A Look at Closed Cooling Water Issues

Brad Buecker, Buecker & Associates, LLC

Posted 11/19/2024

Protecting Cooling Water Systems – Part 6

Introduction

In the previous installments of this series, we examined important water treatment issues for open recirculating cooling systems that have a cooling tower as the primary heat exchanger.  While the main system may directly supply one or more large heat exchangers such as a steam surface condenser, it also supplies numerous closed cooling networks, whose general schematic is shown in Figure 1.  

Part 1 Part 2 Part 3 Part 4 Part 5


Figure 1.  Closed cooling system circuit with primary cooling supplied from a cooling tower. (1)

Reference 2 offers a good description of closed systems.

A “closed” system has no more than one point of interface with a compressible gas or surface.  This means that a system with an open or vented expansion tank is a closed system even though there is some contact with the atmosphere.  An “open” system has more than one point of interface with the atmosphere.  A cooling tower, for example, has points of contact with the atmosphere at the [location where] the water is distributed [to the cooling tower fill] and in the basin.  A commonly used definition of a “tight” closed system is one that loses 5% or less of its system volume on an annual basis.  Systems that meet these criteria minimize the contact between the most common corrosive agent in water, dissolved oxygen, and the metals within the network.  However, chemistry control of closed systems is still very important.  Even though an individual closed network may be just a fractional portion, size-wise, of the overall cooling configuration, a system failure can bring down a unit process, or perhaps even the entire plant.  Accordingly, conscientious water treatment should be part of what IDCON INC emphasizes as their Root Cause Problem Elimination (RCPE) philosophy. 

Closed Cooling Applications

Once upon a time, the author was responsible for the treatment of several closed cooling networks at two coal-fired power plants.  Systems included:

  • Pump bearing cooling
  • Electrical generator hydrogen cooling
  • Lubricating oil cooling
  • Building heat systems

Numerous additional closed cooling applications exist other industrial facilities.  A key issue for this discussion is that many systems, including those listed above, often operate with high-purity condensate as the working fluid.  That aspect usually eliminates scale formation and allows focus on corrosion control, as outlined in the next sections.

Closed Cooling System Metallurgy

“Closed recirculating systems are typically constructed of ferrous (steel) and copper alloys.  In most cases, piping is ‘mild’ (low carbon) steel.  Heat exchangers such as raw water heat exchangers, chiller evaporators and air handlers are constructed of copper, Admiralty brass or 90-10 copper-nickel.  Some heat exchangers may have stainless steel tubes.” (2)  Stainless steel is a common choice for plate and frame heat exchangers, an example of which is shown in Figure 2.  This article focuses on corrosion protection for these metals, although in some cases other metals such as aluminum may be present.

Figure 2.  External view of a plate and frame heat exchanger.  Plate material is 316 stainless steel. (1)

Corrosion Issues and Control Methods      

Part 4 of this series examined the underlying principles of important corrosion mechanisms for open cooling systems.  Many of the general principles also apply to closed systems, especially regarding anode/cathode formation within the water-touched environment and the importance of inhibiting corrosion cell development.  In a tight system with little water loss and minimal makeup requirements, only small amounts of dissolved oxygen enter the system.  This simplifies corrosion control.  The situation changes if large leaks develop, which we will discuss shortly, particularly as it relates to corrosion inhibitor dosages.

Carbon steel piping often constitutes the bulk of the material within a closed system.  Iron is an element that readily attempts to revert to its natural, oxidized state, so a key for mild steel corrosion protection is to induce formation of a passive surface layer.  During the middle of the last century, treatment programs utilizing sodium di-chromate (Na2Cr2O7) became a popular choice for mild steel corrosion control in both open and closed systems.  Chromate ions will form what has been termed a “pseudo stainless steel” layer on carbon steel that is quite protective.  However, toxicity issues with hexavalent chromium (Cr6+) led to elimination of chromate treatment from nearly all cooling water applications.  Two of the most common alternatives are nitrite and molybdate.

Nitrite

Sodium nitrite (NaNO2) represented a safe and inexpensive replacement for chromate.  Formulations often include a pH conditioning agent or buffer such as sodium tetraborate (or perhaps even a small amount of sodium hydroxide) to maintain pH within an 8.5 to 10.5 range. (2)

This author first began working with nitrite in the 1980s.  Chemical feed was straightforward – a once per week charge of granular sodium nitrite/pH buffer into a pot feeder connected to a cooling water slipstream line.

Figure 3.  Basic schematic of a pot feeder configuration.

This design was quite sufficient to maintain nitrite concentrations within guidelines for “tight” networks.  Modern chemical systems are available that potentially offer improved feed control, if needed.  

Nitrite promotes the formation of a passive iron oxide layer on the metal surface.  It first reacts at anodes, and for this reason is known as a “dangerous” inhibitor, because if residuals fall below threshold limits, a small number of anodes can develop in a large cathodic environment.  Rapid pitting is likely.  A usually safe nitrite range is 500-1,000 parts-per-million (ppm) to inhibit general corrosion and pitting, but every application requires careful monitoring and control.  If system leaks prevent the maintenance of adequate residuals, the treatment should be halted until the leaks are repaired. Compounding this problem is that excess leakage pulls in additional oxygen via the makeup.  The combination of no passivating agent and increased oxygen levels can also lead to serious corrosion.

Figure 4.  Oxygen pitting in a condensate return line.  Photo courtesy of ChemTreat.

Proper preventive maintenance involves regular monitoring of makeup water usage and prompt leak repairs if readings indicate substantial water loss.  A water meter on the makeup line can provide the necessary data.  Often, visual observations will alert plant personnel to a leak, but I was involved in several projects over the years in which leaks were not visible, but use of ultrasonic flow meters allowed us to identify the particular circuit that was having problems.  We then could zero in on the specific location.  In one case, the issue was a large leak that occurred in an underground portion of the piping.  Excavation was necessary to repair the pipe.

Another concern is that nitrite is a nutrient for nitrifying bacteria such as Nitrobactera agilis, which can grow rapidly by converting nitrite to nitrate.  For example, the author was once part of an inspection team that visited an automobile assembly plant, where nitrifying bacteria and the protective slime that these microbes produce had partially plugged the small, serpentine cooling water tubes in automatic welders.  Other nitrifying or denitrifying bacteria may also grow within systems treated with sodium nitrite.    

One potential remedy is periodic but regular feed of a non-oxidizing biocide.  Common non-oxidizers include but are not necessarily limited to:

  • Glutaraldehyde
  • Isothiazolones
  • Tetrakishydroxymethyl phosphonium sulfate (THPS)
  • 2,2-dibromo-3-nitrilopropionamide (DBNPA)

Consultation with a chemical treatment expert is important for selecting the best compound.  Furthermore, if the possibility exists for any streams containing these chemicals to enter the facility’s wastewater discharge, plant personnel must receive approval from the appropriate environmental regulators prior to any testing or subsequent permanent use. 

Molybdate

Sodium molybdate (Na2MoO4) is an alternative to nitrite.  Research suggests that molybdate acts similarly to chromate and absorbs onto the carbon steel surface at anodes and forms a protective iron-molybdate layer. 

Evidence further indicates that molybdate acts as a pitting inhibitor per its ability to accumulate within the acidic zone of a pit and block the corrosion process. (3, 4) A common control range for molybdate is roughly 1/3 that of nitrite. Although molybdate is an oxyanion, some research, which has been debated, suggests that the compound requires residual dissolved oxygen to be fully effective.  Enough oxygen may enter through the cooling water makeup to provide the needed amount.  As with nitrite, molybdate formulations typically include a pH buffer to establish moderately alkaline conditions in the cooling water.  Unlike nitrite, molybdate is not a food source/nutrient for microbes.

Molybdate is an expensive chemical, and costs may be prohibitive in some applications.  Programs have been developed that employ both nitrite and molybdate, which act synergistically and lower the concentration of either chemical when utilized alone.

Copper Alloy Corrosion Control

Copper alloys have been a prime choice for heat exchanger tubes for many years due to copper’s excellent heat transfer properties.  While copper is a more noble metal than iron, significant corrosion is possible in certain environments, for example a combination of dissolved oxygen and ammonia.  Azoles are commonly employed to protect copper alloys, via film-forming chemistry.  Figure 5 illustrates the general effect.

Figure 5.  Illustration of copper alloy corrosion inhibition by azoles.  Figure courtesy of ChemTreat.

The nitrogen atoms in azole molecules bond with copper atoms at the metal surface. The plate-like organic rings then form a barrier to protect the metal from the bulk fluid.  Figure 5 shows the simplest compound, benzotriazole, but others including tolyltriazole and 2-mercaptobenzothiazole (MBT) are available.  The modified azoles improve filming efficiency and/or resistance to biocides.   

An azole concentration as low as 1-2 ppm may be sufficient for corrosion control, but higher levels might be necessary depending on system layout and conditions.

Other Passivating Agents

Not uncommon is for a closed cooling treatment formulation to have a reducing agent to help maintain metal passivity.  For years in the power industry, hydrazine (N2H4) served as the common reducing agent for boiler condensate/feedwater systems.  Changes in chemistry programs and safety issues greatly reduced hydrazine applications, but hydrazine substitutes are available for boiler feedwater and closed cooling systems.    

Chemistry Monitoring

As hinted at above, closed system chemistry monitoring is very important, especially if a “dangerous” inhibitor such as sodium nitrite is employed.  Straightforward-to-use test kits are available for monitoring the residual concentrations of the standard corrosion inhibitors.  Bench top instrumentation such as UV-VIS (ultraviolet-visible wavelength) spectrophotometry offers accurate readings.

Figure 6.  A modern UV-VIS spectrophotometer.  Photo courtesy of Hach.

Other important analyses include:

  • pH:  Maintaining pH within the recommended range maximizes inhibitor effectiveness and reduces the potential for general corrosion.  A noticeable pH change may indicate microbiological fouling.
  • Specific Conductivity:  A drop in conductivity may indicate increased system leakage, where water loss is replaced by high-purity, lower conductivity condensate.  A water meter on the makeup line will provide direct measurements of water usage.
  • Nitrate and Ammonia:  An increase in either of these compounds suggests increased microbiological activity.

Because microbial growth occurs frequently in closed systems, regular monitoring can detect the onset of fouling.  Dip slide testing is straightforward and does not require exotic laboratory equipment.  If fouling occurs, specialized tests can identify the problematic microorganisms, including sulfate reducing bacteria (SRB), nitrifying bacteria and denitrifying bacteria. (2)

Common for corrosion monitoring is installation of a corrosion coupon by-pass rack, with coupons having the same metallurgy as the cooling network materials.

Figure 7.  A properly configured corrosion coupon rack.  Illustration courtesy of ChemTreat.

An important feature of correct design is coupon orientation.  As is evident in Figure 7, the orientation is with the water flow along and not against the coupon. This configuration helps to minimize eddy currents.  The piping can be configured to hold multiple coupons, which can be extracted at user-selected intervals.  

A supplemental and effective corrosion monitoring technique is iron analysis, which can also be performed by UV-VIS spectrophotometry.  Because 90% or greater of steel corrosion products usually exist as iron oxide particulates, the test procedure requires a 30-minute digestion process to convert particulate iron to dissolved form.  The total iron concentration provides valuable data on the efficacy of corrosion treatment. (5)

Systems with Glycol Solutions    

Cooling systems that are subject to low-temperature conditions often operate with ethylene or propylene glycol solutions to prevent freezing.  “Both phosphates and nitrites are [acceptable] as ferrous alloy corrosion inhibitors, [and] azoles are [effective] for copper alloy corrosion inhibition [in glycol system solutions].” (2)  An issue with glycol, as it is in other equipment including automobiles, is that over time the chemical will break down to organic acids that lower pH and increase corrosion potential.  Accordingly, regular pH measurements are valuable for monitoring and periodically refreshing glycol-treated cooling systems.

Sidestream Filtration

Even in systems with good chemical treatment some metal corrosion will occur, particularly from the often-massive carbon steel piping network.  These particulates can settle in low flow areas and locations of high heat transfer, i.e., heat exchangers.  Sidestream filtration will remove particulates and reduce deposition within the cooling system.  Equipment may range from basic basket filters that require simple manually cleaning to automatically backwashed units.  Numerous options are available.

Figure 8.  Dual compartment basket strainer on a high-purity makeup water treatment line.  Differential pressure readings alert operators to the need for basket cleaning, at which time they manually switch flow to the other compartment.  Photo by Brad Buecker. (6)

Cleaning the Cold-Water Side of Closed System Heat Exchangers – Case History

While closed systems, and particularly those with condensate as the working fluid, do not normally suffer from scaling issues, the same is not necessarily true in the exchanger that transfers heat from the closed loop to the open loop (refer again to Figure 1).  The water supply coming from a cooling tower or perhaps a once-through system typically contains hardness and alkalinity that precipitate when heated.  Even with proper cooling water treatment, deposits gradually build up on the “open loop” side of the heat exchanger tubes or plates.  These deposits naturally reduce heat transfer and process efficiency.

Many large plants have numerous closed systems scattered over a large area, which can make the logistics of cleaning the exchangers difficult.  Consider the following example, where at one plant my laboratory crew and I worked with the maintenance team to assemble a portable cleaning unit that could be manually wheeled from location to location.

Figure 9.  Cleaning cart showing tank and heater.  Photo by Brad Buecker.

The main cart included a Chromalox heater and blending tank with water connection for loading and mixing of dry chemicals to desired concentrations.  The equipment included a second wheeled cart with a diaphragm pump to circulate warm solution from the heater tank through the heat exchanger and return.  Quick-connect couplings on the tank, pump and heat exchanger chemical cleaning isolation valves allowed rapid hose attachment and removal during projects.

This assembly also allowed us to improve cleaning chemistry.  The previous supervisor was locked in on using solutions containing hydrochloric acid (HCl) for cleaning.  Yes, HCl removed deposits, but it also attacked heat exchanger material, such that samples taken from cleanings typically exhibited a very pronounced greenish color, indicating dissolved metal ions in solution.

With the aid of this portable unit, we began using solutions containing relatively small percentages of sulfamic acid, citric acid (if conditions warranted), and corrosion inhibitor, heated to a range of 100o-150F.  The solution was quite effective at removing hardness deposits without attacking steel and copper alloys.  

As a side note, I was once peripherally involved in a project where the heat exchanger tubes had been fouled with calcium sulfate (CaSO4).  Mineral acids will not dissolve calcium sulfate, but we had success using the chelant EDTA (ethylenediaminetetraacetic acid).  An equipment arrangement such as that outlined above allows plant personnel to prepare a variety of chemical formulations depending on the application.  Of course, safety is the most important consideration during planning and execution of any project, with or without chemical usage. 

Closed Cooling Water Issues – Conclusion

Large industrial facilities frequently have many closed cooling water systems.  Plant personnel may, at times, overlook important issues related to water treatment and corrosion minimization within these networks; that is until a failure brings down a system and perhaps a unit operation, or worse.  An important part of any preventive maintenance program is conscientious monitoring and control of cooling water chemistry.             


References

  1. Post, R., and B. Buecker, “Power Plant Cooling Water Chemistry”; pre-conference seminar to the 33rd Annual Electric Utility Chemistry Workshop, June 11-13, 2013, Champaign, Illinois.
  2. K. A. Selby, “Closed Cooling and Heating Systems in Power Plants”; presented at the 22nd Annual Electric Utility Chemistry Workshop, May 7-9, 2002, Champaign, Illinois.
  3. B. Buecker, “Current Concepts in Cooling Water Chemistry”; pre-conference seminar to the 41st Annual Electric Utility Chemistry Workshop, June 6-8, 2023, Champaign, Illinois.  Acknowledgement to Ray Post, P.E., for contributions of much material to this presentation.
  4. B. Buecker (Tech. Ed.), “Water Essentials Handbook”; 2023. ChemTreat, Inc., Glen Allen, VA.  Currently being released in digital format at www.chemtreat.com.
  5. Hach Water Analysis Handbook
  6. B. Buecker, “Microfiltration: An Up-and-Coming Approach to Pre-Treatment for the Power Industry”; presented at the 26th Annual Electric Utility Chemistry Workshop, May 9-11, 2006, Champaign, Illinois.

Note:  The above reference list includes several papers/presentations from previous Electric Utility Chemistry Workshops.  For over 40 years, this event has provided practical and valuable information (at very reasonable cost) to industry personnel, and not just those in power.  In recognition of that fact, we have renamed the event the Electric Utility & Cogeneration Chemistry Workshop (EUCCW).  For Maintenance World readers at refineries, steel mills, chemical plants, etc., who deal with steam generation, cooling water, makeup water, and industrial wastewater chemistry and treatment, our next workshop will be June 2-4, 2025, in Champaign, Illinois.  


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Brad Buecker

Brad Buecker is president of Buecker & Associates, LLC, consulting and technical writing/marketing. Most recently he served as a senior technical publicist with ChemTreat, Inc. He has many years of experience in or supporting the power industry, much of it in steam generation chemistry, water treatment, air quality control, and results engineering positions with City Water, Light & Power (Springfield, IL, USA) and Kansas City Power & Light Company's (now Evergy) La Cygne, KS, USA, station. His work has also included eleven years with two engineering firms, Burns & McDonnell and Kiewit, and he spent two years as acting water/wastewater supervisor at a chemical plant.

Buecker has a B.S. in chemistry from Iowa State University with additional course work in fluid mechanics, energy and materials balances, and advanced inorganic chemistry. He has authored or co-authored over 250 articles for various technical trade magazines, and has written three books on power plant chemistry and air pollution control. He is a member of the ACS, AIChE, AIST, ASME, AWT, the Electric Utility Chemistry Workshop planning committee, and he is active with the International Water Conference and Power-Gen International.

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