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A Specifying Engineers Guide to Water Treatment | IHS Engineering360

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A Specifying Engineers Guide to Water Treatment

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Many requests-for-proposals (RFP) for new combined-cycle power plants contain a flaw. In the majority of cases, it is
apparent that the project developers (and often the owners engineer) do not fully understand the importance of
water treatment and steam generation chemistry. Often, insufficient raw water quality data is provided at the outset.
This makes precise design of the makeup water system difficult or impossible to achieve. Also, in the competitive
business of bid preparation, projects often are awarded to the low bidder without sufficient thought given to whether
the design or equipment offering is satisfactory. Then, after commissioning, and when systems underperform or even
fail, the owner and operators are placed in a severe bind.
Whats more, many RFPs specify out-of-date or discredited chemical treatment programs. A primary example for heat
recovery steam generators (HRSGs) is a continued belief in the need for oxygen scavengers (a more accurate term
is reducing agent) as a feedwater treatment. This article explores some of these specifying issues.
Makeup Water Treatment Design
Fresh water supplies are no longer ubiquitous for power plant makeup. Increasingly, plants have to use treated
municipal wastewater, poor quality groundwater or other less-than-ideal supplies. Raw water quality greatly impacts
the design, and often the sizing or redundancy, of the makeup water treatment system and pre-treatment equipment.
Here are a few of the constituents in raw water that must be accounted for in system design:
The hardness ions, calcium and magnesium (Ca and Mg). These can react with alkalinity and silica in the water
to form scale in reverse osmosis (RO) systems and ion exchange units.
Bicarbonate alkalinity (HCO3 -). As the concentration increases in an RO unit or as temperature increases in a
heat exchanger, alkalinity can react with calcium to form calcium carbonate (CaCO3 ) deposits.
Silica (SiO2 ). Silica chemistry is complex. Silica can form scale, but more often combines with magnesium and
sometimes calcium to form silicate scales. These are very difficult to remove. Silicate scale formation becomes
more pronounced with increasing pH. However, if no hardness ions are present, higher pH will keep SiO2 in
solution. The latter chemistry is the basis for a membrane-based wastewater treatment technology that is
becoming more popular. [1]
Chloride (Cl). Chloride is a notorious pitting agent of stainless steels, especially underneath deposits.
Sulfate (SO4 ). Sulfate will combine with calcium to form deposits, although the solubility of CaSO4 is
considerably higher than CaCO3 . However, the deposits are difficult to remove. Sulfate will also form tenacious

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scales, particularly in RO systems, with barium and strontium. These metals typically exist in trace quantities in
raw water, but, if present in large enough concentrations, can cause problems.
Iron and manganese (Fe and Mn). These metals exist in a number of valence states. If they enter treatment
systems in dissolved form, they can cause fouling and sometimes corrosion.
Suspended solids can be death to RO membranes and must be removed prior to RO treatment.
As a result, raw water analyses for any new project should include these elements or compounds along with pH, total
dissolved solids (TDS), phosphorus, fluoride, ammonia, oil and grease, and total organic carbon (TOC). Also, for any
system that uses reverse osmosis, silt density index (SDI) tests are a requirement for the RO feed. A single snapshot
analysis set is not sufficient; rather, multiple and historical data are needed.
During large power plant construction in the last century, a common treatment design was clarification/filtration,
followed by ion exchange. While this technology was often effective, problems sometimes arose. Changes in flow,
temperature and other factors caused solids carryover from clarifiers, which, in turn, induced downstream fouling.
Clarifiers were large structures, often circular or cone-shaped, that had broad footprints. A common design criteria
for clarifiers is the rise rate, which is gallons perminute (gpm) of flow divided by the area of the water surface. A
reasonable rise rate for older clarifiers is 1 gpm/ft2 . Modern systems may now be able to achieve rise rates of 25
gpm/ft2 or more in some applications.
A formerly common arrangement for demineralizers was cation-anion-mixed bed ion exchange, although variations
were not infrequent. Regardless, clarification does little or nothing to remove dissolved solids, so the TDS loading on
the cation and anion beds was quite substantial. Resins will quickly exhaust in these conditions, and must be
regenerated regularly with acid (typically sulfuric) and caustic.
For these reasons, makeup water treatment evolved considerably. A common scheme today is micro- or ultrafiltration
(MF, UF) for suspended solids removal, two-pass RO for primary TDS removal, and portable mixed-bed ion exchange
or electrodeionization (EDI) for final polishing. These technologies have greatly improved makeup system reliability
and final water quality, but they are not foolproof. Issues that may arise include:
Excessive surges in suspended solids can foul MF and UF membranes.
Use of cationic polymers for coagulation or flocculation ahead of membrane systems may cause problems, as
the polymers will coat the (typically) negatively-charged membranes.
For MF and UF membranes, the choice of outside-in vs. inside-out flow through the membranes may have

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A Specifying Engineers Guide to Water Treatment | IHS Engineering360

significant consequences.
Membrane cleaning methods may induce scale formation depending upon the concentration of some impurities
in the dilution water.
Although some vendors claim otherwise, in the authors experience, EDI requires feed from a two-pass RO, not
single-pass RO only.
Now let us examine a steam generation chemistry topic that continues to be misunderstood.
Forget the Oxygen Scavenger
Unlike coal-fired power plants, the condensate/feedwater system of an HRSG does not have feedwater heaters other
than perhaps a deaerating heater. Thus, the entire network from the condenser to the low-pressure evaporator is all
steel, with no copper alloys present. Even so, many HRSG proposals continue to call for oxygen scavenger feed to
the condensate. This chemistry has been discredited as it is known that conditions produced by the reducing agent
help to propagate and induce single-phase flow-accelerated corrosion (FAC).
Single-phase FAC occurs at flow disturbances such as elbows in feedwater piping and economizers, locations
downstream of valves and reducing fittings, attemperator piping, and, most notably for the combined-cycle industry,
in low-pressure evaporators. The effect of single-phase FAC is illustrated in the image.

Wall thinning occurs gradually until the

remaining material at the affected
location can no longer withstand the
process pressure. Catastrophic failure
may occur. Temperature and pH also
influence single-phase FAC, with
maximum corrosion occurring at 300o F
and as pH drops towards and below 9.0.
In an HRSG, flow-accelerated corrosion
is typically maximized in the units lowpressure economizer and evaporator,
with their many short-radius elbows and
temperatures in proximity to 300o F.
However, the corrosion also can occur
in other locations including
intermediate-pressure circuits. Also,
equipment such as deaerators that
experience a mixture of water and steam
may be subject to two-phase FAC.
Continued research is improving the
battle against FAC. For those in the
industry who have grasped that the old
AVT(R) program (ammonia or amine
feed for pH control and reducing agent
feed for oxygen removal and metal
passivation) is no longer valid, the
popular replacement is all-volatile
treatment (oxidizing). With AVT(O), the
small amount of oxygen that enters via
condenser air in-leakage is allowed to
remain, and may be supplemented with
a small, pure oxygen feed. Ammonia (or
in some cases amine) is still ued to
Photo of tube-w all thinning caused by single-phase FAC. Im age source: Chem Treat. elevate the feedwater pH. At feedwaterspecific conductivity below 0.2 S/cm,
this chemistry causes the magnetite layer on carbon steel to become interspersed and overlayed with a stronger,
denser layer of ferric oxide hydrate (FeOOH), which essentially eliminates FAC in those locations. New guidelines
recommend a dissolved oxygen concentration of 5 to 10 parts-per-billion at the LP economizer inlet as lower
concentrations might allow gaps to form in the FeOOH coverage.
References
1. B. Buecker, Lessons Learned from a High Recovery RO-Based ZLD System; CTI Journal, Vol. 35, No. 2,
Summer 2014.
To contact the author of this article, email Engineering360Editors@ihs.com

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