capacity of the anion resin is 0.8 eq/l of resin. This is achieved by
applying a regenerant level of 75 gram NaOH( 100%)/l of resin.
Additional information:
- Residual CO2 content in water ex-Degasifier 5 wm
- Equivalent weight CO2 44
- Equivalent weight HCO; 61
- Costs NaOH( 100%) USD 22Okonne
- Number of regenerations per year 600
Exercise:
Calculate the difference in chemical costs per year between options.
M148_32
Confidential
Ml48
MODULE 1
SECTION 3.3
INDESl.DOC; 22/08/97
SUBSECTION 3.3 ION EXCHANGE DESIGN CALCULATIONS
‘Ilk section is under revision, because nowadays, SIOP The Hague uses resin manufacturer’s
computer programmes to calculate the vessel content and diameter, together with runlengths, water
quality and recommended sulphuric acid concentrations. The programme also predicts the imbalance
betweeti excess acid or caustic in order to trim the units for as neutral as possible effluent.
1
Confidential
Ml48
MODULE 1
SECTION 3.4
INDESl.DOC. 22/08/97
SUBSECTION 3.4 ION-EXCHANGE PROBLEMS
TABLE OF CONTENTS
1. INTRODUCTION ..........................................................................................2
2. CHANGED CONDITIONS ..........................................................................,2
2.1 CHANGED RAW WATER CONDITIONS ...........................................2
2.2 CHANGED SERVICE CONDITIONS ....................................................
2.3 CHANGED REGENERATION CONDITIONS ......................................
2.4 PROBLEMS WITH RESINS ..................................................................
2.4.1 Attrition ...................................................................................4
2.4.2 Fouling ....................................................................................4
2.4.2.1 Iron ............................................................................
2.4.2.2 Copper .......................................................................
2.4.2.3 Aluminium.. ..............................................................5
2.4.2.4 Oil ............................................................................6
2.4.2.5 Organic matter on anion units ....................................6
2.4.2.6 Organic matter on cation units ...................................7
2.4.2.1 Calcium and magnesium ............................................7
2.4.2.8 Colloidal silica ..........................................................7
2.4.3 Influence of Temperature ..........................................................7
2.4.4 Degradation of Resins ..............................................................8
M148_34.DOC
-2-
1. INTRODUCTION
In general, following commissioning, ion-exchange units comply with their design duty
requirements in terms of product water quality, chemical consumption, flow rate and head loss.
However, after a period of time, the performance of a unit may experience deterioration, usually
revealing itself in:
- shorter service cycles;

- an adverse change in treated water quality;
- increased rinse water requirements;
- higher pressure drops/reduced flow rate;
- shortened resin lifetime.
Performance deterioration of ion-exchange units can normally be attributed to one (or a

combination) of the following factors:
1) changed raw water conditions;

2) changed service conditions; W
3) changed regeneration conditions;
4) problems with resins.
These factors are expanded upon in more detail below.
2. CHANGED CONDITIONS
2.1 CHANGED RAW WATER CONDITIONS
The operating capacity of an ion-exchange unit is based on the type and concentration of certain
ions present in the raw water. Any increase in the amount of these ions will result in a reduced
throughput of the unit and (or) an adverse change in the treated water quality; e.g. the ion leakage
of cation exchangers depends on the ratio behvcen monovalent cations (sodium and potassium)
and total cations in the raw water; the ion leakage of strongly basic anion exchangers depends on
the silica/total anions ratio in the raw water and the sodium leakage from the upstream-located
cation exchangers. &
Reduced capacity may also be experienced as a result of unforeseen compounds in the raw water,
which adversely influence ion-exchange resins, e.g. carried-over floe, oil etc.
The temperature of the raw water may infhiencc the performance of ion-exchange units. Certain
types of weakly acidic resins are sensitive to reduced water temperatures, resulting in a reduced
operating capacity. Fig. I shows the reduction of exchange capacity of the weakly acidic cation
resin IRC-84 at reduced temperatures.
Ml48 3.4 Problems with Ion Exchange

- 3 -
2.2 CHANGED SERVICE CONDITIONS
A change in service conditions, resulting in the performance deterioration of an ion-exchange unit,

is usually due to human and (or) mechanical imperfections like the following:
- A flow rate below or in excess of the design flow rate may result in “channelling and,
consequently, premature breakthrough.
- An extension of the service run with the aim of economising on regenerant chemicals may
cause excessive pressure drops, reduced flow rates and resin fouling.
- Loss of resin due to poor back washing, leaking nozzles or leaking collectors/distributors, in
combination with attrition of the resin, will result in shorter service cycles.
2.3 CHANGED REGENERATION CONDITIONS
The performance of ion-exchange units may be seriously aft&ted by changes in regeneration

conditions such as the following:
- Non-compliance with regeneration procedures by the operator.
- Changed quality of regenerant chemicals due to change of supplier or contamination during

storage (e.g. conversion of caustic soda to carbonate with carbon dioxide from the
atmosphere).
- Changed concentration or quantity of regenerant chemicals due to malfunctioning of dosing

pumps, ejectors and flow meters or due to changed concentration of bulk regenerant. Too low
a concentration of regenerant chemicals will result in a reduced contact time and,
consequently, in a reduction in the operating capacity of the resin.
Too high a concentration may result in fouling of the resin or clogging-up of slots in the
internal distribution/collection system (e.g. calcium-sulphate precipitation).
- The use of unsuitable water for regeneration or preparation of regenerant solutions (e.g. the
sodium slippage of a cation exchanger influences the pH and silica leakage in the product
water of the downstream-located anion exchanger).
- Changed temperature of regenerant chemicals. Too high a temperature may result in resin
breakdown (in particular, of strongly basic anion resin). Too low a temperature may result in
a reduced resin capacity,
- Inadequate back-washing, which may result in resin fouling and excessive pressure drops

-4-
2.4 PROBLEMS WITH RESINS
The performance of an ion-exchange unit greatly depends on the chemical and physical condition
of the applied resins.
Deterioration of the resins will immediately at&t the unit’s performance.
Resin decay can usually be attributed to one (or a combination) of the following factors:
- Attrition
- Fouling
- Temperature
- Degradation.
2.4.1 Attrition
Attrition is the physical breakdown of resins in the course of time, which cannot be prevented.
Attrition will be caused by:
- purely mechanical damage (e.g. during back-washing, during transportation of resin if

regenerations are performed outside the exchangers etc.);
- expansion and contraction of resin particles as a result of changes in the ionic sizes of the ions
being exchanged.
The broken tine resin particles may result in an increased pressure drop over the exchanger
These particles will normally be removed during back-washing.
In due course, the amount of resin lost this way needs to be replaced by fresh resin.
2.4.2 Fouling
Fouling of the resin particles will result in one (or a combination) of the following problems:
- blockage of the exchange sites and, consequently, loss of resin capacity;

- increase of pressure drop over the exchanger;
- shortening of resin lifetime;
- adverse product water quality;
- reduction of regeneration efficiency;
- increase of rinse water requirements.
The two following types of fouling can be identified:
I) Surface fouling, which is caused by organic and (or) inorganic materials present in solution or
suspension in the feed water which precipitate in the form of a scale or a film on the resin
SUrfaCe.
2) Internal fouling, which is caused by the retention of organic or precipitation of inorganic

material inside the resin structure.

-5-
Materials causing fouling of cation exchange resins are usually inorganic compounds.
Materials causing fouling of anion exchange resins are usually organic compounds.
2.4.2.1 Iron
Iron fouling of resins is normally caused by feedwater corrosion products, contaminated

regenerant chemicals etc.
The three following forms of iron fouling can be identified:
1) Suspended, insoluble iron entering the unit, which will be removed by the filtering action of
the resin bed itself. This iron can be removed by proper back-washing.
2) Iron entering the unit in the insoluble ferric form, which precipitates to form ferric hydroxide.
The ferric hydroxide precipitate is gelatinous in nature and tends to coat the surface of the
resin beads, resulting in a marked decrease in capacity.
Treatment with a reducing agent (e.g. b&&204) is required to reduce the ferric ion to the
more soluble ferrous form. The soluble ferrous ion can then be removed from the resin bed
during back-washing and (or) regeneration.
3) Iron entering the unit in the soluble ferrous form. These ions will be exchanged and will
adhere to the resin exchange sites. The ferrous ions may then be oxidised (e.g. by dissolved
oxygen present in the water supply) to form a precipitate of ferric hydroxide within the resin,
resulting in the blockage of exchange sites and, consequently, a reduction in capacity. If this
precipitation is allowed to age, it becomes increasingly more difficult to remove. In severe
cases of fouling, treatment with inhibited hydrochloric acid is the only effective remedy.
Instructions and procedures for treatment of iron-fouled resins can be found in e.g. Rohm &
Haas’ technical bulletin “treatment of iron fouled resin”. At your request to SIOP this information
will be faxed to you.
2.4.2.2 Copper
Copper fouling of resins is mostly found in condensate polishers and is caused by copper oxides,
from condensate system corrosion/erosion. Copper oxides tend to coat the resin beads, resulting
in a reduction of capacity.
2.4.2.3 Aluminium
Ahuninium is not normally present in fresh water supplies, but it is typically encountered as alum
floe arising from pretreatment systems. This alum floe will coat the resin beads, Aluminium in
the ionic form will normally be exchanged in the cation exchanger. These ions will not be
removed efficiently during regeneration and the operating capacity of the resin will therefore
continuously decrease.

-6-
2.4.2.4 Oil
Oil particles, entering ion-exchange units as a result of inadequate pretreatment facilities, will
cause coating of the resin beads and, eventually, the agglomeration of the beads into larger
masses, resulting in excessive pressure drops, channelling and premature breakthrough of
undesired ions. Oil-fouled resins can be cleaned with low foaming non-ionic surfactants, e.g.
Triton CR-54, Triton DF-12, etc. Instructions and procedures for treatment of oil-fouled resins
can be found in e.g. Rohm & Haas’ technical bulletin “clean up of oil fouled ion exchange resin”.
At your request to SIOP this information will be faxed to you.
2.4.2.5. Organic matter on Anion resin
Raw waters are often contaminated with organic material originating from decomposing
vegetable matter.
These organics are usually high-molecular-weight materials, consisting of large polyvalent

molecules of variable composition, generally referred to as tilvic acids.
J
Although proper pretreatment, such as flocculation/ precipitation, chlorination, activated carbon
filtration, etc., will remove most organic material, even in well designed and operated
pretreatment units some residual organic matter is to be expected.
Organic material may give serious problems in demineraliiation units, especially in anion
exchangers and mix-bed exchangers containing gel-type strongly basic resins.
The fidvic acid molecules are preferentially adsorbed by strongly basic resins. The large organic
molecules relative to the pore size of gel-type resins are not easily eluted during regeneration.
They even tend to penetrate further into the resin beads during each regeneration, resulting in a
reduced resin capacity, an increase in the silica content and the conductivity of the product water
and prolonged rinse periods.
Some cleaning can be achieved with an alkaline brine wash, but often early replacement of
organically fouled resins is required. At Stardow Refinery, high organics content of the water was
dealt with successfi~lly by applying alkaline brine soaks once a week. During normal
regenerations, the effluent of the anions turns brown. During an alkaline brine soak, the effluent is
v
usually very dark black / brown.
In order to prevent the objectionable effects of organic matter in raw water, the following
countermeasures may be taken:
1) Install an additional ion-exchange unit preceding the main unit and containing strongly basic
resin in the chloride form.
This unit is called an “organic trap” or “scavenging unit”. It removes approximately 90% of
the organic matter before the latter reaches the main unit.
2) Apply macroporous or macroreticular resins, which have been specially developed and where
pores are considerably greater than the pores of the normal gel-type resins.

-7-
These resins will easily adsorb/elute organic matter during service/regeneration. However, the
price is higher and the ion-exchange capacity is lower.
3) Apply isoporous resins, in which the cross-links are regularly distributed and the pores have
the same size. The pores are large enough to adsorb/elute larger-sized molecules. The
exchange capacity of these resins is the same as that of the normal gel-type resins, but the
price is much higher.
2.4.2.6 Organic matter on Cation resin
In case of severe upsets of the clarification plant, the cation resin could be affected by organic
(sticky) material as well. A very effective cure was developped at Stanlow, in which a 10% brine
solution was added to the cation resin, optionally followed by adding caustic. Air blowing would
help in removing the organ&, and performancti of the cation unit is (almost) fi~lly recovered after
a double regen.
2.4.2.7 Calcium and magnesium
In ion-exchange units which are preceded by lime/soda softening precipitation of calcium

carbonate and magnesium hydroxide may be experienced due to the carry-over of insoluble
hardness. These precipitates foul the resin beads by coating their surfaces.
Cation exchangers treating raw waters with a high calcium/total cations ratio may suffer from
calcium-sulphate precipitation if highly concentrated sulphuric acid is applied for regeneration.
During rinsing, this precipitate will dissolve, thereby partly exhausting the resin bed.
If the calcium/total cations ratio of the raw water exceeds 20%, the concentration of the sulphuric
acid has to be kept at approximately 2% during the first part of the regeneration.
The sulphuric acid concentration has then to be stepwise increased to the optimum level.
2.4.2.8 Colloidal silica
A typical problem encountered in demineralisation units is caused by the presence of colloidal

silica in some raw waters.
This type of silica, usually referred to as non-reactive silica, is non-ionic and cannot be removed
by ion exchange.
Owing to its high pH and high temperature in the boiler, the non-reactive silica will be converted
into the reactive soluble form, resulting in an increased total silica value for the boiler water.
Consequently, a higher than expected boiler blow-down has to be applied.
Special resins have been developed to intercept this non-reactive silica, via adsorprion in the large
pores of the resin rather than ion exchange.
2.4.3 Influence of Temperature
Depending on the type of resins, the temperature of the treated water and the regenerant solution
may seriously affect the condition and lifetime of a resin.

-8-
Excessive temperatures will cause the resin physical damage, revealing itself in the breakage of
cross-links and the loss of functional groups.
Strongly acid resins have a good resistance to high temperatures. Temperatures of up to 12O’C
(or even higher) can be applied. Weakly acid and weakly basic resins can be applied to
temperatures of 80-100°C.
Strongly basic resins of the OH form can be used only at temperatures of SO-60°C. These resins
are more stable in the Cl form and may then as such be used for temperatures of up to 8O’C. At
higher temperatures strongly basic resin retains it total capacity, but it loses its capability to
exchange weak acids, such as silica, and will gradually become a weakly basic resin.
Type II anion resins are less sensitive to higher temperatures than Type I anion resins.
In general, the exchange capacity of strongly basic resins is greatly affected in the initial
1-2 years of operation. Such resins have au average useful lifetime of only 4-6 years.
2.4.4 Degradation of Resins
Most resins are sensitive to oxidants such as chlorine, potassium permanganate etc. However,
the resistance of cation resins to oxidative attack is considerably better than that of anion resins.
Type II strongly basic resins are more sensitive than Type I resins. Oxidative attack reveals itself
in the loss of functional groups and the breakage of cross-link (decross-linking).
During storage ion-exchange resins should be kept wet. Drying-out of resins may result in the
cracking and breaking of the beads during rewetting.
If resins have dried out, they should be re-hydrated with a strong brine solution (IS-20%) and
progressively transferred to lower brine concentrations (10% and 5%) for approximately
30 minutes, followed by a rinse.
High temperatures, due e.g. to sunlight, should be avoided during storage
Anion resins should be kept stored in the most stable condition (Cl form) following regeneration
with an alkaline brine solution. Cation resins may be stored following exhaustion or regeneration.
If ion-exchange units have to be stored for longer periods, it is recommended to submit the units
to a sterilising programme using a formaldehyde solution in order to prevent damage to the resins
due to bacterial growth.

Confidential
Ml48
MODULE 1
- WATER (Pre-) TREATMENT COURSE
SECTION 3.5 1
INDEXI.WC; 22108/97
SUBSECTION 3.5 REVERSE OSMOSIS
The importance of proper preatreatment

Since the SO’s, Shell has been involved in various attempts to justify Reverse Osmosis units for
Boiler Feed Water make up. One of the most difficult issues has been that water available around
refineries tends to have (oil related) contamination. Trial installations have failed before, due to
improper treatment. Therefore, the pretreatment of the water is one of the most essential parts of a
river or sea water reverse osmosis plants.
Future of Reverse Osmosis in Shell

It will only be a question of time before the first RO unit will be installed on a commercial scale for a
Shell location, because:
RO units don’t use expensive chemicals
RO units do not produce difficult to neutrahse chemicals in the effluent
RO units can handle raw water with a salinity up to sea water
The RO technology is advancing rapidly because of the very wide spread use in pharmaceutical
and electronics industry and breweries.
The disadvantages, however, are:

usually RO plants have to compete with existing demin plants using relatiely low dissolved solids
river water.
For sea water, there’s strong competition of distillation processes, which use usually cheap
refinery produced steam.
the capital expenditure for such a unit is very high
it’s not approved inside Shell yet.
Recommended reading are e.g. the attached DEWRLAN technical bulletins
M14._3!5
A technical bulletin published by
*- Water and effluent treatment
MEMBRANE PROCESSES I
Membrane Processes in General, and Electrodialysis in The Ultrafiltration (UF) Membrane is really an extremely flne
Partkllla# filter which can be made with pores of different desired sizes.
It allows water and small dissolved materials to pass through
All the processes which- have been described in the previous 23 it, but retains larger molecules, colloids and suspended
Bulletins have been in common usefordecades, though of course material. The pore size determines the minimum size of mole-
there has been continuous progress, especially in the detail of cule which will pass. It, too, uses hydraulic pressure to push
plant designs. Membrane processes, as such, are also very old, the waterthrough.
but their introduction into water treatment is much more recent
and they are, therefore, relatively unknown quantities. At present, Electrodialysis (ED) depends on two different membranes,
they represent a means of carrying out special duties, usually at a made essentially of cation and anion exchange material. These
greater cost than the conventional processes. Their costs, how- two membranes allow small cations and small anions to pass
ever, are falling all the time, and at the same time, the special through respectively, but they retain everything else-that is,
requirements for which they are necessary are becoming commo- water, large ions of both signs, non-ionic dissolved materials,
ner.We can therefore expect to have more and more to do with suspended and colloidal material. The driving force for ions in
membrane processes in future. Electrodialysis Is an applied electromotive force.
What Isa Membrane? Mass Transfer
For our purposes all membranes are thin films of solid materials Mass Transfer is one of the basic subjects studied by Chemical
which have some selective property - that is, they allow some Enplneers, and the simple explanation which follows Is intended
classes of substances to pass through them but not others. forthose reared in other disciplines.
Membrane processes. which make use of this selectivity share a The basic features of Mass Transfer are rather similar to those of
number of basic features, though there are several different kinds Heat Transfer (which will be familiar to Mechanical Engineers).
of membrane and membrane processes. In membrane processes we have to transfer some material from
one liquid phase to another liquid phase, across some kind of
The Basic Features of all Membrane Processes separation barrier. This means transferring salts from one solu-
tion to another (in ED), or water from one solution to another
To use the properties of a selective membrane we need an appara- (in RO and UF).
tus which has the following features:
Three variables immediately present themselves as the controlling
1. It has to have two sets of liquid conduits, one for the water we
factors in the rate of transfer:
are going to treat, and anotherfortreated water.
1. The resistance to transfer per unit area of barrier,
2. It has to be built so that the membrane separates these two
conduits, in such a way that there is no direct cross-leakage 2. The driving force promoting transfer, and
between them. 3. The area across which transfer takes place.
3. It has to provide some kind of driving force which will force (Actually, of course, this is the same pattern as in electrical power
through the membrane the substance which the membrane transmission where these three variables are represented by the
allows to pass. resistivity of the conductor, the voltage, and the area of the
conductor, respectively.)
In additional to this, the whole group of processes has intrinsic
Chemical Engineering features with which we are going to deal in As in heat transfer, the resistance of the separation barrier(in our
this Bulletin. These are bound up with the theory of Mass Trans- case the membrane) is composed only in part of the resistance of
fer. the’barrier itself. The material which we are trying to transfer
across has to get to the surface of the barrier on the one face, and
Three Membrane Processes away from the surface on the other face.
Three processes have come into regular use in water treatment, As the barrier presents a discontinuity to flow, there is always a
based on three different kinds of membrane: stagnant layer of fluid on its faces. The thickness of this stagnant
layer varies with the hydrodynamics of the system - convention-
1. The Reverse Osmosis(R0) Membrane comes in very different allycharacterised bythe Reynolds Number(see below).
forms, all of which have the same essential property: they allow
water and very small dissolved, undissociated molecules to Suppose we are looking at an ED anion membrane, and we are
pass through, but they will not pass ionised salts, large mole- trying to get chloride ions to go across the membrane under the
cules, or colloidal and suspended solids. The driving force influence of the electrical field. Fig. 1. shows the conventional
which pushes the waterthrough is hydraulic pressure. picture by which the process is usually illustrated.
This Technical Bulletln is ons of a series issued by Dewplan Ltd. G.S. Solt was Research end Development Dlrector of Dewplan
to promote a better understanding of Water and Effluent Tmatment (WT) Ltd, and was also Honomry Research Fellow at Univemity
‘v’ in industry. The series will cover the full range of processer and Collage, London, where he fectumd on the Economics of Water
equipment supplied by tha Water Treatment Plant industry. For Treatment. He is intematfonafty known for his work on &salinatlon
r e p r i n t s plefw write to DEWPLAN Ltd., Beechwood H a l l , and mveme osmosis, and is Director of the School of Water
Kingsmead Road, High Wycombe. Bucks HP11 1LA. Sciences at Cranfield Institute of Technology.
TB.26
-1. DlAGRAt4ATlC CROSS-SECTION FIc.2 ED. C E L L
ACCFDSS AN ANION KLECTIVE
MEMBRANE,
FIG A. KINETIC RIEMOMENA ON ANION t434BRANES.
FIG 5. KINETIC EFFECT OF MEMBRANE FOUING. FIG 6. CONCENTRATION POLARISATION ON R.O. MEMBRANE.
V’ )
The membrane is represented as being flanked by two completely
stagnant films of water. and outside these stagnant films, the 1. All membrane processes depend on mass transport across a
water is supposed to be in a state of total mixing. In fact this is a selectivemembrane.
slight over-simplification, but the convention serves Chemical
Engineers very well. 2. The rate at which this transport takes place depends on the
resistivity of the separating barrier per unit area. The separat-
In the turbulent region, where there is perfect mixing, the concen- ing barrier in this context includes the liquid films which ine-
tration of chloride ions must be constant, because any change in vitably form on the membrane surfaces, and any fouling film
any part of this region will immediately beevened out by the turbu- which may accumulate in addition.
lence. On the other hand, the stagnant water films present an 3. The amount of transport also depends on the total area of
obstacle to diffusion of chloride ions. It so happens that thefilms barrier available for transport, and on the driving force avail-
actually present more of an obstacle to flow than the anion able.
selective membrane itself. It is therefore rather important to
design the system and its hydrodynamics in such a way as to 4. Because of the selectivity of the barrier, concentration changes
maximise the turbulence measured by the Reynolds Number, in occur in the stagnant liquid films on the membrane surfaces.
order to decrease the film thickness and so reduce the resistance The degree to which the concentration changes occur depends
to Mass Transfer. This sort of argument will be familiar to all on the rate of transfer ,and on the thickness of the film.
those who have studied heat transfer, where the copper tube 5. If the concentration change is allowed to become very great, it
presents less of an obstacle than the waterfilms on it. will eventually reach some limiting condition whereit has some
major and unforeseen effect on the transfer process.
The Reynolds Number, Re, which governs the turbulence and
hence the film thickness is a dimensionless number This concentration phenomenon in the stagnantfilm on the mem-
Re=vep brane film is called polarisation. It has proved one of the most
important and most intractable features of all membrane pro-
cesses. Its actual effect, however, is different in each different
-1 where v is the velocity of flow. < is a linear dimension of the gap
process.
through which the fluid is flowing - for example in pipes e is the
diameter, and in flow between parallel plates it is the distance
between the plates+ is the density of the fluid and pits viscosity. Electrodialysis & Polaris&ion
In Mass Transfer (as in heat transfer) the designer will therefore
attack the variables in the Reynolds Number with a view to increas- ?%ppose we fabricate anion exchange material in the form of a
ing Re. He will, for example, increase v as far as he can without thin sheet.We know that this is a porous substance with fixed
incurring excessive pumping costs. He will try to increase 4, but positively charged groups on it: these groups must have negative
usually there are also important reasons for keeping e small, so ions associated with them, but the negative ions can move in and
here again he will have to compromise. p is generally outside his out ofthe materials-always provided there areotherionsavailable
control, but p, the viscosity, falls as the temperature rises. All to replace them (see TB4). Ion exchange processes use the prefer-
membrane processes work better at higher temperatures - ence which these materials have for some ions rather than others,
subject again to limitations imposed, for example, by the material but in ion exchange membrane processes, these preferences can
of the membrane. be ignored as a first approximation.
Again, as in heat transfer, any additional film which obstructsthe If we dip our anion exchange sheet in a bath of sait solution and
transfer will add an additional resistance to mass transfer. Such apply an EMF across it, then there is nothing to stop chloride ions
films can easily become the controlling element in the procesb. from moving towards the positive electrode, either in the bath or
across the membrane. An electrical current will be set up: in the
solution it will be carried equally by sodium and by chloride ions
moving in opposite directions, but in the membrane it will be
Polaris&ion carried by chloride ions alone, because an anion exchange mater-
ial does not admit cations into its poresWe now have mass trans-
The situation becomes more complicated when we consider that fer of chloride across the anion exchange membrane (called the
the basis of all membrane processes is the selectivity of the anion membraneforshort).
membrane used. The RO membrane, for example, is bombarded
by molecules of water and ions of the salts dissolved in the water. The same thing can be done with a sheet of cation membrane,
The process is based on the ability of the membrane to allow which will transport only sodium ions.
waterto pass through while rejecting the ions. Now suppose we make up a cell as shown on Fig 2, with a cation
Imaginethe concourse of a railway station. Passengers are milling and an anion membrane side by side. If we pass a current across
about in it, and want to go through the turnstile to the train, but the the apparatus, sodium and chloride ions flow across the mem-
ticket collector rejects those without reservations. These now branes and out of the compartment formed by the two membranes,
have to find their way back into the middle of the concourse, so that the solution between the membranes becomes desalted.
against the stream of more passengers converging on the tum- If we go a stage further and make up an apparatus in which cation
stile. If the rush to get to the train is very great, we could end up and anion membranes alternate, as shown in Fig 3, then it will be
with the turnstile completely barricaded by hapless, reservation- soen that the current will desalt all the even numbered compart-
less passengers trying to get back. and thus preventing the ments 2, 4, 6. and so on, while the odd-numbered compartments
movement of passengers tothe turnstile at all. Even if this extreme become enriched in salt, with sodium and chloride ions streaming
state of affairs never arises, the proportion of passengers without in from the two membranes which form the compartment. We can,
reservatmns will be higher in the crowd at and near the turnstile therefore, build an apparatus in which cation and anion mem-
than in the concoursein general. branes alternate, and if the cells formed between the membranes
are connected to two liquid manifolds so that all the even compart-
If, however, the whole station crowd were kept much more on the mentsflow into one and the odd compartments flow into the other,
move, then the rejected travellers would be dispersed much more then we have a means of desalting a stream of water (or of en-
readily, and the congestion at the turnstiles reduced corres- riching the other one). This is called an Electrodialysis Stack
pondingly. (ED Stack for short).
Exactly this state of affairs occurs on the surface of an RO mem- In ED, electrical currentflows through the water being treated. As
brane, where the rejected salt ions wll be found in much greater pure water is almost an insulator, and water really only becomes
concentration than in the bulk of the liquid. conductive by virtue of the dissolved salts in it, this process is no
good for totally demineralising water. Its main use in water treat- There is worse to come. Suppose our saline water contains large L/
ment is for desalting brackish water to potable level. (The en- organic anions, such as the Humic and Fulvic acids described in
richment of the concentrating stream has also been used by the TB 18. Under the influence of the EMF they, too, migrate to the
Japanse for concentrating sea water into strong brine). membrane, but they are too large to get into the pores, let alone
pass through the membrane. Instead, they settle on the surface
Even in brackish water conversion ED has proved quite trouble- of the membrane where they form afllm which has a high resis-
some in some cases, as we shall see in a moment. Its use is rather tance to diffusion by chloride ions (Fig. 5). This film acts like scale
limited, and there is therefore no need to describe ED equipment in a boiler, and becomes the major resistance to mass transfer.
in detail. But the problem of polarisation in ED is rather an inter- Juggling about with the hydrodynamics to make the water films
esting example of the kind of difficulties which we experience with thinner will now do very little to improve the process.
membrane processes.
Let us look at the mass transfer across anion selective ED mem- Poluisation in Reverse Osmosis
branes, to show these difficulties.
The RO membrane lets water pass through, and practically
Fig. 4 shows the membrane with a salt solution on both sides of it, nothing else. Fig. 0 shows the section across the RO membrane.
before the current is switched on. We have the usual staghant If we start with a concentretion of C, agaln, and apply the pressure
films on the membrane face, but as there is no mass transfer which squeezes the water through the membrane, we can see
taking place yet, the concentration of chloride in the films is the what is bound to happen. As water begins to go through the
same as in the turbulent bulk of the limit, and is C, (say). membrane the salts in it get left behind on the membrane surface,
so their concentration rises. A concentration gradient is then set
If ws apply an EMF across the solution and membrane, then the up which promotes diffusion of these salts back into the bulk of
chloride ions will be driven across from left to right, as shown on the fluid, across thefilm. Eventually an equilibrium Is set up, when
thediagram. the diffusion rate back across the film is the same as the rate at
which water passing through the membrane leaves salt behind on
The membrane itself is an excellent conductor, and there is a rush its surface, as shown in Fig. 6. If there are colloide or suspended L(,
of chloride ions across it, with the result that the left-hand mem- materials in the water as well as salts, they will simply settle on the
brane surface begins to gulp chloride ions from the liquid touch- membrane surface and stay there, forming an addltionel barrierto
ing it, while the right-hand surface pumps chloride ions into the diffusion. Both the local rise in concentration and the additional
water. The concentrations on the membrane face are therefore barrier ara very important to RO operation, as we shall see in a
changed. The left-hand face becomes depleted, and so a concen- later Bulletin.
tration difference between the membrane face and the bulk of the -,
liquid arises. Under the influence of this difference, chloride ions
diffuse across the stagnantfilm, forming a concentration gradient Polariration in Ultrafiltration
as shown. On the right-hand face, the opposite happens, with a
high concentration on the membrane face and a concentration The problem is similar to RO, but is not technically called polart-
gradient away from the membrane. satlon. The UF membrane does not retain salts, but only large
molecules and bigger particles. The problem of concentration
After an instant, electrical currents across each of the two films build-up of salts does not arise, but otherwise the operation is
and across the membrane have to become the same, because they similar to RO. Large molecules diffuse much less readily than salt
are electrically in series. The concentration gradients therefore ions, and somehow or other they have to be got off the membrane
end up such that theflow of ions in all parts of the apparatus isthe face if the process is to run continuously. Colloids and bigger
same, and this is the condition shown in Fig. 4b. Here the concen- solids are even worse. Again, we shall go into the detail in a later
tration in the solutions is C,, but on the depleted left-hand face of Bulletin.
the membrane it has fallen to C,, and on the enriched right-hand
face of the membrane it has risen to C,. Electrodlalysis
If wa increase the EMF, the currentflows faster, and the gradients We can now say a last few words on Electrodialysis. As we have
have to become steeper. This is all very well but there is atheore- seen, it only operates economically where. there are enough
tical limit to the amount of current wa can push through the dissolved salts in the water to conduct electricity. This limits the
apparatus. Consider what happens in the depleted film on the left- process to brackish water conversion. Its ideal economic range
hand side of the membrane. As we raise the EMF, and the current is for desalting water of less than Moo ppm down to 500 ppm. If a
flows faster, we have to have a steeper gradient. As C, is constant, we need a lower product TDS, ion exchange has to take over
and assuming a constant thickness of film, this can only come because ED becomes uneconomical. If we start from a high TDS,
from a progressive lowering of the chloride concentration on the RO can do the job more economically. ED cannot deal with water
membrane face, C,. Eventually we reach a point at which C, falls containing organic or colloidal materials, except after pretreat-
to zero - that is, we are exploiting the maximum concentration ment, because very severe filming of the membranes takes place
gradient available to us (fig. 4~). Any further increase in EMF will as described above. Where impurities of this kind have to be
then produce no further increase in current. “Depletion polari- removed, RO can do it (though there may be fouling problems).
zation” has sat in, and is accompanied by the most undesirable Altogether, ED in its present state of development is limited to a
side-effects, which we need not go into in this Bulletin. The only very narrow range of applications in water treatment, and can be
way to increase the rate of transfer would be to reduce the Rim ignored by all but a few specialists.
thickness, or raise the temperature, to reduce the resistance of
thefilm. The next Bulletin will deal in detail with Reverse Osmosis.
Water and effluent treatment
MEMBRANE PROCESSES II
Reverse Osmosis Process Vwiables
The three membrane processes mentioned in the last Bulletin As a first approximation we can say that the flux of water across
were none of them originally intended for purifying water In tem- the membrane (i.e. the Rowrate per unit area) varies with the ap-
perate zones: ED and RO started out as methods of converting plied pressure divided by the resistlvity of the membrane itself.
brackish water to drinking water, and UF was aimed at recovery or We therefore get an equation which is identical to the one which
purification of process liquids. Generally speaking, the three describes the flow of electricity through a conductor:
processes have found their main use in these original aims, but
it turns out that they also have uses in the field of high purity water Flow = Pressurex Area
production. This Bulletin will describe the use of reverse osmosis Resistlvity
in this specialised application. Just es in electrical engineering, where we have the choice of
RO has been the most successful of the three processes in voltage, cable diameter and cable material, in RO we have these
general, and has also found the widest use in water purification. three variables at our disposal.
It performs two quite different duties, for either of which we might
consider its use: The pressure used for RO in water purification applications is
~suallyabout20-40 bars, although in somevery small plants where
RO will remove between 90 and 98% of all dissolved salts in a the capital cost of the membrane is small, much lower pressures
raw water, the removal depending largely on the type of mem- are used for convenience and so under-utilise the membrane.
brane used.
RO also removes large dissolved organic molecules, all colloids The really interesting variables are those of area and resistivity,
and suspended matter, and micro-organisms. because two completely different membrane systems have been
developed:
In removing salts, RO does the ss.me iob as ion exchange, bul
with a less pure product.With ordinary potable water quality as 1. the sheet membrane (originally cellulose acetate, which is still
widely used) which is expensive per unit area but has (I low
starting point, RO is rarely economical and ion exchange is
normally used for demineralisation. At more than 400 ppm TDS, resistivity.
however, it is worth considering RO as a first stage on pi~rely 2. the hollow fibre membrane, which consists of polyamide
economic grounds, and the higher the initial TDS, the better the capillaries the thickness of human hair, which is very cheap per
prospects for RO become. unit area, but has a high reslstivity.
On the other hand, the power of RO to remove all large molecules The sheet membrane is most commonly used in “spiral wound”
and all particles makes it a useful stage in the production of ultra- modules in which it is wound round a former like a Swiss Roll.
pure water. It is frequently used, for example, in the micro- The raw waterflows along the axis of the roll. under pressure. The
electronics industry to remove organic and colloidal material from permeate which flows across the membrane flows spirally out
raw waters.’ through a separate outlet (see fig. 1).
The Basis of the Process The hollow fibre module consists of a U-shaped hank of fibres
enclosed in a pressure vessel. The open ends of the U are sealed
In simplified terms, RO consists of pushing waterthrough a mem- by being cast into an epoxy tube plate (see fig. 2) rather like a
brane under hydraulic pressure. The hydraulic pressure has first floating head heat exchanger.
to overcome the osmotic pressure caused by the difference in
salt concentration on the two sides of the membrane, and the These two different approaches result in RO being used in rather
surplus pressure then supplies the driving force pushing water different ways, as we shall see later.
through the membrane. When treating low TDS waters for our
particular purpose, the osmotic pressure can largely be ignored.
Product Purity
*One mqor UK eleclromc component maker has e works which It is not y& quite clear just how the RO membrane works. One odd
draws on such a clean water. derived from the chalk measures fact is that the salt passage (the ratio of permeate TDS to feed
around the Marlborough Downs that. with ion exchange alone. TDS) of a membrane is constant over a wide range of conditions.
he can obtain 18 megohm water - i.e. of theoretical conductiiity. Since higher pressure leads to higherflux this constant salt pass-
Most of Britain’s other electronic firms have set up where they use age results in lower percentage salt residual in the permeate -
some of (he most difficult wsters in Britain - in Scotland. in Wales, another reason for using high pressure. As membranes age. their
on Ihe Bedfordshire Ouse. They would be unable to operate resistivity rises and the flux drop%, and so does the treated water
wthoul the RO 10 help prodcuce the ultra-pure wete, needed for quality. Salt passage tends to increase with age which makes the
washing micro-chips. situation worse.
This Technical Bulletm IS one of a series issued by Dewplan Ltd. to G.S. Solt was Research and Development Director of Dewplan 0
L promote a better understanding of Water and Effluent Treatment m Ltd, and was also Honorary Research Fellow at University College,
industry. The series wll cover the full range of proceeses and London, where he lectured on the Economics of Water Treatment.
equipment supplied by the Water Treatment Plant industry. For reprints He is internationally known for his work on deeelination and reverse
please write to DEWPlAN Ltd., Beechwood Hall, Kingsmead Road, osmosis, and is Director of the School of Water Sciences at Cranfield
High Wycombe, Bucks HP11 1LA. Institute of Technology.
TB.21
MESH SPACER
RC MEMBRANE
PROOUCT
RO MEMBRANE
PERMEATE
CARRIER
FIG.1 ?iPIRiL WOUND MODULE.
%&a ‘U’ SHAPED HANK OF HOLLOW FISRES
/ CAST TUBE SHEET
PERMEATE
COLLECTION
CHAMBER
FIG.2 HOLLOW FIBRE MODULE.

1 _ I I I
1 at STAGE 2nd STAGE
CONCENTRATE CONCENTRATE
- 3rd STAGE
CONCENTRATE
TO DRAIN
FIG.3 3 STAGE RO SYSTEM WITH CONCENTRATE RECOVERY
As might be expected, the RO membrane rejects large multi- at the membrane surface. The contigurstion of a hollow ffbre
valent ions most efficiently, so that Cs++, Mg++ and SO,-- are module is such that concentrate tlows across the membrane
taken out to a greater extent than Nsf and Cl-. Silica passage surfaces are inherently lower. Since the salts accumulate slowly
varies, and up to half the silica can be passed through, depending this is acceptable.
on circumstances. The membrane does not reject CO, at all.
Small non-dissociated organic materials dissolved in water pass Conversion
through unchanged, and so do dissolved gases like 0,.
The difference in concentrate flow rates is important because it
The Stagnant Film affects “conversion” - that is the permeate flow expressed ss a
percentage of feed flow. The configuration of s hollow fibre
The last Bulletin described the stagnant film on the membrane module with its low concentrate flow rate can give up to 66%
surface which occurs in all membrane processes, and has a major conversion. A single element in s spiral wound system rarely
influence on the operation of each of them. achieves more than loO/, and to achieve 50”~ in such a system
requires 6 elements in series resulting in a module considerably
The first important factor is that the membrane only “sees” the longer and ususlly more expensive.
solution as it exists inside theglm, on the membrane face. As the
film on the raw water side in RO becomes more concentrated than In large plants, this disadvantage can readily be overcome by an
L_,j the bulk solution (see Bulletin No. 261, this mesna that the percen- arrangement of modules in series, and parallel. Concentrate
tsgeof salts passing through the membrane is based on this more from the first stage is used aa feed to the second and so on, each
concentrated solution, and not on the bulk of the solution, away successive stage employing fewer modules ss the flow reduces.
from the membrane. The concentration in the stagnantfilm must, Fig. 3 shows a typical arrangement.
therefore, not be allowed to rise too high, or the product will
suffer. In small plants, where there are not enough modules to make this
kind of arrangement possible, the spirally wound membrane
Another danger, of course, is that if the concentration in the film remains at s disadvantage.
gets beyond the solubility of some of the salts in it (CsSO. is the
most obvious danger), then scale will form on the raw water side On the face of it, a low conversion does not seem to be a serious
of the membrane due to the precipitation of the super-saturated problem-water is cheap (or so a lot of people think) and anyway
salts. the waste from an RO plant producing ultra-pure water can be
re-used for cooling orfor rough washing.
The last Bulletin showed that the concentration changes which
take place in the stagnantfilm depend on two factors -the degree In fact a low conversion is likely to be rather costly. The water
of turbulence in the water, which controls the film thickness, and fed to an RO plant has almost inevitably been pretreated to remove
the rate at which the membrane process is functioning and at dirt, to adjust its pH, and to remove its hardness. or dosed to avoid
which (in the csae of RO) it piles up salts on the membrane face. scaling. These costs are referred to the flow of raw water pumped
in, and together with the cost of pumping, form the main running
The two alternative membrane systems handle the polarisstion costs.
problem in different ways.
Moreover, a low conversion means that the pre-treatment equip-
The flux across a spiral wound membrane is high and salts ment and the high-pressure pump all have to be over-sized, and so
accumulate quickly at the membrane surface. High concentrate the capital cost will also be affected.
flows are necessary to sweep away these salts. The configuration
allowa for these high flows and spacers in the “swiss roll” are The choice of module therefore becomes straightforward in most
designed to promote turbulence. cases. Really small plants cannot function economically with
L) spirally wound modules, because of the recovery problem. Below.
By comparison. fluxes in hollow tibre membranes are an order of say, lOm’/hr the hollow fibre module is likely to be the economic
magnitude lower. Salts therefore accumulate much more slowly choice, although other considerations can apply.
Physical Blocking Bugs L Ultra-Pure Water
Particulate and colloidal material, whether organic or mineral, will One of the problems in producing ultra-pure water Is keeping it
not pass through RO membranes but may cause physical block- free of micro-biological growth. RO does remove bacteria (an?
ing. The higher surface velocities in spiral wound modules make even viruses) very efficiently, but that is no guarantee that the+&
them less prone to this type of blocking and easier to clean than will not breed again in the purified water. If they grow on the RO
the hollow Rbre type. This is a particularly important factor in the membrane itself, of course, they may block it. The hollow fibre
choice of larger plant. membrane, in particular, is a very good breeding ground for
bacteria-especially as it cannot be kept sterile with chlorine.
The ability of a particular water to foul a membrane is character-
ised by the “silt density index”. This is a measure of the rate of In theory, no bacteria should ever get through to the clean side of
build up of resistance to flow and is determined by filtering the the membrane but special precautions should be taken against
water through a 0.45 urn membrane filter and measuring the time contamination creeping up the treated water lines, which should,
taken (t, minutes) for 5W mls to pass through at 2 bar inlet pres- for example, be isolated from atmospheric contact. To inhibit bug
sure. Flow through the filter is continued for a further period, T growth when using RO in these circumstances routine sterilisa-
minutes, at the same pressure and the 500 mls test is repeated tion of the modules is advisable.
giving a new time(i minutes).
The Silt Density Index is given by
Flow Sheets for Ultra-Pure Water
The main users of ultra-pure water are the electronic component
SDI= ~ ’ manufacturers, whose main preoccupation is to have water of the
T lowest possible conductivity, and the pharmaceutical users who
(i.e. the percentage change in flow rate divided by the time taken want to exclude bacteria and pyrogens, and are less interested in
for the change to occur). total removal of inorganic salts.
Another statement of fouling potential, and one that is not speci- These two objectives lead to two different types of flow sheet.
fic to the particular test period, T. is the “plugging factor” which The electronic users instal RO ahead of Ion exchange, but after
is simply the SDI mulhplied by the duration of the test in minutes, whatever pretreatment is necessary to protect the RO plant from
i.e. PF = TX SDI. This is a derivative of the test and it is normal to fouling. In this way they get the benefit of partial demineralisatio&&
state the pressure at which the test is carried out. e.g. PF,,. before the ion exchange plant removes the last traces of salts to
There are various other versions of these formulae, and most give a product of 18 megohm orthereabouts.
membrane manufacturers will provide advice as to how their Since its acceptance by the U.S. Pharmacopoeia for producing
particular index is measured and what index their membranes will pyrogen-free water, the use of RO has grown in the pharmaceu-
tolerate, so that the need for pretreatment can be assessed. A -tical industry when this quality of water is specified. Here it Is used
gored rule of thumb is that the SDI (as defined above) of RO feed as a final polishing stage after deionisation has reduced the
should be less than Band should betittered to5ym or less. mineral content to acceptable limits.
Some more Variables

The two systems, with the conventional type of membrane fitted. Summary
vary in other respects. Polyamide is extremely sensitive to oxi- RO is a relatively expensive process for demineralisation and,
dation by chlorine, which must be removed from the water.
given conventional sources of potable water, it is not normally
Cellulose acetate, whilst still suffering smne deterioration, will economical merely for that purpose.
tolerate up to a !_vrn of Cl, in comparative safety.
Its main use in water purification relies on its ability to removs a
Both types of membrane suffer degradation by hydrolysis and
large group of materials which no other process can be guaran-
this is accelerated as the pH of the feed deviates from neutral. teed to remove. It is therefore widely used when ultra-pure water
Cellulose acetate membranes deteriorate rapidly if the pH falls has to be produced.
outside the 4-6 band. Polvamide hollow fibres are more tolerant
of high pH and can operatein the range4-11. This picture may change in the future. As our water supplies get
worse, and RO technology improves, we may find an increasing
The resistivity of the membrane system depends on the viscosity number of applications for RO as a first-stage demineralisation
of water, and so falls quite sharply if the water is warmed. If the process.
product is going to be heated anyway, then large economies can
be made by preheating the raw water and reducing the size of the ‘,J
RO plant for a given output. The spirally wound membrane can
withstand up to about 30°C, and the hollow tibre module about
35OC, but of course, the rate of hydrolysis is increased at these
highertemperatures. The next bulletin will be concerned with ultra-filtration.
‘- Water and effluent treatment
MEMBRANE PROCESSES III

ULTRAFILTRATION and PRETREATMENT FOR MEMBRANE PROCESSES
by G.S. SOLT
ThisBulletin contmues with U/lrafWation, the thudmembranepmcess This thin-skin technique means that the pressure loss across the
us&in walerlreabnent,andthemoslracenl. Itdescribes itscapabilities, membrane is kept to a minimum. As there is no need in UF to choose
which are al present most useful fiw the prcduclion of ultra-pure waler. a membrane material which will have semi-permeable properties, UF
though it is nc4 yet clear to what extent the process will establish il.&f in membranes can be made in a much wider range of materials, and they
practice. A final review deals with the need for establishing the fouling therefore offer a much wider range of resistance to aggressive
properties of water to bs treated by allmambranepmesses. and the fact chemical conditions.
fhat pretreatment of some hind is a/m& always needed.
Going further up the range of pore sizes for UF membranes, we find
What’s in a name?’ Just when “RO” as an abbrewation for Reverse ourselves merging into “Membrane Filtration”, which is a much older
b 1 Osmosis has become unwersal, we start to come across people who process. Classical membrane filters are developments of the familiar
prefer to use the word “Hyperfiltration” instead. What is the point of chemist’s filter paper: they are mats or sinters. of controlled uniform
this cumbersome new word? pore size through the whole depth of the membranes. Modern
membranes for membrane filtration are, not surprisingly, begunning
The best clue here is that the manufacturing company which is to look very similar to UF membranes. The distinction is therefore an
especially keen on “Hyperfittration” rather than “RO” makesa whole _prtiicial one: quite arbitrarily. we could say that the lower limit of
series of membranes, with a very wide range of pore sues. The membrane filtration is 02 microns. Anything with a smaller pore size
smallest-pore membranes are intended for what we will obstinately is ultrafiltration.
continue to call RO: they reject dissociated ions - by a process
which, as we have seen, is still not perfectly understood -and also
filter out all molecules larger than about molecular weight TX). At the
same time, of course. they hold back all colloids and suspended UF Apparatus
particles.
We have seen that on all membrane processes. oneof thecontrollmg
With a larger pore sue than these RO membranes, the membrane’s problems is how to disperse the concentration changes which take
power to relect ions rapidly disappears but they can still serve as place on the working face of the membrane. In ED the working face is
filters, capable of straining out molecules and particles of progres- depleted, and in RO the problem is due to rising concentration of
swely larger sizes. There is no mystery about the mechanics ?f this saltson themembrane. In UFwearefaced witha similar problem: the
process, which is sample tea-straining with a very fine sieve. molecules and particles which have been retamed on the membrane
face have to be got back into the bulk of the concentrate somehow,
Presumably the process by which large molecules and particles are and their accumulatron on the membrane face has to be stabilised at
rejected from an RO membrane is also simple tea straining. With a workable level.
respect to that kind of use to which RO can be put, it is therefore
reasonable to call the process “Hyperfiltration”. Moreover. RO In UF we are rejectmg only large and therefore sluggish particles
applications merge mto “Ultrafiltration” without any very clearly from themembraneface. Thesediffuse slowly and would like nothmg
defined distinction, so there IS something to be said for having a better than to settle down on the membrane surface. Getting them
- ) similar name for the two processes. away from there is the mam limitation in UF operations.
On the other hand UF membranes, with their large pores, offer a low
Ultrafiltration pressure loss provided they can be kept clean. In the absence of any
salt rejection. there is of course. no questton of osmotic pressure
Wethusapply “Ultratiltration”toa truefiltration processdesigned to opposing the applied pressures as happens in RO. UF plants thus
deal with the smallest filterable particles down to molecules of, say operateat much lower pressures than RO.
molecular weight 5OC0. but without the accompanying reduction in We have seen m previous bulletins that there are two ways of dealing
dissociated salts which we get in RO. with the concentration effect on the membrane surface: one is to limtt
RO membranescan be made”loose”or”tight” to control thefluxand the flux to limlttherateat which rejected material builds up,and there-
rejection properties of RO membranes. UF membranes are made by fore the rate at which it has to be dispersed. The other is to create as
an extension of these techniques but wth a looser structure so that much turbulence in the liquid as possible and so reduce the
the salt rejection IS zero. UF membrane manufacturers have learned thickness of the film across which the accumulated material has to
to control the pore sne with great accuracy and uniformity, and are diffuse. The same arguments apply to OF, only even more strongly,
therefore able to make membranes designed to have very accurate because of the sluggfsh nature of the materials with which we are
cut-off properties for different sizes of molecules. dealing. In UF apparatus and design, therefore, it is important to
obtain the highest possible liquid turbulence on the concentrate
The membranes areasymmetrical. like RO membranes- that is, they side. At the same time it is necessary to keep the flux low, even
consist of a thin skin which is the actual membrane, which sits on a though the low hydraulic resistance of the membrane itself seems to
porous substrate whose duty is to give strength and act as a carrier. offer the prospects of high fluxes.
* W. Shakespeare
This Technical Bulletin IS one of a series issued by Dawpfan Ltd. to G.S. Solt was Research and Development Director of Dewplan (WT)
L promote a better understanding of Water and Effluent Treatment in Ltd. and was alSo Honorary Resaarch Fellow at University College,
mdustry The senes -will cover the full range of processas and London, where he lectured on the Economics of Water Treatment.
equipment supplied by tha Water Traatnwnt Plant industry. For r@nts He is internationally known for his work on desalination and reverse
please wte to DEWPLAN Ltd., Beachwood Hall, Kingsmead Road, osmosis, and is Director of the School of Water Sciences at Cranfield
High Wycombe. Bucks HP11 1lA. Institute of Technology.
TG.20
If the character of the application is such that the membrane is th mgeneration cycle of an ion exchange plant. This makes sense if L/
removing liffle or no material, then the flux can be quite high. With a the cleaning process has to be carried out very frequently - for
heavy load, on the other hand, the normal flux on UF is no greater than exampledaily.’
it is with RO - but of course this flux is obtained at far lower
pressures. Thesmalldiameter tubular membranes have the advantage that they
can withstand pressure applied both from the inside and from the
As far as configuration is concerned, the tine capillary membrane is outside, becausa their support is integral with the membrane itself.
out of the question because it is impossible in practice to get high This means that they can be backflushed by applying clean water
turbulence in a vessel packed with fine Rbres. The smallest practical under pressure on the outside of the tubes: the water passes through
tubular UF membranes are about O.M.5mm in diameter. In contrast the substrate and the working skin, and loosens deposits from the
to RO, these are used with the pressure and the working surface on insideofthetube. Largediametertubularmembranes can becleaned
the inside of the tube. The advantage of small tubes is that they are with sponge ball “pigs” which are a tight Rt in the tube: water
made with their own integral reinforcement in the form of a specially pressure forces them down the tube so that the surface of the
powerful substrate, and then they are strong enough to resist both membrane can be wiped clean. With suitably chosen membrane
internal and external pressure without further support. Larger tubes materials, quits aggressive chemical conditions can be used for
ara also used, of the order of 1Omm diameter, but they need to be cleaning, including acids, alkalis, disinfectants and enzymes.
carried in a porous supporting tube and the apparatus physically together with detergents.
resembles a hee4 exchanger in its layout. Yet another manufacturer
uses flat sheet membrane carried on mouldad plastic plates The object of pilot trials is to establish operating and cleaning
assembled into a stack whose construction resembles that of a filter regimes which will allow the membranes to work for three years or
press. longer before being replaced - a lifetime similar to that of RO
membranes.
Appliutlons forUF UF in Water Treatment
UF is the youngest of the three membrane processes, and we are still In the process applications mentioned above, UF can perform dubes u
finding out what kind of duties it performs best. Its earliest uses have for which no other process is suitable. In water treatment this is not
-naturally enough-been to recover valuable materials, when the lure the case: we can use UF instead of RO or membrane filtration
of large profits makes risk-taking most attractive. As a result, UF is in because it seems economically more favourable. On the other hand.
widespread use for a number of uses where a suspension, or water treatment applications are, on the whole, less demanding than
emulsion, or a solution of large molecular weight materials has to be --process applications: UF will operate at higher fluxes, lower
concentrated, and preferably when at the same time unwanted pressures. and with less frequent and rigorous cleaning regimes.
dissolved or small-molecule impurities can be washed away.
The duties which UF can perform in water treatment include the
A good illustration of what UF can do in this way (though by no removal of suspended matter and colloids. of large organics. and of
means the most common application) is the production of de bacteria. RO will do all these, and remove most of the dissolved salts
alcoholised beer. Ordinary beer is recirculated through a UF plant, so as well, but at a higher cost. Membrane flltration will remove all these,
that water and alcohol pass through the membranes whose pore size except the large organics. The main field in which this kind of removal
is chosen such that they retain all the large molecules which give the IS needed is in the production of ultra-pure water, above all for the
beer its taste and aroma. The water loss is made up by adding fresh manufacture of microchips and microelectromc components, and
water, so that the only change in the beer is a progressive lowering of also for other industries such as pharmaceutical manufacture.
thealcohol content, until the resulting fluid (it is hard to bring oneself
to call it beer) is fit to be sold, for example, at motorway service The classical flow sheet (if we can use the word “classical” for a
stations. Alternatively, a beer concentrate could be made in this way process which is only a decade old) for ultra-pure water production is
for reconstitution by adding water. RO-DI-membrane filter. (A dirty water may need pretreatment before
RO. and exceptionally clean waters may not even need RO at all.) The
There are more agreeable-sounding uses for UF. now in common final membrane filter serves to remove particles and bacteria which
use: the purification of paint in paint baths, or its recovery from wash have slipped through the prewous processes or been generated m
waters, and the concentration and purification of antibiotics and them-sometimesthereisacentral membranefilteratthewaterpurifi-
similar products from broths. In all these applications, UF not only cation plant outlet, but point-of-use filters are commoner. They ate
providesan economic method of recovering thevaluable material in a always installed for really demanding applications.
concentrated form, but at the same time the process recovers it in a w
purified form. In many of these applications it also performs a wtal In this “classical” flow sheet, UF could replace the RO ahead of the
service in alding serious effluent disposal problems. deionisers, but UF will not of course remove any dissolved salts, so
that the DI plant would then have to cope with the full raw water
The flow sheets for such applications vary widely, but generally they salinity. Alternatively, UF could be used as a final polisher. Can UF
provide for a very high recirculating flowthrough the plant. so that the perform either of these duties better than the “classical” alternative?
concentrate flow may be up to 100 times that of the product flow. In some cases, it appears, it can.
Applied pressures may bearound 10 bars.
UF inultra-Pure W ater Production

Cleaning rhc Membranes
Where the water has a low TDS. the economical advantage of having
Without the high liquid velocities obtained by recirculat!on. the most of the salts removed by RO is small. UF will perfon the same
process would come to a stop very quickly because of accumulation kind of duty with respect to removing the large size impurities, and
on the surface of the membrane. Even with the cleansing effect will do so at a much lower pressure. If the water is relatively clean,
created by high turbulence, all these processes depend on regular then the flux can be up to five times greater than that on a spirally
backflushing and cleaning of the membranes to maintain normal wound module, so a much smaller membrane area has to be instal-
performance levels. led for the same flow rate. Pressures tend to be lower than in process
applications, at perhaps 5 bars. In suitable applications these
It is usually sensible to establish with pilot tests just what cleanmg economies will be greater than the additional capital and operating
methods and chemicals will have to be used, and what regime will costs which are incurred by the deionisation plant having to remove
have to ba practised. The full scale plant can then be built to the entire TDS of the raw water.
incorporate the necessary equipment - backflushing lines. dosing
points for cleaning chemicals, etc. On some plants the whole The most common use for UF m ultra-pure water production,
cleanmg cycle (which can be quite complex) is made automatic. like however, seems to be as a post-filter after the deionisation plant,
LI
v
)where It IS mstalled for two potential benefits: The secret of satisfactory operation in all three processes is
As UF has a much smaller pore size than any membrane filter, its therefore a satisfactory raw water quality and a suitable regime of
use at this point will result in a better final water quality. membrane cleaning. In most cases this maans that sonm form of
Experience shows that UF actually seems to raisa the resistivity pretreatment is required to protact the membrane plant.
of the water, which is not easy to explain.
The other benefti is that UF plant has a modest and predictable RO plant in particular should never be installed without at least a 5
operating cost-especially in this position as post-filter, where it micron filter to remove coarser suspended particles. Tests using
is fed with very clean water. Membrane fllters, on the other hand, membrane filter discs will establish the “Fouling Index” or “Silt
are throwaway items which have to be fitted with new cartridges Density Index” of the water (see TB.27). and will indicate whether
when clogged. This can lead to very high operating costs if, for further pretreatment is needed. Dissolved or suspended iron in the
some reason, the water IS high in filtrable materials. feed water is one of the most damaging foulants: most of it is
removed by ion exchange softening, so this is a very common term of
UF does not replace point-of-use filters, which are still necessary as
pretreatment for smaller-scale plants. It is reliable and simple, and on
final Safeguards, but it is generally used as a central polisher after the
the small scale the cost is modest
water purification plant. In some cases it is claimed the installation of
such a UF plant has paid for itself in reduced filter cartridge costs
within a year. Flocculation and coagulation is a more a4Rcient form of pretreatment,
but the process is impracticable on small-scale flow and especially
We have just come across two areas of ignorance - how a UF plant on intermittent operation. It is normally restricted to large potable
can increase the resistivity of a water, and why there are some plants
water plants, but if imperfectly operated it can produce a water full of
which produce a highly purified water which is still high in flltrable unreacted aluminium salts and fine AI( floe (see TE.tB), which
materials. We have to be clear in our minds about this kind of thing: can be more damaginp than the untreated water would have been.
when working in the realms of ppb and sub-ppb concentrations of
impurities, we are very often in the dark. As we are operating at the
\ limits of our methods of analysis. this is hardly surprising. In this kind Flocculation/coagulation plant is always followed by sand filters:
- bf work there is, as yet, no substitute for experience and trial-and- sometimes the sand filter on its own is sufficient. Other pretreatment
error. options include ion exchange scavengers and activated carbon
filters. Even UF itself can be considered to protect an RO plant.
Pretreatment forMembrane Processes

aith so many options available, it is difficult to decide on the best
We can now look back and review all three membrane processes combination ot security and economy. In each case we have to
described in this group of three Bulletins. consider the interaction between the nature of the raw water and the
desired quality of the treated water, the type of membrane module to
One common factor emerges strongly from them all - membrane be installed, and the scale of the plant and its patterns of utilisation. It
processes are above all governed by the occurrence and prevention is in resolving complex problems like this that skilled design and
of fouling of the membrane surfaces. operation show their true worth.
Confidential
Ml48
MODULE I
SECTION 3.6
INDEXI.DOC:22!08197
-I-
SUBSECTION 3.6 REVIEW OF DESALINATION PROCESSES

CONTENTS:
1. Introduction 2
1.1 Background information 2
1.2 Water needs and uses 2
2. Desalination processes 3
2.1 Terminology 3
2.2 Selection criteria 3
3. Other considerations 4
4. Multi-stage Flash Evaporator O/T 5
5. Multi-stage Flash Evaporator Brine rec. 6
6. Multi-e&ct Spray Film evaporator 8
7. Multi-efFect Distillation 10
8. Vapour compression evaporator I1
9. Thermal compression spray film evaporator 12
10. Electrodialysis 13
11. Freezing 14
12. Hydrate process 15
App A. World Health Water Purity Limits 16

Figures 17
M148_36 Desalination
-2-
1. INTRODUCTION
W
1 .l BACKGROUND INFORMATION
The purpose of this paper is two-fold :
- firstly to present a brief review of desalination processes, the majority of which are currently
available on a commercial scale. Others, however, are still limited to laboratory scale prototypes
- secondly to provide engineers and technologists; who may at some stage be involved with the
selection, evaluation and operation of desalination equipment; with an understanding of the basic
principles of commonly applied processes such as multi-stage flash, multi-effit and vapour
compression.
Note: Although this Handout contains some general information on the reverse osmosis pcess it will be dealt with fully
in * separate lecture session.
1.2 WATER NEEDS AND USES

W
In general desalination facilities are only necessary in arid/ semi-arid, underdeveloped locations or
where quantitative and qualitative water requirements cannot be met by other means. Potable
(drinking) water normally has to meet World Health Organisation (WHO) requirements and, as such,
can be produced satisfactorily by almost all of the desalination technologies commercially available.
On the other hand, boiler feed water or make-up requirements are dictated by the operating
pressure/temperature conditions applicable to the installed steam raising equipment. In most Group
locations the VGB (German Boiler Authority) guidelines are applied. Details of these are fully
described in a separate section of this course.
Appendix A tabulates the permissible contaminant levels for drinking water as set out by the World
Health Organisation.
The quantity of water produced by all of the desalination plants operational throughout the world was
estimatedat2.1 x 109gaVdin 1982.
The price of this water per 1000 gal varied from USD 0.60-USD 0.80 for large brackish water reverse -
osmosis plants in the United States to about USD 15 .OO-USD 25 .OO for distillation processes in the
Caribbean and almost twice that or more in some plants located in the Arabian Peninsula.
-3-
2. DESALINATION PROCESSES
-.--
2.1 TERMINOLOGY
For those unfamiliar in the field of de&nation the terminology used can often be confusing and
misleading. Some of the commonly encountered processes and their respective abbreviations are as
follows:
Multi-Stage Flash Once-Through MSF-OT

Multi-Stage Flash Brine Recycle MSF-BR
Multi-Effect Stack (high temperature) MES
Multi-Effect (low temperature) LTME
Mechanical Vapour Compression MVC
Thermo-Compression TC
Reverse Osmosis RO
High Temperature Electrodialysis HTED
Freezing Crystallisation Processes
not normally applied
Hydrate Process
on a commercial scale
Conceptual diagrams and simplified flow schemes for the above processes are contained in
Appendix B.
2.2 SELECTION CRITERIA
As can be seen from the list of processes in 2.1 there are several technologies available for desalting. It
is often difficult to determine which is the most appropriate for a given application. In general the long
established MSF and ME processes are to the forefront in selection of new plants, however, over the
last five years or so RO has rapidly developed as a serious contender for production of potable water
from seawater.
‘-’
A broad distinction can be drawn between “heat consuming” and It power consuming” processes.
MSF, ME, TC fall into the former category whilst MCV, RO, HTED, freezing and hydrate processes
come under the latter.
Preliminary selection of the most suitable process is therefore dependent on availability of steam or
electricity. Another important aspect is the desired product quality. In most cases steam consuming
processes result in high quality (low TDS) product whereas a TDS of 500 ppm is typical for other
processes. An exception is the two-stage RO plant which can achieved levels with TDS of 50-70 ppm.
Close attention must also be paid to the subject of material selection as this is of great importance and
failure to recognise this, in the quest for lowest cost, has resulted in some devastating consequences.
Application of inadequate materials of construction combined with poor operation has led to rapid
deterioration and failure, well short of estimated design life.
In the case of MSF plants Group companies now specify extensive use of stainless steel in the higher
temperature stages of the process. Another interesting development in this case with LTME is that the
major portion of the plant is constructed from aluminium.
-
Ml48_36 Desalination
-4-
The effect of scale and corresponding preventative measures are an important aspect when considering
distillation type desalination processes. The relationship between scaling propensity, concentration
ratio and operating temperature applicable for MSE-BR and MES is shown in Appendix D.
The impact of high temperature anti-scaiant additives (of which Belgard, developed by Ciba-Geigy is
probably the most widely used) has resulted in much lower fouling factors for heat transfer surfaces
leading to longer operating period at design gamed output ratio and energy economy.
3. OTHER CONSIDERATIONS
Apart from the normal economic and technical criteria used in project evaluation the following items
should be given special attention during the specification/selection stages of a desalination plant:
- Distillate Quantity/Quality
Be realistic in respect of distillate requirements. Do not over-specify as this will lead to substantially
higher investment.
- Feed Water Analysis
Ensure that vendors are provided with fully detailed analyses covering as long a period as possible and
including seasonal variations. If feed water is chemically treated, e.g. chlorine/ b&ides, the vendor
should be made aware of this and select materials to suit.
- Instrumentation/Sampling
Product quality can only be assured if all analytical instrumentation required is installed. The number
and location of quality instruments and sampling points necessary to promote ease of operation. without
excessive operator intervention, should be discussed in detail with the vendor prior to order.
Troubleshooting can be simplified, especially with MSF units if numerous sampling/measuring are
incorporated at the basic design stage.
- Vendor Experience
Short-listed vendors should be requested to provide a reference list of plants in which materials
specified for the current project have been in service for a period of at least three years. Permission
should be obtained to allow direct contact with operators of these plants to establish performance.
- Acceptance Tests/Guarantees
The minimum recommended duration for an acceptance test of desalination unit is five days at
continuous design distillate output following successful commissioning. In some cases tests as long as
forty days are specified. It is essential that maintenance planning is arranged such that the new unit can
be taken out of service for a full inspection at the end of guarantee period, usually after twelve months
service, and this should be carried out in conjunction with the vendor.
-5-
V
4.0 MULTI-STAGE FLASH EVAPORATOR ONCE-THROUGH (Fig. 1)
THEORY OF OPERATION
The Multi-Stage Flash Evaporator produces distilled water from feed water by heating it until it is
ready to flash. The flashed vapour is drawn to the cooler tube bundle surfaces where it is condensed
and collected as distillate.
Flashing occurs when heat brine is turbulated in a chamber which is maintained at a lower vapour
pressure than that of the entering heated brine. Heat is given up by the brine and a portion converted
into vapour until the temperature of the brine reaches the saturation temperature corresponding to the
chamber pressure. In other words, the heated brine is flashed off by a pressure reduction.
Entrained brine droplets are removed from the vapour by entrainment separators and the pure vapour
condenses into distillate on the condenser tubes. The distillation process operates from a low vacuum
V in the first stage to a high vacuum in the last stage, with stage-to-stage pressure differential being the
key to the repeated flashing.
Initial vacuum in the stages is created by the high-pressure steamdriven air ejector/condenser vacuum
system.
The once-through system is designed to operate at temperatures up to 90°C. In order to achieve Iong-
run operation of the unit, it is necessary to retard the formation of scale on the heat transfer surfaces.
This is accomphshed through the chemical treatment systems described later.
PROCESS DESCRIPTION
Filtered raw feed water is chemically treated for scale control purposes and pumped through the
condenser tubes from the last stage to the first stage.
As the feed water flows through the condenser tubes, it is progressively heated in each stage by flashing
brine vapour condensing on the outer tube surfaces. The feed water then passes through the tubes of
- the feed water heater for final heating to the design terminal temperature.
The heated feed water is directed to the shell side of the first stage for flashing. The brine flows
successively from the first to the last stage, flashing in each stage, and is discharged from the last stage.
CONDENSATE FLOW
Low-pressure steam is used to heat the feed water flowing though the tubes of the feed water heater.
When so specified, high-pressure steam turbines can be used to drive the feed and/or brine blowdown
pumps, with the turbine exhaust steam also being used in the feed water heater.
The low-pressure steam is piped into the shell side of the feed water heater and, by transfer of its heat
to the feed water flow, condenses on the tube outer surfaces. Thus, the feed water is heated to its
design terminal temperature. Condensate formed by the condensing steam is piped to the condensate
pump and is pumped to the condensate return system.
-6-
DISTILLATE FLOW
Distillate is formed on the stage condenser tubes by condensing of the flashed brine vapour.
The distillate collects in a distillate trough which is common to all stages and flows from the first stage
to the last ‘stage. From there it is pumped into the distillate storage system.
VACUUM SYSTEM
Venting of the evaporator is essential to the operation of the distilling plant. High-pressure steam is
used to drive air ejectors to create the initial vacuum in the evaporator. Once the plant is in normal
operation, the vacuum is maintained by the condensing action in each stage, supported by the air
ejectors. Tbe air ejectors also evacuate non-condensibles from the evaporator. The spent high-pressure
steam and the non-condensibles are discharged from the air ejectors into condensers where the steam is
condensed and the non-condensibles are vented to atmosphere.
CHEMICAL TREATMENT SYSTEMS
A measured amotmt of feed water treatment compound is continuously injected into the feed water flow \i/
to retard the formation of hard scale in the stage and feed water heater condenser tubes. Anti-foam
compound also can be introduced into the feed water when needed. Post-distillate treatment can be
employed to reduce corrosion of the product water storage and distribution systems.
5.0 MULTI-STAGE FLASH EVAPORATOR BRINE RECIRCULATION (Fig. 2)
THEORY OF OPERATION
The Multi-Stage Flash Evaporator produces distilled water from feed water by heating it until it is
ready to flash. The flashed vapour is drawn to the cooler tube bundle surfaces where it is condensed
and collected as distillate.
Flashing occurs when heated brine is turbulated in a chamber which is maintained at a lower vapour
pressure than that of the entering heated brine. Heat is given up by the brine and a portion is converted
into vapour until the temperature of the brine reaches the saturation temperature corresponding to the
chamber pressure. In other words, the heated brine is flashed off by a pressure reduction.
Entrained brine droplets are removed from the vapour by entrainment separators and the pure vapour
condenses into distillate on the condenser tubes. The distillation process operates from a positive
pressure in the first stage to a high vacuum in the last stage, with stage-to-stage pressure differential
being the key to the repeated flashing.
Initial vacuum in the stages is created by a high-pressure steam-driven air ejector/condenser vacuum
system.
The brine recirculation system is designed to operate at temperatures up to 121°C. In order to achieve
long-run operation of the unit, it is necessary to retard the formation of scale on heat transfer surfaces.
This is accomplished through an acid treatment system described later.
-7-
The acid-treated brine recirculation system permits operation at higher evaporator temperatures and, at
L the same time, reduces the amount of feed water chemical treatment required compared with that which
would be required for once-through operation at the same temperature.
PROCESS DESCRIPTION
Filtered raw feed water is pumped through the condenser tubes of the heat rejection stages and is
discharged. The cool feed water flowing through the condenser tubes dissipates the heat in these last
stages.
A portion of this cooling water is withdrawn as make-up water and the major portion is returned to the
ocean. The make-up water is deaerated to remove the non-condensible gases and is treated with
sulphuric acid for scale control purposes. The deaerated feed water is introduced into the brine section
of the last stage and mixes with the recirculating brine flow. The mixture of recirculated brine and
deaerated feed water is pumped through the condenser tubes of the heat recovery stages and the brine
heater by the brine recirculating pump.
In order to maintain a material balance in the system (controlling the brine density), a portion of the
L concentrated brine from the last stage is discharged to the ocean as blowdown. The blowdown flow
rate is controlled by the brine level in the last stage.
As the brine flows through the condenser tubes of the heat recovery stages, it is progressively heated in
each stage by flashing brine vapour condensing on the outer tube surfaces. The brine then passes
through the tubes of the brine heater for final heating to the design terminal temperature.
The heated recirculating brine is directed to the shell side of the first stage for flashing. the recirculating
brine flows successively from the first to the last stage, flashing in each stage, and is discharged from
the last stage.
CONDENSATE FLOW
Low-pressure steam is used to heat the recirculating brine flowing through the tubes of the brine heater.
When so specified, high-pressure steam turbines can be used to drive the feed and/or brine recirculating
pumps, with the turbine exhaust steam also being used in the brine heater.
‘v
The low-pressure steam is piped into the shell side of the brine heater and, by transfer of its heat to the
recirculating brine flow, condenses on the outer tube surfaces. Thus, the recirculating brine is heated to
its design terminal temperature. Condensate formed by the condensing steam is piped to the condensate
pump and is pumped to the condensate return system.
DISTILLATE FLOW
Distillate is formed on the stage condenser tubes by condensing of the flashed brine vapour.
The distillate collects in a distillate trough which is common to all stages and flows from the first stage
to the last stage. From there it is pumped into the distillate storage system.
VACUUM SYSTEM
Venting of the evaporator is essential to the operation of the distilling plant. High-pressure steam is
used to drive air ejectors to create the initial vacuum in the evaporator. Once the plant is in normal
-8-
operation, the vacuum is maintained by the condensing action in each stage, supported by the air
ejectors. The air ejectors also evacuate non-condensibles from the evaporator. The spent high-pressure
steam and the non-condensibles are discharged from the air electors into condensers where the steam is
condensed and the non-condensibles are vented to atmosphere.
A measured amount of feed water treatment compound is continuously injected into the feed water flow
to retard the formation of hard scale in the stage and feed water heater condenser tubes. Anti-foam
compound also can be introduced into the feed water when needed. Provisions also can be made to add
sodium sulphite to scavenge oxygen from the recirculating brine flow. Post-distillate treatment can be
employed to reduce corrosion of the product water storage and distribution systems.
6.0 MULTI-EFFECT SPRAY FILM EVAPORATOR (Figs 3 and 4)
THEORY OF OPERATION
The Multi-Effect Spray-Film evaporator produces distilled water by boiling fresh water vapour from
feed water. The vapour produced is drawn to the inside of cooler evaporator tube bundle surfaces
where it is condensed and collected as distillate.
The Multi-Effect Spray-Film evaporator employs two or more evaporator effects, each operating at a
successively lower temperature and pressure. The first effect (highest temperature) is heated by low-
pressure steam or hot water on the inside of the effect evaporator tube bundle. Vapour is generated
from the feed water sprayed on the outside of this tube bundle and is directed to the second (lower
temperature) effect where it condenses inside its evaporator tube bundle, producing additional vapour.
This process is repeated several times, multiplying the effectiveness of the original low-pressure steam
in the first effect, thereby giving the process its name.
The Spray-Film principle refers to the method employed to efficiently distribute the fluid to be
evaporated over the outside surfaces of the evaporator tube bundle. In each effect there are several
spray nozzles which distribute the effect feed over the evaporator tube bundle in a rain of fine droplets.
The high velocity of the droplets as they leave the spray nozzles and fall on the evaporator tube bundle
assures even brine distribution in a thin liquid film creating a high heat transfer rate.
As vapour is generated outside the evaporator tube bundle, it flows downward with the liquid feed.
This down-flow action pulls the feed liquid through the evaporator tube bundle at high velocity, thereby
maintaining a high heat transfer rate.
PROCESS DESCRIPTION
Feed water is pumped into the final condenser of the plant and serves as a coolant to condense the
vapour produced in the last effect. The major portion is returned to the source. A portion of the feed
water is withdrawn as make-up water and is passed through the last effect preheater where it is
warmed. It is then treated with a scale-inhibiting chemical, is sprayed over a pack-bed deaerator in a
special section of the last effect, and is fed to the make-up pump. This stream maintains the material
balance in the plant. The make-up water passes through a series of tubular preheaters, where it is
warmed by condensing the generated vapour from each effect. After leaving each effect preheater, a
portion of the make-up water is withdrawn and sprayed over the evaporator tube bundle in that effect.
-9-
A fraction of the make-up water entering the first effect is vapor&d as it is sprayed over the evaporator
tube bundle in which the low-pressure heating steam is condensed. The vapour produced passes
through an entrainment separator and is drawn to the second-effect evaporator tube bundle where it
serves as the heat source for vapor&g the feed water spray entering that effect. Some of the vapour
from the first effect passes through the second-effect evaporator tube bundle to the secondeffect
preheater where it condenses and heats the make-up water.
The portion of the make-up water not vapor&d in the first effect passes to the second effect through a
loop seal. As it enters the second effect, a fiaction flashes due to the lower pressure and temperature,
producing more vapour.
The vapour and liquid flows described above are repeated in each effect of the plant. The blowdown is
pumped from the system out of the last effect. The vapour produced in the last effect is condensed in
the final condenser.
CONDENSATE FLOW
-- Low-pressure steam enters the evaporator tube bundle of the first effect, gives up its heat by
condensing inside the evaporator tube bundle and preheater, and is pumped to the condensate return
system. When steam is not available, hot water heaters or engine jacket water heating sources can be
employed.
DISTILLATE FLOW
Distillate is formed in the evaporator tube bundles and preheaters by condensation of the vapour.
The distillate collects in a distillate trough in each effect and flows from the first effect to the last effect.
From there it is pumped into the distillate storage system.
VACUUM SYSTEM
Venting of the evaporator is essential to the operation of the distilling plant. Air and other non-
condensible gases in the system are vented from effect to effect, and are collected and removed from the
system by means of a high-pressure steam-jet air ejector system. The exhaust steam and gas mixture
- from the air ejector system are condensed in a special section of the first-effect evaporator tube bundle,
or in a water-co&d barometric-type condenser. When steam is not available, mechanical vacuum
pumps can be employed.
For systems with a maximum seawater temperature of 9OT a measured amount of feed treatment
compound like polyphosphate is continuously injected into the make-up flow to retard the formation of
scale on the evaporator tube bundle. For plants above 90°C sulphuric acid is used to retard scale
formation. An anti-foam compound also can be injected into the make-up when needed. Provisions
also can be made to add sodium sulphite to scavenge oxygen from the brine flow. Distillate post
treatment can be employed to reduce corrosion of the product water storage and distribution systems.
-lO-
7.0 MULTI-EFFECT DISTILLATION (MED) (Fig. 5)
THEORY OF OPERATION
Low-pressure steam is throttled down to 0.35 bara and supplied to the hottest effect. There it
condenses, giving up its latent heat to the salt water flowing over the outer surface of the tubes. While
condensation takes place on the inside of the tubes, a nearly equal amount of evaporation occurs on the
outside. After passing through a brine drop separator to maintain purity of the distillate, the vapour is
drawn into the tubes of the next effect, which operates at a slightly lower temperature and pressure.
The evaporation-condensation process is repeated along the entire series of effects, each of which
contributes a significant amount of additional distillate. From the last effect all remaining vapour is
liquefied in the heat rejection condenser by seawater coolant.
PROCESS DESCRIPTION
Seawater, deaerated and preheated in the condenser, is divided into two flows. One acts as coolant, the
other becomes feed for the distillation process (see appropriate Figure).
The feed is treated with a harmless polyphosphate additive to inhibit scaling, then fed into the lowest
temperature group of Heat Recovery Effects. A spray nozzle system distributes it over the top rows of
tubes in each effect. As the feed flows in thin films down each bank of tubes, part of it vaporises as it
absorbs the latent heat released by the motive steam inside the tubes.
The remaining feed, now slightly concentrated, is pumped to the next group of effects, which operate at
a higher temperature. There the spray procedure is repeated, the remaining feed being pumped onward
again until it leaves the hottest group of effects as concentrated brine.
Fourteen times more distillate by weight than required motive steam - most impressive Economy Ratio.
Latent heat given off by the motive steam is re-used in successive effects, with each step taking place at
a slightly lower temperature-pressure liquid-vapour equilibrium point. Finally, in the Heat Rejection
Condenser, latent heat remaining in the system is rejected by using it to raise the temperature of
incoming seawater.
THE DISTILLATE
Fresh water from the first effect is collected in a condensate tank. Part of this distillate is returned to
the steam generator; the excess, above the original quantity of motive steam, flows into the first of a
series-of special chambers which collect the distillate from each effect. Since the vapour space of each
collector is ducted to the cooler condensing section of the next effect, part of the distillate flashes off,
cooling the remaining product stream while recovering heat and returning it to the malt body of Heat
Recovery Effects. The flowing product stream is thus cascaded and flash-cooled in stages; the heat
which is given off increases the total efficiency of the process. The cooled distillate is finally
discharged to storage by the product delivery pump.
The product is totally pure water. It is fresh, potable and soft, averaging only 20 ppm of dissolved
solids.
-11-
BRINE AND NCG DISPOSAL

L‘
The concentrated brine from the hottest effect is, like the distillate, cascaded and flash-cooled to recover
its heat. After cooling, it is returned to the sea via the brine pump.
Non-Condensible Gases (NCG) are bled from each tube and flow collectively from one effect to the
next. They are eventually concentrated at the coolest end of the Heat Rejection Condenser, and are
finally evacuated by a steam jet ejector or mechanical vacuum pump.
8.0 VAPOUR COMPRESSION EVAPORATOR 0%. 6)
PROCESS DESCRIPTION
Filtered raw feed water is chemically treated for scale control purposes and is pumped through the heat
exchanger where it is preheated by the outgoing distillate and blowdown.
-
The treated feed water enters the brine recirculation header, mixes with the recirculated brine, and is
sprayed over the evaporator tube bundle, where boiling occurs and a fraction is converted to vapour.
The brine which does not vaporise is colkcted in the evaporator sump and is recirculated. A portion of
the concentrated brine is withdrawn as blowdown and is discharged, after preheating the make-up feed
water.
The generated vapour is drawn through the entrainment separators to the compressor where the
temperature and pressure of the vapour are increased. The vapour is then discharged into the
evaporator tube bundle where it is condensed.
The starting and make-up steam required for operation of the evaporator is produced in the evaporator
boiler by means of low-pressure steam or electric heaters.
THEORY OF OPERATION
The Vapour Compression Evaporator is of the horizontal Spray-Film design operating on the heat
V pump principle. The feed water to be evaporated is recirculated and sprayed over the evaporator tube
bundle. Fresh water vapour is generated by boiling, is compressed, and is introduced into the inside of
the evaporator tube bundle at an increased temperature and pressure.
The compressed vapour condenses inside the evaporator tubes and the heat of condensation released by
the vapour provides the necessary energy for continued boiling of the feed water.
Entrained brine droplets are removed from the vapour by entrainment separators as the vapour is drawn
to the compressor.
The evaporator operates under positive pressure and is vented directly to the atmosphere
The recirculating brine stream is designed to operate at temperatures up to IO 1 *C. In order to achieve
long-run operation of the unit, it is necessary to retard the formation of scale on heat transfer surfaces.
This is accomplished through the chemical treatment systems described later.
- 12-
DISTILLATE FLOW
Distillate is formed inside the evaporator tubes by condensation of the compressed vapour.
The distillate is collected at the bottom of the evaporator steam chest and is pumped through the heat
exchangers, where it is cooled, and then it is discharged to storage.
CHEMICAL TREATMENT SYSTEM
A measured amount of feed treatment compound is continuously injected into the feed water flow to
retard the formation of scale on the evaporator tube bundle surfaces. An acid cleaning system is
provided, to periodically inject anti-scaler into the brine recirculation steam to remove any scale that
has formed on the evaporator tube bundle.
9.0 THERMAL COMPRESSION SPRAY FILM EVAPORATOR (Figs 7 and 8)
THEORY OF OPERATION
The evaporation principle used is horizontal-tube thin-film evaporation. The fluid to be evaporated is
heated by steam condensing inside the tubes, which transfers heat to the fluid film outside the tubes.
Evaporation takes place at the outer surface of this film.
The Spray-Film principle refers to the method employed to efficiently distribute the fluid to be
evaporated over the outside surfaces of the evaporator tube bundle. In each effect there are several
spray nozzles which distribute the effect feed over the evaporator tube bundle in a rain of fine droplets.
The high velocity of the droplets as they leave the spray nozzles and fall on the evaporator tube bundle
assures even fluid distribution in a thin liquid film creating a high heat transfer rate.
PROCESS DESCRIPTION
Cold feed is pumped through the distillate cooler and the feed heater. Depending on the feed
temperature, all or part of the feed is introduced into the evaporator sump as make-up. The remainder
of the feed is returned from the process. W
The make-up mixes with the unevaporated fluid in the sump and is pumped out of the evaporator where
a portion is discharged to waste (blowdown) to maintain the design concentration in the sump. The
remainder is recycled to the spray nozzles and is sprayed over the evaporator tube bundle. Vapour
formed flows through an entrainment separator which removes any liquid droplets present. A small
portion of vapour condenses in the feed heater section. The remainder flows to the compressor suction
where it ’ is compressed and mixed with the compressor motive steam. This vapour mixture is at a
higher pressure and temperature than the liquid on the outside of the evaporator tube bundle and is
condensed within the tubes, providing the energy for continued vapour generation.
CONDENSATE FLOW
Since the compressor motive steam is mixed with the final product, a reboiler is provided so that this
steam is pure and not contaminated with boiler chemicals. Reboiler make-up is provided from the
distillate, and condensed motive steam is returned to the boiler system.
MIAs-36 Desalination
- 13 -
DISTILLATE FLOW
Distillate is formed in the evaporator tube bundle by condensation of the evaporated vapour. The
distillate coUects in a distillate water box and is pumped from there through the distillate cooler and into
the distillate storage system.
VACUUM SYSTEM
Venting ofthe evaporator is essential to the operation of the distilling plant. Air and other non-
condensible gases in the system are collected and removed from the system by means of a high-pressure
steam-jet air ejector system. The exhaust steam and gas mixture from the air ejector system are
condensed in a water-cooled condenser, and the non-condensible gases are vented to the atmosphere.
CHEMICAL TREATMENT SYSTEM
Chemical treatment of the feed to retard scaling or foaming, if required, is added through a chemical
injection system. Distillate post treatment can be employed to reduce corrosion of the product water
storage and distribution system.
10.0 ELECTRODIALYSIS 0%. 9)
THEORY OF OPERATION
Electrodialysis involves the passage of electric current through brackish or low-salinity water in a
chamber in which many closely spaced ion-selective membranes are placed, thus dividing the chamber
into compartments. The electric current causes the salts to be concentrated in alternate compartments
with reduced salt content in the remainder. The constraints of electrodialysis are such that feed water
up to 2000 ppm may be processed to give a product with 300 ppm total dissolved solids. Where a
high-purity product is desired, the costs may be unacceptable compared to water obtainable from
distillation. A principal disadvantage of electrodialysis is that power consumption of proportional to
total dissolved solids and its range of cost and performance effectiveness is with low-salinity waters.
Also high sodium chloride content in the feed water will require a product purity of less than 250 ppm,
which also adds to the cost - this restriction also applies to reverse osmosis.
PROCESS DESCRIPTION
Ion movements in the electrodialysis process (see figure).
a. Many of the substances which make up the total dissolved solids in brackish water are strong
electrolytes. When dissolved in water, they ionise, i.e. the compounds dissociate into ions which
carry an electric charge. Typical of the ions in brackish water are:
Cl-, Na+, HCO;, Mg2’, SOi- and Ca2+.
These ions tend to attract the dipolar water molecules and to be diffused, in time, fairly evenly
throughout a solution.
- 14-
b. Iftwo electrodes are placed in a solution of ions, and energised by a battery or other direct-
current source, the current is carried through the solution by the charged particles and the ions
tend to migrate to the electrode of the opposite charge.
C. If alternatively fixed-charged membranes, which are selectively permeable to ions of the opposite
charge, are placed in the path of the migrating ions, the ions are trapped between the alternate
cells formed. A positively fixed-charge (anionic) membrane allows negative ions to pass but
repels positive ions. A negatively fixed-charge (cationic) membrane allows positive ions to pass,
but repels negative ions.
d. If this continues, almost all the ions become trapped in the alternate cells, which lack ions, have a
lower level of dissolved constituents, and have a high resistance to current flow.
e. The phenomenon illustrated above is used in electrodialysis to remove ions from incoming saline
water on a continuous basis. Feed water enters both the concentrate and product cells. Up to
about half of the Ions in the product cells migrate and are trapped in the concentrate cells. Two
streams emerge from the device: one of con-concentrated brine and the other with a much lower
concentration of TDS (product water).
\c/
11.0 FREEZING (Fig. 104
THEORY OF OPERATION
The concept of the freezing desalination process is based upon thermodynamics and the phase diagram
of an NaCI-Hz0 solution. As the temperature of the solution is reduced to the freezing point of water,
pure water solidifies, leaving a more concentrated, lower freezing brine. A freezing desalination
process must have a freezer, a means of washing the ice crystals formed from brine on their surface and
a melter to process the ice formed. Schematically, these components are given in the associated figure.
There are two important advantages that make such freeze-desalting, in principle, most desirable and
seemingly competitive. Specifically, the heat of solidification is much less than that of evaporation,
offering energy savings. Second, the freeze process operates at relatively low temperature, reducing the
corrosion problem and, in turn, cost of materials. These two features of freezing-based desalination
have provided considerable incentive in process development. A number of systems and pilot plants
d
have resulted, but no commercial freezing desalination installation is yet in service and no firm plans to
build any. The inability to develop sound engineering and economically competitive systems after 30
years and considerable financial investment is perhaps a classic example of a conceptually simple
process that is suppressed by the engineering complexity to realise it.
Even with an engineering breakthrough, freeze-desalting is unlikely to emerge as an economic

competitor for water conversion for some time. It could, however, have important use in the processing
of complex industrial-waste fluids where resource recovery could enhance the economics.
PROCESS DESCRIPTION
The freezing of a salt solution causes crystals of pure water to nucleate and grow, leaving a brine
concentrate behind. One commonly proposed freezing method is the use of a secondary refrigerant in
which butane is evaporated in direct contact with seawater to remove the latent heat of crystallisation,
as described below.
- 15 -
Seawater is precooled by heat exchange with the product water and waste brine streams. The seawater
L’ then enters the freezer where liquid butane is bubbled through the seawater. The butane vaporises and
lowers the water temperature. This results in the formation of salt-free ice crystals in a more
concentrated seawater or brine. Approximately one-half of the seawater is frozen into ice crystals. The
ice-brine slurry is then pumped to a washer-melter. The sluny rises within the washer and the ice
crystals are compacted into a porous bed of ice. The bed of ice is moved upward by a slight positive
pressure caused by the brine flowing through the bed and outward through screens positioned near the
middle of the column. The rising ice bed is washed with less than 5% of the total product water. The
ice is then removed by means of a mechanical scraper into the outer a~ulus; that is, the melter. The
butane vapour, which contains the heat removed to form the ice, is compressed in the primary
compressor and then introduced into the melter where it condenses on the ice. Heat is given up and the
ice is melted. The condensed butane and the product water flow together to a decanting unit where the
two liquids are separated.
From the decanter, the product water leaves the process and the liquid butane is recycled back to the
freezer. Butane vapour not required for ice melting is further compressed by the secondary compressor
and then condensed in the butane condenser, which is cooled by seawater. The liquid butane is recycled
to the freezer.
12.0 HYDRATE PROCESS (Fig. lob)
THEORY OF OPERATION
Water-insoluble but hydrate-forming gas reacts under conditional temperature, with pressurised
concentrated seawater. The generated hydrate cr)/stals are separated and washed with fresh water.
Then the hydrates are decomposed by lowering the pressure or increasing the temperature. The gas is
separated and re-used, while the product and the brine leave the plant separately.
For this process, like the freezing process, no commercial application has materialised.
- 16-
APPENDIX A 4
WORLD HEALTH ORGANISATION WATER PURITY LIMITS
Substance Maximum concentration permissible

in public water supplies, ppm
Carbon dioxide 20
Carbonates of sodium and potassium 150
Chlorides 250
Chlorine (fke) 1.0
Copper 3.0
Detergents 1.0
w
Fluorine (as fluorides) 1.5
Iron 0.3
Lead 0.1
Magnesium 125
Nitrates 10
Phenols 0.001
Sulphates 250
zinc 15
Total solids in suspension 500
Maximum NaCl 250
_I
- IQ_
I
CHEMICAL ’ H.P HP L.P
FEEDWATER TRE, MEN1 CONDENS rE ST ‘EA M L fENT S T E A M S AM
I
_-_ -+
I I JM
IM
IIII_I +
FE’EDWATER
HEAT RECOVERY STAGES HEATER
XSTILLATE BRI-NE CONOE-NSATE

BLOWDOWN
FLOW DIAGRAM
MULTISTAGE FLASH EVAPORATOR
(ONCE-THROUGH SYSTEM)
CONDLNSATC msllLLA1
j\MPLlFIED CONTROL bAGRAM M.S.F. ONCE 7l+W1lGH SYSTEM.

FIG1

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WATER (Pre-) TREATMENT

section 1 Basic Water Chemistry pre--reading material

WATER (Pre-) TREATMENT COURSE

2. CONTAMINATION OF PURE WATER 2

3. PHYSICAL AND CHEMICAL TERMS 4

M148_10 Basic Water Chemistry

Per day 1000 l lo6 m3 evaporate from the sea

2. CONTAMINATION OF PURE WATER

Contamination of pure ram water starts the moment it is formed:

M148_10 Basic Water Chemistry

2.1. SUSPENDED MATTER

The settling of suspended matter is governed by Stokes law:

V = free fatling speed of particles

Settling time for particles of different size in water

Particle diameter Time to settle

M148_10 Basic Water Chemistry

2.2 SOLUBLE MATTER

SO: + Org. mat -+ S” + 2H+ + Hz0 (H2.S)

F e (HCO& + Fe(OH)z + 2 CO2

4 Fe(OH)2 + 02 + 2 Hz0 -+ 4 Fe(OH)34

Quantities of iron over 0.5 ppm stain clothes.

3.1. DISSOLVED SOLIDS

NaCl -+ Na+ + CI-

M148_IO Basic Water Chemistry

Magnesium Mg++ Carbonate co;

Sodium (Natrium) Na+ Sulphate so,=

Potassium (Kaliwn) Kt Nitrate NO;

Iron (Femun) Fe*/Fe- Fluoride F-

zinc zn++V==) Nitrite NO;

M andpalkalinities are reported as ppm CaC03.

1gionSOl = 32+4x16 = 96g

M 148-l 0 Basic Water Chemistry

The valency is 2. Therefore the equivalent weight of 1 g eq. SO: is 96 : 2 - 48 g

I mg eq. SO; is 48 mg.

Ion Ion weight Equivalent weight

(I-I”) = concentration of H+ ions (g/ion/l.)

The product (I-I”) x (OH-) is constant (at 25’C) = 10-14.

l 1 mg/mol. is amount equal to molecular weight in mg.

M148_10 Basic Water Chemistry

Example: pH of water to which hydrochloric acid HCI is added.

HCI is fully dissociated into H+ and Cl-

pH = 1 -log.5 (0.7) = 0.3

Example: pH of water to which caustic soda (NaOH) is added.

NaOH is fully dissociated into Na+ and OH-

The conductivity is related to

I. the concentration of the electrolyte (Ci&)

Ml48_10 Basic Water Chemistry

Conductivity of water of high purity at 2oOC

Type of water Conductivity-m

Theoretical minimum conductivity 0.04

NaOH Ca(OH)z Mg(OH)z

NaOH + HCI + NaCl + H20

Na2CO3 + HCl -+ N a H C 0 3 + NaCl

NaHC03 + HCI + NaCl + Hz0 + CO2

M148_10 Basic Water Chemistry

Thus P-Alkylinity is a measure of

Total hydroxide + % Carbonate

And M-Alkylinify is a measure of

(Total hydroxide + % Carbonate) + % Carbonate + Total bicarbonate.

Result of titration Hydroxyl (OH-) Carbonate (CO, Bicarbonate (HCO;)

If p = 0.8 mg eq/l. and m = 5 mg eq/l.

From Table if 2 p < m hydroxide = 0