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DEPARTMENT OF CHEMICAL & ENVIRONMENTAL ENGINEERING

CEE DESIGN CONSULTANTS

DESIGN GUIDANCE MONOGRAPHS

Water Systems

DOCUMENT No CEEDG007

REVISION HISTORY

Date Rev. Purpose Author Approver


26/11/16 0 Draft for Review Richard Hill
12/12/16 1 Issue Richard Hill Roger Freestone
26/09/17 2 General Update and Process Water Richard Hill Roger Freestone
Section added
Water Systems

Contents

REVISION HISTORY........................................................................................ 1
CONTENTS .................................................................................................... 2
1.0 INTRODUCTION ..................................................................................... 3
2.0 ONCE THROUGH COOLING SYSTEMS ....................................................... 3
3.0 OPEN EVAPORATIVE COOLING SYSTEMS .................................................. 4
4.0 HUMIDIFICATION SYSTEMS .................................................................... 7
5.0 CLOSED WATER SYSTEMS ...................................................................... 8
6.0 COLD AND HOT WATER SYSTEMS ............................................................ 9
7.0 FIRE WATER SYSTEMS ......................................................................... 10
8.0 PROCESS WATER SYSTEMS................................................................... 10
9.0 PHARMACEUTICAL WATER SYSTEMS ...................................................... 11
APPENDIX 1 ................................................................................................ 13
APPENDIX 2 ................................................................................................ 15
APPENDIX 3 ................................................................................................ 16

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1.0 INTRODUCTION
Modern industry uses water for many applications including heating, cooling, chemical processing and
product rinsing as well as for "domestic" uses such as drinking, cooking, washing and flushing of WC's.
The problems of scaling and corrosion of mechanical equipment have long been recognised and many
water treatment techniques have been developed to overcome them. However, it is only over the last
decade or so that there has been increasing awareness and growing concern about potential health
hazards associated with water services of various types in modern industrial plant and buildings.

The principle water systems that concern chemical process design engineers are steam raising boilers
(see CEEDG006) and open cooling water systems, although chilled water and hot water are also
sometimes required particularly in batch processing plants like pharmaceutical manufacturing. Many of
the water systems are the province of the Building Services Engineer – potable, hot and cold supplies,
space heating, air cooling and humidification are necessary for staff welfare, so it is useful to have
some background knowledge. All water systems are prone to problems of scale, corrosion and
microbiological contamination. The effects can vary from minimal – maybe a leaking pipe – to
economic – fouled heat exchange surfaces are inefficient – to catastrophic – think release of high
temperature process streams from a corroded heat exchanger or an outbreak of Legionnaires’ disease.

Properly controlled water treatment, combining techniques such as filtration, softening, deionisation or
reverse osmosis together with chemical conditioning, by scale and corrosion inhibitors and disinfecting
agents, protects expensive plant by preventing corrosion, scale deposition and biological fouling in
boilers, cooling towers and heating systems.

In this monograph we shall look at some of the types of water systems and the engineering problems
associated with them.

2.0 ONCE THROUGH COOLING SYSTEMS


In once through cooling systems heat is rejected from a process stream – this may be any kind of
chemical stream or steam condenser – into a lower temperature water stream which has been taken
from a river, lake or the sea and is simply returned to the source at a higher temperature. The return
temperature will be controlled by the local
environmental regulations (typically return to a river
might be at a maximum of 25°C. That limits the use of
once through systems to sea water cooling unless the
warm cooling water is itself cooled by a cooling tower
(see below) prior to discharge. This is common practice
in large power stations and similar installations. For
example Fiddlers Ferry Power Station takes 195Ml/day
of water from the River Mersey, uses it for condenser
cooling then uses eight natural draught cooling towers
to drop the temperature to 30°C before returning it to
the river.

Coastal power stations and chemical plants frequently take sea water, use it for cooling and then
return it directly to the sea. These systems may be direct – that is the sea water is pumped through
heat exchangers around the site – or indirect where heat exchangers are cooled by a primary closed
circuit filled with treated fresh water and the primary circuit is then cooled by a single heat exchanger
which is directly cooled by sea water. To limit the return temperature, flows are very high and sea
water has a whole series of associated problems like corrosion and biological fouling.

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3.0 OPEN EVAPORATIVE COOLING SYSTEMS


Where once through systems cannot be used either because the plant is not located near to a river or
other natural water source or where abstraction is limited, cooling water is recirculated. This requires
the circulating water to be cooled. Open evaporative cooling systems or atmospheric cooling systems,
including evaporative condensers and cooling tower systems, are used to remove heat from once
through or recirculating water in plant and air conditioning cooling systems either directly or indirectly
via a heat exchanger or refrigeration condenser. In conventional open evaporative cooling systems
water is evaporated by contact with a natural or forced draught of air in and, in doing so, takes in
latent heat of vaporisation from the surrounding water which is thus cooled. Heat is rejected with the
water vapour into the atmosphere. A typical evaporative system will comprise a cooling tower, a water
collection sump or pond and a cooling water circuit. Typically, an atmospheric cooling tower will
operate over a temperature differential of up to 10°C, with return water at about 5°C above wet bulb
temperature (Appendix 1).

3.1 Cooling Towers

Cooling towers are either natural draught or forced draft. In either case the incoming hot
water is distributed over a packing material to enhance contact with the air stream to
maximise heat and mass transfer. Natural draught towers are used for large scale duties and
are of hyperbolic cross section and constructed from reinforced concrete. Air is drawn upwards
by convection. Capital costs are very high but operating costs are low.

Natural Draught Tower

In smaller applications where footprint is important or restrictions on water abstraction mean


that cooling water has to be conserved by recirculation, forced draught towers are the norm.
They vary in size from large multi-cell units capable of cooling 10,000m3/h to small, single cell
packaged types for commercial air conditioning systems.

The draught of air may be generated by a fan at the top of the


tower which draws air out of the tower (induced draught) or a
blower at the bottom of the tower blowing air in (forced
draught). The water entering the top of the tower flows over a
packing material or fill which creates a thin film to improve

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contact between water and air. This is, typically, a proprietary structured plastic medium.

Multi-cell and single cell induced draught and single cell forced draught towers

3.2 Mass and Heat Balance

An atmospheric cooling tower takes C m3/h of recirculating cooling water at T2 °C and cools it
to T1 °C by evaporation. As water evaporates it takes in latent heat (about 2450kJ/kg) from
surrounding water which is, consequently, cooled. The evaporation loss (E m3/h) together with
the loss from windage and drift (W m3/h) is made up by make-up water (M m3/h TDS m mg/l).
Evaporation removes water as vapour leaving salts behind so the circulating water becomes
more concentrated (TDS b mg/l) and the “concentration factor” (CF) of the tower is b/m
(usually this test is carried out using chloride as the test parameter since other salts may be
precipitated as their solubility product is exceeded). The concentration is limited to an
acceptable level by discharging B m3/h of circulating water as blowdown or bleed-off.

Windage consists of large droplets (0.5-2.0mm) of water lost from the sides of the tower and
is typically up to 0.02% circulation rate although well designed side louvers should reduce it to
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less than 0.01%. The typical windage zone is 5-10m from the tower sides. Drift is the loss of
small (50-100µm) droplets of water which are entrained in the air flow leaving the tower.
Efficient drift eliminators should reduce this to less than 0.01% circulation rate. The drift zone
may be up to 500m depending on height and wind speed.

A mass balance around the tower shows:

M=E+B+W
Mm = Bb + Wb
 M = (B + W)CF
E = (B + W)(CF - 1)
B + W = E/(CF - 1)
M = E.CF/(CF - 1)

A heat balance shows:

C x 4.2 x T1 = C x 4.2 x T2 + E x 2450


C x 4.2 x C = E x 2450
E/C = C x 0.0017

That is the evaporation rate is about 0.2% of circulation rate per °C temperature drop across
the tower.

3.3 Scaling in Cooling Towers

We have seen how water in a recirculatory system becomes more concentrated and this
means that the solubility of low solubility salts like calcium sulphate, calcium phosphate and
can be exceeded. We can predict this by looking at the concentrations of low solubility salts in
the circulating water and calculating solubility products (Appendix 2). Note that calcium and
magnesium salts generally exhibit reverse solubility curves, becoming less soluble with
increasing temperature.

The most common type of scale is calcium carbonate and it’s a double edged sword. A thin
film of calcium carbonate on metal surfaces protects them from corrosion but a thicker deposit
reduces heat transfer and can block pipes and damage the cooling tower fill. Keeping a
balance is not easy. Wilfred Langelier, an American water chemist, developed the Langelier
Saturation Index1 (Appendix 3) to control cooling water chemistry. There are nomographs and
on-line calculators for determining LSI but a reasonable arithmetic approximation for most
systems is:

CaH MAlk
LSI  pH  log  log  (2.65  0.0167T )
2000 1000
Where CaH is the calcium concentration or calcium hardness of the circulating water in meq/l
MAlk is the total alkalinity of the circulating water in meq/l
T is the temperature in C

A positive LSI indicates that the water will deposit calcium carbonate whilst a negative value
indicates that the water will dissolve calcium carbonate. Controlling the value between
±0.5 should ensure that the water should cause neither scale nor corrosion. That is not easy
and sometimes not possible. Scaling can be prevented by limiting the concentration factor by

1
Langelier WF (1936) The analytical control of anti-corrosion water treatment. JAWWA 28(10):1500–1521

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blowdown, the addition of scale inhibiting chemicals (mainly phosphonates) provided that the
LSI is <2, reducing the LSI by acid dosing or by softening the make-up water.
3.4 Corrosion in Cooling Towers

Contacting water and air in a cooling tower results in the water having a high dissolved
oxygen content producing favourable conditions for aqueous corrosion. If LSI adjustment
cannot achieve protection then it may be necessary to add corrosion inhibiting chemicals
which suppress one or both of the half cell reactions by forming a protective film. These may
be zinc salts which form a zinc hydroxide protective film or amines which form an organo-
metallic film over all metal surfaces. Any break in the protective film will result in intense and
rapid corrosion at the break and the corrosion may spread unobserved beneath the film.

3.5 Microbiological Aspects

Conditions in cooling systems are conducive to a variety of microbiological problems. Iron


bacteria like Gallionella, Lepothrix and Crenothrix consume iron from metal surfaces whilst
sulphate reducing bacteris like Desulphovibrio desulphuricans and Thiobacillus thiooxidans
create low pH conditions resulting in acidic corrosion. Some bacteria, like Pseudomonas, form
sticky biofilms which cover parts of metal surfaces excluding air and creating differential
aeration corrosion cells. If allowed to grow, these films can cause fouling of heat transfer
surfaces and even pipework blockages. Legionella pneumophila, the causative agent of
Legionnaires’ disease2 can also thrive in cooling towers presenting a serious public health risk.

Note: In the UK all open cooling towers have to be registered with the UK Health and
Safety Executive due to the risk of legionella. Guidance on design is provided by the
HSE in a Technical Guidance Document “HSG274 Part 1: The control of legionella
bacteria in evaporative cooling systems” (free to download from HSE).

To minimise microbiological problems sodium hypochlorite or hypobromite are usually added


to the circulating water to maintain a free residual of about 0.5mg/l Cl 2 or Br2. However,
sometimes resistant bacteria grow and then an alternative non-oxidising biocide like
glutaraldehyde or sodium pentachlorophenate, has to be shot dosed to kill them. Ideally the
total viable bacteria count (TVC) should not exceed about 100cfu/ml (20 - 22oC, 3days).
Routine cleaning and sanitisation of the system is also required to control the microbial burden.

3.6 Suspended Solids

Suspended solids can be scrubbed from the atmosphere and can contribute to corrosion and
fouling.

4.0 HUMIDIFICATION SYSTEMS

Humidifiers increase the humidity of air in air conditioning systems by evaporating water into the air
stream. The preferred types of humidification system are the direct type where steam or water is
injected into the air-stream from a boiler or atomising unit. Other types include ultrasonic, spray, air
washer or pan type humidifiers in which water at room temperature is passed through a humidifying
device in which some water is evaporated whilst the remainder is recirculated. In this section of the
document "humidifier" is taken to include not only the humidifying device itself but also any storage
tank, valves and associated equipment.

2
HSE Approved Code of Practice L8 Legionnaires’ Disease : The Control of Legionella Bacteria in Water Systems

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Scale can be deposited in these units as a result of evaporation. Corrosion can also occur due to
'oxygen rich' conditions and galvanic action between dissimilar metals. Contacting of water with air as
part of the humidification process provides ample opportunity for ingress of dust, debris and microbial
agents. The latter can grow to hazardous levels if conditions are favourable causing health risks, e.g.
humidifier fever.

Humidifier fever is an allergenic reaction caused by the inhalation of fine droplets of water, carried
over in the airstream from humidifiers which have become contaminated with various micro-organisms.
It is characterised by chest tightness and other flu-like symptoms which typically occur on the first day
of a workshift and then reduce during the next few days giving a cyclic pattern.
Biocides, scale and corrosion inhibitors must not be used as these can be carried over in the air
stream and inhaled. Control of microbial growths is achieved by the regular programme of off-line
cleaning and disinfection. This may be supplemented by further off-line disinfection if needed.

Scale and deposit control is best achieved by using softened or low solids water for make-up. In hard
supply water areas make-up water should be pretreated by either base exchange softening or
demineralisation. Corrosion protection should be afforded by the use of corrosion resistant materials.

Electrode type steam humidifiers must be fed with water which has been pretreated to achieve a total
hardness of less than 0.1meq/l and must be regularly blowndown. Regular bleed-off should be
provided for water storage humidifiers to control the levels of dissolved and suspended solids.

5.0 CLOSED WATER SYSTEMS


5.1 Closed Hot Water Systems

Heating systems are categorised on the basis of temperature as:

 Low Temperature Hot Water (LTHW) (80oC)


 Medium Temperature Hot Water (MTHW) (80 - 110oC)
 High Temperature Hot Water (HTHW) (110oC).

Systems consist of a hot water boiler or steam heated heat exchanger (called a calorifier), a
pumping station and recirculation pipework. Corrosion and scale deposition are accentuated in
hot water heating systems due to the operating conditions (i.e. temperatures and pressures).
Scaling problems can arise at temperatures above 60C when solids precipitate from solution.
Corrosion processes are accelerated at high temperatures and in the presence of oxygen rapid
pitting corrosion of water lines and boiler internals can occur. Microbial contamination is not
normally a problem with the system owing to the high temperatures but can occur in systems
where lower temperatures (below 60C) occur.

Pretreatment of the make-up and initial fill water should be considered for HTHW and MTHW
systems, which should preferably be filled and made-up with water containing 50 mg/litre
dissolved solids or less as recommended by the boiler manufacturer. If permitted by the
boiler manufacturer base exchange softened water may be used as an alternative. LTHW
systems with boilers having high heat release rates or modular boilers with a low water
content should be filled and made-up with softened water having a total hardness of less than
0.1meq/l. Other LTHW systems should be filled with mains water or a blended water with a
total hardness not exceeding 2meq/l.

Chemical conditioning requirements for these systems are dependent upon the make-up water
quality and system operating temperatures and pressures. In HTHW and MTHW systems
chemical conditioning programmes should aim to minimise the accumulation of dissolved
solids. These should typically include an oxygen scavenger for controlling corrosion, a pH
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elevant to assist corrosion control and a dispersant to assist in scale and sludge control.
Chemical conditioning for LTHW systems is usually based upon the formation of passive films
over the metal surface rather than utilising the oxygen scavenging approach. It is important
therefore that the conditioning agents used are compatible with and can provide effective
corrosion control for all metals present in the system. Typical chemical conditioning agents
used in these systems include corrosion inhibitors, dispersants for scale/sludge control and
compatible non-oxidising biocides for microbial control if necessary.

5.2 Closed Chilled Water Systems

Closed chilled water systems including closed condenser systems and direct expansion units,
are pressurised and normally operated in the temperature range of 5 to 16 oC. They comprise
a chilled water circuit, chiller batteries and chiller plant. These systems can be affected by
corrosion and to a lesser extent microbial contamination and scale/deposit accumulation. At
low temperatures it is ususal to add glycol to the water to prevent freezing on the chiller coil
and this reduces the heat transfer coefficient. Both microbial growth and scale deposition are
suppressed by low temperatures. Corrosion problems are most frequently encountered due to
the ingress of dissolved gases, principally oxygen and carbon dioxide with the make-up water
and to microbial activity which can also produce biofilms causing pipework blockage.

Pretreatment of make-up water should be considered for chilled water systems. They should
preferably be filled with a mains water or a blended water with a total hardness not exceeding
2meq/l. Make-up requirements are usually small because only minimal evaporation or
concentration of the recirculating water occurs at the low operating temperatures. Corrosion
inhibitors – typically nitrite/borate mixtures – should be dosed as required to accommodate
any make-up to the system and chemical degradation. Microbial activity should be controlled
using a non-oxidising biocide which is dosed when needed.

6.0 COLD AND HOT WATER SYSTEMS

Cold and hot water down services supply water for domestic purposes other than drinking.
Conventional vented systems usually consist of a cold water storage cistern feeding a cold water
distribution system or a hot water distribution system via a hot water storage vessel (e.g. calorifier or
direct feed boiler).
Tanks should be inspected at least annually and where excessive microbial growth is observed or
bacterial dip-slide checks exceed 105cfu/ml tanks should be cleaned and disinfected in accordance
with BS6700.

The distribution systems serve the individual outlets including taps, mixing valves and showers. Hot
water can be produced directly by heating appliances or indirectly on the secondary side of steam or
hot water calorifiers. Both cold and hot water services are vulnerable to microbial contamination,
which on formation of aerosols can be inhaled causing respiratory illnesses, such as Legionnaires'
Disease or Pontiac Fever. Water from these systems can also be ingested, if they are used
inadvertently for the preparation of food or drinks.

In order to restrict microbial growth a water temperature ideally below 15°C but not exceeding 20oC
should be maintained in cold water storage and distribution systems whilst hot water services must
ensure a water temperature leaving the hot water storage vessel or calorifier of 60 oC and a minimum
in distribution and delivery to the water service outlets of 50oC.

Water treatment by chemical conditioning is normally unnecessary for supply waters in the United
Kingdom. If chemical conditioning agents are deemed necessary they must be approved for use in
potable water. Scaling, corrosion and discolouration can be controlled by using proprietary chemicals
based upon complexed phosphates or silicates. Chemicals should be dosed either into the cistern or

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the cold supply pipe downstream. Where water supplies are particularly hard or where a building has
a history of scaling problems consideration should be given to partial softening of the water for hot
and cold services.

7.0 FIRE WATER SYSTEMS


The requirements for storage of water for fire-fighting vary from industry to industry but, typically,
there will be a storage tank and emergency pumping system feeding sprinklers and hydrants. In the
absence of any other guidance, fire water storage tanks should be sized for a capacity equivalent to 4
hours pump operation at full rate. Fire water systems do not normally require treatment other than
that intended for proper function. Tanks associated with such
systems may be treated with slow release chlorine briquettes if
biological growth is observed.
In process plants the fire water system usually comprises a ring
main which is constantly pressurised with a small motor driven
jockey pump to 6.0barg at the most remote location. As soon
as any significant flow is taken from the fire water ring main
the pressure drops and this causes a motor driven main fire
pump to start. If the motor driven fire pump fails to start a
second diesel driven main fire pump is started. The auto start
systems are normally tested on a weekly basis to ensure they
are fully functioning when required.

Much of the fire protection guidance used in process industries is based on the US National Fire
Protection Association standards3. In the UK, fire protection in industrial plant is covered by COMAH
regulations. HSE provide guidance in their Technical Measures - Active and Passive Fire Protection
Systems4. In the case of active fire protection systems, delivery rates and durations for various types
of application are specified in BS 5306 Code of practice for fire extinguishing installations and
equipment on premises. For fire engulfment protection a water rate of 0.6m 3/h/m2 over the exposed
vessel surface and its supports is standard. Automatic sprinkler systems for commercial and industrial
premises are covered by BS EN 12845:2004 – Fixed Fire Fighting Systems.

Note that, in the event of a fire, fire water has to be contained and, if required, treated prior to
discharge to prevent a possible pollution incident5.

8.0 PROCESS WATER SYSTEMS


Process water is water that is directly used in the process as, for example, a solvent, for
product washing, cleaning in place (CIP) of equipment etc. It may also be incorporated into
the product as, for example, in liquid chemical products, soft drinks, brewing, pharmaceutical
and cosmetic products and, of course, bottled water and drinking water supply. Process water
has to meet water quality standards which are specific to the application, and will set
maximum concentrations for impurities including insoluble solids, dissolved inorganic salts,
dissolved organic substances, dissolved gases and microbiological contaminants (bacteria,
fungi, viruses etc). They may be set by legislation, regulation or by industry or company
standards. The quality of drinking water in public supply is set by legislation (in the UK this is
set out in the Water Supply (Water Quality) Regulations) but other legislation applies to
bottled water (The Natural Mineral Water, Spring Water and Bottled Drinking Water
Regulations and the Food Safety (General Food Hygiene) Regulations). Companies like

3
http://www.nfpa.org/
4 http://www.hse.gov.uk/comah/sragtech/techmeasfire.htm
5
HSE Guidance Note EH 70, the control of fire water run-off from CIMAH sites to prevent environmental damage, HSE, 1995

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international brewers ABInBev, and soft drinks manufacturers Coca Cola and Pepsico, work to
much tighter in-house standards to ensure consistency and shelf life of their product wherever
it is produced. Other examples of in-house process water standards include water for surface
finishing in the automotive industry (Ford, VW), water for concrete mixing in construction
(Wimpey) and water for . Again these are predicated on product quality. The pharmaceutical
industry, for obvious reasons, is strictly regulated and has developed engineering standards to
ensure that water quality is met and maintained. This is discussed in the next section and
similar standards are increasingly being applied in healthcare and food and beverage process
water systems. The purest water, with maximum contaminant concentrations measured in
ng/l, is that used for manufacturing silicon chips. The need to prevent this water from
becoming contaminated by contact with construction materials resulted in the development of
a range of pipework and fitting made from high purity PVDF (See CEEDG204).

Note that water systems should include appropriate water storage to ensure a constant supply
even if plant components fail. If water is taken from a municipal drinking water supply it will
be necessary to provide isolation to prevent possible contamination of the supply by
backsiphonage and this will be covered by local water bye-laws. In the water supply industry,
materials of construction and products such as pipe fittings and valves must comply with local
legislation (in the UK this requires approval by the Drinking Water Inspectorate).

9.0 PHARMACEUTICAL WATER SYSTEMS


Water used for manufacturing pharmaceutical products has to comply with the quality requirements
set out in the national pharmacopoeia. Any pharmaceutical products which could be sold on the US
market have to be manufactured in facilities that are inspected and approved by the US Food & Drugs
Administration (FDA) who, in turn, require compliance with the US Pharmacopoeia (USP). This means
that the de facto standard for water in pharmaceutical manufacture is the USP. The USP and, indeed,
other national pharmacopoeias, defines two qualities of water: Purified Water and Water for Injection
(WFI).

9.1 Purified Water

Purified Water is used for most pharmaceutical


(and many cosmetics) products. It is generally
produced by ion exchange softening (if
necessary), single or double pass reverse
osmosis, electrodeionisation and UV
disinfection to meet a quality standard at point
of use of conductivity <1.3µS/cm and total
organic carbon <0.5mg/l. There is no bacterial
standard in the USP but most operating
companies work to a TVC <10cfu/ml (colony
forming units/ml). Purified Water is stored in
stainless steel tanks protected by bacterial
(0.2µm) vent filters to prevent the ingress of
airborne bacteria. The water is continuously
recirculated through stainless steel pipes (velocity generally >2m/s) and treated by in-line UV
disinfection. Routine sanitisation of Purified Water systems by pasteurisation (typically heated
to 80OC for 1 hour) or by overnight ozonisation followed by de-ozonisation by UV is normal
practice.

9.2 Water for Injection

WFI is used for the manufacture of parenteral solutions (vaccines, saline drips and other
products that are injected rather than ingested). The standards are similar as for Purified

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Water with the addition of standards for bacterial endotoxins


(pyrogens) of 0.25EU/ml and TVC <10cfu/100ml. Traditionally
the USP required WFI to be produced from Purified Water by
distillation but the latest edition allows reverse osmosis. The
bioburden in Water for Injection (WFI) systems must be tightly
controlled to meet the USP specification and this is usually
ensured by maintaining it at high temperature (>80°c). WFI
systems are usually periodically sterilised with clean steam at
121°C for 30 minutes. Point of use heat exchangers
(generally double tube sheet to ensure no leakage at the tube
sheet welds between the process and service streams) are
installed where cold water is required by the process user.

9.3 Engineering

Pharmaceutical water systems are normally


constructed in internally polished 316L stainless steel
and designed to minimise microbiological
contamination of the water. Storage tanks should be
provided with a tangential inlet to ensure walls are
wetted, a bottom central outlet to obviate stagnant
areas where bacteria might proliferate, and a spray
ball on the return connection to wet the top dished
end. To prevent ingress of airborne bacteria as the
tank “breathes” it should either be nitrogen blanketed or else fitted with a 0.2µm absolute
rated membrane air filter. Distribution of pharmaceutical grade water should be by means of a
continuous flow recirculatory ring main. The pipework should be orbitally welded with industry
standard hygienic pipework (see CEEDG204), which should be taken close to the point of use
to minimise “dead legs” and “zero dead-leg” valves. Pipe velocities should be greater than
2m/s to minimise biofilm formation and heat exchangers should be hygienic plate type. The
whole system should be heat sanitisable or, in the case of WFI, steam sterilisable. The best
engineering reference is the ISPE guide6.

6
ISPE Baseline Guide Volume 4: Water and Steam Systems

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APPENDIX 1

COOLING TOWER DESIGN

In a cooling tower, heat and mass transfer occur simultaneously driven by a difference in enthalpy.

WATER IN AIR + STEAM OUT


L kg/h G + E kg/h/m2
T1°C T1°C
hw1 kJ/kg ha2 kJ/kg

WATER OUT AIR IN


L - E kg/h G kg/h/m2
T2°C T2°C
hw2 kJ/kg ha2 kJ/kg

The controlling equation is the Merkel equation which gives the number of transfer units required:

T
KaV 1 dT
  NTU
L h  ha
T2 i

where: K = mass transfer coefficient (kg/h/m2)


a= contact area/tower volume
V = active cooling volume/plan area
L = water rate (kg/h/m2)
T1 = hot water temperature (°C)
T2 = cold water temperature (°C)
hi = enthalpy of saturated air at water temperature Ti (kJ/kg dry air)
ha = enthalpy of saturated air at wet bulb temperature (kJ/kg dry air)

We can represent this graphically as follows. Here:


ha1 = enthalpy of saturated air at outlet water temperature T2 (kJ/kg)
ha2 = enthalpy of saturated air at inlet water temperature T1 (kJ/kg)
 = tan-1 (L/G)
L = liquid flow rate kg/h/m2
G = gas flow rate kg/h/m2

The values can be found by reference to the psychrometric chart

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h

EQUILIBRIUM LINE
ENTHALPY

ha2

OPERATING LINE

ha1

APPROAC H T

Tw T2 T1
TEMPERATURE

Document No: CEEDG007 Revision 2


Effective Date: September 2017 Page 14 of 17
Owner: CEE Design Consultants
Water Systems

APPENDIX 2

SOLUBILITY PRODUCTS

At the limit of its equilibrium solubility, a compound is said to form a saturated solution in the
water. If the ions reach a concentration higher than saturation, they precipitate. This can
happen if a saturated solution is cooled. The dissolution of a solid salt is represented by the
equation:

Cm An  mCn+ + nAm-

Where M is the cation and A the anion and the equilibrium constant is given by:

KSP = [ C ]m [ A ]n

Where [] indicate concentration in mol/L. For example for calcium sulphate we have:

CaSO4  Ca2+ + SO42- KSP = [Ca].[SO4]

The constant KSP is called the “molar solubility product” of the salt. If the product of the
concentrations of the ions dissolved in water exceed the solubility product then precipitation
will occur forming scale on heat transfer surfaces and within the fill. For example adding
sodium sulphate to a solution of calcium chloride is likely to cause the solubility product of
calcium sulphate to be exceeded and calcium sulphate will precipitate to form scale. Values for
the molar solubility products of some common scale forming salts are given in the table below.
Note that these refer to pure water, as the presence of other contaminants can influence the
solubility of a compound.

Salt Formula KSP at 25C


Barium sulphate BaSO4 1x 10-10
Calcium sulphate CaSO4 2x 10-4
Calcium phosphate Ca3(PO4)2 2x 10-33
Calcium carbonate CaCO3 6x 10-9
Calcium fluoride CaF2 4x 10-11
Calcium hydroxide Ca(OH)2 5x 10-6
Magnesium carbonate MgCO3 6x 10-6
Magnesium hydroxide Mg(OH)2 5x 10-12
Magnesium fluoride MgF2 5x 10-11
Magnesium phosphate Mg3(PO4)2 1x 10-24

Document No: CEEDG007 Revision 2


Effective Date: September 2017 Page 15 of 17
Owner: CEE Design Consultants
Water Systems

APPENDIX 3

LANGELIER SATURATION INDEX

The compounds CO2, HCO3- and CO32- are actually linked by a complex series of reversible
reactions leading to kinetic equilibria. The reactions are normally collectively referred to as
carbonate chemistry. They begin with CO2 in the atmosphere. When atmospheric air comes
into contact with pure water, CO2 dissolves in water, the amount varying with the partial
pressure according to Henry's Law. Dissolved CO2 combines with water to form carbonic acid
(H2CO3) in another reversible reaction and then bicarbonate and finally carbonate:

CO2(dissolved) + H2O  H2CO3  H+ + HCO3-  2H+ + CO32-

Carbonic acid is an extremely unstable compound, so unstable that it only exists temporarily
before breaking down to form carbon dioxide and water, or else dissociating to form acid and
bicarbonate. It none-the-less exists in solution, if only fleetingly, and forms part of the
sequence of reactions of carbonate, all of which are subject to the Law of Mass Action when
the reactions are all in equilibrium.

The equilibrium constant for the reaction is given by:

-
[H + ] [HCO 3 ]
K =  4.14  10 7
[CO 2 ]

We can rewrite this equation in logarithmic form as:

logK = log[H+] + log[HCO3-] - log[CO2]

Using the definition of pH = -log[H+] and putting in the numerical value of K we have:

[HCO3 ]
log10  pH  6.38
[CO2 ]

In the case of normal waters, in which Ca2+ is the major cation, this equation holds quite well
between pH 4.5 and 8.2 and we can use it to predict changes in pH resulting from acid or
alkali dosing. Adding one mole of acid converts one mole of bicarbonate alkalinity to one mole
of carbon dioxide:

HCO3- + H+ = CO2 + H2O

So dosing x mole of acid gives:

[HCO3  x]
log10  pH  6.38
[CO2  x]

Similarly adding one mole of hydroxide converts one mole of CO2 into one mole of bicarbonate

CO2 + OH- = HCO3-

Document No: CEEDG007 Revision 2


Effective Date: September 2017 Page 16 of 17
Owner: CEE Design Consultants
Water Systems

The term Total Alkalinity or M Alkalinity, when used in water treatment parlance, refers to the
total concentration of bicarbonate, carbonate (usually low) and hydroxide (negligible at pH
<8.5) ions in water, so the bicarbonate concentration can usually be taken as the Alkalinity.

In an evaporative cooling tower the draft of air strips carbon dioxide from solution. If no
dissolved CO2 is available HCO3- ions take up H+ ions reverting to H2O and CO2. The CO2 which
is produced in this way is continuously taken away also, so that no equilibrium can be
established. H+ ions are therefore consumed and the pH rises. When it reaches 8.3, the
bicarbonate ions start to dissociate to form carbonate:

H+ + HCO3-  2H+ + CO32-

The equilibrium constant is:

-
[H+] [CO 3 ]
K =
[HCO3]

The CO32- forms CaCO3 with any Ca2+ in the water and precipitates, which is how a scale or
“fur” forms in kettles and pipes. The overall reaction can be written:

Ca(HCO3) = CaCO3 + CO2 + H2O

The solubility product of calcium carbonate is:

KSP = [Ca] [CO3]

The amount of hardness which will precipitate in this way is called the Temporary Hardness or
Carbonate Hardness. It is the amount of hardness or bicarbonate in the analysis, whichever is
the lower. In most waters the HCO3- content is lower than the hardness. The hardness which
is left after that is called the Permanent Hardness or Non-carbonate Hardness.

If we consider a water which is just saturated with calcium carbonate (that is, it will neither
deposit nor dissolve scale) we can write, using the shorthand form of pX = -logX:

pKSP = pCa + pCO3


pK = pH + pCO3 - pHCO3

Combining these two equations by eliminating pCO3 gives:

pH = pKSP -pK - pCa – pHCO3

This calculated value of pH is called the saturation pH and is designated as pHs. The difference
between the actual pH of the water and its theoretical pH s value (pH - pHs) is called the
Langelier Saturation Index and indicates whether the water will deposit calcium carbonate
(“scaling”) or dissolve calcium carbonate (“corrosive”). A positive LSI value indicates a scaling
water and a negative LSI a corrosive water.

Document No: CEEDG007 Revision 2


Effective Date: September 2017 Page 17 of 17
Owner: CEE Design Consultants