TSP-POGC-NIGC

COURSE
SUBJECT

T.T.F.
OIL AND GAS TECHNOLOGY
WATER TREATMENT

CODE
P/TM/TRG/P.WT/001

Objectives: Upon completion of the unit, the trainees should be able to:

Describe & explain water treatment processes

Available in the oil and gas Industry

Contents:
1. Introduction
2. Water Source (Impurities and Chemistry)
3. Clarification
4. Filtration
5. Preparation softening
6. Ion exchange
7. Desalination

TSP-POGC-NIGC
Prepared

T.T.F.

Safaei

Checked
by

9 July. 2000

Date

b
y
Date
SUBJECT

Yeganeh
Larijani

16
July.
2000
WATER TREATMENT

Approved
by
Date
CODE
P/TM/TRG/P.WT/001

1.INTRODUCTION
The water is a necessity of living for nature and human.
Nearly 70% of the surface of the earth is with water in the form of seas, rivers, and lakes.
This water is not purified and that is a major problem in industrial water.
Abundant supplies of fresh water are essential to the development of industry. Enormous
quantities are required for cooling of products and equipment in process, for boiler feed,
and for sanitary and potable water supply.
Pure water (H2O) is colorless, tasteless and odorless. It is composed of Hydrogen &
Oxygen because water becomes contaminated by the substances with which it comes into
contact it is not available for use in its pure state.
The solvency power of water can pose a major threat to industrial equipment that is why we
need purified water for industrial uses.
Purification can be in defined in five stages.
1. Clarification
2. Filtration
3. Precipitation (softening)
4. Ion Exchange
5. Desalination

WATER SOURCES IMPURITIES AND CHEMISTRY

Abundant supplies of fresh water are essential to the development of industry. Enormous
quantities are required for the cooling of products and equipment, for process needs, for
boiler feed, and for sanitary and potable water supply.
THE PLANTETARY WATER CYCLE
Industry is a small participant in the global
water cycle. The finite amount of water on the
planet participates in a very complicated
recycling scheme that provides for its reuse.
This recycling of water is teemed the
Hydrologic Cycle (See Figure 1-1).
Evaporation under the influence of sunlight
takes water from a liquid to a gaseous phase.
The water may condense in clouds as the
temperature drops in the upper atmosphere.
Wind transports the water over great distances

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T.T.F.

before releasing it in some form of precipitation.

As the water condenses and falls to the ground,
it absorbs gases from the environment. This is
the principal cause of acid rain and acid snow.
SUBJECT

WATER TREATMENT

CODE
P/TM/TRG/P.WT/001

WATER AS A SOLVENT
Pure water (H2O) is colorless, tasteless, and odorless. It is composed of hydrogen and
oxygen. Because water becomes contaminated by the substances with which it comes into
contact, it is not available for use in its pure state. To some degree water can dissolve every
naturally occurring substance on the earth. Because of this property, water has been
termed a universal solvent.
Although beneficial to mankind, the solvency power of water can pose a major threat to
industrial equipment. Corrosion reactions cause the slow dissolution of metals by water.
[Deposition reactions which produce scale on heat transfer surfaces represent a change in
the solvency power of water as its temperature is varied.] The control of corrosion and
scale is the major focus of water treatment technology.
WATER IMPUTRITIES
Water impurities include dissolved and suspended solids. Calcium bicarbonate is a soluble
salt. A solution of calcium bicarbonate is clear, because the calcium and bicarbonate are
present as atomic-sized ions, which are not large enough to reflect light. Some soluble
minerals impart a color to the solution. Soluble iron salts produce pale yellow or green
solutions, some copper salts form intensely blue solutions. Although colored these solutions
are clear.
Suspended solids are substances that are not completely soluble in water and are present
as particles. These particles usually impart a visible turbidity to the water.
Dissolved and suspended solids are present in most surface waters. Seawater is very high
in soluble sodium chloride: suspended sand and silt make it slightly cloudy. An extensive list
of soluble and suspended impurities found in water is given table 1-1.

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T.T.F.

Figure 1- Global water cycle. (Source: U.S. Geological Survery)

SUBJECT

WATER TREATMENT

CODE
P/TM/TRG/P.WT/001

Table 1-1 Common impurities found in fresh water.

Constituent

Chemical Formula

Difficulties Caused

Means of treatment

Turbidity

none-expressed in
analysis as units

Imparts unsightly
appearance to water:
deposits in water lines,
process equipment, etc.:
interferes with most process
uses

Coagulation, settling
and filtration

Hardness

calcium and
magnesium salts.
Expressed as
CaCO3

Chief source of scale in

heat exchange equipment,
boilers, pipelines, etc.;
forms curds with soap.
Interferes with dyeing, etc.

Softening:
demineralization:
internal boiler water
treatments; surfaceactive agents

Alkalinity

Bicarbonate
(HCO3-), carbonate
(CO3-2) and
hydroxide (OH-),
expressed as
CaCO3

Foam and carryover of

solids with steam;
embrittlement of boiler
steel; bicarbonate and
carbonate produce CO2 in
steam, a source of
corrosion in condensate
lines.

Lime and lime-soda

softening; acid
treatment; hydrogen
zeolite softening,
deminalization
dealkalization by
anion exchange

Free Mineral
Acid

H2SO, HCl, etc.

Expressed as
CaCO3

Corrosion

Neutrlization with
alkalies

Carbon
Dioxide

CO2

Corrosion in water lines,

particularly steam and
condensate lines

Aeration,
deaeration,
neutralization with
alkalies

PH

PH varies according to
acidic or alkaline solids in
water; most natural waters
have a pH of 6.0-8.0

PH can be
increased by
alkalies and
decreased by acids

Sulfate

Hydrogen ion
concentration
defined as: PH=log
1
[H ]
SO-2

Adds to solid content of

water, but in itself is not
usually significant;
combines with calcium to
from calcium sulfate scale

Demineralization,
reverse osmosis,
electro dialysis,
evaporation

Chloride

Cl-

Adds to solids content and

increases corrosive
character of water

Demineralization,
reserve osmosis,
electro dialysis,
evaporation

Nitrate

NO3-

Adds to solids content, but

is not usually significant
industrially; high
concentrations cause

Demineralization,
reserve osmosis,
electro dialysis,
evaporation

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T.T.F.
methemoglo-binemia in
infants; useful for control of
boiler metal embrittlement
WATER TREATMENT

SUBJECT

CODE
P/TM/TRG/P.WT/001

Table 1-1, Continued

Constituent

Chemical Formula

Difficulties Caused

Means of treatment

Fluoride

Cause of mottled enamel in

teeth also used for control
of dental decay; not usually
significant industrially

Adsorption with
magnesium
hydroxide, calcium
phosphate. Or bone
black; alum
coagulation

Sodium

Na-

Adds to solid content of

water; when combined with
OH-, causes corrosion in
boilers under certain
conditions

Demineralization,
reverse osmosis,
electrodialysis.
Evaporation

Silica

SiO2

Scale in boilers and cooling

water systems; insoluble
turbine blade deposits due
to silica vaporization

Hot and warm

process removal by
magnesium salts
anion exchange
resins, in
conjunction with
demineralization,
reverse osmosis,
evaporation

Iron

Fe2- (ferrous)
Fe3+ (ferric)

Discolors water on
precipitation: source of
deposits in water lines
boilers, etc.; interferes with
dyeing tanning,
papermaking, etc.

Aeration:
coagulation and
filtration lime
softening carlon
exchange; contact
filtration surfaceactive agents for
iron retention

Manganese

Mn2+

Same as iron

Same as iron

Aluminum

Al3+

Usually present as a result

of floc carryover from
clarifier; can cause deposits
in cooling systems and
contribute to complex boiler
scales

Improved clarifier
and filter operation

Oxygen

O2

Corrosion of water lines,

heat exchange equipment,
boilers, return lines, etc.

Dearation ; sodium
sulfide: corrosion
inhibitors

Hydrogen
sulfide

H2S

Cause of rotten egg odor;

corrosion

Aeration,
chlorination highly
basic anion
exchange

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Ammonia

T.T.F.

NH3

SUBJECT

Corrosion of copper and

zinc alloys by formation of
complex soluble ion

WATER TREATMENT

Cation exchange
with hydrogen
zeolite, chlorination;
dearation

CODE
P/TM/TRG/P.WT/001

Table 1-1, Continued

Constituent
Dissolved
Solids

Chemical Formula
None

Difficulties Caused
Refers to total amount of
dissolved matter,
determined by evaporation;
high concentrations are
objection able because
interference and as a cause
of foaming in boilers

Means of treatment
Lime softening and
cation exchange by
hydrogen zeolite;
demineralization,
reverse osmosis,
electrodialysis,
evaporation

Suspended

None

Refers to the measure of

undissolved matter,
determined gravimetrically;
deposits in heat exchange
equipment, boilers, water
lines, etc.

Subsidence,
filtration, usually
preceded by
coagulation and
settling

Total Solids

None

Refers to the sum of

dissolved and suspended
solids, determined
gravimetrically

See dissolved
Solids and
Suspended Solids

TSP-POGC-NIGC

SUBJECT

T.T.F.

WATER TREATMENT

CODE
P/TM/TRG/P.WT/001

CLARIFICATION
Suspended matter in raw water supplies is removed by various methods to provide water
suitable for domestic purposes and most industrial requirements. The suspended matter
can consist of large solids, settleable by gravity alone without any external aids, and
nonsettleable material, often colloidal in nature. Removal is generally accomplished by
coagulation, flocculation, and sedimentation. The combination of these three processes is
referred to as conventional clarification. Coagulation is the process of destabilization by
charge neutralization. Once neutralized, particles no longer repel each other and can be
brought together. Coagulation is necessary for the colloidal-sized suspended matter.
Flocculation is the process of bringing together the destabilized, or coagulated, particles
to form a larger agglomeration, or floc,
Sedimentation refers to the physical removal from suspension, or settling, that occurs once
the particles have been coagulated and flocculated. Sedimentation or subsidence alone,
without prior coagulation, results in the removal of only relatively coarse suspended solids.

Figure 1.2- Upflow sludge blanket clarifier. (Courtesy of the Permutit Company Inc.)

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SUBJECT

T.T.F.

WATER TREATMENT

CODE
P/TM/TRG/P.WT/001

Figure 1.3- Solids-contact clarifier. (courtesy of infilco degremont. Inc.)

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T.T.F.
FILTRATION

Filtration is used in addition to regular coagulation and sedimentation for removal of solids
from surface water or wastewater. This prepares the surface water for use as potable,
boiler, or cooling make up. Wastewater filtration helps users meet more stringent effluent
discharge permit requirements.
Filtration, usually considered a simple mechanical process, actually involves the
mechanisms of adsorption (physical and chemical), staining, sedimentation, interception,
diffusion, and inertial compaction.
Filtration does not remove dissolved solids, but may be used together with a softening
process, which does reduce the concentration of dissolved solids. For example, anthracite
filtration is used to remove residual precipitated hardness salts remaining after clarification
in precipitation softening.
In most water clarification or softening processes where coagulation and precipitation
occur. At least a portion of the clarified water is filtered. Clarifier effluents of 2-10 NTU may
be improved to 0.1-1.0 NTU by conventional sand filtration. Filtration ensures acceptable
suspended solids concentrations in the finished water even when upsets occur in the
clarification processes.
TYPICAL CONSTRUCTION
Conventional gravity and pressure rapid filters operate down flow. The filter medium is
usually a 15-30 in, deep bed of sand or anthracite. Single or multiple grades of sand or
anthracite may be used.
SUBJECT

WATER TREATMENT

CODE
P/TM/TRG/P.WT/001

A large particle bed supports the filter media to prevent fine sand or anthracite from
escaping into the under drain system. The support bed also serves to distribute backwash
water. Typical support beds consist of 1/8 11/2 in. gravel or anthracite in graded layers to a
depth of 12-16in.

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T.T.F.

Figure 1.4- vertical-type pressure sand filter. (Courtesy of the Permutit Company, Inc.)

PRECIPITATION SOFTENING
Precipitation softening processes are used to reduce raw water hardness, alkalinity, silica,
and other constituents. This helps prepare water for direct use as cooling tower makeup or
as a first stage treatment followed by ion exchange for boiler makeup or process use. The
water is treated with lime or a combination of lime and soda ash (carbonate ion). These
chemicals react with the hardness and natural alkalinity in the water to form insoluble
compounds. The compounds precipitate and are removed from the water by sedimentation
and, usually, filtration. Waters with moderate to high hardness and alkalinity concentrations
(150-500 ppm as CaCO3) are often treated in this fashion.
CHEMISTRY OF PRECIPITATION SOFTENING
In almost every raw water supply, hardness is present as calcium and magnesium
bicarbonate, often referred to as carbonate hardness or temporary hardness. These
compounds result from the action of acidic, carbon dioxide laden rainwater on naturally
occurring minerals in the earth, such as limestone. For example:
CO2
+
H2O =
H2CO3
Carbon
Water
Carbonic
Dioxide
acid
SUBJECT

WATER TREATMENT

CODE
P/TM/TRG/P.WT/001

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H2CO3
Carbonic
acid

CaCO3
Calcium
Carbonate

Ca (HCO3)2
Calcium
Bicarbonate

Hardness may also be present as a sulfate or chloride salt, referred to as

noncarbonate or permanent hardness. These salts are caused by mineral acids
present in rainwater or the solution of naturally occurring acidic minerals.
The significance of carbonate or temporary hardness as contrasted to
noncarbonate or permanent hardness is that the former may be reduced in
concentration simply by heating. In effect, heating reverses the solution reaction:
Ca (HCO3)2 +
Calcium
Bicarbonate

Heat =

CaCO1 +
calcium
carbonate

H2O +
water

CO2
carbon
dioxide

The reduction of noncarbonate hardness. By contrast, requires chemical addition. A

combination of lime and soda ash, along with coagulant and flocculant chemicals, is added
to raw water to promote a precipitation reaction. This allows softening to take place.

Figure 1.5
SUBJECT

WATER TREATMENT

CODE
P/TM/TRG/P.WT/001

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Figure 1.6
For improved silica reduction, sludge is recirculated from the cone back to the top of the
unit.
For optimum silica reduction, a sludge-contact unit (shown in figure 7-8) is used. Water and
chemicals enter the top of the unit and flow to the bottom of the softener through a
downcomer. The sludge level is maintained in such a way that the downcomer always
discharges into the sludge bed. This ensures good contact with the sludge, which is rich in
magnesium hydroxide. Also, the sludge bed acts as a filter, entrapping finer solids before
the water exits near the top of the vessel, sludge recycle may also be used.
The upflow design also lends itself to easier incorporation of internal compartments for filter
backwash storage and return, and condensate or treated water deaeration.

ION EXCHANGE
All natural waters contain, in various concentrations, dissolved salts which dissociate in
water to form charged ions. Positively charged ions are called cations; negatively charged
ions are called anions. Ionic impurities can seriously affect the reliability and operating
efficiency of a boiler or process system. Overheating caused by the buildup of scale or
deposits formed by these impurities can lead to catastrophic tube failures, costly production
losses, and unscheduled downtime. Hardness ions, such as calcium and magnesium, must
be removed from the water supply before it can be used as boiler feed water. For highpressure boiler feedwater systems and many process systems, nearly complete removal of
all ions, including carbon dioxide and silica, is required. Ion exchange systems are used for
efficient removal of dissolved ions from water.
SUBJECT

WATER TREATMENT

CODE
P/TM/TRG/P.WT/001

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Ion exchangers exchange one ion for another, hold it temporarily, and then release it to a
regenerant solution. In an ion exchange system, undesirable ions in the water supply are
replaced with more acceptable ions. For example, in a sodium zeolite softener, scaleforming calcium and magnesium ions are replaced with sodium ions.

H2SO1 SO1

2HCl 2Z.OH 2Cl 2H2O
2HNO 2NO
3 3

WBA resins possess the same efficiency characteristic as WAC resins and can be
regenerated with caustic soda, soda ash, or ammonia. WBA resins are more resistant than
SBA resins to organics present in many water supplies. They can be used upstream of SBA
resins for improved regeneration efficiency and protection of the SBA resin.
SODIUM ZEOLITE SOFTENING
Sodium zeolite softening is the most widely applied use of ion exchange. In zeolite
softening, water containing scale-forming ions, such as calcium and magnesium, passe
through a resin bed containing SAC resin in the sodium form. In the resin, the hardness
ions are exchanged with the sodium, and the sodium diffuses into the bulk water solution.
The hardness-free water, termed soft water, can then be used for low to medium pressure
boiler feedwater, reverse osmosis system makeup some chemical processes, and
commercial applications, such as laundries.
Principles of Zeolite Softening
The removal of hardness from water by a zeolite softening process is described by the
following reaction.

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SO4 NaSO4

Ca 2Cl Na.Z Ca 2NaCl
2
Mg 2HCO Mg 2NaHCO
3 3

T.T.F.

Water from a properly operated zeolite softener is nearly free from detectable hardness.
However, some small amounts of hardness, known as leakage, are present in the treated
water. The level of hardness leakage is dependent on the hardness and sodium level in the
influent water and the amount of salt used for regeneration.

SUBJECT

Figure 1.7
WATER TREATMENT

CODE
P/TM/TRG/P.WT/001

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Figure 1.8- sodium zeolite softener. (Courtesy of graver water division, ecodyne corporation.)

SUBJECT

WATER TREATMENT

CODE
P/TM/TRG/P.WT/001

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After final rinse, the softener produces a low, nearly constant level of hardness until the ion
exchange resin nears exhaustion. At exhaustion, the effluent hardness increases sharply,
and regeneration is required.
As illustrated by the softening reactions. SAC resin readily accepts calcium and magnesium
ions in exchange for sodium ions. When exhausted resin is regenerated, a high
concentration of sodium ions is applied to the resin to replace calcium and magnesium. The
resin is treated with a 10% sodium chloride solution, and regeneration proceeds according
to the following equation:

Ca Ca
Z. 2CI NaZ CI
2Mg(conetrad) Mg

During regeneration, a large excess of regenerant (approximately 3 times the amount of
calcium and magnesium in the resin) is used. The eluted hardness is removed from the
softening unit in the waste brine and by rinsing.
After regeneration, small residual amounts of hardness remain in the resin if resin is
allowed to sit in a stagnant vessel of water. Therefore, at the initiation of flow, the water
effluent from a zeolite softener can contain hardness even if it has been regenerated
recently. After a few minutes of flow, the hardness is rinsed from the softener, and the
treated water is soft.
The duration of a service cycle depends on the rate of softener flow, the hardness level in
the water, and the amount of salt used for regeneration. Table 8-1 shows the effect of
regenerant level on the softening capacity of a gelular strong cation resin. Note that the
capacity of the resin increases as the regenerant dosage increases, but the increase is not
proportional. The regeneration is less efficient at the higher regenerant levels. Therefore,
softener operating costs increase as the regenerant level increase. As shown by the data in
table 8-1, a 150% increase in regnerant salt provides only a 67% increase in operating
capacity.

HOT ZEOLITE SOFTENING

Zeolite softeners can be used to remove residual hardness in the effluent from a hot
process lime or lime soda softener. The hot process effluent flows through filters and then
through a bed of strong acid cation resin in the sodium form figure 8-7. The equipment and

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operation of a hot zeolit softener is identical to that of an ambient temperature softener,

except that the valves, piping, controllers, and instrumentation must be suitable for the high
temperatures of up to 270F, but for a longer service life a premium gel or macroreticular
resin is recommended. When operating a zeolite system following a hot process softener, it
is important to design the system to eliminate flow surges in the hot lime unit. Common
designs include the use of backwash water storage tanks in the hot lime unit and extended
slow rinses for the zeolite in lieu of a standard fast rinse.

SUBJECT

WATER TREATMENT

CODE
P/TM/TRG/P.WT/001

Figure 1.9
DEMINERALIZATION PROCESSES
The standard cation-anion process has been modified in many systems to reduce the use
of costly regenerants and the production of waste. Modifications include the use of
decarbonators and degassers, weak acid and weak base resins, strong base anion caustic
waste (to regenerate weak base anion exchangers), and reclamation of a portion of spent
caustic for subsequent regeneration cycles several different approaches to demineralization
using these processes are shown in figure 1-10.

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SUBJECT

T.T.F.

WATER TREATMENT

CODE
P/TM/TRG/P.WT/001

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Figure 1.10

SUBJECT

WATER TREATMENT

CODE
P/TM/TRG/P.WT/001

DESALINATION
In most cases water that is to be desalted is sew water. Sea water has an normal salinity of
35gr but it may go up to 55gr/L.
A sample of red sea water contains:
Sodium
Magnesuium
Calcium
Potassium
Chloride
Sulphate
Bicarbonate

(Na+)
(Mg++)
(Ca++)
(K+)
(Cl-)
(So4--)
(Hco3-)

13.60 g/l
1.78
0.49
0.57
24.49
3.60
0.17

Total: 45.00 g/l

The most common distillation processes are single or multi-effect distillation
A. Single-Effect Distillation
The easiest arrangement for a distillation unit is the single effect evaporator.
A horizontal tube bundle is installed in a thermally insulated chamber. It is fed by heating
fluid. The make-up sea water is sprayed over the tubes and the internal heating fluid. The
make-up sea water is sprayed over the tubes and the internal heating fluid causes it to boil.
Vapor so generated is condensed on the tube bundle of a sea water cooled condenser
placed in the same chamber. Distillate flowing down the condenser is collected in a tray and
extracted by a pump. The make-up sea water in an amount greater than the production is
introduced at the upper part of the chamber in order to form a fluid film flowing down the
heating bundle. Concentrated sea water, the brine, is collected under this bundle and
extracted by a pump.
An ejector keeps the
required vacuum level
in
the chamber.

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SUBJECT

T.T.F.

WATER TREATMENT

CODE
P/TM/TRG/P.WT/001

B. Multi-Effect Distillation
The single effect distillation does not allow to supply great quantities of water at low cost. In
order to reduce the specific heat consumption the heat introduced in the cycle is utilized
several times: this is the principle of Multi-Effect distillation.

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It is common knowledge that the boiling temperature of water depends on its pressure. The
lower the pressure, the lower the boiling temperature. The vapor produced when
evaporating sea water in a first effect can be used as heating fluid for the second effect.
The boiling temperature and pressure of cell 2 will be lower than those of cell 1. this
recovery of heat from effect to effect can be repeated several times.
The heat supplied to the evaporator is then only that necessary to heat the sea water
make-up in the first cell and to vaporize the production of this cell.

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