Water Treatment

Kostas D. Demadis

Investing in chemical cooling

water treatment
Precipitation fouling and corrosion create major problems in cooling systems within
the process industry. To prevent unexpected shutdowns and conserve water, Assistant
Professor Kostas D. Demadis of the Department of Chemistry at University of Crete
presents a strategic analysis of the entire chemical treatment process, starting from
proper selection of the treatment program, to proper application, to effective moni-
toring and maintenance of system performance.

hazardous) chemical cleaning (Frenier, 2001)

of the adhered scale after deposition occurs.

I
ndustrial water systems face several

Common examples of scales that require labo-

challenges related to formation of spar-

rious mechanical and potentially dangerous

ingly soluble electrolytes, corrosion and

cleaning are silica and silicate salts.

biofouling (Cowan and Weintritt, 1976).

Phosphorus-containing compounds and poly-

Cooling water systems, reverse osmosis

meric additives are integral parts of water

installations, boiler water systems, oilfield

treatment programs (Demadis, 2004). They have imposed additional challenges in

wells, all serving important industries (power

function as scale inhibitors by adsorbing onto treating process waters. Therefore, the
generation, municipal water, steam gener-

crystal surfaces of insoluble salts and prevent discovery and successful application of
ation, oil and gas production) may suffer from

Utility plants, manufacturing facilities, air- further crystal growth. chemical additives that have mild environ-
a multitude of water-originating problems.

conditioning systems are some applications mental impact have been the focus of several
that use “hot” processes for their operations. researchers (Demadis, 2005).
These processes have to be cooled by using (d) Cost considerations. Chemicals that
Investing wisely on a chemical water

water as the universal cooling medium In most water treatment programs, other constitute multi-component treatment
treatment program

because it is cost effective and has a high heat components are often formulated with scale programs have a cost associated with them.
capacity (Kemmer, 1988). After cooling water inhibitors. For example, “yellow metal” There are cost-effective programs and more
comes in contact with the “hot” process, it (copper, admiralty brass) corrosion inhibitors, costly ones. Budgetary concerns rather than
needs to be re-cooled for reuse. This cooling is dispersant polymers and tracers can be technological considerations often are respon-
achieved by evaporation in the cooling tower components of the same treatment, whereas sible for program selection. Either way, one
(Tanis, 1987). The end result is concentration biocides for microbial control, such as chlorine should taking into account the capabilities,
of all species found in water until reaching a or bromine, are usually fed separately. limitations, and costs of a variety of chemical
critical point of “scaling,” leading to precipi- Many factors must be taken into account treatment programs in order to select the most
tation, and ultimately to deposition of mineral during the chemical treatment program appropriate that fits the needs of the
salts. Species usually associated with these selection process. Among the most critical particular operation.
deposits, depending on water chemistry, are ones are the following: The success of a chemical treatment
calcium carbonate, calcium phosphate(s), (a) Water chemistry. Before selecting a program program depends largely on whether it is
silica/metal silicates, etc. Such undesirable one needs to know the species present in the properly applied so it fits the needs of the
deposition issues can be avoided with careful “make-up” (or raw) water and the process individual water system.
application of chemical water treatment tech- (recirculating) water. Increasing economical (a) Target cycles of concentration. Certain areas
nologies (Figure 1), which can be symbolized pressures dictate use of low quality water for have challenging make-up waters; others have
with a triangle. The sides of this triangle cooling purposes. This poses severe limita- very high water costs. Make-up water quality
represent three strategic approaches: (a) tions with regards to achieving high cycles of and cost will dictate the concentration cycles.
scale/deposit inhibition; (b) corrosion control; concentration because fouling becomes a (b) Definition of need for inhibitor dosage.
and (c) microbiological fouling prevention serious concern. Presence of other species in Chemical wastage can be avoided when
(Demadis, 2003). Prevention of scale formation water will dictate the treatment approach. For system operators have knowledge on water
is greatly preferred by industrial water users example, high chloride and sulfate content chemistry and requirements for actives levels.
to the more costly (and often potentially increase the risk for localized corrosion, Underfeeding may cause severe scaling
therefore measures have to be taken toward and/or corrosion phenomena, and over-
protecting the system from corrosion than feeding wastes chemicals.
from deposition. (c) Mechanical engineering integrity. Chemical
(b) Water tendency. In general, waters can be feed pumps have to be properly functioning at
either corrosive or scaling. “Soft” make-up all times, serviced frequently and checked
waters have virtually no scaling potential due periodically. This ensures that chemical feed is
ION

SC

to low concentrations of scaling ions, but can uninterrupted and at proper levels.
AL
OS

E
RR

be extremely corrosive. “Hard” waters on the To ensure satisfactory performance of the

DE

INDUSTRIAL
CO

PO

other hand pose a scaling/fouling risk that treatment program, operators are required to
WATER
S
ITS

PROBLEMS

requires treatment. The type of make-up water perform several physicochemical measure-
will dictate the final treatment approach. ments either in the field or in the laboratory to
(c) Environmental concerns. Increasing environ- provide proper monitoring. These are useful
BIOFOULING

¢ Figure 1. The water treatment “triangle”. mental concerns and discharge limitations indicators on whether a certain >>

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Water Treatment

CHEMICAL WATER TREATMENT PROGRAM SELECTION PROCESS

Program Program Program

Selection Application Operation
Criteria Assurance

Water Cycles of Corrosion

Chemistry Concentration Monitoring

Water Inhibitor Scale/Deposition

Tendency Dosage Monitoring

Environmental Mechanical Microbio

Concerns Engineering Monitoring
Integrity
Cost “Actives”
Monitoring

pH Control

¢ Figure 2. Chemical water treatment: from program selection to application to assurance.

component of the program is failing, or al., 1999). Water treatment chemicals can
whether the program is performing according degrade over time, or be depleted due to
to initial goals. precipitation. Occasionally, scale inhibitors
Corrosion monitoring can be done on-line precipitate as calcium salts because of over-
with commercially available corrosion feeding or because of high hardness.
monitors. An important point is that these Dispersant polymers can be consumed due to
need to be maintained properly, calibrated adsorption onto surfaces and oxidizing
frequently and the measurements have to be biocides to oxidize treatment chemicals.
complemented by observations based on Control of pH by use of acid is not
corrosion coupons. Monitoring of underde- uncommon. Failure to control pH can result in
posit corrosion is vital in systems with history pH upsets. These can cause corrosion rates to
of severe deposition problems. dramatically increase, thus endangering the
Scale monitoring can be accomplished by use integrity of the system.
of properly calibrated and functioning on-line Monitoring the efficiency of a heat exchanger
instruments. Water chemistry tests performed ensures proper system performance. If the effi-
on-site also offer great benefits. By monitoring ciency is lower than specified, then cleaning
▲Cycles (Cycles based on a non-scaling ion – (chemical or mechanical) may be needed to
Cycles based on scaling ion, eg. calcium), loss of restore system performance.
soluble species can be determined. Theoretically, The above strategic and holistic approach is
▲Cycles should be zero. A small increase is a represented schematically in Figure 2.
warning sign, whereas a “split” of 1 or higher
indicates active precipitation and deposition.
Microbiological growth monitoring in bulk
Author’s Note

water may be useful, however it can also be

Demadis is an Assistant Professor of Chemistry at the

deceiving, since it does not take into account

University of Crete in Greece. He is Head of the Crystal

biofilm growth, a critical phenomenon that

Engineering, Growth and Design Laboratory. He consults for

can have direct effects on heat transfer.

national and international chemical companies in the water

Usually maintenance of a low biocide residual

and wastewater treatment market and has extensive expe-

that is monitored carefully will ensure process

rience in water treatment research, product development

waters free of major problems.

and technical/field support. He can be contacted at +30

Monitoring of critical chemical treatment

2810 393651, via e-mail at demadis@chemistry.uoc.gr or

actives is necessary, ensures performance, and

http://www.chemistry.uoc.gr/en/

can indicate a problem in its genesis (Hale et

personnel/faculty/demadis.htm.

References
Cowan, J.C., Weintritt, D.J., 1976, Water-Formed Scale Deposits, Gulf Publishing Co., Houston, TX, U.S.A.
Demadis, K.D. and Katarachia, S.D. Metal-Phosphonate Chemistry: Preparation, Crystal Structure of Calcium-
Amino-tris-Methylene Phosphonate and CaCO3 Inhibition, Phosphorus, Sulfur, Silicon, 2004, 179, 627.
Demadis, K.D., Combating Heat Exchanger Fouling and Corrosion Phenomena in Process Waters, in Compact Heat
Exchangers and Enhancement Technology for the Process Industries; Editor: Shah, R.K, Begell House Inc.; New
York: 2003, p. 483.
Demadis, K.D. et al., Inorganic Foulants in Membrane Systems: Chemical Control Strategies and the
Contribution of “Green Chemistry”, Desalination 2005, 179, 281.
Frenier, W.W., Technology for Chemical Cleaning of Industrial Equipment, NACE Press, Houston, Texas, 2001.
Hale, E.R., Hoots, J.E., Nicolich, S.N., 1999, Tracers track down water problems, Power Engineering,
September, p. 21.
Kemmer, F.N., 1988, The Nalco Water Handbook, McGraw-Hill Company, New York.
Tanis, J.N., 1987, Procedures of Industrial Water Treatment, Ltan Inc., Ridgefield, CT.

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