By Greg Reyneke, MWS
The granular ion exchangers used in water softening systems were historically referred to as zeolites and nowadays, simply as resin when discussing synthetic ion exchange softening media. Natural zeolites exhibit unique porous structures and contain compounds of minerals that allow for true ion exchange to occur within their structures. These zeolites have been used in commercial water treatment for almost two hundred years and until the 1930s, it was the only way to consistently soften water. Natural zeolites exhibit many unique behaviors at the nano-level and should not be overlooked in today’s water treatment applications. We are only now discovering some of the benefits of these materials and when properly deployed and synthetically grown, aluminosilicate zeolites continue to prove themselves as powerful tools for manipulating water chemistry. For the purposes of this article and to enhance simplicity, we will assume that the ion exchange media discussed is a synthetic polymeric resin.
Most water treatment dealers are familiar with the concept of sodium or potassium salt-based ion exchange softening, and possibly even chloride-form anion exchange to address nitrates, sulfates and other similar contaminants, but there is much more to know. Simply stated, ion exchange is the reversible interchange of ions between a solid and a liquid in which there is no permanent change in the structure of the solid. An ion is an unbalanced atom or molecule that has a positive or negative charge resulting from this imbalance. Ions in water (aqueous ions) are what we work with in the field of water quality management.
Aqueous ion exchange can involve anions or cations, depending on the contaminants to be addressed. Tables 1 and 2 list some common ions that are typically involved in water treatment applications.
Ion exchange technology is used in residential, commercial and industrial processing applications to soften, condition and even to purify water. Ion exchange resins are also used in wastewater processing, horticulture and even aquatic ecosystems.
The first step in understanding ion exchange is to emphasize the actual exchange process, where one ion is exchanged for another, with the resulting byproduct(s) of exchange remaining in the treated water stream. Aqueous metallic ions are positively charged (cations); non-metallic ions are usually negatively charged (anions). Selection of resin for treatment, as well as the operating performance of that resin, depends on the concentration of contaminants in the water, including the resin’s relative affinity for the contaminants and their interfering factors.
Starting with soft water
The word hardness is a common term to describe the total amount of hard-water contaminants in water. The term was colloquially used to describe certain waters that caused difficulty in using soap; i.e., they made soap hard to lather. Untreated hardness can not only cause an increase in soap consumption, with the inevitable production of sticky soap curd (soap scum) deposits, but also result in the accumulation of scale in piping, boilers and water heaters that can waste energy and possibly even cause physical damage.
Since the term ‘easy water’ sounds awkward, the term ‘soft water’ was coined to describe water that doesn’t exhibit the common hard-water symptoms related to soap efficiency and scale accumulation. For most residential, commercial and non-critical industrial applications, hard water contains at least one gpg (17.1 mg/L) of calcium hardness. While many divalent and trivalent metallic cations can contribute to hard-water symptoms, the most commonly referenced hardness contaminants are calcium and magnesium ions, expressed as calcium carbonate (CaCO3). Strong acid cation (SAC) resin is used to soften water, using sodium or potassium salt as a regenerant.
As you can see in Table 3, a typical SAC resin is highly attracted to certain metals and less so to the regenerant ions (sodium and hydrogen), which is why we can deploy SAC so effectively in high-sodium waters and still be able to remove calcium (with some ionic leakage). The resin’s affinity varies with the ionic size and charge of the aqueous ion, generally favoring large, highly charged ions.
During regeneration, a less attractive ion (such as sodium) is used to regenerate the resin and the only reason it can force the entrained ions off the resin’s functional groups is because of its high level of concentration. This phenomenon is referred to as mass action. From a design perspective, we need to consider mass action carefully when calculating brine/rinse rates on high hardness waters and deciding on the brine-injection system design, since drawing the brine solution through the resin bed too slowly can result in reversal of the regeneration reaction and cause contaminants to be driven back into the resin media. I see this when dealers try to use undersized equipment on water with high hardness, high overall TDS or where there are significant amounts of other interfering metallic ions in the water. Remember that when working with cold water, you need fast-acting, highly structured resin beds with as much uniform surface contact as possible to ensure uniform performance.
While the stable cation exchange reaction during water softening is very forgiving of operator error, you have a duty to your clients to minimize chloride discharge, backwash water usage and regenerant consumption, all while promoting the operational longevity of the system itself. You can accomplish this by utilizing high-quality resins, advanced-control electronics and incorporating best practices for regeneration efficiency, as well as protecting the media from oxidative damage.
Referring back to Table 3, we can also observe the relative affinity of strong base anion (SBA) resin, which is the second-most popular resin used by water quality improvement professionals in the US. Many dealers have used SBA resin to address sulfates, nitrates and silicates in water, but all too often the rationale for use and an understanding of complicating factors in the water are grossly misunderstood. Unless specifically engineered to be selective for one anion over others, SBA resins are attracted to all the ‘-ates’ in descending order by their molecular size and valence charge.
A common oversight when using SBA for nitrate removal is to deploy a general purpose SBA in sulfate-bearing waters where the sulfate concentration overwhelms the nitrate-laden resin as it becomes exhausted. This results in potentially dangerous dumping of nitrates back into the water. Look at the big picture in cases like this and either use a nitrate-selective resin or properly calculate the impact of sulfates and silicates in the water, which will enable you to calculate the true capacity of the resin during service instead of merely its capacity for the one thing that you’re wanting to address.
Modern purpose-built macroporous SBA resins are highly effective at removing tannins from water. I encourage dealers to use tannin-selective resins as part of the treatment train when dealing with colored-water issues involving natural organic materials, such as fulvic or humic acid compounds. Remember again that even though you are addressing tannins, SBA ion exchange resin is attracted to other contaminants in the water, which means that you should test for them to ensure the system will to work as anticipated.
Type 2 strong base anion resin is less selective for general anions and employed primarily in dealkalization applications while operating in the chloride form. When regenerated with acid, the resin will split alkaline salts, converting them to carbonic acid. This resin boasts extremely high regeneration efficiencies and usually receives its functional exchange capacity from carboxylic groups. Countless low-pressure boilers worldwide are being effectively protected by the combination of a sodium softener and chloride dealkalizer. A properly designed anion dealkalizer can remove as much as 95 percent of the carbonate (CO32-) and bicarbonate (HCO3–) alkalinity as well as up to 99 percent of the sulfates (SO42-) and nitrates (NO3–). A dealkalizer will yield substantially higher capacity when regenerated with both salt (for chloride) and a hydroxyl donor like caustic soda.
Weak acid cation (WAC) resin has a high selectivity for divalent cations, such as copper and nickel (especially at neutral to alkaline pH levels), so it is naturally an excellent choice in wastewater applications as a cost-efficient alternative to chelating resins. WAC resins have the highest capacity of any currently known ion exchange material in the general marketplace, which makes it ideal for deployment in conjunction with SAC resin to maximize performance and cost efficiency. This high-capacity naturally means that it both shrinks and swells significantly under various conditions of operation, so exercise appropriate caution if you decide to mix SAC and WAC in the same tank.
Ion exchange is one of the most cost-effective and reliable water quality improvement technologies in the marketplace today, proving itself year after year as the gold standard for cost, performance, simplicity and consistent dependability. From where your resin is sourced, under which standards it was manufactured, where it was stored and most importantly how it is deployed, are factors that will have a significant impact on the success of your projects. Take the time to learn more about the resins that you use and would like to use; evaluate their sustainability cycle, best practices for use and of course, buy from reputable distributors who are willing and able to support you.
Images courtesy of C.F. ‘Chubb’ Michaud
About the author
Greg Reyneke, Managing Director at Red Fox Advisors, has two decades of experience in the management and growth of water treatment dealerships. His expertise spans the full gamut of residential, commercial and industrial applications, including wastewater treatment. In addition, Reyneke also consults on water conservation and reuse methods, including rainwater harvesting, aquatic ecosystems, greywater reuse and water-efficient design. He is a member of the WC&P Technical Review Committee, Past President of the PWQA Board of Directors and chairs the Technical and Education Committee. You can follow him on his blog at www.gregknowswater.com